Chemical enhanced oil recovery (cEOR) relies on the interactions between surface-active components (SACs) of the oil-in-place and injected chemicals to induce favorable physico-chemical changes. This study investigates the effect of oil chemistry on the performance of chemically-tuned waterflooding (CTWF) in carbonate rocks. Coreflood experiments were performed at 90°C using four model oils, each containing a single SAC (acetic acid, decanoic acid, stearic acid or quinoline) to evaluate the effect of oil composition on oil recovery. Complementary characterization techniques including thermal gravimetric analysis (TGA), attenuated total reflectance (ATR-FTIR) and zeta potential (ζ) were used to understand the underlying rock-oil-brine interactions that take place during CTWF, including SAC adsorption to the rock surface, strength of adsorption, partitioning into the brine phase, and electrostatic interactions, respectively. Sessile drop contact angle measurements were also performed to quantify the wetting behavior of the different SACs. Results of this study show that oil chemistry plays a significant role in triggering different oil-brine-rock interactions. Characterization of those interactions is crucial to explain the discrepancies in oil recovery observed in the CTWF literature. In this study, differences in the underlying oil-brine-rock interactions translated into significant variation in oil recovery ranging between 8.9 and 43.9 % after one pore volume injected (PVI). ATR-FTIR results showed that in-situ soap generation was detected for oils with longer chain carboxylic acids, whereas no soaps were observed for oils that have acetic acid or quinoline. Combined with sessile-drop contact angle measurements, a relationship is observed between SAC partitioning into the brine phase and water-wetting behavior. Additionally, TGA measurements suggested that long chain carboxylic acids chemisorb to the rock surface, making wettability alteration to a less oil-wetting state during CTWF more challenging, whereas intermediate chain carboxylic acids only physisorb leading to a more pronounced wettability alteration to a less oil-wetting state, ultimately yielding the highest recovery of ∼49.9 %. Finally, TAN was found to be an insufficient oil descriptor, where oils with the same TAN yielded different CTWF effects. Hence, a more robust oil analysis is crucial for more accurate prediction and modeling of CTWF behavior.
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