Ammonia is a refractory intermediate during supercritical water oxidation (SCWO) of nitrogen-containing wastes, and alcohols are usually introduced as auxiliary fuels to accelerate its degradation. The kinetics of methanol/ethanol assisted oxidative degradation of ammonia in supercritical water have been investigated in a flow reactor, covering alcohol-to-ammonia ratios of 0.2–2.0. During SCWO of ammonia-methanol mixtures, ammonia was mostly converted to N2, with N2O as the main by-product. Increasing methanol concentration facilitated effectively the degradation of ammonia. For the cases with ethanol assistance, high concentrations of HCN were detected at the investigated temperature. Increase in ethanol concentration enhanced ammonia conversion, but had a non-monotonic influence on N2 production. A detailed chemical kinetic model was developed by integrating the nitrogen chemistry with methanol/ethanol mechanisms. The model performance was further validated by comparing to the present and literature data. The model reproduced the ammonia conversions at different conditions fairly well, but overpredicted the N2 yield and underpredicted the NO2 and HCN yields slightly. Based on the model, reaction mechanism was inferred and important elementary steps were identified through kinetic analyses. Finally, the influence of process parameters on ammonia degradation rate was numerically explored. This study is expected to facilitate the application of SCWO technology for N-containing wastes treatment.
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