Molecular Characterization of Nonvolatile Fractions of Algerian Petroleum with High-Resolution Mass Spectrometry.

Abstract

Algerian crude oil displays a marked propensity for asphaltene precipitation, leading to solid deposits during extraction, transportation, and storage. The relationship between precipitation and chemical composition is unclear; in fact, Algerian crude oil actually features a low asphaltene concentration, despite its relatively large rate of deposit formation. The rationalization of the precipitation process and its remediation should benefit from a molecular characterization of the crude oil. In this study, two unstable asphaltene fractions (A1 and A2) from two different deposits, and two resin crude oil fractions (R1 and R2) from the Hassi-Messaoud Algerian field have been characterized at the molecular level by means of high-resolution mass spectrometry with an Atmospheric Pressure Chemical Ionization (APCI) source. Positively and negatively charged compounds with molecular weights 200-1200 m/z were detected. Several thousand molecular stoichiometries were identified and classified for each sample, in terms of heteroatom content and aromaticity, searching for trends characteristic of the two asphaltenes and of the associated resins. The A2 asphaltene, from a downstream storage tank, displays a higher aromaticity and O-heteroatom content, which correlates with an enhanced aggregation propensity, in comparison to the A1 fraction, collected at the well bore. The resin fractions are found to be abundant in aliphatic hydrocarbons and heteroatomic compounds of moderate aromaticity. The more polar resin fraction, R2, is enriched in N-containing species, with respect to the less polar resin fraction R1, which correlates with the stabilizing function observed in previous works. The results stress the view of crude oil fractions as complex mixtures, rather than in terms of average prototypical compounds, when facing the understanding of asphaltene deposition conditions.