Selection of Entrainer and Vapour–Liquid Equilibrium Data for Cyclohexene and Cyclohexane Near-Boiling Systems at 101.3 kPa.

In the production of cyclohexene by benzene hydrogenation, the by-product cyclohexane forms an azeotrope with cyclohexene. For the extraction and distillation of the binary azeotrope (cyclohexene + cyclohexane), the selectivity and relative volatility of 24 different entrainers were compared and the intermolecular interaction forces and interaction energies were analyzed by the DMol3 module of Materials Studio (MS). <italic>N</italic>, <italic>N</italic>-dimethylformamide (DMF) was identified as the entrainer, and vapour–liquid equilibrium (VLE) data were measured at atmospheric pressure for the binary system {cyclohexane + cyclohexene} with a temperature range of 354 K to 356 K, the binary system {cyclohexane + DMF} with a temperature range of 354 K to 390 K, and the binary system {cyclohexene + DMF} with a temperature range of 357 K to 421 K. In addition, the thermodynamic consistency of the experimental data was checked using the Wisniak and Van Ness method. The Wilson, NRTL, and UNIQUAC models were used to regress and fit the experimental data to optimize the binary interaction parameters, and the root mean square (<italic>RMSD</italic>) and average absolute deviation (<italic>AAD</italic>) values of all models were below 0.01%, indicating that the experimental data provide a basis for the simulation and optimization of the extractive distillation process. [ABSTRACT FROM AUTHOR]