Untreated and hydrotreated nitrogen-concentrated distillation fractions (483−504 °C) from Syncrude oil have been analyzed by electron ionization, field desorption ionization, and electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry. The routinely attainable mass resolving power ≥300 000 at m/z 300 and sub-ppm mass accuracy allowed for resolution and elemental compositional assignment of various compound classes. Multiple closely spaced mass doublets (with mass differences <10 mDa) were detected. Although hydrotreatment reduced the relative abundances of several heteroatomic classes (N2, S3, NS2, NOS, O3, OS2, and O2S) below detectability, N-, S-, O-, O2-, OS-, and NO-containing compounds survived hydrotreatment. Analysis of N-, S-, and O-containing compounds and hydrocarbon compounds at the molecular level exposes compositional changes and reveals the effectiveness of the hydrotreating process.

We analyzed three vacuum gas oil distillation fractions, 295−319 °C, 319−456 °C, and 456−543 °C, with a home-built external electron ionization (EI) 7 T Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometer. EI at 10 eV allows soft ionization of aromatic compounds in the vacuum gas oil range. Unambiguous elemental composition assignment provides insight into compositional variations at the molecular level; for example, ultrahigh resolving power (m/Δm 50% ≈ 300 000 at m/z 300) and mass accuracy (<0.4 ppm) readily resolve C3/SH4 doublets (3.4 mDa mass difference) across the full m/z range of interest. To our knowledge, this is the first time that hydrocarbons and sulfur-containing hydrocarbons have been completely mass-resolved across the full VGO range. Aromatic hydrocarbons are the major detected components in all three samples. In addition, many sulfur-, nitrogen-, and oxygen-containing compounds were directly observed. The concentrations of the heteroatomic species increase with boiling point. Detailed data analysis revealed compound types (rings plus double bonds) and their carbon number distributions for hydrocarbon and heteroatomic compounds in the distillation fractions and increasing average molecular weight (or carbon number distribution) and aromaticity with increasing boiling temperature of the petroleum fractions. The present analysis requires only micrograms of sample, is fast (single time-domain data set acquired in a few seconds), and highly reproducible.

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