Study on separation of methanol and dimethyl carbonate azeotropic system with deep eutectic solvents

• Published in: Journal of molecular liquids Vol. 399; p. 124301
• Main Authors: Li, Renting, Chu, Suying, Cui, Chuanxin, Jia, Kai, Li, Jun
• Format: Journal Article
• Language: English
• Published: Elsevier B.V 01.04.2024
• Subjects: Deep eutectic solvent; Extractive distillation; Quantum chemistry calculation; Separation of binary azeotropes; Quantum chemistry calculation; Deep eutectic solvent; Extractive distillation; Separation of binary azeotropes
• ISSN: 0167-7322; 1873-3166
• DOI: 10.1016/j.molliq.2024.124301

•Five choline chloride-based DESs screened by the COSMO-SAC model for DMC-MeOH separation.•VLE experiments confirm ChCl-urea DES excels in DMC-MeOH azeotrope separation.•Mechanism of DES (choline chloride-urea) formation and extraction explained using quantum chemistry.•Hydrogen bonds play a key role in separating DMC-MeOH azeotrope. Dimethyl carbonate (DMC) is an important diesel and gasoline additive that is also a low-toxic and environmentally friendly chemical raw material. However, it will form an azeotrope with methanol (MeOH) during the actual chemical production process. Therefore, separating high-purity DMC from the azeotrope is of significance. In extractive distillation, deep eutectic solvents (DESs) have demonstrated superior separation performance as green extractants. This study calculated the σ-profiles of DMC, MeOH, and DESs by the COSMO-SAC model to examine the most appropriate DES for the MeOH and DMC separation. Eventually, DES1(1:2 choline chloride (ChCl): malonic acid (MA)), DES2(1:2 ChCl: urea), DES3(1:2 ChCl: glycerol (G)), DES4(1:2 ChCl: ethylene glycol (EG)), DES5(1:2 ChCl: pyruvic acid (PA)) were designated as preferred extractants. The vapor pressures of five DESs at different temperatures were determined using a thermogravimetric analyzer, while their critical properties, normal boiling points, and acentric factors were predicted. The vapor–liquid equilibrium (VLE) data measured for DMC + MeOH + DESs ternary systems at 101.3 kPa showed that the addition of 15 mol % of any of the five DESs could successfully break the azeotrope and DES2 achieved a higher degree of separation in the MeOH-DMC binary azeotrope compared to the other DESs evaluated. The binary interaction parameters between MeOH/DMC and DESs were calculated through the NRTL (Non-Random Two-Liquid) model, and the fitting results were found to be consistent with the experimental data. The mechanism of the MeOH-DMC separation by DES2 was elucidated through quantum chemical (QC) calculations. The improved independent gradient model (IGMH) and the theory of atoms in molecules (AIM) demonstrated that the stronger interaction between DES2 and MeOH molecules is the key for DES2 to break the azeotrope of the system.