Abstract
Adsorption is an important phenomenon in surface chemistry, especially for nano-porous shales. In the shale gas-in-place, adsorbed gas could contribute up to 85%. However, adsorption is hard to quantitatively characterize due to different adsorption mechanisms, patterns, surfaces, and pore sizes. Moreover, key thermodynamic parameters, such as the enthalpy of adsorption, are challenging to determine due to uncertainties in adsorbed gas densities used in constructing absolute isotherms. In this paper, we revisit the Brunauer, Emmett, and Teller (BET) model, analytically simplify Ono-Kondo (OK) models for subsurface shales, and compare commonly used mono- and multilayer adsorption models (e.g., Langmuir, supercritical Dubinin-Radushkevich (SDR), supercritical BET (SBET), and simplified OK (OKs) models) with recently proposed pressure-dependent adsorption densities to develop a practical and reliable methodology that can be used in the supercritical state, typical for subsurface black shale conditions.
Three independent data sets were used for nitrogen and methane adsorption isotherms at different temperatures. We demonstrate that adsorption predicted by the SDR model is comparable or lower than that predicted by the SBET model, but higher than the amounts predicted by Langmuir and OK models. The nitrogen BET method tends to underestimate the accessible SSA for methane. Measurement of isosteric heat of adsorption is suggested instead of the experimental fitting method, due to the significant difference between the calculated results by two commonly used methods. Experimental fitting and simulation methods are also briefly reviewed to guide future research on shale gas adsorption.
