Molecular-Level Characterization of Asphaltenes Isolated from Distillation Cuts

• Published in: Energy & fuels Vol. 33; no. 3; pp. 2018 - 2029
• Main Authors: McKenna, Amy M, Chacón-Patiño, Martha L, Weisbrod, Chad R, Blakney, Gregory T, Rodgers, Ryan P
• Format: Journal Article
• Language: English
• Published: American Chemical Society 21.03.2019
• ISSN: 0887-0624; 1520-5029
• DOI: 10.1021/acs.energyfuels.8b04219

Asphaltenes challenge nearly all analytical techniques because of their immense polydispersity in molecular composition and structure. This operationally defined fraction of crude oil, insoluble in n-alkanes but soluble in aromatic solvents, is known to concentrate in vacuum residues and islinked to fouling and deposition issues. However, presence and subsequent characterization of asphaltenes are seldom discussed in conventional/unconventional distillate fractions. Here, we isolate asphaltenes from conventional (<593 °C/1099 F) and unconventional (>593 °C) distillation cuts and provide molecular-level characterization by electrospray ionization and atmospheric pressure photoionization Fourier transform ion cyclotron resonance mass spectrometry as a function of boiling point. Our results indicate that asphaltene molecular composition starts in the vacuum gas oil range and extends into vacuum residues. Moreover, we report that distillable asphaltene composition exists as both highly polar (heteroatom rich), aliphatic (atypical asphaltenes) species as well as condensed aromatic structures (classical asphaltenes). As a function of distillation temperature, asphaltene compounds exhibit structural trends consistent with thermal cracking that starts between 510 and 538 °C, increases between 538 and 593 °C, and is readily observed at temperatures up to 700 °C. Above 600 °C, low molecular weight compounds (expected to boil at much lower temperatures) that are n-heptane insoluble are detected across all heteroatom classes. Results herein suggest that these compounds are formed through structural rearrangement of archipelago asphaltenes because of thermal cracking reactions that occur during distillation and precipitate as asphaltenes. We report the isolation and mass spectral characterization of asphaltenes isolated from distillation cuts and propose that quantification of asphaltenes in distillates is critical to predict and prevent problems related to catalyst deactivation.