Methane Diffusion in a Flexible Kerogen Matrix

• Published in: The journal of physical chemistry. B Vol. 123; no. 26; pp. 5635 - 5640
• Main Authors: Obliger, Amaël, Valdenaire, Pierre-Louis, Ulm, Franz-Josef, Pellenq, Roland J.-M, Leyssale, Jean-Marc
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 05.07.2019
• Subjects: Chemical Sciences; or physical chemistry; Theoretical and
• ISSN: 1520-6106; 1520-5207
• DOI: 10.1021/acs.jpcb.9b03266

It has been recognized that the microporosity of shale organic matter, especially that of kerogen, strongly affects the hydrocarbon recovery process from unconventional reservoirs. So far, the numerical studies on hydrocarbon transport through the microporous phase of kerogen have neglected the effect of poromechanics, that is, the adsorption-induced deformations, by considering kerogen as a frozen, nondeformable, matrix. Here, we use molecular dynamics simulations to investigate methane diffusion in an immature (i.e., with high H/C ratio) kerogen matrix, while explicitly accounting for adsorption-induced swelling and internal matricial motions, covering both phonons and nonperiodic internal deformations. However, in the usual frozen matrix approximation, diffusivity decreases with increasing fluid loading, as evidenced by a loss of free volume, accounting for adsorption-induced swelling that gives rise to an increase in free volume and, hence, in diffusivity. The obtained trend is further rationalized using a Fujita–Kishimoto free volume theory initially developed in the context of diffusion in swelling polymers. We also quantify the enhancing effect of the matrix internal motions (i.e., at fixed volume) and show that it roughly gives an order of magnitude increase in diffusivity with respect to a frozen matrix, thanks to fluctuations in the pore connectivity. We eventually discuss the possible implications of this work to explain the productivity slowdown of hydrocarbon recovery from shale immature reservoirs.