It is well known that saturates, aromatics, resins and asphaltenes (SARA) separations can provide a significant amount of insight into processing behavior of crude oils and residues, and it can also provide information about the physical behavior of asphalts and pitch materials. The automated HPLC based saturates, aromatics, resins-Asphaltene Determinator (SAR-AD<sup>TM</sup>) provides additional resolution over traditional SARA separations as it provides 3 aromatics fractions and 3 asphaltene fractions. The Aromatics 1 fraction contains 1 ring aromatics, the Aromatics 2 fraction contains predominantly 2-3 fused ring aromatics and the Aromatics 3 fraction contains 4+ fused ring aromatics. For the asphaltenes fractions, they are separated by precipitation on an inert phase and extracted by solvents of increasing strength using cyclohexane, toluene and dichloromethane. Despite this additional level of resolution over traditional SARA separations, the SAR-AD is unable to provide adequate discrimination between some petroleum based materials and other hydrocarbons. To help provide even higher resolution, the SAR-AD has been fitted with a fluorescence detector so that the emission spectra for each fraction can now be obtained. By using this hybrid technique, it is now possible to distinguish differences in several of the SAR-AD fractions. For example, the emission spectra of the Aromatics 1, Aromatics 2 and Aromatics 3 fractions of a West Texas Intermediate (WTI) vacuum residue are significantly red shifted compared to the emission spectra of the same fractions from a Lloydminster vacuum residue. This is consistent with the fact that the WTI fractions contain higher MW material than Lloydminster, partially by having larger fused ring systems in the fractions. The larger fused ring systems however need to be balanced out with steric bulk of aliphatic substituents on the fused aromatic ring systems to explain their chromatographic behavior. Evidence will be provided showing that the elution pattern of the Aromatics 3 fraction is consistent with the steric bulk of alkyl substituents on aromatic units. Several other comparisons will be shown between different vacuum residues, with air blowing, with visbreaking, for petroleum pitch, gilsonite, and coal tar pitch.

Coupling fluorescence spectroscopy with the SAR-AD: Additional insights into molecular differences within chromatography fraction due to hydrocarbon source

Macromolecular Chemistry: The Second Century

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ACS Spring 2020 National Meeting & Expo

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