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Compositional characterization of pyrolysis fuel oil from Naphtha and vacuum gas oil

(2018) ENERGY & FUELS. 32(2). p.1276-1286
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Abstract
Steam cracking of crude oil fractions gives rise to substantial amounts of a heavy liquid product referred to as pyrolysis fuel oil (PFO). To evaluate the potential use of PFO for production of value-added chemicals, a better understanding of the composition is needed. Therefore, two PFO’s derived from naphtha (N-PFO) and vacuum gas oil (V-PFO) were characterized using elemental analysis, SARA fractionation, nuclear magnetic resonance (NMR) spectroscopy, and comprehensive two-dimensional gas chromatography (GC × GC) coupled to a flame ionization detector (FID) and time-offlight mass spectrometer (TOF-MS). Both samples are highly aromatic, with molar hydrogen-to-carbon (H/C) ratios lower than 1 and with significant content of compounds with solubility characteristics typical for asphaltenes and coke (i.e. n-hexane insolubles). The molar H/C ratio of V-PFO is lower than the one measured for N-PFO, as expected from the lower molar H/C ratio of the VGO. On the other hand, the content of n-hexane insolubles is lower in V-PFO compared to the one in N-PFO (i.e., 10.3 ± 0.2 wt % and 19.5 ± 0.5 wt %, respectively). This difference is attributed to the higher reaction temperature applied during naphtha steam cracking, which promotes the formation of poly aromatic cores and at the same time scission of aliphatic chains. The higher concentrations of purely aromatic molecules present in N-PFO is confirmed via NMR and GC × GC−FID/ TOF-MS. The dominant chemical family in both samples are diaromatics, with a concentration of 28.6 ± 0.1 wt % and 27.8 ± 0.1 wt % for N-PFO and V-PFO, respectively. Therefore, extraction of valuable chemical industry precursors such as diaromatics and specifically naphthalene is considered as a potential valorization route. On the other hand, hydro-conversion is required to improve the quality of the PFO’s before exploiting them as a commercial fuel.

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Chicago
Ristic, Nenad, Marko Dokic, Elisabeth Delbeke, Arturo González Quiroga, Christian Stevens, Kevin Van Geem, and Guy Marin. 2018. “Compositional Characterization of Pyrolysis Fuel Oil from Naphtha and Vacuum Gas Oil.” Energy & Fuels 32 (2): 1276–1286.
APA
Ristic, N., Dokic, M., Delbeke, E., González Quiroga, A., Stevens, C., Van Geem, K., & Marin, G. (2018). Compositional characterization of pyrolysis fuel oil from Naphtha and vacuum gas oil. ENERGY & FUELS, 32(2), 1276–1286.
Vancouver
1.
Ristic N, Dokic M, Delbeke E, González Quiroga A, Stevens C, Van Geem K, et al. Compositional characterization of pyrolysis fuel oil from Naphtha and vacuum gas oil. ENERGY & FUELS. 2018;32(2):1276–86.
MLA
Ristic, Nenad, Marko Dokic, Elisabeth Delbeke, et al. “Compositional Characterization of Pyrolysis Fuel Oil from Naphtha and Vacuum Gas Oil.” ENERGY & FUELS 32.2 (2018): 1276–1286. Print.
@article{8551895,
  abstract     = {Steam cracking of crude oil fractions gives rise to substantial amounts of a heavy liquid product referred to as
pyrolysis fuel oil (PFO). To evaluate the potential use of PFO for production of value-added chemicals, a better understanding of the composition is needed. Therefore, two PFO{\textquoteright}s derived from naphtha (N-PFO) and vacuum gas oil (V-PFO) were characterized using elemental analysis, SARA fractionation, nuclear magnetic resonance (NMR) spectroscopy, and comprehensive two-dimensional gas chromatography (GC {\texttimes} GC) coupled to a flame ionization detector (FID) and time-offlight
mass spectrometer (TOF-MS). Both samples are highly aromatic, with molar hydrogen-to-carbon (H/C) ratios lower than
1 and with significant content of compounds with solubility characteristics typical for asphaltenes and coke (i.e. n-hexane
insolubles). The molar H/C ratio of V-PFO is lower than the one measured for N-PFO, as expected from the lower molar H/C ratio of the VGO. On the other hand, the content of n-hexane insolubles is lower in V-PFO compared to the one in N-PFO (i.e., 10.3 {\textpm} 0.2 wt \% and 19.5 {\textpm} 0.5 wt \%, respectively). This difference is attributed to the higher reaction temperature applied during naphtha steam cracking, which promotes the formation of poly aromatic cores and at the same time scission of aliphatic chains. The higher concentrations of purely aromatic molecules present in N-PFO is confirmed via NMR and GC {\texttimes} GC\ensuremath{-}FID/ TOF-MS. The dominant chemical family in both samples are diaromatics, with a concentration of 28.6 {\textpm} 0.1 wt \% and 27.8 {\textpm} 0.1 wt \% for N-PFO and V-PFO, respectively. Therefore, extraction of valuable chemical industry precursors such as diaromatics and specifically naphthalene is considered as a potential valorization route. On the other hand, hydro-conversion is required to improve the quality of the PFO{\textquoteright}s before exploiting them as a commercial fuel.},
  author       = {Ristic, Nenad and Dokic, Marko and Delbeke, Elisabeth and Gonz{\'a}lez Quiroga, Arturo and Stevens, Christian and Van Geem, Kevin and Marin, Guy},
  issn         = {0887-0624 },
  journal      = {ENERGY \& FUELS},
  language     = {eng},
  number       = {2},
  pages        = {1276--1286},
  title        = {Compositional characterization of pyrolysis fuel oil from Naphtha and vacuum gas oil},
  url          = {http://dx.doi.org/10.1021/acs.energyfuels.7b03242},
  volume       = {32},
  year         = {2018},
}

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