TG/DTG, FT-ICR Mass Spectrometry, and NMR Spectroscopy Study of Heavy Fuel Oil

Handle URI:
http://hdl.handle.net/10754/583899
Title:
TG/DTG, FT-ICR Mass Spectrometry, and NMR Spectroscopy Study of Heavy Fuel Oil
Authors:
Elbaz, Ayman M.; Abdul Jameel, Abdul Gani; Hourani, Nadim ( 0000-0003-4272-5395 ) ; Emwas, Abdul-Hamid M.; Sarathy, Mani ( 0000-0002-3975-6206 ) ; Roberts, William L. ( 0000-0003-1999-2831 )
Abstract:
There is an increasing interest in the comprehensive study of heavy fuel oil (HFO) due to its growing use in furnaces, boilers, marines, and recently in gas turbines. In this work, the thermal combustion characteristics and chemical composition of HFO were investigated using a range of techniques. Thermogravimetric analysis (TGA) was conducted to study the nonisothermal HFO combustion behavior. Chemical characterization of HFO was accomplished using various standard methods in addition to direct infusion atmospheric pressure chemical ionization Fourier transform ion cyclotron resonance mass spectrometry (APCI-FTICR MS), high resolution 1H nuclear magnetic resonance (NMR), 13C NMR, and two-dimensional heteronuclear multiple bond correlation (HMBC) spectroscopy. By analyzing thermogravimetry and differential thermogravimetry (TG/DTG) results, three different reaction regions were identified in the combustion of HFO with air, specifically, low temperature oxidation region (LTO), fuel deposition (FD), and high temperature oxidation (HTO) region. At the high end of the LTO region, a mass transfer resistance (skin effect) was evident. Kinetic analysis in LTO and HTO regions was conducted using two different kinetic models to calculate the apparent activation energy. In both models, HTO activation energies are higher than those for LTO. The FT-ICR MS technique resolved thousands of aromatic and sulfur containing compounds in the HFO sample and provided compositional details for individual molecules of three major class species. The major classes of compounds included species with one sulfur atom (S1), with two sulfur atoms (S2), and purely hydrocarbons (HC). The DBE (double bond equivalent) abundance plots established for S1 and HC provided additional information on their distributions in the HFO sample. The 1H NMR and 13C NMR results revealed that nearly 59% of the 1H nuclei were distributed as paraffinic CH2 and 5% were in aromatic groups. Nearly 21% of 13C nuclei were distributed in aromatic groups, indicating that most paraffinic CH2 groups are attached to aromatic rings. A negligible amount of olefins was present, and an appreciable quantity of monoaromatic and polyaromatic content was observed. Molecular connectivity between the hydrogen and carbon atoms using HMBC spectra was utilized to propose several plausible skeletal structures in HFO.
KAUST Department:
Clean Combustion Research Center; Imaging and Characterization Core Lab
Citation:
TG/DTG, FT-ICR Mass Spectrometry, and NMR Spectroscopy Study of Heavy Fuel Oil 2015 Energy & Fuels
Publisher:
American Chemical Society (ACS)
Journal:
Energy & Fuels
Issue Date:
12-Nov-2015
DOI:
10.1021/acs.energyfuels.5b01739
Type:
Article
ISSN:
0887-0624; 1520-5029
Additional Links:
http://pubs.acs.org/doi/10.1021/acs.energyfuels.5b01739
Appears in Collections:
Articles; Advanced Nanofabrication, Imaging and Characterization Core Lab; Clean Combustion Research Center

