Wide Range Experimental and Kinetic Modeling Study of Chain Length Impact onn-Alkanes Autoxidation

Abstract

The control of deposit precursors formation resulting from the oxidative degradation of alternative fuels relies strongly on the understanding of the underlying chemical pathways. Although C8–C16 n-alkanes are major constituents of commercial fuels and well-documented solvents, their respective reactivities and selectivities in autoxidation are poorly understood. This study experimentally investigates the influence of chain length, temperature (393–433 K), purity, and blending on n-alkanes autoxidation kinetics under concentrated oxygen conditions, using both Induction Period (IP) and speciation analysis. It also numerically constructs new detailed liquid-phase chemical mechanisms for n-C8–C14 obtained with an automated mechanism generator. Macroscopic reactivity descriptors such as IP, combined to microscopic ones, obtained from GC-MS analyses, are herein used to emphasize similarities and discrepancies in n-alkanes autoxidation processes. Experimental results highlight a nonlinear IP evolution with n-al...