Abstract
The pyrolysis of isopropylamine (IPA) was studied in a jet-stirred reactor at 1 atm within 670–1100 K. Pyrolysis products and intermediates were identified and quantified with both synchrotron vacuum ultraviolet photoionization mass spectrometry and gas chromatography analysis. Propiolonitrile, propanenitrile, 1-methylethenylamine, 3-butenenitrile, pyridine and benzonitrile were newly identified compared with previous studies of amines. HCN and 1-methylethenylamine were found to be the dominant N-containing species in IPA pyrolysis. The peak mole fractions and temperatures of C1-C2 hydrocarbons are generally higher than C3-C4 ones. The peak temperatures tend to rise with the increase of degree of unsaturation for hydrocarbons with the same C numbers. Based on the observations, a detailed kinetic model consisting of 429 species and 2407 reactions was developed with reasonable predictions against the measured data. Rate-of-production analysis indicates that IPA is mainly consumed by the H-abstraction at the Cα atom: (CH3)2CHNH2+H = (CH3)2CNH2+H2. Sensitivity analysis shows that the unimolecular decomposition via CC bond cleavage and H-abstraction at the Cα atom play promoting roles. The H-abstraction of propene by H-atom yielding allyl radical and self-combination of methyl radicals forming ethane exhibit inhibiting effects. Compared to the pyrolysis of n-propylamine (NPA), more amine- or imine-like species were generated during NPA pyrolysis while more nitriles were detected in IPA pyrolysis. Moreover, the peak temperatures of hydrocarbons in both NPA and IPA pyrolysis shift to higher values with the increase of degree of unsaturation. The results will enrich the understanding of IPA for further combustion kinetic studies of low sooting fuels.
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