Effective Absorption of Dichloromethane Using Carboxyl-Functionalized Ionic Liquids

Abstract

Dichloromethane (DCM) is recognized as a very harmful air pollutant because of its strong volatility and difficulty to degrade. Ionic liquids (ILs) are considered as potential solvents for absorbing DCM, while it is still a challenge to develop ILs with high absorption performances. In this study, four carboxyl-functionalized ILs—trioctylmethylammonium acetate [N1888][Ac], trioctylmethylammonium formate [N1888][FA], trioctylmethylammonium glycinate [N1888][Gly], and trihexyl(tetradecyl)phosphonium glycinate [P66614][Gly]—were synthesized for DCM capture. The absorption capacity follows the order of [P66614][Gly] > [N1888][Gly] > [N1888][FA] > [N1888][Ac], and [P66614][Gly] showed the best absorption capacity, 130 mg DCM/g IL at 313.15 K and a DCM concentration of 6.1%, which was two times higher than the reported ILs [Beim][EtSO4] and [Emim][Ac]. Moreover, the vapor–liquid equilibrium (VLE) of the DCM + IL binary system was experimentally measured. The NRTL (non-random two-liquid) model was developed to predict the VLE data, and a relative root mean square deviation (rRMSD) of 0.8467 was obtained. The absorption mechanism was explored via FT-IR spectra, 1H-NMR, and quantum chemistry calculations. It showed a nonpolar affinity between the cation and the DCM, while the interaction between the anion and the DCM was a hydrogen bond. Based on the results of the study of the interaction energy, it was found that the hydrogen bond between the anion and the DCM had the greatest influence on the absorption process.