Experimental and kinetic modeling study of C5 cyclic hydrocarbons pyrolysis at elevated pressures: Effect of unsaturation on the reactivity and PAH formation

•High-pressure pyrolysis behaviors of three C5 cyclic hydrocarbons were investigated.•A universal kinetic model for three C5 cyclic fuels was proposed and validated.•Differences among three fuels specific decomposition pathways were evaluated.•Effects of unsaturation on intrinsic reactivity and PAH formation were revealed. To further explore the decomposition behaviors of C5 cyclic hydrocarbons, important components in the transportation fuels and pivotal intermediates in high-density liquid fuels, the pyrolysis of cyclopentane, cyclopentene and cyclopentadiene with different unsaturation degrees were investigated. The experiments of cyclopentane and cyclopentene were performed at 1.0, 30.0 atm and 773–1173 K in a flow tube reactor. The mole fraction profiles of pyrolysis species, involving C1-C5 small hydrocarbons and monocyclic, bicyclic as well as polycyclic aromatic hydrocarbons (MAHs, BAHs and PAHs), were provided. A universal kinetic model for three C5 cyclic fuels pyrolysis chemistry was proposed and reasonably predicted the speciation profiles newly reported in this work and literature, where rate coefficients of the crucial reactions were compared and upgraded. The differences among three fuels specific pathways were evaluated and the effects of unsaturation on the pyrolysis characteristics of intrinsic reactivity and aromatics formation were revealed. Cyclopentene has the highest pyrolysis reactivity, followed by cyclopentane and cyclopentadiene. Simultaneously formed fuel radicals and key intermediates in three C5 cyclic fuels influence the formation channels of small products, MAHs and BAHs. The saturated cyclopentane is easily occur the ring-opening reaction to generate more C2 and C3 species, whereas the increase in unsaturation promotes MAHs and BAHs formation in cyclopentene and cyclopentadiene pyrolysis, especially the toluene, styrene, indene and naphthalene. The rate of production analysis shows the formations of these MAHs and BAHs are strongly dependent on the concentration levels of cyclopentadienyl resonance stabilized radical (RSR). Differently, the dominated growth pathways of three- and four-ring PAHs are barely influenced by the specific fuel chemistry and indenyl plays a crucial role via the typical RSR chain reactions at high pressures.