The pre‐separation of oxygen containing compounds in oxidised heavy paraffinic fractions and their identification by GC‐MS with supersonic molecular beams.

The heavy petroleum fractions produced during refining processes need to be upgraded to useable products to increase their value. Hydrogenated heavy paraffinic fractions can be oxidised to produce high value products that contain a variety of oxygenates. These heavy oxygenated paraffinic fractions need to be characterised to enable the control of oxidation processes and to understand product properties. The accurate identification of the oxygenates present in these fractions by electron ionisation (EI) mass spectrometry is challenging due to the complexity of these heavy fractions. Adding to this challenge is the limited applicability of EI mass spectral libraries due to the absence of molecular ions from the EI mass spectra of many oxygenates. The separation of oxygenates from the complex hydrocarbon matrix prior to high temperature GC‐MS (HT‐GC‐MS) analysis reduces the complexity of these fractions and assists in the accurate identification of these oxygenates. Solid phase extraction (SPE) and supercritical fluid chromatography (SFC) were employed as prefractionation techniques. GC‐MS with supersonic molecular beams (SMBs) (also named GC‐MS with cold‐EI) utilises a SMB interface with which EI is done with vibrationally cold sample compounds in a fly‐through ion source (cold‐EI) resulting in a substantial increase in the molecular ion signal intensity in the mass spectrum. This greatly enhances the accurate identification of the oxygenates in these fractions. This study investigated the ionisation behaviour of oxygenated compounds using cold‐EI. The prefractionation by SPE and SFC and the subsequent analysis with GC‐MS with cold‐EI were applied to an oxygenated heavy paraffinic fraction.