Revealing the critical role of radical-involved pathways in high temperature cyclopentanone pyrolysis

Dong, Xiaorui; Ninnemann, Erik; Ranasinghe, Duminda S.; Laich, Andrew; Greene, Robert; Vasu, Subith S.; Green, William H.

doi:10.1016/j.combustflame.2020.03.001

Revealing the critical role of radical-involved pathways in high temperature cyclopentanone pyrolysis

Journal Article · Sat Apr 04 04:00:00 EDT 2020 · Combustion and Flame

DOI:https://doi.org/10.1016/j.combustflame.2020.03.001· OSTI ID:1763636

^[1]; ^[2]; Ranasinghe, Duminda S. ^[3]; Laich, Andrew ^[2]; Greene, Robert ^[2]; Vasu, Subith S. ^[2]; Green, William H. ^[3]

Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States); Massachusetts Institute of Technology
Univ. of Central Florida, Orlando, FL (United States)
Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)

Cyclopentanone (CPO) is a promising biofuel for spark-ignition engines due to its ring strain and high auto-ignition resistance. Understanding CPO decomposition is crucial for building a high-temperature combustion model. Here we present a comprehensive kinetic model for high-temperature pyrolysis of CPO with verified results from high-pressure shock tube (HPST) measurements. The time- histories of carbon monoxide (CO), ethylene (C₂H₄), and CPO absorbances over the temperature range of 1156-1416 K and pressure range of 8.53-10.06 atm were measured during current experiments. A corresponding detailed kinetic model was generated using the Reaction Mechanism Generator (RMG) with dominant unimolecular/radical-involved decomposition pathways from either previous studies or quantum calculations within the current work. The obtained model containing 821 species and 79,859 reactions exhibited a good agreement with the experimental results. In this study, the absorbance ratio between C₂H₄ and CO was used as an important factor to validate models and to prove that radical-involved bimolecular pathways were as significant as unimolecular decomposition of CPO. The rate of production (ROP) analysis showed H radicals play a major role in the decomposition, and the whole decomposition process could be divided into three stages based on the H radical concentration. Finally, the insights from present work can be used to generate a better CPO combustion model and help evaluate CPO as an advanced biofuel.

View Accepted Manuscript (DOE)

Research Organization:: Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE), Transportation Office. Bioenergy Technologies Office

Grant/Contract Number:: EE0007982

OSTI ID:: 1763636

Alternate ID(s):: OSTI ID: 1608354

Journal Information:: Combustion and Flame, Journal Name: Combustion and Flame Vol. 216; ISSN 0010-2180

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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