Detailed kinetic modeling of dimethoxymethane. Part Ⅱ: Experimental and theoretical study of the kinetics and reaction mechanism

摘要

In this study (Part II), the oxidation of dimethoxymethane (DMM) is investigated and a detailed chemical reaction model developed for a comprehensive description of both high- and low-temperature oxidation processes. The sub-mechanism of DMM is implemented using AramcoMech2.0 as the base mechanism. Rate coefficients are based on analogies with those for dimethyl ether, diethyl ether, and n-pentane oxidation. Furthermore, theoretical studies from recent works are also included in the present model and new calculations for the dissociation kinetics of (Q) over dotOOH radicals have been carried out at the CCSD(T)/CBS(aug-cc-pVXZ; X=D, T) // B2PLYP-D3/6-311 + + G(d,p) level of theory. For validation, new ignition delay time experiments have been performed in a shock tube (ST), a rapid compression machine (RCM), and in a laminar flow reactor covering a wide range of conditions (p = 1-40 bar, T= 590-1215 K, phi = 1). In addition, the kinetic model is validated against laminar burning velocities, jet-stirred reactor, plug flow reactor and further ST and RCM experimental datasets from the literature. Pathway and sensitivity analyses were used to identify critical reaction pathways in the DMM oxidation mechanism. These show that the reactivity of DMM at intermediate temperatures is controlled by the branching between pathways initiated on the primary or secondary fuel radical. While primary fuel radicals eventually lead to chain branching, secondary fuel radical consumption is controlled by fast beta-scission over a wide range of temperatures, which inhibits reactivity. (C) 2018 Published by Elsevier Inc. on behalf of The Combustion Institute.