Energy & Fuels, Vol.34, No.11, 13673-13685, 2020
Modeling the Multicomponent Compositional Effects of Asphaltenes on Interfacial Phenomena
The polydisperse nature of asphaltenes is not usually considered in studies of asphaltenes adsorption effects at interfaces, e.g., water-oil interfaces. We recently proposed a methodology that takes into account the mixture nature of asphaltenes and showed that a binary mixture model for diffusion-limited adsorption at water-oil interfaces could describe qualitatively all of the features of asphaltenes' interfacial dilatational rheology [Liu, F.; et al. Langmuir 2017, 33, 1927-1042, DOI: 10.1021/acs.langmuir.6b03958]. On the quantitative side, however, use of only two pseudocomponents did not adequately predict some other aspects of their behavior, such as dynamic interfacial tension over the full range of time scales. To address these limitations, a methodology for calculating interfacial rheological properties for an n-component mixture was first developed [Liu, F.; et al. Colloids Surf. A 2017, 532, 140-143, DOI: 10.1016/j.colsurfa.2017.05.080]. To capture, first, the interfacial tension behavior and then the rheological properties within the same methodological structure, we discuss here an approach using a multicomponent model that inversely solves the Ward-Tordai equations and extracts the properties of individual pseudocomponents (concentration and adsorption coefficient) from dynamic interfacial tension measurements. Using ternary mixture models proves sufficient to capture the data obtained for asphaltenes over large adsorption time scales (up to 24 h) and large frequency range. Quaternary mixture models do not significantly improve the predictions. Another feature revealed by this methodology is the aggregation behavior of the different pseudocomponents. For dilute solutions, the calculated sum of the pseudocomponents' concentrations falls in the range of the actual asphaltenes concentration. As the actual asphaltenes concentration is increased, the calculated concentration of the most surface-active pseudocomponents levels offs, indicating that the most surface-active asphaltenes are also the most prone to aggregate due perhaps to pi-pi interactions. This result would be expected as asphaltenes adsorption at the water-oil interface appear to be driven by the interactions of the it electrons of their aromatic cores as previously demonstrated [Rane, J. P.; et al. Energy Fuels 2015, 29, 3584-3590, DOI: 10.1021/acs.energyfuels.51.100179]. Finally, the result obtained by this model indicates that the presence of a very small fraction of extremely surface-active asphaltenes components could explain both the "everlasting" interfacial tension decay observed and the apparent irreversibility of adsorption during washout experiments.