Laminar flame speed and shock-tube multi-species laser absorption measurements of Dimethyl Carbonate oxidation and pyrolysis near 1 atm

Abstract

Dimethyl Carbonate (DMC) is a carbonate ester that can be produced in an environmentfriendly way from methanol and CO2. DMC is one of the main components of the flammable electrolyte used in Li-ion batteries, and it can also be used as a diesel fuel additive. Studying the combustion chemistry of DMC can therefore improve the use of biofuels and help developing safer Li-ion batteries. The combustion chemistry of DMC has been investigated in a limited number of studies. The aim of this study was to complement the scarce data available for DMC combustion in the literature. Laminar flame speeds at 318 K, 363 K, and 463 K were measured for various equivalence ratios (ranging from 0.7 to 1.5) in a spherical vessel, greatly extending the range of conditions investigated. Shock tubes were used to measure time histories of CO and H2O using tunable laser absorption for the first time for DMC. Characteristic reaction times were also measured through OH* emission. Shock-tube spectroscopic measurements were performed under dilute conditions, at three equivalence ratios (fuel-lean, stoichiometric, and fuel-rich) between 1260 and 1660 K near 1.3±0.2 atm, and under pyrolysis conditions (98%+) ranging from 1230 to 2500 K near 1.3±0.2 atm. Laminar flame speed experiments were performed around atmospheric pressure. Detailed kinetics models from the literature were compared to the data, and it was found that none are capable of predicting the data over the entire range of conditions investigated. A numerical analysis was performed with the most accurate model, underlining the need to revisit at least 3 key reactions involving DMC.

Experimental and kinetic study on the laminar burning speed, Markstein length and cellular instability of oxygenated fuels

“…Figure 2b plotted the comparison for DMC. For 363 K, the present data are in reasonable agreement with the literature data from Bardin et al [35] and Atherley et al [37]. For 423 K, the present data experimental results are still in reasonable agreement with that from Atherley et al [37] and Yu er al.…”

“…Laminar burning speed was measured at elevated temperature and pressure and the propensity of flame instability varying with initial pressure and equivalence ratio was evaluated. Atherley et al [37] reported the latest research on DMC oxidation and pyrolysis. They measured the laminar flame speeds at an initial pressure of 1.013 bar, initial temperature of 318 K, 363 K, and 423 K for various equivalence ratios in a spherical vessel.…”

Investigation of Laminar Burning Velocities and Cellular Instability for Dimethyl Carbonate at Elevated Pressures

“…The reliability validation of the present experimental facility and data post-processing procedure has been tested in our previous work . To further verify the current experimental results, the LBVs of DMC/air measured at initial pressure of 1 atm and initial temperatures of 358 and 373 K were compared with literature data, which were obtained from the heat flux method performed by Bardin et al and the spherical propagation flame method investigated by Atherley et al, as shown in Figure . It was found that the experimental data of 373 K are slightly larger than those of 363 K, and all the experimental data showed the same trend with the change of the equivalence ratio at all temperatures.…”

“…The above models have been extensively validated on the ignition delay times, whereas further validation of these models in predicting laminar burning velocities (LBVs) has been impeded due to the lack of more accurate experimental data. To the best of our knowledge, only two experimental studies were performed regarding LBV measurements of DMC. , Bardin et al measured the LBVs of DMC at 1 atm for the first time by a heat flux method, over the initial temperature range of 298–358 K. Most recently, Atherley et al performed measurements of LBVs at 318, 363, and 423 K in a spherical vessel, upon a pressure of 1 atm. It is noteworthy that investigations on LBVs of DMC have only been conducted at 1 atm, information concentrated on the role of elevated pressure playing in the LBVs of DMC is barely involved yet.…”

Unknown Knowns: Case studies in uncertainties in the computation of thermochemical parameters

“…This species, methoxy oxomethoxy or the methyl carbonate radical, can give rise to problematic vibrational spectra which is particularly evident for double-hybrid functionals but has very little impact on derived values such as entropy, etc as pointed out recently. 43 It has featured in recent experimental and modelling work on the reaction of alkyl carbonate radicals with lipid components, 44 on the pyrolysis and combustion [45][46][47][48] of dimethyl carbonate 49 and is a product in the thermal decomposition of methyl fluoroformyl peroxycarbonate. 50…”