Abstract

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.

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