Water chemistry has been shown to affect oil recovery by affecting surface charge and rock dissolution. The single-well chemical-tracer (SWCT) test is a field method to measure residual oil saturation (Sor), in which hydrolysis reaction of an ester has been known as a key process that could displace the equilibrium state of a reservoir by changing formation-water (FW) composition.

Because oil mobilization during the SWCT tests causes an error in the measurement of Sor, changes in water chemistry might be a concern for the accuracy of Sor measurements. In our previous work, the extent to which different reservoir parameters might change water composition and the effect of water-chemistry changes on the calcite dissolution and the oil liberation from the carbonate-rock surfaces were extensively evaluated. In this study, the effect of water-chemistry changes on surface-charge alteration at the carbonate/brine interface has been studied by constructing and applying a surface-complexation model (SCM) that couples bulk aqueous and surface chemistry. We present how the pH drop induced by the displacement of the equilibrium state and changes in water chemistry in the formation affect surface charge in a pure-calcite carbonate rock during the SWCT tests.

The results show that a pH drop during the SWCT tests while calcium concentration is held constant in the FW by ignoring calcite dissolution yields a less-positive/more-negative surface charge so that wettability of carbonate rock might be altered to a less-oil-wetting state, when the oil is negatively charged. In reality, however, calcite dissolves by water-chemistry changes during the SWCT tests, which leads to an increasing calcium concentration in the FW. Consequently, an SWCT test in carbonates is accompanied by increasing calcium concentration while pH drops, which yields an increase in the surface charge of carbonate rocks. Therefore, the pH drop does not directly affect the surface charge of carbonate rock during an SWCT test, and calcium concentration increased from calcite dissolution could control the surface charge more significantly.

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