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Advances in Asphaltene Petroleomics. Part 4. Compositional Trends of Solubility Subfractions Reveal that Polyfunctional Oxygen-Containing Compounds Drive Asphaltene Chemistry

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journal contribution
posted on 10.03.2020, 13:22 authored by Martha L. Chacón-Patiño, Donald F. Smith, Christopher L. Hendrickson, Alan G. Marshall, Ryan P. Rodgers
Asphaltenes have traditionally been conceived as highly aromatic, alkyl-deficient compounds enriched in pericondensed aromatic “island” motifs. This structural definition evolved into the general notion that aromatic core-dominated interactions (π-stacking) drive asphaltene aggregation, and heteroatom-based intermolecular forces have no significant effect on the overall solubility and aggregation behavior. However, the exclusion of heteroatoms in asphaltene chemistry is inconsistent with the Boduszynski continuum and known asphaltene properties, such as increased heteroatom content relative to maltenes, interfacial activity, and strong adsorption to polar stationary phases. Thus, to determine whether or not heteroatoms are involved in solubility, we have separated asphaltene fractions enriched in single-core (island) or multicore motifs (archipelago) according to their partitioning in n-heptane by two fractionation methods. In the first separation procedure, the acetone fraction from Wyoming deposit n-heptane asphaltenes (island-enriched) was adsorbed on polytetrafluoroethylene powder and Soxhlet extracted with n-heptane. Subfractions were collected after one day, one week, one month, and three months of extraction, and the residue, n-heptane insoluble material, was recovered with a mixture of toluene and dichloromethane. In the second method, the acetone fraction from Athabasca bitumen n-heptane asphaltenes (archipelago-enriched) was fractionated by differential precipitation in mixtures of n-heptane and toluene. The molecular composition of the asphaltene subfractions was accessed by positive-ion atmospheric pressure photoionization coupled to 9.4 T Fourier transform ion cyclotron resonance mass spectrometry and structures were determined by infrared multiphoton dissociation. The compositional trends for heteroatom content, double bond equivalents, and alkyl substitution suggest that the Boduszynski continuum can be extended to asphaltenes. In particular, the compositional range of polyoxygenated asphaltene compounds shifts toward lower aromaticity, whereas oxygen-depleted species are more aromatic. Moreover, the results demonstrate that polyoxygenated species (e.g., O3 and S2O3 classes) are pivotal in asphaltene solubility, as they concentrate in the most polarizable and insoluble asphaltene subfractions. Therefore, the results support the existence of atypical asphaltene species with remarkably low aromaticity that reside in the most insoluble asphaltene subfractions because of their high heteroatom content. Such asphaltene compounds preferentially ionize as protonated molecules rather than radical cations and overlap the compositional range of interfacially active species, consistent with their tendency to participate in hydrogen bonding. Collectively, the results highlight the need for an asphaltene molecular model based on the existence of polyfunctional species capable of interacting with neighboring asphaltene molecules through several intermolecular forces, including London dispersion forces between aliphatic moieties, π-stacking of aromatic cores, hydrogen bonding between nitrogen and oxygen-containing functionalities, and acid/base interactions between carboxylic acids and pyridine rings.