Korean Journal of Chemical Engineering, Vol.22, No.6, 882-888, November, 2005
Kinetic Analysis for Decomposition of 2,4-Dichlorophenol by Supercritical Water Oxidation
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2,4-Dichlorophenol (2,4-DCP), as a halogenated model pollutant, was decomposed by using supercritical water oxidation (SCWO) in a batch reactor made of Hastelloy C-276. SCWO experiments for 2,4-DCP decomposition were performed in the range of 380-420 ℃, 230-280 bar and 0.074-0.221 mol/L H2O2. The effect of oxidant concentration on decomposition rate and efficiency was significant near the critical temperature of 380 ℃. However, the role of the oxidant concentration in the SCWO process decreased with an increase in temperature; also, excess oxidant played a key role in quite significantly decreasing the activation energy of 2,4-DCP oxidation. Variation of the reaction rate by the change of pressure was negligible even at a near critical temperature. The kinetic rate for the decomposition of 2,4-DCP in the SCWO process was well described by a simple first-order kinetic and global reaction rate model. From the SCWO experiments, the various intermediates identified with a GC/MS implied that the first reaction pathway for 2,4-DCP decomposition led to dimers such as dichlorophenoxyphenols, and the second led to single-ring and ringopening products.
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