US EPA

1182565 

Journal Article 

A comprehensive mechanism for methanol oxidation 

Held, TJ; Dryer, FL 

1998 

Yes 

International Journal of Chemical Kinetics
ISSN: 0538-8066
EISSN: 1097-4601 

30 

11 

805-830 

10.1002/(SICI)1097-4601(1998)30:11<805::AID-KIN4>3.0.CO;2-Z 

WOS:000076608700004 

A comprehensive detailed chemical kinetic mechanism for methanol oxidation has been developed and validated against multiple experimental data sets. The data are from static-reactor, flow-reactor, shock-tube, and laminar-name experiments, and cover conditions of temperature from 633-2050 K, pressure From 0.26-20 atm, and equivalence ratio from 0.05-2.6. Methanol oxidation is found to be highly sensitive to the kinetics of the hydroperoxyl radical through a chain-branching reaction sequence involving hydrogen peroxide at low temperatures, and a chain-terminating path at high temperatures. The sensitivity persists at unusually high temperatures due to the fast reaction of CH2OH + O-2 = CH2O + HO2 compared to CH2OH + M = CH2O + H + M. The branching ratio of CH3OH + OH = CH2OH/CH3O + H2O was found to be a more important parameter under the higher temperature conditions, due to the rate-controlling nature of the branching reaction of the H-atom formed through CH3O thermal decomposition. (C) 1998 John Wiley & Sons.