Langmuir, Vol.37, No.5, 1725-1742, 2021
Time Evolution and Effect of Dispersant on the Morphology and Viscosity of Water-In-Crude-Oil Emulsions
This study examines the time evolution and effects of adding dispersant (Corexit 9500A) at varying concentrations on the microscopic morphology and bulk viscosity of saltwater-in-crude-oil (Louisiana) mechanically mixed emulsions. Rheology is used for measuring the viscoelastic properties and viscosity, the latter at varying shear rates. Microscopy, followed by machine-learning-based analysis, is used for characterizing the size and spatial distribution of the water droplets in the emulsions. Initially, the water droplets appear as a multiscale lattice with a Sauter diameter of 5.3 mu m and a polydispersity of 0.43, with small droplets aggregating around large ones. The corresponding bulk viscosity decreases with increasing shear rate from 2 orders of magnitude to 5 times higher than that of the weathered crude oil. After 7 days, the number of submicron droplets increases, the nearest-neighbor distance decreases, indicating preferential aggregation, and the viscosity increases by 56-112% at high shear rates (5-100 s(-1)). After 14 and 21 days, some droplets coalesce resulting in loss of clusters and a decrease in viscosity. These trends suggest that changes in the aggregation contribute to the variations in viscosity. Subsequent analysis applies previously developed models for the effect of aggregation on the properties of the emulsion. While the reduction in viscosity is predicted by this model, matching of rates requires modification to the assumed relationship between yield stress and interdroplet forces. Adding dispersant without mixing generates Marangoni-driven flows as the water droplets coalesce. In time, part of the water separates, a fraction forms clouds of submicron droplets, and the rest remains unchanged. Mixing dispersant at low concentration with the emulsion accelerates the coalescence and phase separation. The removed water fraction increases with dispersant concentration, reaching 99.6% for a dispersant-to-emulsion concentration of 10(-3). The remaining emulsion consists of fine droplets with Newtonian viscosity that is still 4 times higher than that of the fresh crude oil but only 14% higher than that of the weathered oil.