School of Environmental Science and Engineering, Shanghai Jiao Tong University, Shanghai 200240, China.
School of Environmental Science and Engineering, Shanghai Jiao Tong University, Shanghai 200240, China; Shanghai Institute of Pollution Control and Ecological Security, Shanghai 200092, China.
Chemosphere. 2019 Mar;218:384-390. doi: 10.1016/j.chemosphere.2018.11.048. Epub 2018 Nov 8.
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) were 0.130-0.392 min. 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), played a significant role in TOC removal, which implied the more q(H) value was, the easier H atom could lose, resulted in higher k 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 followed the order that benzenesulfonic acid (BSA) > phenol > methylbenzene (MB) > 3-phenylpropionic acid (3-PPA), as well as BPA < OP < NP.
超临界水氧化（SCWO）处理了 15 种芳香族化合物，包括双酚 A（BPA）、壬基酚（NP）和辛基酚（OP），在温度和反应时间分别为 350-550°C 和 0.5-6 分钟，氧气过量 300%的条件下进行，总有机碳（TOC）的降解速率常数（k）为 0.130-0.392 min。为了进一步探讨 TOC 去除与分子特性之间的关系，采用密度泛函理论（DFT）方法计算了 15 种芳香族化合物的量子描述符。相关分析的结果表明，H 原子上的最正部分电荷（q（H））对 TOC 去除起着重要作用，这意味着 q（H）值越高，H 原子越容易失去，导致更高的 k 常数。苯环上不同的取代基会导致不同的 TOC 去除效率。结果表明，F（0）值越高，越容易被自由基攻击，因此，k 的顺序为苯磺酸（BSA）>苯酚>甲苯>3-苯丙酸（3-PPA），以及 BPA<OP<NP。
