Lawrence Berkeley National Laboratory

The behavior of fluids in confined spaces is important in several research fields, including the oil and gas industry, because of the importance of confined hydrocarbons in unconventional shale reservoirs. A large percentage of the hydrocarbons are contained in nanoscale shale pores, and as a result, interactions between fluid molecules and the pore walls become significant to the fluid behavior and cause deviations of the fluid properties from bulk properties. In this work, classical molecular dynamics (MD) simulations and grand canonical Monte Carlo (GCMC) simulations are performed to model kerogen pores in shale reservoirs and their effect on adsorption selectivity and phase equilibria of hydrocarbon mixtures in a wide range of temperatures and pressures. A slit pore made of graphite walls is used to represent the basic unit where a fluid may be stored in shale reservoirs. The separation between graphite layers is varied to observe the effect of confinement on the adsorption selectivity and phase equilibrium of methane-ethane mixtures. Results from GCMC and MD simulations show that ethane is preferred over methane in the confined system. Moreover, most fluid molecules in the confined system tend to be adsorbed on the pore walls instead of remaining in the gas phase. Preferential interactions between the fluid molecules and the pore walls induce changes in the phase diagram in the confined system. Results from GCMC simulations show shifts with respect to the bulk pressure-composition phase diagram that becomes more pronounced as the pore size decreases. (Figure Presented).