Surface Reactivity Analysis of the Crude Oil-Brine-Limestone Interface for a Comprehensive Understanding of the Low-Salinity Waterflooding Mechanism

Low-salinity waterflooding (LSWF) has proven to improve oil recovery in carbonate formations through rock wettability alteration, although the underlying mechanism remains elusive. Multivalent ionic exchange and calcite dissolution have usually been investigated using geochemical analysis in secondary coreflooding. In this work, coreflooding, in tertiary mode, coupled with a surface reactivity analysis approach was employed to investigate the interplay of wettability alteration mechanisms such as mineral dissolution, electrostatic bond attraction, and the effect of pH at in situ conditions. Improved oil recovery (IOR) in tertiary mode observed by coreflooding in Indiana limestone rocks showed an ionic strength dependence, that is, reducing brine ionic strength resulted in an increase in oil recovery. Coreflooding results showed that the seawater and low-salinity brines deprived of Mg2+ ions resulted in the lowest IOR in tertiary mode, indicating the significance of Mg2+ on IOR in limestone rocks. Similar results were observed through the contact angle measurement showing the limestone rock wettability state dependence on ionic strength and the effect of Mg2+ ions. Surface reactivity analysis showed an increase in solution pH, Ca2+ and Mg2+ ions concentration in the effluent solution from the coreflooding in tertiary mode using low salinity brines (about 40 and 20% increase in the effluent composition for Ca2+ and Mg2+, respectively). These changes in solution composition were used to calculate the in situ oil-brine and rock-brine zeta potential using a validated surface complexation model, showing the changes of zeta potential as brine is injected into limestone rocks. The results show that using seawater-like brine in tertiary mode resulted in no mineral dissolution or ionic exchange. However, improved oil recovery (IOR) using such seawater-like brine was due to wettability alteration caused by reduced electrostatic bond attraction associated with Mg2+ ions [from 2.6 x 10(-13) (mol/m(2))(2) for formation water salinity to 1.5 x 10(-13) (mol/m(2))(2) for seawater salinity]. Using low-salinity brines in tertiary mode improved oil recovery by mineral dissolution, resulting in oil desorption and an increase in solution pH. The increase in solution pH also resulted in reduced electrostatic bond attraction which lead to rock wettability alteration using low-salinity brines.