Ethanol is partially oxidized in a continuous supercritical water reactor at temperatures from 500 to 530 °C, constant pressure of 25 MPa, initial ethanol concentration of 5 wt %, residence times of 3−8 s, and oxidant-to-fuel stoichiometric equivalence ratios of 5, 7.5, and 10%. The experimental conditions are selected to study the regime where ethanol oxidation happens rapidly but below the temperature necessary to initiate hydrolysis reactions. The reactions and interactions of intermediate species can be analyzed, leveraging previous experimental results and the existing body of literature on ethanol hydrolysis, pyrolysis, and oxidation. Higher oxidant concentration increases ethanol destruction and gasification efficiency, although significant coke/char buildup is qualitatively observed within the reactor. Product yields from the experiments are used to infer significant reaction mechanisms, and a pathway is postulated for the counterintuitive formation of char under the studied conditions.

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<p>A small-scale supercritical water oxidation reactor is designed and fabricated to study the destruction of hazardous wastes. The downward bulk flow is heated with the introduction of pilot fuel (ethanol/water mixture), and oxidant (H₂O₂/water mixture). Both streams are introduced coaxially. The fuel dilution is varied from 2 to 7 mol% ethanol/water, and the oxidant-to-fuel stoichiometric equivalence ratio (Φ_AF), is varied from 1.1 to 1.5. Higher ethanol concentrations in the pilot fuel stream and operation near-stoichiometric results in a more stratified temperature profile, i.e., highest local fluid temperatures near the top and the lowest temperatures at the bottom of the reactor. Steady operation at 603.5 °C is achieved with a nominal residence time of 25.3 s at 7 mol% fuel dilution and Φ_AF of 1.1. At the lowest pilot fuel dilution (2 mol%), the temperature profile is nearly uniform, approaching a distributed reaction regime.</p>

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