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

Abstract

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 canmore » be used to generate a better CPO combustion model and help evaluate CPO as an advanced biofuel.« less

Authors:
ORCiD logo [1]; ORCiD logo [2];  [1];  [2];  [2];  [2];  [1]
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  1. Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
  2. Univ. of Central Florida, Orlando, FL (United States)
Publication Date:
Research Org.:
Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Transportation Office. Bioenergy Technologies Office; USDOE
OSTI Identifier:
1763636
Alternate Identifier(s):
OSTI ID: 1608354
Grant/Contract Number:  
EE0007982; EE007982
Resource Type:
Accepted Manuscript
Journal Name:
Combustion and Flame
Additional Journal Information:
Journal Volume: 216; Journal ID: ISSN 0010-2180
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
09 BIOMASS FUELS; Cyclopentanone; pyrolysis; reaction mechanism; shock tube

Citation Formats

Dong, Xiaorui, Ninnemann, Erik, Ranasinghe, Duminda S., Laich, Andrew, Greene, Robert, Vasu, Subith S., and Green, William H. Revealing the critical role of radical-involved pathways in high temperature cyclopentanone pyrolysis. United States: N. p., 2020. Web. doi:10.1016/j.combustflame.2020.03.001.
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Dong, Xiaorui, Ninnemann, Erik, Ranasinghe, Duminda S., Laich, Andrew, Greene, Robert, Vasu, Subith S., & Green, William H. Revealing the critical role of radical-involved pathways in high temperature cyclopentanone pyrolysis. United States. https://doi.org/10.1016/j.combustflame.2020.03.001
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Dong, Xiaorui, Ninnemann, Erik, Ranasinghe, Duminda S., Laich, Andrew, Greene, Robert, Vasu, Subith S., and Green, William H. Sat . "Revealing the critical role of radical-involved pathways in high temperature cyclopentanone pyrolysis". United States. https://doi.org/10.1016/j.combustflame.2020.03.001. https://www.osti.gov/servlets/purl/1763636.
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@article{osti_1763636,
title = {Revealing the critical role of radical-involved pathways in high temperature cyclopentanone pyrolysis},
author = {Dong, Xiaorui and Ninnemann, Erik and Ranasinghe, Duminda S. and Laich, Andrew and Greene, Robert and Vasu, Subith S. and Green, William H.},
abstractNote = {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.},
doi = {10.1016/j.combustflame.2020.03.001},
journal = {Combustion and Flame},
number = ,
volume = 216,
place = {United States},
year = {Sat Apr 04 00:00:00 EDT 2020},
month = {Sat Apr 04 00:00:00 EDT 2020}
}
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Publisher's Version of Record
https://doi.org/10.1016/j.combustflame.2020.03.001
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