Kinetics and mechanism of methane oxidation in supercritical water

Phillip E. Savage, Jianli Yu, Nicole Stylski, Eric E. Brock

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Abstract

We oxidized methane in supercritical water at 250 atm and at temperatures between 525 and 587°C. The methane conversions ranged from 3 to 70%. CO was the product present in the highest yields at low conversions (< 10%), but CO2 became the most abundant product at higher conversions. These experimental results were used to test the predictions of a detailed chemical kinetics model, which is based on gas-phase oxidation mechanisms and kinetics and comprised 150 elementary reaction steps. The model predicted methane disappearance rates that were about 30-50% faster than those observed experimentally. This behavior led to consistently high predictions of the methane conversion and the CO2 yield. However, the model accurately predicted the yields of CO and CO2 as a function of the methane conversion. The predicted activation energy for the pseudo-first-order rate constants of 36±3 kcal/mol is similar to the experimental value of 44±6 kcal/mol. Overall, the ability of the model to predict several of the experimental observations demonstrates that the analogy between gas-phase oxidation and oxidation in supercritical water is a good one. A sensitivity analysis revealed that the calculated methane concentration is most sensitive to the kinetics of OH+H2O2=HO2+H2O, OH+HO2=H2O+O2, H2O2=OH+OH and HO2+HO2=O2+H2O2. These reactions control the concentration of OH radical, which is the main oxidant under SCWO conditions.

Original languageEnglish (US)
Pages (from-to)141-153
Number of pages13
JournalJournal of Supercritical Fluids
Volume12
Issue number2
DOIs
StatePublished - Apr 1998

All Science Journal Classification (ASJC) codes

  • Chemical Engineering(all)
  • Condensed Matter Physics
  • Physical and Theoretical Chemistry

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