Characterization of crude oil asphaltenes by coupling size-exclusion chromatography directly to an ultrahigh-resolution mass spectrometer

Rationale: Fossil fuels are one of the most important energy resources until new sustainable materials become available. To optimize the upgrading processes of these materials characterization of the remaining heavy materials is of great importance. Methods: Asphaltenes are the most difficult fraction of crude oil to process due to the limited number of solvents in which they can be dissolved. Chromatographic separation methods need to consider the difficulties associated with these limitations. Size-exclusion chromatography (SEC) in combination with Fourier transform Orbitrap mass spectrometry (MS) combines the capabilities of ultrahigh resolution and very high mass accuracy with a separation method that allows using solvents as mobile phase for asphaltene separation. Results: A chromatographic method was developed that shows the separation of asphaltenes according to their molecular mass. A simplification of the samples was achieved by reducing the number of compounds present in a single spectrum compared to infusion data. Direct detection by mass spectrometry additionally allows a distinction of different isomers present in the complex samples. Conclusions: Direct coupling of SEC with ultrahigh-resolution mass spectrometry allows the study of the most difficult to analyze fraction of crude oil, the asphaltene fraction. Separation reduces the complexity of individual spectra and, therefore, also reduces suppression and discrimination effects. The separation of structural isomers which cannot be characterized by MS alone gives an added dimension to the analysis of asphaltenes. Copyright © 2016 John Wiley & Sons, Ltd