Effects of Sulfate Ions on Crude Oil Adsorption/Desorption on Carbonate Rocks: Experimental and Molecular Simulations

In the background of the strong oil wettability and low production by water flooding in carbonate reservoirs, low-salinity water containing sulfate ions can significantly change the surface wettability of carbonate rocks and thus increase the sweeping area; however, the absorption and desorption mechanisms of the oil film in the carbonate rock surface remain unclear. This paper analyzed the wettability alternation of carbonate rocks' surface in pure water and sodium sulfate solution. At the same time, MD (Materials Studio) software was used to simulate the formation process of the oil film and the effect of sulfate ions on the desorption of the oil film on the surface of carbonate rocks. The experimental results showed that sodium sulfate solution could accelerate the rate from oil-wet to water-wet and the final contact angle (49°) was smaller than that in pure water. The simulation results showed that dodecane molecules moved to the surface of calcite to form a double layer of the oil film and that the oil film near the calcite surface had a high-density stable structure under the van der Waals and electrostatic action. The hydrating sulfate ions above the oil film broke through the double oil film to form a water channel mainly under the action of electrostatic force and a hydrogen bond and then adsorbed on the calcite surface. A large number of water molecules moved down the water channel based on a strong hydrogen bonding force and crowded out the oil molecules on the surface of the calcite, resulting in the oil film detachment. This work aims to explain the interaction of oil molecules, water molecules, and SO₄^2- ions at the molecular scale and guide the practical application of low-salinity water flooding in carbonate reservoirs.