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Combined characterization using HT-GC × GC-FID and FT-ICR MS: A pyrolysis fuel oil case study

Author:
Djokic, Marko R., Muller, Hendrik, Ristic, Nenad D., Akhras, Abdul Rahman, Symoens, Steffen H., Marin, Guy B., Van Geem, Kevin M.
Source:
Fuel processing technology 2018 v.182 pp. 15-25
ISSN:
0378-3820
Subject:
boiling, case studies, comprehensive two-dimensional gas chromatography, cracking, feedstocks, flame ionization, fractionation, fuel oils, mass spectrometry, petroleum, polycyclic aromatic hydrocarbons, pyrolysis, steam
Abstract:
In this work the composition of a hydrotreated distilled crude oil fraction (HTAL-FEED) and its heaviest steam cracking product fraction, the so-called pyrolysis fuel oil (HTAL-PFO), have been characterized in detail using high-temperature comprehensive two-dimensional gas chromatography (HT-GC × GC) coupled to a flame ionization detector (FID) and Fourier Transform-Ion Cyclotron Resonance Mass Spectrometry (FT-ICR MS). Moreover, the HTAL-FEED and HTAL-PFO were characterized using elemental analysis and SARA fractionation to determine their bulk properties. Although the main compounds are saturates, the HTAL-FEED contains significant amounts of aromatic compounds, primarily mono- and di-aromatics but even up to penta-aromatics, which are responsible for the growth of large polycyclic aromatic hydrocarbons (PAH) formed during steam cracking that almost entirely make up the HTAL-PFO product. Quantitative results are obtained based on the HT-GC × GC-FID chromatograms and the use of well-chosen internal standards, allowing ~90 wt% of the feedstock and ~60 wt% of HTAL-PFO to be quantified. FT-ICR MS analyses confirmed the presence of molecules heavier than penta-aromatics in the HTAL-FEED, as well as the very heavy character of HTAL-PFO consisting of highly condensed aromatic molecules with up to 16 fused aromatic rings. The analytical methodology can be applied to other steam cracking products, providing a near-molecular level insight into conversion and coke formation precursors during steam cracking of wide boiling range hydrocarbons.
Agid:
6196637