Insights into the role of VOCs properties on thermal desorption behaviors of two porous polymeric resins

Desorption is a critical process in the recovery or post-treatment of adsorbents saturated with volatile organic compounds (VOCs). In this study, the thermal desorption behaviors for eight VOCs on hypercrosslinked polymeric resin (HPR) and macroporous polymeric resin (MPR) were investigated through isothermal desorption and temperature programmed desorption (TPD). Compared with MPR, HPR with more micropores exhibited a lower desorption rate constant, lower desorption efficiency and higher desorption activation energy due to the strong binding energy generated between VOCs molecules and narrow micropores. As the polarizability of VOCs increased, the desorption rate constants on two porous polymeric resins decreased, while the desorption activation energy showed an incremental trend. Excellent linear correlations were observed between VOC polarizability and desorption rate constants (R2 = 0.957 for HPR and R2 = 0.940 for MPR) as well as between VOC polarizability and desorption activation energy (R2 = 0.981 for HPR and R2 = 0.969 for MPR). Furthermore, a polyparameter linear free energy relationship (PP-LFER) was developed to explore the influences of intermolecular interactions on desorption behaviors of VOCs on porous polymeric resins. The results indicated that the dispersive interaction, which is directly related to polarizability of VOCs, was the primary factor influencing the desorption activation energy of VOCs on porous polymeric resins. The find from this study helps evaluate fleetly and availably the desorption properties of VOCs based on their polarizability.