Configurational diffusion transport of water and oil in dual continuum shales

Understanding fluid flow in shale rocks is critical for the recovery of unconventional energy resources. Despite the extensive research conducted on water and oil flow in shales, significant uncertainties and discrepancies remain in reported experimental data. The most noted being that while oil spreads more than water on shale surfaces in an inviscid medium, its uptake by shale pores is much less than water during capillary flow. This leads to misjudgement of wettability and the underlying physical phenomena. In this study, therefore, we performed a combined experimental and digital rock investigation on an organic-rich shale including contact angle and spontaneous imbibition, X-ray and neutron computed tomography, and small angle X-ray scattering tests to study the potential physical processes. We also used non-equilibrium thermodynamics to theoretically derive constitutive equations to support our experimental observations. The results of this study indicate that the pre-existing fractures (first continuum) imbibe more oil than water consistent with contact angle measurements. The overall imbibition is, however, higher for water than oil due to greater water diffusion into the shale matrix (second continuum). It is shown that more water uptake into shale is controlled by pore size and accessibility in addition to capillary or osmotic forces i.e. configurational diffusion of water versus oil molecules. While the inorganic pores seem more oil-wet in an inviscid medium, they easily allow passage of water molecules compared to oil due to the incredibly small size of water molecules that can pass through such micro-pores. Contrarily, these strongly oil-wet pores possessing strong capillarity are restricted to imbibe oil simply due to its large molecular size and physical inaccessibility to the micro-pores. These results provide new insights into the previously unexplained discrepancy regarding water and oil uptake capacity of shales.