The total organic carbon (TOC) disappearance kinetics of the model organic sulfur heteroatom,
thiodiglycol [TDG, (HOC2H4)2S], was investigated in an isothermal continuous tubular reactor
under supercritical water oxidation (SCWO) conditions. The experiments were conducted at a
temperature of 397−617 °C and a fixed pressure of 25 MPa, with a residence time that ranged
from 9 s to 40 s. The initial TOC concentrations of TDG were varied from 1.75 mmol/L to 21.04
mmol/L and the oxygen concentrations were varied from 110% to 440% of the stoichiometric
requirement. All the TOC conversions were >90% under the above experimental conditions.
The major sulfur-containing products of the reaction were sulfuric acid and hydrogen sulfide,
whereas the carbon-containing products included carbon monoxide, methane, and carbon dioxide.
By taking into account the dependence of the oxidant and TOC concentration on the reaction
rate, a global TOC disappearance rates expression was regressed from the data of 58 experiments,
to a 95% confidence level. The resulting activation energy was determined to be 41.53 ± 1.65
kJ/mol, and the pre-exponential factor was (1.64 ± 0.55) × 102 L1.12 mmol-0.12 s-1. The reaction
orders for the TOC and the oxidant were 1.02 ± 0.01 and 0.10 ± 0.01, respectively.
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