Dehydration[edit]
There are basically three dehydration processes to remove the water from an azeotropic ethanol/water mixture. The first process, used in many early fuel ethanol plants, is called azeotropic distillation and consists of adding benzene or cyclohexane to the mixture. When these components are added to the mixture, it forms a heterogeneous azeotropic mixture in vapor–liquid-liquid equilibrium, which when distilled produces anhydrous ethanol in the column bottom, and a vapor mixture of water, ethanol, and cyclohexane/benzene.
When condensed, this becomes a two-phase liquid mixture. The heavier phase, poor in the entrainer (benzene or cyclohexane), is stripped of the entrainer and recycled to the feed—while the lighter phase, with condensate from the stripping, is recycled to the second column. Another early method, called extractive distillation, consists of adding a ternary component that increases ethanol's relative volatility. When the ternary mixture is distilled, it produces anhydrous ethanol on the top stream of the column.
With increasing attention being paid to saving energy, many methods have been proposed that avoid distillation altogether for dehydration. Of these methods, a third method has emerged and has been adopted by the majority of modern ethanol plants. This new process uses molecular sieves to remove water from fuel ethanol. In this process, ethanol vapor under pressure passes through a bed of molecular sieve beads. The bead's pores are sized to allow absorption of water while excluding ethanol. After a period of time, the bed is regenerated under vacuum or in the flow of inert atmosphere (e.g. N2) to remove the absorbed water. Two beds are often used so that one is available to absorb water while the other is being regenerated. This dehydration technology can account for energy saving of 3,000 btus/gallon (840 kJ/L) compared to earlier azeotropic distillation.[25]