Interfacial rheology of petroleum asphaltenes at the oil-water interface.

A biconical bob interfacial shear rheometer was used to study the mechanical properties of asphaltenic films adsorbed at the oil-water interface. Solutions of asphaltenes isolated from four crude oils were dissolved in a model oil of heptane and toluene and allowed to adsorb and age in contact with water. Film elasticity (G') values were measured over a period of several days, and yield stresses and film masses were determined at the end of testing. The degree of film consolidation was determined from ratios of G'/film mass and yield stress/G'. Asphaltenes with higher concentrations of heavy metals (Ni, 330-360 ppm; V, 950-1000 ppm), lower aromaticity (H/C, 1.24-1.29), and higher polarity (N, 1.87-1.99) formed films of high elasticity, yield stress, and consolidation. Rapid adsorption kinetics and G' increases were seen when asphaltenes were near their solubility limit in heptane-toluene mixtures (approximately 50% (v/v) toluene). In solvents of greater aromaticity, adsorption kinetics and film masses were reduced at comparable aging times. Poor film forming asphaltenes had yield stress/G' values ((1.01-1.21) x 10(-2)) more than 4-fold lower than those of good film forming asphaltenes. n-heptane asphaltenes fractionated by filtering solutions prepared at low aromaticity (approximately 40% toluene in mixtures of heptane and toluene) possessed higher concentrations of heavy metals and nitrogen and higher aromaticity. The less soluble fractions of good film forming asphaltenes exhibited enhanced adsorption kinetics and higher G' and yield stress values in pure toluene. Replacing the asphaltene solutions with neat heptane-toluene highlighted the ability of films to consolidate and become more elastic over several hours. Adding resins in solution to a partially consolidated film caused a rapid reduction in elasticity followed by gradual but modest consolidation. This study is among the first to directly relate asphaltene chemistry to adsorption kinetics, adsorbed film mechanical properties, and consolidation kinetics.