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Abstract To optimize CO2 EOR operations, such as Huff and Puff (HnP), it is necessary to have a good understanding of oil- CO2 transport both at nanopore and at reservoir scales. In this study, experiments were performed to investigate how pore adsorbed CO2 can mediate oil flow in analog nanopore arrays. These experiments quantified how much interfacial CO2 contributed to improving permeability to oil in nanopores, in addition to increasing mobility by viscosity reduction. The experimental procedure involved flowing C10 (decane) with and without CO2 through an Anodic Aluminum Oxide (AAO) membrane at a defined differential pressure and recording flow rate. Viscosity obtained from correlations was then used to calculate membrane pore permeability. Inlet pump pressure was lower than the oil-CO2 miscibility pressure at the test conditions. Pore permeability improvement due to pore wall adsorbed CO2 was computed by isolating the effect of viscosity reduction of the bulk fluid. An overall pore-permeability increase of 15% was observed in the CO2 and C10 mixture experiments compared to the C10-only experiments, due to interfacial CO2. These results lend support to the previous molecular dynamics simulations, which predicted that interfacial CO2 can significantly modulate C10 flow in nanopores up to 10 nm diameter (Moh et al. 2020). Some differences from the molecular dynamics simulations of Moh et al. (2020) observed in the experimental study also verify the potential contribution of other phenomena to the permeability enhancement of the nanoporous membrane in the presence of CO2. Therefore, this study provides further impetus for exploring the unique nanofluidic physics of oil and CO2 transport arising from CO2 at oil-wall interfaces. The demonstrated significance of the unique nanopore phenomena, which have not been observed and incorporated into large-scale flow models, emphasizes the importance of identifying and incorporating nanofluidic physics into commercial reservoir simulators' transport models for better representation of CO2 and oil flow in unconventional reservoirs.
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Experimental and Molecular Insights on Sieving of Hydrocarbon Mixtures in Niobrara Shale
In nanoporous rocks, potential size/mobility exclusion and fluid-rock interactions in nano-sized pores and pore throats may 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 Niobrara samples possess such sieving properties on hydrocarbon molecules. Molecular dynamics simulation of hydrocarbon adsorption was 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. To understand the potential effects of hydrocarbon-rock interactions on their transport, molecular dynamics simulations were performed to clarify the adsorption of C10 and C17 molecules on calcite surfaces using all-atom models. Experimental results show that the heavier component (C17) in the injected fluid was noticeably hindered. After the start of the experiment, the fraction of the lighter component (C10) in the produced fluid gradually increased and eventually reached levels that fluctuated within a range above the fraction of C10 in the original fluid; besides, the fraction of C17 increased in the fluid upstream of the sample. Both observations indicate the presence of membrane properties of the sample to this hydrocarbon mixture. 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, providing a mechanism that directly supports the experimental observations. Some experimental observations suggest that size/mobility exclusion should also exist. This experimental study is the first evidence that nanoporous reservoir rocks may possess membrane properties that can filter hydrocarbon molecules. Component separation due to membrane properties has not been considered in any reservoir simulation models. The consequence of this effect and its dependence on the mixture and environmental conditions (surface, pressure, temperature) are worthy of further investigations.
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- Award ID(s):
- 1705287
- PAR ID:
- 10106361
- Date Published:
- Journal Name:
- SPE/AAPG/SEG Unconventional Resources Technology
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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