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Research Papers: Fuel Combustion

Products and Pathways of Aldehydes Oxidation in the Negative Temperature Coefficient Region

[+] Author and Article Information
Ghazal Barari, Batikan Koroglu

Center for Advanced Turbomachinery
and Energy Research (CATER),
Mechanical and Aerospace Engineering,
University of Central Florida,
Orlando, FL 32816

Artëm E. Masunov

NanoScience Technology Center,
Department of Chemistry,
Department of Physics,
University of Central Florida,
Orlando, FL 32816

Subith Vasu

Center for Advanced Turbomachinery
and Energy Research (CATER),
Mechanical and Aerospace Engineering,
University of Central Florida,
Orlando, FL 32816
e-mail: subith@ucf.edu

Contributed by the Advanced Energy Systems Division of ASME for publication in the JOURNAL OF ENERGY RESOURCES TECHNOLOGY. Manuscript received March 14, 2016; final manuscript received March 18, 2016; published online July 11, 2016. Editor: Hameed Metghalchi.

J. Energy Resour. Technol 139(1), 012203 (Jul 11, 2016) (9 pages) Paper No: JERT-16-1133; doi: 10.1115/1.4033589 History: Received March 14, 2016; Revised March 18, 2016

Aldehydes are major intermediates in oxidation and pyrolysis of hydrocarbons and particularly biofuels. While the high temperature oxidation chemistry of C3–C5 aldehydes have been studied in the literature, a comprehensive low temperature kinetics remains unaddressed. In this work, acetaldehyde, propanal, and 2-propenal (acrolein) oxidation was investigated at low-temperature combustion condition (500–700 K). The isomer-specific product concentrations as well as the time-resolved profiles were studied using Sandia's multiplexed photoionization mass spectroscopy (MPIMS) with synchrotron radiation from the advanced light source (ALS). The laser-pulsed photolysis generates chlorine atoms which react with aldehydes to form the parent radicals. In the presence of excess oxygen, these radicals react with O2 and form RO2 radicals. The temperature-dependent product yields are determined for 500 K to 700 K and the competition between the channels contributing to the formation of each product is discussed. In acetaldehyde oxidation, the formation of the main products is associated with HO2 elimination channel from QOOH or direct H atom elimination from the parent radicals. In propanal oxidation, the most intensive signal peak was associated with acetaldehyde (m/z = 44) which was formed through the reaction of α′-R with O2.The α′-RO2 intermediate decomposes to acetaldehyde+OH+CO via Waddington mechanism and formation of five-member ring transition state. In 2-propenal oxidation, the unsaturated radical produced from α-R reacts with O2 to form the primary products.

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Figures

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Fig. 1

Integrated difference mass spectra for Cl-initiated oxidation of acetaldehyde at 550 K and 700 K, integrated over the photon energy 9.5–11.5 eV and kinetic times until 25 ms after the laser photolysis

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Fig. 2

Primary products photoionization spectra of acetaldehyde Cl-initiated oxidation at 550 and 700 K compared to the corresponding standard PIE

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Fig. 3

The scaled time profiles of m/z = 30 (formaldehyde), 42 (ketene), 47 (methylperoxy), and 60 compared to the inverted depletion rate of parent fuel, m/z = 44 (acetaldehyde) in Cl-initiated oxidation of acetaldehyde at 700 K

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Fig. 4

The scaled time profiles of m/z = 30 (formaldehyde), 42 (ketene), 47 (methylperoxy), and 60 in Cl-initiated oxidation of acetaldehyde at 550 K

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Fig. 5

Temperature-dependent time profiles of the products in Cl-initiated oxidation of acetaldehyde

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Fig. 6

Integrated difference mass spectra for Cl-initiated oxidation of Propanal at 550 K and 700 K, obtained by integration over the photon energy 9.5–11.5 eV and the kinetic times until 25 ms after the laser photolysis

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Fig. 7

Primary products photoionization spectra of propanal Cl-initiated oxidation at 550 and 700 K compared to the corresponding standard PIE

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Fig. 8

Temperature-dependent time profiles of the products in Cl-initiated oxidation of propanal

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Fig. 9

Integrated difference mass spectra for Cl-initiated oxidation of 2-propenal at 550 K obtained by integration over the photon energy 9.5–11.5 eV and the kinetic times until 25 ms after the laser photolysis

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Fig. 10

Primary products photoionization spectra of 2-propenal Cl-initiated oxidation at 550 compared to the corresponding standard PIE

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Fig. 11

Comparison of the photoionization spectra of the peak at m/z = 44 with the corresponding standard PIE of ethenol and acetaldehyde, along with the data fit, in 2-propenal Cl-initiated oxidation at 550

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