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Experiments were conducted in Sandia`s supercritical fluids reactor (SFR) to generate data for the design of a transpiration-wall supercritical water oxidation (SCWO) reactor. The reactor is intended for the disposal of hazardous material generated on naval vessels. The design parameters for the system require an accurate knowledge of destruction efficiency vs. time and temperature. Three candidate materials were selected for testing. The experiments consisted of oxidizing these materials in the SFR at isothermal conditions over the temperature range of 400-550C at 24.1 MPa. A small extrapolation of the results shows that these materials can be adequately destroyed (to 99.9% destruction removal efficiency, DRE, based on total organic carbon (TOC) in the effluent) in approximately 5 seconds at 600C. The results vary smoothly and predictably with temperature such that extrapolation to higher temperatures beyond the experimental capabilities of the SFR can be made with reasonable confidence. The preliminary design of the transpiration-wall reactor has a rapid heat-up section within the reactor vessel that requires the addition of a fuel capable of quickly reacting with oxygen at temperatures below 500C. Candidate alcohols and JP-5 jet fuel were evaluated in this context. Oxidation rates for the alcohols were examined using in situ Raman spectroscopy. In addition, the potential utility of supplying the oxidizer line with hydrogen peroxide as an additive to enhance rapid initiation of the feed at unusually low temperatures was investigated. Experiments were conducted in the Supercritical Constant Volume Reactor (SCVR) using hydrogen peroxide as the initial oxidizing species. The results show that this concept as a method of enhancing low temperature reactivity appears to fail because thermal decomposition of the hydrogen peroxide is more rapid than the fuel oxidation rate at low temperatures. 8 refs., 16 figs., 5 tabs

Kinetic investigation of the oxidation of naval excess hazardous materials in supercritical water for the design of a transpiration-wall reactor