▎ 摘　　要

This x-ray microtomography study investigates the dynamic pore-scale displacement of a dense non-aqueous phase liquid (DNAPL) such as heavy crude oil in a heterogeneous aquifer rock using carbonaceous nanoparticles. The nanoparticles were synthesized from Wyoming coal and consisted of a mixture of graphene quantum dots (GQD) and engineered graphene quantum dots (E-GQD) in equal proportions. Synergistic interactions between GQD and E-GQD at the oil/water interface reduced the DNAPL/brine interfacial tension (IFT) from 13.4 mN/m to 5.4 mN/m. In addition, the nanofluid mixture altered the wettability of the minerals found in the rock (quartz, carbonate, and feldspar) from oil-wet to water-wet with average contact angles of 66 degrees, 51 degrees, and 60 degrees, respectively. The wettability alteration was more pronounced in carbonates due to the tendency of GQD to adsorb on these surfaces. Analyses of the saturation profiles and pore-scale fluid occupancy maps revealed that the wettability alteration was not instantaneous and required a short soaking time for the fluid-rock interactions to take place. IFT reduction alone was not enough to displace the DNAPL at the early stages of nanofluid flooding because of the high density and viscosity of the oil. As a result, the nanofluid did not outperform brine after 1 pore volume (PV) of injection. On the other hand, the nanofluid was able to invade small pores that were not accessible to brine after 3 PV of injection due to both IFT and contact angle reduction, which lowered the threshold capillary pressure of these pores. Subsequently, more medium and large pores were invaded by the nanofluid as the injection continued, leading to an 11% increase in DNAPL recovery after 20 PV of nanofluid injection, as compared to waterflooding. This incremental recovery is significant considering that the experiments were performed with a heavy oil at ambient temperature, which is more representative of aquifer conditions. Thus, the GQD-based nanofluid has the potential to achieve much larger recoveries in deeper heavy oil reservoirs provided enough soaking time is allowed. The insights provided by this study could be used to validate pore-scale network models or guide in the design and selection of more effective nanomaterials for aquifer remediation or enhanced oil recovery applications.