This practice of adding an entrainer which forms a separate phase is a specific sub-set of (industrial) azeotropic distillation methods, or combination thereof.
The addition of a material separation agent, such as benzene to an ethanol/water mixture, changes the molecular interactions and eliminates the azeotrope.
Greater deviations from Raoult's law make it easier to achieve significant changes in relative volatility with the addition of another component.
The added entrainer should be recovered by distillation, decantation, or another separation method and returned near the top of the original column.
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.