Rock-Fluid Interactions of Alkyl Ether Carboxylate Surfactants with Carbonates: Wettability Alteration, ζ-Potential, and Adsorption

This work evaluated the rock-fluid interactions of two linear alkyl ether carboxylate (AEC) surfactants C₁₁E₁₁A and C₁₂E₇A in carbonates: wetting ability, ζ-potential, and adsorption capacity. Contact angle measurements showed that the ability of AECs to hydrophilize the surface is strongly affected by the ethylene oxide (EO) chain length and the presence of electrolytes. An AEC with a shorter EO chain C₁₂E₇A demonstrated a better wetting ability and decreased the contact angle value on the limestone surface from 113 to 27 ± 11° in deionized (DI) water and until 17 ± 5° in 5 wt % NaCl. The mechanism of surfactant action was assessed through thermodesorbed hydrocarbon analysis and organic matter characterization with the help of the Rock-Eval (RE) pyrolysis technique for the first time. The analysis results revealed that all surfactant compositions partially removed free oil and heavy oil components from limestone samples. Also, the presence of C₁₂E₇A molecules was detected in the samples after surfactant treatment that indicates that a better wetting ability is achieved by the combination of washing hydrocarbons and adsorption of surfactants on clean sites. The combination of ζ-potential measurements and static adsorption test on crushed limestone demonstrated that the adsorption of AECs in deionized water is not governed by electrostatic interactions and mainly occurs due to hydrogen bonding. Salinity has a significant effect on the adsorption behavior of AECs and leads to the partial destruction of hydrogen bonds and the shift from monomolecular adsorption in DI water to polymolecular adsorption in brines. The adsorption of C₁₁E₁₁A achieved ∼9 mg/g-rock and was higher than that of C₁₂E₇A, showing a maximum value of ∼4 mg/g-rock. This work provides a set of experiments that characterize the behavior of AECs during interactions with carbonate rock and describes a novel approach of the wettability shift mechanism assessment through RE pyrolysis.