Decomposition of 15 aromatic compounds in supercritical water oxidation

Supercritical water oxidation (SCWO) of 15 aromatic compounds, including bisphenol A (BPA), nonylphenol (NP) and octylphenol (OP), was investigated under temperature and reaction time ranged of 350-550 °C and 0.5-6 min, respectively, with 300% excess oxygen, resulted in the degradation rate constants of total organic carbon (k_TOC) were 0.130-0.392 min^-1. To further explore the relationship between TOC removal and molecular characteristics, density functional theory (DFT) method had been used to calculate the quantum descriptors of the 15 aromatic compounds. The result of correlation analysis showed that the most positive partial charge on the H atom, namely q(H)_x, played a significant role in TOC removal, which implied the more q(H)_x value was, the easier H atom could lose, resulted in higher k_TOC constant. Different substituent groups in the phenyl ring could lead to different TOC removal efficiencies. It presented that the more F(0) value was, the more easily to be attacked by radicals, as a result, the k_TOC followed the order that benzenesulfonic acid (BSA) > phenol > methylbenzene (MB) > 3-phenylpropionic acid (3-PPA), as well as BPA < OP < NP.