Reaction Mechanism of Pyrolysis and Combustion of Methyl Oleate: A ReaxFF-MD Analysis

Abstract

As an emerging environmentally friendly fuel, biodiesel has excellent fuel properties comparable to those of petrochemical diesel. Oleic acid methyl ester, as the main component of biodiesel, has the characteristics of high cetane number and low emission rate of harmful gases. However, the comprehensive chemical conversion pathway of oleic acid methyl ester is not clear. In this paper, the reactive force field molecular dynamics simulation (ReaxFF-MD) method is used to construct a model of oleic acid methyl ester pyrolysis and combustion system. Further, the chemical conversion kinetics process at high temperatures (2500 K–3500 K) was studied, and a chemical reaction network was drawn. The research results show that the density of the system has almost no effect on the decomposition activation energy of oleic acid methyl ester, and the activation energies of its pyrolysis and combustion processes are 190.02 kJ/mol and 144.89 kJ/mol, respectively. Ethylene, water and carbon dioxide are the dominant and most accumulated products. From the specific reaction mechanism, the main pyrolysis path of oleic acid methyl ester is the breakage of the C-C bond to produce small molecule intermediates, and subsequent transformation of the ester group radical into carbon oxides. The combustion path is the evolution of long-chain alkanes into short-carbon-chain gaseous products, and these species are further burned to form stable CO2 and H2O. This study further discusses the microscopic combustion kinetics of biodiesel, providing a reference for the construction of biodiesel combustion models. Based on this theoretical study, the understanding of free radicals, intermediates, and products in the pyrolysis and combustion of biomass can be deepened.