Experimental and Molecular Dynamics Simulation Study on the Effects of the Carbon Chain Length of Gemini Surfactants on the Inhibition of the Acid-Rock Reaction Rate.

Abstract

A series of gemini surfactants were synthesized to examine their adsorption properties. The properties of gemini surfactants, including critical micelle concentration, electrostatic potential distributions, charge, occupied volume, lowest unoccupied molecular orbital (LUMO), and highest occupied molecular orbital (HOMO), were evaluated using conductivity and density functional theory (DFT) calculations. The calculation results indicated that the electrostatic potential distributions were similar among the four gemini surfactants. Moreover, surfactants with longer carbon chains are more likely to be oblique on the rock surface according to the energy gap between the HOMO of the surfactants and the LUMO of the calcite surface. Experimental tests and molecular dynamics (MD) simulations were conducted to analyze the calcite-surfactant interactions. Combined with the free energy (ΔG) based on the contact angle and adsorption energy (E) based on MD simulation, the adsorption ability increases as the carbon chain length decreases. MD simulation is used to understand the form of surfactant molecules on the calcite at an atomic scale at different times. An obvious aggregation of gemini surfactants was found with an increase in the carbon chain length, which reduces the adsorption density and covered area of the surfactant. The adsorption behavior of the gemini surfactant is beneficial for isolating H+ transfer and retarding the acid reaction with the rock. The retarding ability and etching morphology were studied by acid etching. The acid-rock reaction rate showed that 12-4-12 had the best inhibition performance. Meanwhile, the uneven surface pattern following 12-4-12 etching is beneficial for maintaining the acid fracturing conductivity.