Physicochemical Characterization of Petroleum Fractions: the State of the Art

Abstract : High-boiling-point petroleum fractions (350°C+) are known to be enriched in the most polar compounds such as resins and asphaltenes. Asphaltenes contain molecules of variable aromaticity with different contents of heteroatoms, metals and functional groups. An asphaltene fraction is a complex mixture of polydispersed molecules in terms of size and chemical composition. Such structures cannot be represented by only one model molecule. Several models have been proposed in the literature to describe these structures (continental and archipelago types). Due to this high polydispersity, specific properties such as aggregation are observed. Detailed characterization of such highly complex products is difficult and the choice of analytical techniques that can be used is quite limited. Average structural information has been obtained, but it cannot be representative of all chemical and structural variety that such matrices may contain. The aggregation state of asphaltene macromolecules strongly depends on the experimental conditions (concentration, temperature and solvent). Significant variations in measurement may be induced if the operating conditions used are not similar. The techniques being based on different theories and being run in different experimental conditions are consequently not equivalent. The asphaltenic structures are not measured in the same aggregation state. Heavy product characterizations can be divided into two types: the chemical and colloidal characterizations. The first one gives information on both chemical composition and main functional groups as well as the structural state of metals and heteroatoms in macromolecules. Numerous techniques are used such as high-performance liquid chromatography (HPLC), pyrolysis coupled with gas chromatography and mass spectrometry (PyGC-MS), 13C nuclear magnetic resonance (NMR), and spectroscopic techniques (IR, XPS, EXAFS and XANES). Colloidal characterization consists of the investigation of the dispersion of heavy fractions (asphaltenes and resins) as macromolecules in a good solvent or in their natural medium (maltenes). The main parameters that can define the colloidal structure are the molecular weight and the mass or size polydispersity of aggregates. Various techniques may be employed, such as mass spectrometry, scattering techniques (small-angle X-ray and neutron scattering), pulsed-field gradient nuclear magnetic resonance (PFG-1H NMR), as well as different separation methods (ultracentrifugation, solvent separation and size-exclusion chromatography). As a preliminary step, fractionations have to be carried out in order to simplify these matrices, too complex to be directly characterized.
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I. Merdrignac, D. Espinat. Physicochemical Characterization of Petroleum Fractions: the State of the Art. Oil & Gas Science and Technology - Revue d'IFP Energies nouvelles, Institut Français du Pétrole, 2007, 62 (1), pp.7-32. ⟨10.2516/ogst:2007002⟩. ⟨hal-02005619⟩

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