The Role of Hydrogen Bonding in the Dehydration of Bioalcohols in Hydrophobic Pervaporation Membranes

The dehydration of bioalcohols is considered one of the major factors contributing to the cost of biofuel production. In this study, liquid phase separation of water from methanol and ethanol in a siliceous MFI pervaporation membrane was studied by performing concentration gradient driven molecular dynamic (CGD-MD) simulations. CGD-MD simulations work by imposing a higher concentration in the feed side and a lower concentration in the permeate side of the membrane. This creates a concentration gradient across the membrane that facilitates the diffusion of molecules from the feed to the permeate side, mimicking the experimental pervaporation membrane set up. Fluxes of methanol, ethanol and water were calculated in single component permeation simulations and in equimolar methanol-water and ethanol-water mixture separation simulations. It was found that water formed hydrogen bonding with the silanol (Si-OH) groups on the external surface of the MFI and did not enter the membrane in the single component permeation simulation. While this may suggest that MFI can be used to effectively dehydrate bioalcohols, our simulations showed that water permeated through the MFI membrane when it was in a mixture with either methanol or ethanol. Furthermore, in the alcohol-water mixture simulations, the fluxes of methanol and ethanol were significantly lower than that of expected based on their single component fluxes. A detailed analysis of hydrogen bonding in the alcohol-water mixture separation simulations revealed that water preferred making hydrogen bonds with methanol and ethanol rather than with the silanol groups. This resulted in drifting of water molecules along with permeating alcohol molecules in to the MFI membrane in mixture simulations, while slowing the permeation of methanol and ethanol fluxes.