Detailed chemical kinetics model for supercritical water oxidation of C{sub 1} compounds and H{sub 2}

Journal Article · Tue Aug 01 04:00:00 EDT 1995 · AIChE Journal

DOI:https://doi.org/10.1002/aic.690410806· OSTI ID:106219

Brock, E E; Savage, P E ^[1]

---

1. Univ. of Michigan, Ann Arbor, MI (United States). Dept. of Chemical Engineering

A detailed chemical kinetics model comprising 148 reversible elementary 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 O{sub 2} during methanol and hydrogen oxidation were essentially zero, and that the O{sub 2} 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 H{sub 2} oxidation t 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 elementary reactions largely controlled the oxidation kinetics for the compounds studied. Nearly half of these reactions involved HO{sub 2}, 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 HO{sub 2}, but this value is lower than other recently recommended values.

• OSTI ID: 106219
• Journal Information: AIChE Journal, Journal Name: AIChE Journal Journal Issue: 8 Vol. 41; ISSN 0001-1541; ISSN AICEAC
• Country of Publication: United States
• Language: English

Related Subjects

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATION
54 ENVIRONMENTAL SCIENCES
ACTIVATION ENERGY
CARBON MONOXIDE
CHEMICAL REACTION KINETICS
HYDROGEN
HYDROPEROXY RADICALS
MATHEMATICAL MODELS
METHANE
METHANOL
OXIDATION
POLLUTANTS
SIMULATION
SUPERCRITICAL STATE
WASTE WATER
WATER TREATMENT
WATER VAPOR