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Title: Experimental and Theoretical Study of Cyclopentanone as a Catalyst for Low Temperature Alkene Oxidation: Preprint

Abstract

Cyclopentanone was evaluated for spark-ignition fuel properties to determine potential as a bio-blendstock. Although key properties such as octane numbers and energy density are promising, when blended with commercial gasoline the oxidation stability was significantly reduced. Oxidation stability determination exposes fuel to mild oxidative conditions of 700 kPa oxygen followed by temperature increase to 100 degrees C, resulting in a final pressure of ~ 900 kPa. Oxygen consumption is determined by monitoring for decrease in pressure over time - the results evaluate potential for autoxidation during storage. An increase in oxidation rate from cyclopentanone was not anticipated given the relatively low reactivity of this compound. Detailed hydrocarbon analysis of blends before and after oxidation revealed cyclopentanone was not consumed, but alkenes were oxidized to a significantly higher degree with this compound present. Experiments with surrogate blends of isooctane, cyclopentanone, and linear isomers of hexene demonstrated that cyclopentanone catalyzes alkene oxidation to form epoxides under mild oxidative conditions. This unexpected behavior observed may have implications in low temperature combustion of alkenes when ketone fuels are present, as well as epoxidation chemistry. This study proposes a detailed mechanism for a catalytic cycle evaluated with quantum chemical calculations performed with density functional theory.

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1];  [2]; ORCiD logo [1]
  1. National Renewable Energy Laboratory (NREL), Golden, CO (United States)
  2. Colorado State University
Publication Date:
Research Org.:
National Renewable Energy Lab. (NREL), Golden, CO (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Bioenergy Technologies Office (EE-3B); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V)
OSTI Identifier:
1566800
Report Number(s):
NREL/CP-5100-74904
DOE Contract Number:  
AC36-08GO28308
Resource Type:
Conference
Resource Relation:
Conference: Presented at the 11th U.S. National Combustion Meeting, 24-27 March 2019, Pasadena, California
Country of Publication:
United States
Language:
English
Subject:
09 BIOMASS FUELS; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; biofuels; oxidation; cyclopentanone; density functional theory; DFT

Citation Formats

Christensen, Earl D, Kim, Seon Ah, Fioroni, Gina M, Paton, Robert S., and McCormick, Robert L. Experimental and Theoretical Study of Cyclopentanone as a Catalyst for Low Temperature Alkene Oxidation: Preprint. United States: N. p., 2019. Web.
Christensen, Earl D, Kim, Seon Ah, Fioroni, Gina M, Paton, Robert S., & McCormick, Robert L. Experimental and Theoretical Study of Cyclopentanone as a Catalyst for Low Temperature Alkene Oxidation: Preprint. United States.
Christensen, Earl D, Kim, Seon Ah, Fioroni, Gina M, Paton, Robert S., and McCormick, Robert L. Fri . "Experimental and Theoretical Study of Cyclopentanone as a Catalyst for Low Temperature Alkene Oxidation: Preprint". United States. https://www.osti.gov/servlets/purl/1566800.
@article{osti_1566800,
title = {Experimental and Theoretical Study of Cyclopentanone as a Catalyst for Low Temperature Alkene Oxidation: Preprint},
author = {Christensen, Earl D and Kim, Seon Ah and Fioroni, Gina M and Paton, Robert S. and McCormick, Robert L},
abstractNote = {Cyclopentanone was evaluated for spark-ignition fuel properties to determine potential as a bio-blendstock. Although key properties such as octane numbers and energy density are promising, when blended with commercial gasoline the oxidation stability was significantly reduced. Oxidation stability determination exposes fuel to mild oxidative conditions of 700 kPa oxygen followed by temperature increase to 100 degrees C, resulting in a final pressure of ~ 900 kPa. Oxygen consumption is determined by monitoring for decrease in pressure over time - the results evaluate potential for autoxidation during storage. An increase in oxidation rate from cyclopentanone was not anticipated given the relatively low reactivity of this compound. Detailed hydrocarbon analysis of blends before and after oxidation revealed cyclopentanone was not consumed, but alkenes were oxidized to a significantly higher degree with this compound present. Experiments with surrogate blends of isooctane, cyclopentanone, and linear isomers of hexene demonstrated that cyclopentanone catalyzes alkene oxidation to form epoxides under mild oxidative conditions. This unexpected behavior observed may have implications in low temperature combustion of alkenes when ketone fuels are present, as well as epoxidation chemistry. This study proposes a detailed mechanism for a catalytic cycle evaluated with quantum chemical calculations performed with density functional theory.},
doi = {},
journal = {},
number = ,
volume = ,
place = {United States},
year = {2019},
month = {9}
}

Conference:
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