Subcontinuum mass transport of condensed hydrocarbons in nanoporous media

Although hydrocarbon production from unconventional reservoirs, the so-called shale gas, has exploded recently, reliable predictions of resource availability and extraction are missing because conventional tools fail to account for their ultra-low permeability and complexity. Here, we use molecular simulation and statistical mechanics to show that continuum description--Darcy's law--fails to predict transport in shales nanoporous matrix (kerogen). The non-Darcy behaviour arises from strong adsorption in kerogen and the breakdown of hydrodynamics at the nanoscale, which contradict the assumption of viscous flow. Despite this complexity, all permeances collapse on a master curve with an unexpected dependence on alkane length. We rationalize this non-hydrodynamic behaviour using a molecular description capturing the scaling of permeance with alkane length and density. These results, which stress the need for a change of paradigm from classical descriptions to nanofluidic transport, have implications for shale gas but more generally for transport in nanoporous media.