2-Chlorophenol oxidation in supercritical water: Global kinetics and reaction products

2‐Chlorophenol (2CP) was oxidized in near‐critical and supercritical water in a high‐pressure plug‐flow reactor. The global kinetics for 2CP disappearance were described by a rate law that was 0.88±0.06 order in 2CP, 0.41±0.12 order in O2, and 0.34±0.17 order in water. The activation energy was 11.0±3.8 kcal/mol, and the Arrhenius pre‐exponential factor was 102.0±1.2 M−0.63 S−1. The uncertainties represent 95% confidence intervals. The products of 2CP oxidation included CO, CO2, HCl, other chlorophenols, chlorohydroxybenzaldehydes, dichlorophenoxyphenols, dichlorobiphenols, and chlorinated dibenzodioxins and dibenzofuran. The molar yields of the organic products were determined for a set of experiments at 380°C and 278 atm. The most abundant products were 2CP dimers such as dichlorophenoxyphenols and dichlorobiphenols, and the highest yield observed for any individual product was 0.6%. Although the yields of these products were low, their selectivities were high. For example, at 3.6 s, the shortest residence time studied under these conditions, about 50% of the carbon in the 2CP that reacted appeared in 2CP dimers, 18% appeared as CO2, and the balance (32%) was presumably in single‐ring and ring‐opening products. A reaction pathway analysis using the Delplot methodology revealed that the evolution of products from 2CP oxidation in supercritical water was consistent with a reaction network comprising two parallel primary reactions. One primary reaction path led to dichlorophenoxyphenols and dichlorobiphenols whereas the second primary reaction led to single‐ring and ring‐opening products. The 2CP dimers were convereted to single‐ring and ring‐opening products, which were, in turn, ultimately oxidized to CO2.