Colloidal structure of heavy crudes and asphaltene solutions

Many industrial problems that arise during petroleum processing are related to the high concentration of asphaltenes. A good knowledge of the chemical composition of these macromolecules and a detailed understanding of the evolution of the colloidal structures present in oil and its derivatives can play a decisive role in improving processing facilities. Asphaltenes are defined by their insolubility in n-heptane. Soluble molecules are called maltenes which can be fractionated by liquid chromatography in so-called resins, aromatic and saturated fractions. The major part of the research carried out on these complex molecules concerned the chemical composition determination from powerful techniques measurements as for instance IR or NMR methods. Nevertheless, very little information on the colloidal structure of asphaltenes or resins in pure solvent or in real systems is accessible. The molecular weight determination was the first objective; several techniques, as vapour pressure osmometry (VPO), were used. The main conclusion of these determinations was the huge variation of the molecular weight measured by different methods. We used X-ray and neutron small angle scattering techniques in order to deduce the size polydispersity and the weight average molecular weight. Different systems as (i) asphaltenes or resins in solution with different solvents, or (ii) asphaltene and resin mixtures in suspension with good or bad solvents were investigated as a function of temperature increase. We have exhibited that the aggregation number, i.e. the number of smaller entities, can strongly vary with solvent composition and temperature. Resins appear as very good solvent for asphaltene molecules. Scattering measurements often exhibit strong scattered intensity at small scattering vector, showing the presence in the suspension of large heterogeneities in diluted solutions of asphaltenes and resins. We can suggest that these heterogeneities are due to concentration fluctuations. It exists in the diluted suspension regions more or less extended, where the asphaltene concentration is greater than the average asphaltene concentration. Cryo-scanning electron microscopy has confirmed the system inhomogeneity. A two phase system was clearly highlighted. The flocculation process was followed during n-heptane addition by scattering measurements and microscopy observations. Small angle X-ray scattering (SAXS) appears as a powerful tool for non-fractionated systems, as crude oil or other heavy derivatives. Density fluctuations were observed for a vacuum residue.