Adsorption and Phase Behavior of Pure/Mixed Alkanes in Nanoslit Graphite Pores: An iSAFT Application.

The prediction of fluid phase behavior in nanoscale pores is critical for shale gas/oil development. In this work, we use a molecular density functional theory (DFT) to study the effect of molecular size and shape on partitioning to graphite nanopores as a model of shale. Here, interfacial statistical associating fluid theory (iSAFT) is applied to model alkane (C1 - C8) adsorption/desorption/phase behavior in graphite slit pores for both pure fluids and mixtures. The pure component parameters were fit to the bulk saturated liquid density and vapor pressure data in selected temperature ranges. The potential of interaction between the fluid and graphite is modeled with a Steele 10-4-3 potential that is fit to the potential of mean force from single-molecule simulations. Good agreement is found between theory and molecular simulation for the density distributions of pure components in slit pores. The critical properties of methane, ethane, and their mixtures as well as the shift in bubble point and dew point densities were studied, showing good agreement with simulation. The competitive adsorption of mixtures of normal and branched alkanes in graphite pores was also studied. Heavier components more strongly adsorb up to the point that the entropic penalty due to confinement reduces adsorption.