Characterization of shale using Helium and Argon at high pressures

In order to estimate the shale gas in place and the eventual recovery during shale gas operations, one of the key requirements is to accurately characterize the shale's petrophysical and transport properties such as porosity, permeability, diffusivity, and storage capacity. Despite the many efforts reported in the technical literature aiming to provide an improved understanding of the complex pore structures and the associated fluid flow in gas shales, a complete characterization of organic-rich shale samples still poses a big challenge. In this work, we have characterized mass transfer and sorption in shale at different length scales using Helium (He) and Argon (Ar) as probe gases. Thermogravimetric analysis (TGA) with a shale cube of similar to 1 cm(3) in size and gas expansion experiments with a full-diameter core (3.5 '' in diameter) were used to measure sorption kinetics/isotherms and mass transfer, respectively. Both samples are from the same depth/location in the Marcellus shale formation. The TGA steady-state technique was initially used to generate excess sorption isotherms for Ar, while dynamic TGA experiments were used to study its sorption kinetics. The TGA experiments demonstrate that Ar, which has a similar sorption potential as Methane, but is generally assumed to be inert, adsorbs onto the surfaces of the mesoporous and microporous regions of the shale samples according to a Langmuir-type behavior. Helium expansion experiments, on the full-diameter core, were used to measure the overall porosity, on the basis that He is a non-sorbing and inert gas as compared to Ar. The He expansion experiments, furthermore, allow us to delineate the mass transfer of gas across the inherent hierarchy of pore sizes, including macropores (macro- and micro-cracks), mesopores and micropores. Similar expansion experiments were also performed with Ar to study the combined impact of mass transfer and sorption. A triple-porosity model (TPM) was utilized to interpret the He expansion experiments with the shale core and to extract (estimate) relevant transport parameters. We report and compare here the diffusivities and permeabilities of the whole core for both He and Ar, as calculated from the modeling and fitting of the experimental data. On the premise that the shale cube is representative of the matrix region of the core, the Ar sorption kinetics from the cube experiments were subsequently combined with the transport parameters extracted from the He experiments to predict the behavior of the Ar expansion test with the full-diameter core. An excellent agreement is observed between the model predictions and the experimental data. The experimental observations and their interpretation indicate that one must be cautious when using Ar to estimate the true porosity and permeability of shales. In addition, we demonstrate that He and Ar probe gases, when used in tandem, can be employed effectively as a tool to characterize shales in terms of mass transfer and sorption dynamics across scales.