Pathways toward PAH Formation during Fatty Acid and Triglyceride Pyrolysis.

Molecular beam mass spectrometry was used to follow model triglyceride pyrolysis with temperature. A selectively formed set of PAHs (276, 352, 444 amu) arose with increasing temperature. They were attributed to association of up to five C7-C8 sized fragments (observed in abundance by pyrolysis with gas chromatography), presumably due to their propensity to form stable benzyl radicals. Results were surprisingly similar regardless of triglyceride fatty acids (FAs), containing 0-2 C=C double bonds (14 to 18 carbon atoms). However, the absence of C=C double bonds shifted the process to higher temperatures. Shorter FA chains, particularly 14:0, enhanced generation of shorter size fragments, facilitating the alternate formation of nonselective PAH homology series. An increase in the length of the glass wool filled sample stage enhanced the formation of two more PAHs, 316 and 388 amu. They appear to involve the formation of indenyl in addition to benzyl radicals as key intermediates.

Influence of early stages of triglyceride pyrolysis on the formation of PAHs as coke precursors.

Molecular beam (MB) time-of-flight mass spectrometry has been used to investigate thermal decomposition of triolein, to reveal the mechanisms of low temperature soot/coke formation characteristic for triglycerides (TGs). Mass detected pyrolysis products were observed at incremented temperatures using both VUV single photon ionization (general product detection) and REMPI based selective detection of aromatic products. To augment the simple mass characterizations, we have employed stoichiometric considerations; we have supplemented the analysis further by using the detailed information available from product analysis of batch reactor TG cracking. Both the VUV photoionization and batch reactor studies indicated that formation of C7-sized stable products is a marker of significant triolein decomposition that is coupled with PAH formation. A significant fraction of the C7 species observed likely formed as a result of a C-C bond scission at the allylic position to the ω-9 double bond of oleic acid. REMPI detection indicated a high specificity for PAH formation at three distinct molecular weight values, 276, 352 and 444 amu (the latter being a fullerene precursor). The stoichiometric analysis has shown that these PAHs likely arise from condensation reactions of either C7- or C8-sized fragments (three, four and five, respectively). The C8-sized intermediate would become essential whenever the PAH product of C7 fragment condensation contained an odd number of carbon atoms, resulting in a less stable aromatic structure with an incomplete double bond conjugation. MB experiments involving either addition or in situ generation of hydrogen resulted in an enhancement of lower molecular weight PAH formation, i.e., a decrease in the effective number of condensing fragments. In contrast, an increase in temperature yielded the opposite effect.

PAH/Aromatic Tar and Coke Precursor Formation in the Early Stages of Triglyceride (Triolein) Pyrolysis.

There has been a limited understanding of high MW polycyclic aromatic hydrocarbon (PAH) product chemistry in the pyrolysis of triglycerides (TGs), though the subject has important implications for both fuel production from TGs and food science. Previous TG pyrolysis studies have been able to identify only relatively low MW GC-elutable aromatics occurring in the bulk liquid phase; products occurring in the solid phase have remained inaccessible to chemical analysis. In contrast, cold gas expansion molecular beam methods, where pyrolysis products are analyzed in real time as they are entrained in gas expansions, remove product collection difficulties, thereby allowing for analysis of coke/tar PAH precursors. In this study, the model TG triolein was heated and the ensuing products in the molecular beam were soft photoionized, enabling time-of-flight mass detection. Use of 266 nm pulses enabled selective photoionization of aromatic products. Unlike previous work on analysis of the liquid phase TG cracking products, a different and distinct pattern of rather large PAHs, up to 444 amu, was observed, at nontrivial relative product fractions. With an increase of temperature to ∼350 °C, a small number of PAHs with MW ≥ 276 amu increasingly dominated the aromatic product distribution. Surprisingly, PAH product detection ensued at rather low temperatures, as low as ∼260 °C. For tentative PAH product identification and product chemistry rationalization, we observed the product homology pattern and applied a stoichiometric analysis. The latter, combined with the known homology profiles of TG cracking products, indicated specific patterns of intermediate fragment association that facilitated large-MW PAH formation as a result of TG cracking.