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Hydroxyl radical reactions with 2-chlorophenol as a model for oxidation in supercritical water

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Abstract

To determine the detailed mechanism of 2-chlorophenol (2-CP) oxidation in supercritical water, both the experiments and theoretical calculations were conducted in this paper. A set of experiments was performed to oxidize 2-CP in supercritical water under temperatures of 380–420 °C, pressure of 25 MPa, residence times of 0–60 s, and H2O2 as oxidant. By determining the molar yields of products, the primary single-ring products were identified as chlorohydroquinone, 2,4-dichlorophenol (2,4-DCP), 2,6-DCP, and 4-CP. The trends for the molar yields of the four products were analyzed at various temperatures and residence times. And built upon the trends, the possible reaction pathways were conjectured. Subsequently, the reaction mechanism was further verified by theoretical calculations, in which density functional theory was adopted as the computational method. The calculated results have well illustrated the experimental results and ascertained the reaction paths we proposed.

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Acknowledgments

This research is supported by the National High Technology Research and Development Program of China (863 Program, the Project No. 2007AA05Z235). We acknowledge the research foundation of Shandong Environmental Protection Bureau for support. We also thank the independent innovation project for the University Institutes of Jinan Technology Bureau (No. 201 102 046).

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Authors and Affiliations

  1. School of Environmental Science and Engineering, Shandong University, Jinan, 250100, China

    Jiaming Zhang, Chunyuan Ma & Xiaohua Ren

  2. National Engineering Laboratory for Coal-fired Pollutants Emission Reduction, Shandong University, Dongpeilou 601, No. 17923, Jingshi Road, Jinan, 250061, China

    Jiaming Zhang & Chunyuan Ma

  3. School of Municipal and Environmental Engineering, Shandong Jianzhu University, Jinan, 250101, China

    Youmin Sun

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  1. Jiaming Zhang
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Correspondence to Chunyuan Ma.

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Zhang, J., Ma, C., Sun, Y. et al. Hydroxyl radical reactions with 2-chlorophenol as a model for oxidation in supercritical water. Res Chem Intermed 40, 973–990 (2014). https://doi.org/10.1007/s11164-012-1015-x

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