Nitrogenated hydrocarbons (NHCs) produced from biomass are a potential source of renewable energy. Recently, the sooting tendencies of a series of NHCs have been measured using the Yield Sooting Index (YSI) approach. The measured YSIs show that NHCs generally have lower sooting tendencies than the corresponding hydrocarbons, which implies that the nitrogen atom would have a strong impact on soot formation from biomass-derived fuels. However, there has been few studies on the effect of fuel nitrogen on soot formation and soot-relevant reaction pathways. This work seeks to help understand the experimentally observed trends in YSI of C6H15N amines, dipropylamine (DPA), di-isopropylamine (DIPA), and 3,3-dimethylbutylamine (DMBA), using Density Functional Theory (DFT) calculations and ReaxFF-based Molecular Dynamic (MD) simulations. DFT calculations are employed to identify possible decomposition pathways of the amines. ReaxFF simulations are performed to extend the DFT results and investigate decomposition reactions in chemical environments closer to the measurement conditions. Initial decomposition of amines is found to occur predominantly by unimolecular C-N bond fission and bimolecular H-abstraction. The DFT and ReaxFF simulations predict that C2H4, C3H6, and C4H8 are the main products of DPA, DIPA, and DMBA, respectively. The theoretical methods predict that sooting tendency increases in the order of DPA, DIPA, and DMBA, which is consistent with the trend in measured YSI. This work demonstrates that sooting tendencies and soot-relevant reaction pathways of fuels with unknown chemistry can be identified through combined DFT and ReaxFF simulations.

Identifying decomposition pathways of C6H15N isomers relevant to soot formation using theoretical methods

Macromolecular Chemistry: The Second Century

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ACS Spring 2020 National Meeting & Expo

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.