Detailed chemical kinetics model for supercritical water oxidation of C1 compounds and H2

Eric E. Brock, Phillip E. Savage

Research output: Contribution to journalArticle

88 Scopus citations

Abstract

A detailed chemical kinetics model comprising 148 reversible elementory reactions for the supercritical water oxidation (SCWO) of methane, methanol, carbon monoxide and hydrogen was developed. Rate constants were taken from previous critical evaluations. The Lindemann model, at times modified with a broadening parameter, was used to account for the effects of pressure on the kinetics of unimolecular reactions. Model predictions were compared with published experimental SCWO kinetics data for 450–650°C and 240–250 atm. The model correctly predicted global reaction orders for all four fuels to within their uncertainties. In addition, the model correctly predicted that the global reaction orders for O2 during methanol and hydrogen oxidation were essentially zero, and that the O2 concentration had the greatest effect on the methane oxidation rate. The pseudo‐first‐order rate constants predicted by the model were consistently higher than the experimental values, but the global activation energies were predicted correctly for methane oxidation and for CO and H2 oxidation at high temperatures. The model's predictions generally became worse as the temperature decreased toward the critical point of water. A sensitivity analysis revealed that fewer than 20 elementaty reactions largely controlled the oxidation kinetics for the compounds studied. Nearly half of these reactions involved HO2, which is an important free radical for SCWO. Quantitative agreement with the experimental methane conversions was obtained by adjusting the preexponential factors for three elementary reactions within their uncertainties. It could also be obtained by using the JANAF value (0.5 kcal/mol) for the standard heat of formation of HO2, but this value is lower than other recently recommended values.

Original languageEnglish (US)
Pages (from-to)1874-1888
Number of pages15
JournalAIChE Journal
Volume41
Issue number8
DOIs
StatePublished - Aug 1995

All Science Journal Classification (ASJC) codes

  • Biotechnology
  • Environmental Engineering
  • Chemical Engineering(all)

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