In nanoporous rocks, potential size/mobility exclusion and fluid-rock interactions in nano-sized pores and pore throats can turn the rock into a semi-permeable membrane, blocking or hindering the passage of certain molecules while allowing other molecules to pass freely. In this work, we conducted several experiments to investigate whether CO2 can mitigate the sieving effect on the hydrocarbon molecules flowing through Niobrara samples. Molecular dynamics simulations of adsorption equilibrium with and without CO2 were performed to help understand the trends observed in the experiments. The procedure of the experiments includes pumping of liquid binary hydrocarbon mixtures (C10 C17) of known compositions into Niobrara samples, collecting of the effluents from the samples, and analysis of the compositions of the effluents. A specialized experimental setup that uses an in-line filter as a mini-core holder was built for this investigation. Niobrara samples were cored and machined into 0.5-inch diameter and 0.7-inch length mini-cores. Hydrocarbon mixtures were injected into the mini-cores and effluents were collected periodically and analyzed using gas chromatography (GC). After observing the membrane behavior of the mini-cores, CO2 huff-n-puff was performed at 600 psi, a pressure much lower than the miscibility pressure. CO2 was injected from the production side to soak the sample for a period, then the flow of the mixture was resumed and effluents were analyzed using GC. Experimental results show that CO2 huff-n-puff in several experiments noticeably mitigated the sieving of heavier component (C17). The observed increase in the fraction of C17 in the produced fluid can be either temporary or lasting. In most experiments, temporary increases in flow rates were also observed. Molecular dynamics simulation results suggest that, for a calcite surface in equilibrium with a binary mixture of C10 and C17, more C17 molecules adsorb on the carbonate surface than the C10 molecules. Once CO2 molecules are added to the system, CO2 displaces C10 and C17 from calcite. The experimentally observed increase in the fraction of C17 thus can be attributed to the release of adsorbed C17. This study suggests that surface effects play a significant role in affecting flows and compositions of fluids in tight formations. In unconventional oil reservoirs, observed enhanced recovery from CO2 huff-n-puff could be partly attributed to surface effects in addition to the recognized gas-liquid interaction mechanisms.

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