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

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    Type
    Article
    Authors
    Elbaz, Ayman M.
    Abdul Jameel, Abdul Gani cc
    Hourani, Nadim cc
    Emwas, Abdul-Hamid M.
    Sarathy, Mani cc
    Roberts, William L. cc
    KAUST Department
    Chemical Engineering Program
    Clean Combustion Research Center
    Combustion and Pyrolysis Chemistry (CPC) Group
    Imaging and Characterization Core Lab
    Mechanical Engineering Program
    NMR
    Physical Science and Engineering (PSE) Division
    high-pressure combustion (HPC) Research Group
    Date
    2015-11-18
    Online Publication Date
    2015-11-18
    Print Publication Date
    2015-12-17
    Permanent link to this record
    http://hdl.handle.net/10754/583899
    
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    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.
    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
    DOI
    10.1021/acs.energyfuels.5b01739
    Additional Links
    http://pubs.acs.org/doi/10.1021/acs.energyfuels.5b01739
    ae974a485f413a2113503eed53cd6c53
    10.1021/acs.energyfuels.5b01739
    Scopus Count
    Collections
    Articles; Imaging and Characterization Core Lab; Physical Science and Engineering (PSE) Division; Chemical Engineering Program; Mechanical Engineering Program; Clean Combustion Research Center

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