Structural study of water/alcohol mixtures adsorbed in MFI and MEL porosils

•Recovery of alcohols from aqueous media by adsorption onto silicicalite-1 and silicalite-2.•Pore filling mechanisms are mostly driven by hydrogen bonding.•Coordination with the zeolite is mainly controlled by energetic and entropic factors for alcohols and water respectively.•Despite MFI/MEL and methanol/ethanol similarities, water adsorption is affected by the zeolite and the co-adsorbed alcohol.•Relatively more selective adsorption of short alcohols into MFI compared to MEL zeolite.