Mechanistic study of wettability alteration using surfactants with applications in naturally fractured reservoirs.

In naturally fractured reservoirs, oil recovery from waterflooding relies on the spontaneous imbibition of water to expel oil from the matrix into the fracture system. The spontaneous imbibition process is most efficient in strongly water-wet rock where the capillary driving force is strong. In oil- or mixed-wet fractured carbonate reservoirs, however, the capillary driving force for the spontaneous imbibition process is weak, and therefore the waterflooding oil recoveries are low. The recovery efficiency can be improved by dissolving low concentrations of surfactants in the injected water to alter the wettability of the reservoir rock to a more water-wet state. This wettability alteration accelerates the spontaneous imbibition of water into matrix blocks, thereby increasing the oil recovery during waterflooding. Several mechanisms have been proposed to explain the wettability alteration by surfactants, but none have been verified experimentally. Understanding of the mechanisms behind wettability alteration could help to improve the performance of the process and aid in identification of alternative surfactants for use in field applications. Results from this study revealed that ion-pair formation and adsorption of surfactant molecules through interactions with the adsorbed crude oil components on the rock surface are the two main mechanisms responsible for the wettability alteration. Previous researchers observed that, for a given rock type, the effectiveness of wettability alteration is highly dependent upon the ionic nature of the surfactant involved. Our experimental results demonstrated that ion-pair formation between the charged head groups of surfactant molecules and the adsorbed crude oil components on rock surface was more effective in changing the rock wettability toward a more water-wet state than the adsorption of surfactant molecules as a monolayer on the rock surface through hydrophobic interaction with the adsorbed crude oil components. By comparing two anionic surfactants with different charge densities, we propose that wettability alteration processes might be improved through the use of dimeric surfactants, which have two charged head groups and two hydrophobic tails. Gemini surfactants where the molecules are joined at the head end are likely to be effective when ion-pair formation is the wettability alteration mechanism, and bolaform surfactants, in which molecules are joined by the hydrophobic tails, should be more effective in the case of surfactant monolayer adsorption.