Hydrocarbon recovery from shale reservoirs provides an increasing share of world energy. These resources are multicomponent fluid mixtures within multiscale geometries, and understanding their associated phase-change thermodynamics presents an array of challenges for experimentalists, theorists, operators, and policy makers. Here, we quantify hydrocarbon mixture phase behavior via direct imaging of connected channels spanning 4 orders of magnitude (10 nm to 10 μm) with supporting density functional theory. The methane/propane mixture dew point shifts, with early condensation of heavy components in nanopores because of a combination of capillarity and competitive surface adsorption. The bubble point in nanoconfinement is found to be deeply suppressed (∼3-fold), to below the bulk dew point of the original mixture, because of the exchange of mixture components with larger connected volumes. The trapping of the heaviest components of hydrocarbon mixtures within the smallest connected pores has implications for shale operations, reserve estimation, and ultimately energy security.

Accurate characterization of the bubble point pressure of hydrocarbon mixtures under nanoconfinement is crucial to the prediction of ultimate oil recovery and well productivity of shale/tight oil reservoirs. Unlike conventional reservoirs, shale has an extensive network of tiny pores in the range of a few nanometers. In nanopores, the properties of hydrocarbon fluids deviate from those in bulk because of significant surface adsorption. Many previous theoretical works use a conventional equation of state model coupled with capillary pressure to study the nanoconfinement effect. Without including the inhomogeneous molecular density distributions in nanoconfinement, these previous approaches predict only slightly reduced bubble points. In this work, we use density functional theory to study the effect of nanoconfinement on the hydrocarbon mixture bubble point pressure by explicitly considering fluid−surface interactions and inhomogeneous density distributions in nanopores. We find that as system pressure decreases, while lighter components are continuously released from the nanopores, heavier components accumulate within. The bubble point pressure of nanoconfined hydrocarbon mixtures is thus significantly suppressed from the bulk bubble point to below the bulk dew point, in line with our previous experiments. When bulk fluids are in a two-phase, the confined hydrocarbon fluids are in a single liquid-like phase. As pore size increases, bubble point pressure of confined fluids increases and hydrocarbon average density in nanopores approaches the liquid-phase density in bulk when bulk is in a two-phase region. For a finite volume bulk bath, we find that because of the competitive adsorption in nanopores, the bulk bubble point pressure increases in line with a previous experimental work. Our work demonstrates how mixture dynamics and nanopore−bulk partitioning influence phase behavior in nanoconfinement and enables the accurate estimation of hydrocarbon mixture bubble point pressure in shale nanopores.

Production of hydrocarbons from shale is a complex process that necessitates the extraction of multi-component hydrocarbons trapped in multi-scale nanopores.

No abstract