In chemistry, azeotropic distillation is any of a range of techniques used to break an azeotrope in distillation. In chemical engineering, azeotropic distillation usually refers to the specific technique of adding another component to generate a new, lower-boiling azeotrope that is heterogeneous (e.g. producing two, immiscible liquid phases), such as the example below with the addition of benzene to water and ethanol. This practice of adding an entrainer which forms a separate phase is a specific sub-set of (industrial) azeotropic distillation methods, or combination thereof. In some senses, adding an entrainer is similar to extractive distillation.
Material Separation Agent
The addition of a Material Separation Agent, such as benzene to an ethanol/water mixture, changes the molecular interactions and eliminates the azeotrope. Added in the liquid phase, the new component can alter the activity coefficient of various compounds in different ways thus altering a mixture's relative volatility. Greater deviations from Raoult's law make it easier to achieve significant changes in relative volatility with the addition of another component. In azeotropic distillation the volatility of the added component is the same as the mixture, and a new azeotrope is formed with one or more of the components based on differences in polarity. If the material separation agent is selected to form azeotropes with more than one component in the feed then it is referred to as an entrainer. The added entrainer should be recovered by distillation, decantation, or another separation method and returned near the top of the original column.
Distillation of ethanol/water
A common historical example of azeotropic distillation is its use in dehydrating ethanol and water mixtures. For this, a near azeotropic mixture is sent to the final column where azeotropic distillation takes place. Several entrainers can be used for this specific process: benzene, pentane, cyclohexane, hexane, heptane, isooctane, acetone, and diethyl ether are all options as the mixture. Of these benzene and cyclohexane have been used the most extensively. However, because benzene has been discovered to be a carcinogenic compound, its use has declined. While this method was the standard for dehydrating ethanol in the past, it has lost favor due to the high capital and energy costs associated with it. Another favorable method and less toxic than using benzene to break the azeotrope of the ethanol-water system is to use toluene instead.
Another method, pressure-swing distillation, relies on the fact that an azeotrope is pressure dependent. An azeotrope is not a range of concentrations that cannot be distilled, but the point at which the activity coefficients of the distillates are crossing one another. If the azeotrope can be "jumped over", distillation can continue, although because the activity coefficients have crossed, the water will boil out of the remaining ethanol, rather than the ethanol out of the water as at lower concentrations.
To "jump" the azeotrope, the azeotrope can be moved by altering the pressure. Typically, pressure will be set such that the azeotrope will be closer to 100% concentration. For ethanol, that may be 97%. Ethanol can now be distilled up to 97%. It will actually be distilled to something slightly less, like 96.5%. The 96.5% alcohol is then sent to a distillation column that is under a different pressure, one that pulls the azeotrope down, maybe to 96%. Since the mixture is already above the 96% azeotrope, the distillation will not get "stuck" at that point and the ethanol can be distilled to whatever concentration is needed.
For the distillation of ethanol for gasoline addition, the most common means of breaking the azeotrope is the use of molecular sieves. Ethanol is distilled to 96%, then run over a molecular sieve which adsorbs water from the mixture. The concentration is now above 96% and can be further distilled. The sieve is heated to remove the water and reused.
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