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Title: Detailed Experimental and Kinetic Modeling Study of Cyclopentadiene Pyrolysis in the Presence of Ethene

Abstract

A combined experimental and kinetic modeling study is presented to improve the understanding of the formation of polycyclic aromatic hydrocarbons at pyrolysis conditions. The copyrolysis of cyclopentadiene (CPD) and ethene was studied in a continuous flow tubular reactor at a pressure of 0.17 MPa and a dilution of 1 mol CPD/1 mol ethene/10 mol N 2. The temperature was varied from 873 to 1163 K, resulting in cyclopentadiene conversions between 1 and 92%. Using an automated reaction network generator, RMG, we present an elementary step kinetic model for CPD pyrolysis that accurately predicts the initial formation of aromatic products. The model is able to reproduce the product yields measured during the pyrolysis of pure cyclopentadiene and the copyrolysis of cyclopentadiene and ethene. The addition of ethene as coreactant increases the benzene and toluene selectivity. In the absence of ethene, benzene formation is initiated by addition of a cyclopentadienyl radical to cyclopentadiene, following a complicated series of isomerizations and loss of a butadienyl radical. In the presence of ethene, the main pathway for the formation of benzene + CH 3 shifts to ethene + cyclopentadiene. Toluene formation is initiated by vinyl radical addition to cyclopentadiene. Without the addition of ethene, vinylmore » radicals are mainly formed by hydrogen radical addition to ethyne. As a result, when ethene is added as coreactant, vinyl radical production happens via hydrogen abstraction from ethene.« less

Authors:
 [1];  [1];  [2]; ORCiD logo [1];  [3]; ORCiD logo [1]; ORCiD logo [3]; ORCiD logo [1]
  1. Ghent Univ., Gent (Belgium)
  2. ExxonMobil Research and Engineering, Annandale, NJ (United States)
  3. Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Combustion Energy Frontier Research Center (CEFRC); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1480083
Grant/Contract Number:  
SC0001198; SC0014901; AC02-05CH11231
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Energy and Fuels
Additional Journal Information:
Journal Volume: 32; Journal Issue: 3; Journal ID: ISSN 0887-0624
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Vervust, Alexander J., Djokic, Marko R., Merchant, Shamel S., Carstensen, Hans-Heinrich, Long, Alan E., Marin, Guy B., Green, William H., and Van Geem, Kevin M. Detailed Experimental and Kinetic Modeling Study of Cyclopentadiene Pyrolysis in the Presence of Ethene. United States: N. p., 2018. Web. doi:10.1021/acs.energyfuels.7b03560.
Vervust, Alexander J., Djokic, Marko R., Merchant, Shamel S., Carstensen, Hans-Heinrich, Long, Alan E., Marin, Guy B., Green, William H., & Van Geem, Kevin M. Detailed Experimental and Kinetic Modeling Study of Cyclopentadiene Pyrolysis in the Presence of Ethene. United States. doi:10.1021/acs.energyfuels.7b03560.
Vervust, Alexander J., Djokic, Marko R., Merchant, Shamel S., Carstensen, Hans-Heinrich, Long, Alan E., Marin, Guy B., Green, William H., and Van Geem, Kevin M. Wed . "Detailed Experimental and Kinetic Modeling Study of Cyclopentadiene Pyrolysis in the Presence of Ethene". United States. doi:10.1021/acs.energyfuels.7b03560. https://www.osti.gov/servlets/purl/1480083.
@article{osti_1480083,
title = {Detailed Experimental and Kinetic Modeling Study of Cyclopentadiene Pyrolysis in the Presence of Ethene},
author = {Vervust, Alexander J. and Djokic, Marko R. and Merchant, Shamel S. and Carstensen, Hans-Heinrich and Long, Alan E. and Marin, Guy B. and Green, William H. and Van Geem, Kevin M.},
abstractNote = {A combined experimental and kinetic modeling study is presented to improve the understanding of the formation of polycyclic aromatic hydrocarbons at pyrolysis conditions. The copyrolysis of cyclopentadiene (CPD) and ethene was studied in a continuous flow tubular reactor at a pressure of 0.17 MPa and a dilution of 1 mol CPD/1 mol ethene/10 mol N2. The temperature was varied from 873 to 1163 K, resulting in cyclopentadiene conversions between 1 and 92%. Using an automated reaction network generator, RMG, we present an elementary step kinetic model for CPD pyrolysis that accurately predicts the initial formation of aromatic products. The model is able to reproduce the product yields measured during the pyrolysis of pure cyclopentadiene and the copyrolysis of cyclopentadiene and ethene. The addition of ethene as coreactant increases the benzene and toluene selectivity. In the absence of ethene, benzene formation is initiated by addition of a cyclopentadienyl radical to cyclopentadiene, following a complicated series of isomerizations and loss of a butadienyl radical. In the presence of ethene, the main pathway for the formation of benzene + CH3 shifts to ethene + cyclopentadiene. Toluene formation is initiated by vinyl radical addition to cyclopentadiene. Without the addition of ethene, vinyl radicals are mainly formed by hydrogen radical addition to ethyne. As a result, when ethene is added as coreactant, vinyl radical production happens via hydrogen abstraction from ethene.},
doi = {10.1021/acs.energyfuels.7b03560},
journal = {Energy and Fuels},
issn = {0887-0624},
number = 3,
volume = 32,
place = {United States},
year = {2018},
month = {2}
}

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