Characterising high mass materials in heavy oil fractions by size exclusion chromatography and MALDI-mass spectrometry

Several petroleum vacuum residues and a Maya asphaltene have been examined using size exclusion chromatography (SEC), using 1-methyl-2-pyrrolidinone as eluent. Aliphatic components are not dissolved in this solvent. All the samples showed a bimodal distribution. Material under the early eluting peak, excluded from column porosity corresponded to apparently very large molecular masses. The later eluting peak corresponded to molecules with a smaller range of masses and was relatively intense. The material excluded from column porosity is concentrated in the heptane-insoluble fraction; the peak of this fraction corresponding to smaller molecules shifted to earlier times than was found for the whole sample. In UV-fluorescence spectrometry, the heptane-insoluble materials did not fluoresce strongly. Materials excluded from column porosity showed no fluorescence, indicating that UV-fluorescence based methods are unable to detect high mass materials. MALDI-mass spectrometry indicated a bimodal distribution for the Maya asphaltene with a mass range up to m/z 40,000. Comparison of the low mass range of the spectrum with the small-size molecules detected by SEC indicated broad agreement for masses up to about 5000 u. However, if the excluded peak of SEC corresponds to the higher mass range up to m/z 40,000, then it is likely that these molecules are adopting three-dimensional conformations. Data from the hydrocracking of heavy oils was used to confirm some of the outlined findings.