The results of extensive nonequilibrium molecular dynamics (MD) simulations of flow and transport of several binary mixtures Of CO2 and an n-alkane chain, from CH4 to C4H10, through a model porous membrane composed of three pores in series with significantly different sizes and in the presence of an external pressure gradient, are reported. The technique that we use for the simulations is a combination of the configurational-bias Monte Carlo method (used for efficient generation of molecular models of n-alkane chains) and the dual control-volume grand-canonical MD method. The selectivity of the membrane changes qualitatively as the length of the alkane chain increases, resulting in high separation factors in favor of the alkanes. Moreover, we find that, under supercritical conditions, unusual phenomena occur that give rise to direction- and pressure-dependent permeabilities for the fluids. The results, which are also in agreement with a continuum formulation of the problem, indicate that the composite nature of the membrane gives rise to the direction-dependent permeabilities. Hence, modeling flow and transport of supercritical fluid mixtures in porous materials with the type of morphology considered in this paper (such as supported porous membranes) would require using effective permeabilities that depend on both the external pressure drop and the direction along which it is applied to the materials. (c) 2007 Elsevier Ltd. All rights reserved.