1 Department of Management Engineering, Technical University of Denmark2 UNEP Risø Centre, Department of Management Engineering, Technical University of Denmark3 Department of Chemical and Biochemical Engineering, Technical University of Denmark4 CHEC Research Centre, Department of Chemical and Biochemical Engineering, Technical University of Denmark5 University of Zaragoza6 DNV KEMA Energy & Sustainability7 University of North Texas
A detailed chemical kinetic model for oxidation of CH3OH at high pressure and intermediate temperatures has been developed and validated experimentally. Ab initio calculations and Rice–Ramsperger–Kassel–Marcus/transition state theory (RRKM/TST) analysis were used to obtain rate coefficients for CH 2 OH ⇌ CH 2O+H, CH 3O⇌ CH 2O+H, CH 3O⇌ CH 2 OH , and CH 3O+O2⇌ CH 2O+ HO 2. The experiments, involving CH3OH/O2 mixtures diluted in N2, were carried out in a high‐pressure flow reactor at 600–900 K and 20–100 bar, varying the reaction stoichiometry from very lean to fuel‐rich conditions. Under the conditions studied, the onset temperature for methanol oxidation was not dependent on the stoichiometry, whereas increasing pressure shifted the ignition temperature toward lower values. Model predictions of the present experimental results, as well as rapid compression machine data from the literature, were generally satisfactory. The governing reaction pathways have been outlined based on calculations with the kinetic model. Unlike what has been observed for unsaturated hydrocarbons, the oxidation pathways for CH3OH under the investigated conditions were very similar to those prevailing at higher temperatures and lower pressures. At the high pressures, the modeling predictions for onset of reaction were particularly sensitive to the CH 3 OH + HO 2⇌ CH 2 OH +H2O2reaction.
International Journal of Chemical Kinetics, 2013, Vol 45, Issue 5, p. 283-294