Full metadata record

DC FieldValue Language
dc.contributor.authorElbaz, Ayman M.en
dc.contributor.authorAbdul Jameel, Abdul Ganien
dc.contributor.authorHourani, Nadimen
dc.contributor.authorEmwas, Abdul-Hamid M.en
dc.contributor.authorSarathy, Manien
dc.contributor.authorRoberts, William L.en
dc.date.accessioned2015-12-15T09:25:20Zen
dc.date.available2015-12-15T09:25:20Zen
dc.date.issued2015-11-12en
dc.identifier.citationTG/DTG, FT-ICR Mass Spectrometry, and NMR Spectroscopy Study of Heavy Fuel Oil 2015 Energy & Fuelsen
dc.identifier.issn0887-0624en
dc.identifier.issn1520-5029en
dc.identifier.doi10.1021/acs.energyfuels.5b01739en
dc.identifier.urihttp://hdl.handle.net/10754/583899en
dc.description.abstractThere is an increasing interest in the comprehensive study of heavy fuel oil (HFO) due to its growing use in furnaces, boilers, marines, and recently in gas turbines. In this work, the thermal combustion characteristics and chemical composition of HFO were investigated using a range of techniques. Thermogravimetric analysis (TGA) was conducted to study the nonisothermal HFO combustion behavior. Chemical characterization of HFO was accomplished using various standard methods in addition to direct infusion atmospheric pressure chemical ionization Fourier transform ion cyclotron resonance mass spectrometry (APCI-FTICR MS), high resolution 1H nuclear magnetic resonance (NMR), 13C NMR, and two-dimensional heteronuclear multiple bond correlation (HMBC) spectroscopy. By analyzing thermogravimetry and differential thermogravimetry (TG/DTG) results, three different reaction regions were identified in the combustion of HFO with air, specifically, low temperature oxidation region (LTO), fuel deposition (FD), and high temperature oxidation (HTO) region. At the high end of the LTO region, a mass transfer resistance (skin effect) was evident. Kinetic analysis in LTO and HTO regions was conducted using two different kinetic models to calculate the apparent activation energy. In both models, HTO activation energies are higher than those for LTO. The FT-ICR MS technique resolved thousands of aromatic and sulfur containing compounds in the HFO sample and provided compositional details for individual molecules of three major class species. The major classes of compounds included species with one sulfur atom (S1), with two sulfur atoms (S2), and purely hydrocarbons (HC). The DBE (double bond equivalent) abundance plots established for S1 and HC provided additional information on their distributions in the HFO sample. The 1H NMR and 13C NMR results revealed that nearly 59% of the 1H nuclei were distributed as paraffinic CH2 and 5% were in aromatic groups. Nearly 21% of 13C nuclei were distributed in aromatic groups, indicating that most paraffinic CH2 groups are attached to aromatic rings. A negligible amount of olefins was present, and an appreciable quantity of monoaromatic and polyaromatic content was observed. Molecular connectivity between the hydrogen and carbon atoms using HMBC spectra was utilized to propose several plausible skeletal structures in HFO.en
dc.language.isoenen
dc.publisherAmerican Chemical Society (ACS)en
dc.relation.urlhttp://pubs.acs.org/doi/10.1021/acs.energyfuels.5b01739en
dc.rightsThis document is the Accepted Manuscript version of a Published Work that appeared in final form in Energy & Fuels, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see http://pubs.acs.org/doi/10.1021/acs.energyfuels.5b01739.en
dc.titleTG/DTG, FT-ICR Mass Spectrometry, and NMR Spectroscopy Study of Heavy Fuel Oilen
dc.typeArticleen
dc.contributor.departmentClean Combustion Research Centeren
dc.contributor.departmentImaging and Characterization Core Laben
dc.identifier.journalEnergy & Fuelsen
dc.eprint.versionPost-printen
dc.contributor.institutionFaculty of Engineering-Mataria, Helwan University, Cairo-11795, Egypten
dc.contributor.affiliationKing Abdullah University of Science and Technology (KAUST)en
kaust.authorElbaz, Ayman M.en
kaust.authorAbdul Jameel, Abdul Ganien
kaust.authorHourani, Nadimen
kaust.authorEmwas, Abdul-Hamid M.en
kaust.authorSarathy, Manien
kaust.authorRoberts, William L.en
All Items in KAUST are protected by copyright, with all rights reserved, unless otherwise indicated.