Determination of the absolute adsorption/desorption isotherms of CH4 and n-C4H10 on shale from a nano-scale perspective

The adsorption/desorption test results show that both CH4 and n-C4H10 exhibit more adsorption as temperature decreases or pressure increases. Their adsorption/desorption isotherms exhibit hysteresis phenomenon and this phenomenon weakens as temperature increases. Comparatively, the hysteresis behavior observed for n-C4H10 is more obvious than that for CH4. Compared with CH4, n-C4H10 has higher adsorption capacity under the same condition, indicating its higher affinity towards the shale with organic matters. As for the conventional approaches, the density calculated from the van der Waals constant b or the liquid hydrocarbon density can be used to reasonably well evaluate the absolute adsorption isotherms of n-C4H10 on shale, but tends to underestimate the absolute adsorption of CH4 on shale. GCMC simulations show that the density of the adsorption phase is strongly correlated with system pressure, temperature, and pore size. Compared to the conventional approaches, GCMC simulations can better capture the in-situ density of adsorption phase; on the basis of the in-situ density of adsorption phase, we can then achieve more accurate determination of the absolute adsorption isotherms of a given hydrocarbon on shale. This study raises the imperativeness of leveraging more sophisticated simulation tools (such as GCMC) for more accurate determination of absolute adsorption isotherms.