Continuum-Scale Gas Transport Modeling in Organic Nanoporous Media Based on Pore-Scale Density Distributions

This paper presents a continuum-scale diffusion-based model informed by pore-scale data for gas transport in organic nanoporous media. A mass transfer and adsorption model is developed by considering multiple transport and storage mechanisms, including bulk diffusion and Knudsen diffusion for free phase, surface diffusion for sorbed phase, and multilayer adsorption. The continuum-scale diffusion-based governing equation is developed solely based on free phase concentration for the overall mass conservation of free and sorbed phases, carrying a newly-defined effective diffusion coefficient and a capacity factor to account for multilayer adsorption. Diffusion of free and sorbed phases is coupled through the pore-scale simplified local density method based on the modified Peng-Robinson equation of state for confinement effects. The model is first utilized to analyze pore-scale adsorption data from the krypton (Kr) gas adsorption experiment on graphite. Then we implement the model to conduct sensitivity analysis for the effects of pore size on gas transport for Kr-graphite and methane-coal systems. The model is finally used to study Kr diffusion profiles through a coal matrix obtained through X-ray micro-CT imaging. The results show that the sorbed phase occupies most of the pore space in organic nanoporous media due to multilayer adsorption, and surface diffusion contributes significantly to the total mass flux. Therefore, neglecting the volume of sorbed phase and surface diffusion in organic nanoporous rocks may result in considerable errors. Furthermore, the results reveal that implementing a Langmuir-based model may be erroneous for an organic-rich reservoir with nanopores during the early depletion period when the reservoir pressure is high.

Liquid intrusion in and extrusion from non-wettable nanopores for technological applications

In this article, we review some recent theoretical results about intrusion and extrusion of non-wetting liquids in and out of cavities of nanotextured surfaces and nanoporous materials. Nanoscale confinement allows these processes to happen at conditions which significantly differ from bulk phase coexistence. In particular, the pressure at which a liquid penetrates in and exits from cavities is of interest for many technological applications such as energy storage, dissipation, and conversion, materials with negative compressibility, ion channels, liquid chromatography, and more. Notwithstanding its technological interest, intrusion/extrusion processes are difficult to understand and control solely via experiments: the missing step is often a simple theory capable of providing a microscopic interpretation of the results, e.g., of liquid porosimetry or other techniques used in the field, especially in the case of complex nanoporous media. In this context, simulations can help shedding light on the relation between the morphology of pores, the chemical composition of the solids and liquids, and the thermodynamics and kinetics of intrusion and extrusion. Indeed, the intrusion/extrusion kinetics is determined by the presence of free energy barriers and special approaches, the so-called rare event techniques, must be used to study these processes. Usually, rare event techniques are employed to investigate processes occurring in relatively simple molecular systems, while intrusion/extrusion concerns the collective dynamics of hundreds to thousands of degrees of freedom, the molecules of a liquid entering in or exiting from a cavity, which, from the methodological point of view, is itself a challenge.