Can liquids be made a lot purer than by fractional distilation?
Since ethanol and the water-ethanol azetrope boil at a lower temperature than water, if you start with a lot of water with a smaller amount of ethanol  then you can "distill" (however you do it...) all the ethanol out and be left with "pure" water. 

But water and ethanol form an azeotrope which is 95.5% ethanol by weight and boils at 78.1 °C. For the water-ethanol azeotrope the wt. % ethanol in the liquid is the same as the wt % of ethanol in the vapor. Thus there is no way to exploit liquid to gas phase transition to enrich the ethanol more than that.