Wettability reversal on oil-wet calcite surfaces: Experimental and computational investigations of the effect of the hydrophobic chain length of cationic surfactants

[Display omitted] Oil recovery from carbonate reservoirs is often low, in a large part due to the oil-wet state of the constituent rocks. Cationic surfactants are among the most effective compounds capable of reversing the carbonate wettability to more water-wet, which significantly enhances oil recovery. Screening for the most effective cationic surfactants can be facilitated by studying the effects of specific molecular properties, such as the hydrophobic chain length, on the wettability reversal efficiency using molecular dynamics (MD) simulations. Wettability reversal by quaternary ammonium cationic surfactants with varying hydrophobic chain length was studied by the combination of MD simulation and experimental contact angle measurements on oil-wet calcite chips. Both experiments and simulations also featured model oils consisting of different size hydrocarbons in order to explore the potential size-specific interactions between the surfactants and oil molecules. We found strong correlation between the wettability reversal and the surfactant length, with the longer surfactants universally rendering calcite surfaces more water-wet. By contrast, the wettability reversal is independent of the model oil used, implying that the effect is not due to specific hydrocarbon size. Instead, the superior wettability reversal performance of the more hydrophobic surfactants is due to their greater affinity to the oil/brine interfaces.