Rate-Controlled Constrained-Equilibrium Calculations of Methanol-Oxygen Kinetics Using Reduced Chemistry

According to the underlying concept of the rate-controlled constrained-equilibrium (RCCE) method, the relaxation of a complex reacting system towards the final equilibrium state is governed by a set of active and passive constraints imposed by the internal dynamics of the system that is considerably smaller in dimension than the original system. A set of 10 constraints, able to accurately model the dynamic evolution of the methanol oxidation over a wide range of initial temperatures and pressures is proposed. Based on rational analysis of the important rate-limiting steps a further reduced set is obtained, which when is used in conjunction with RCCE is able to give excellent predictions for dynamic evolution of the system at low temperatures at different pressures. Some salient features of RCCE are explored. The detailed kinetic scheme involves only C1 chemistry and includes 132 reactions along with 29 species without nitrogen chemistry.