Carboxybetaine visco-elastic surfactants have been applied in acid diversion, matrix acidizing and fracturing treatments, in which high temperatures and low pH are usually involved. Amido-carboxybetaine surfactants are subject to hydrolysis under such conditions due to the existence of a peptide bond (-CO-NH-) in their molecules, leading to alteration of the rheological properties of the acid. The objective of this paper is to study the impact of hydrolysis at high temperatures on the apparent viscosity of carboxybetaine visco-elastic surfactant-based acids, and determine the mechanism of viscosity alterations by molecular dynamics (MD) simulations.

Surfactant-acid solutions with different compositions (surfactant concentration varied from 4 to 8 wt%) were incubated at 190°F for 1 to 6 hours. Solutions were then partially spent by CaCO3 until the sample pH was 4.5, and the apparent viscosity was measured using a HT/HP viscometer. To determine the mechanism for viscosity alteration on molecular level, MD simulations were carried out on spent surfactant-acid aqueous systems using the Materials Studio 5.0 Package.

It was found that short time hydrolysis at high temperatures (for example, 1 to 2 hours at 190°F) led to a significant increase in surfactant-acid viscosity. However, after long time incubation, phase separation occurred and the acid lost its viscosity. Simulation results showed that the viscosity alteration of amido-carboxybetaine surfactant-acid by hydrolysis at high temperatures may be due to different micellar structures formed by carboxybetaine and fatty acid soap, its hydrolysis product. The optimum molar ratio of amido-carboxybetaine and fatty acid soap was found to be nearly 3:1 from our simulations.

Our results indicate that hydrolysis at high temperatures has great impact on surfactant-acid rheological properties. Short time viscosity build-up and effective gel break-down can be achieved if surfactant-acid treatments are carefully designed; otherwise, unexpected viscosity reduction and phase separation may occur, which will affect the outcome of acid treatments.

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