Abstract
This contribution focuses on surface complexes in the calcite-brine-surfactant system. This is relevant for the recovery of oil when using a new hybrid enhanced oil recovery (EOR) method, which combines smart-water (i.e., ionically modified brine) and foam-flooding (SWAF) of light oil with dissolved carbon dioxide (CO2) at high pressure in carbonate (i.e., calcite) reservoirs. Using this new hybrid EOR-method (i.e., the SWAF-process) is not only economically attractive (i.e., it reduces opex costs) but also enhances the effectiveness of the production process, and thus reduces the environmental impact. Ionically modified brine (i.e., low-salinity) has a dual improvement effect. It not only leads to more stable foam lamellae, but also helps to change the carbonate rock wettability, leading for some conditions to more favorable relative permeability behavior. The mechanism for the modified permeability behavior in the presence of ionically modified brine is only partly understood. Therefore, we study this process initially in a zero dimensional (thermodynamics) setting, which can be used for the one dimensional (1D) displacement process with an oleic phase that contains carbon dioxide (CO2) and an aqueous phase that contains both carbon dioxide (CO2) and all the ionic substances. Using DLVO theory and surface complexation modeling to better understand the mechanism(s) of ionically modified brine as wettability modifier and foam stabilizer. We perform simulations using both (NaCl) and (MgCl2) to show the effect of a divalent ion at the high-salinity (8500 mmol/kg-w) and low-salinity (0.4 mmol/kg-w) for both ambient-conditions at (25 degrees C) and at the reservoir-conditions (80 degrees C). We confine our analysis to a description that uses the Dzombak-Morel model of surface complexes, which is based on the Debye-Huckel theory (i.e., valid up to ionic strength of 0.3 (mol/kilogram of water)). We also investigate the effect of carbon dioxide (CO2) on the stability of low-salinity foamlaminae. We model the foam-laminae, which contain as surface complex a (cationic) surfactant in an aqueous phase. We use the PHREEQC-software to calculate the surface charge and the surface potential. The presence of a carbon dioxide (CO2) phase leads to dissolution of four valent C(IV) compounds in the aqueous film. PHREEQC also calculates the equilibrium concentrations and surface potential and allows the study of the effect of salinity and the carbon dioxide (CO2) gas pressure. For the soap-film (foam-film) in a carbon dioxide (CO2) atmosphere we do use Pitzer activity coefficients (i.e., valid up to 6 (mol/kilogram of water)). As our aim is to show the methodology and the versatility of this approach, we leave more realistic choices of these parameters for future work.sFor the conditions considered we can qualitatively state that, in the presence of (NaCl i.e., at pH > 10) and (MgCl2 i.e., pH > 10.3), the low-salinity case shows a more stable water-film behavior at (25 degrees C) and at (80 degrees C) than the high-salinity case for both (25 degrees C) and (80 degrees C). Moreover, high carbon dioxide (CO2) pressures have a destabilizing effect on the film, as they reduce the surface potential. A reduced surface potential leads to a decreasing electrostatic double layer repulsion and thus destabilizes the foam-film, whereas low-salinity leads to less screening of the surface potential and thus improves the stability of the foam-film.
The low-salinity flow is characterized by a high residual oil saturation and low end-point permeability for the two phase oil-water flow. This leads to a more favorable mobility ratio and thus a more favorable displacement process. For the calcite surface an enhanced stability helps to stabilize the water film on the calcite surface if the oil-water surface charge has the same sign as the surface charge on the calcite surface. Our calculations show the pH range where the sign of these charges is the same or opposite at low-salinity and high-salinity conditions. Admittedly these calculations only show trends, but can be used to delineate optimal conditions for the application of "Smart Water Assisted Foam (SWAF) Flooding". It is expected that the SWAF-process under the optimum conditions will make the proposed new hybrid Enhanced Oil Recovery (EOR) process environmentally and economically attractive.