Separation of highly non-ideal mixtures with the use of extractive heterogeneous-azeotropic distillation (EHAD) has been successful in the last few years. In contrasts, most researches have focused on mixtures with containing minimal boiling homoazeotropes. Despite the fact that maximum boiling azeotropes are fewer in numbers it is important to examine if the use of EHAD method is viable. It is important to note that the EHAD method does not exclude maximum boiling azeotropes despite the fact that these types of azeotropes can not be heterogeneous. In the fine chemical industry, large amounts of used solvent have to be disposed, in many cases with incineration. Because of the high cost it is advisable to concentrate and dehydrate of the liquid wastes. The work is motivated by an industrial environmental problem, which is concentration and dehydration of used, waste solvent contains maximal boiling azeotrope in one step with EHAD. The separation of highly non-ideal Water-Acetone-Chloroform-Methanol quaternary mixture is investigated and optimized in professional flowsheet environment. The aim is to reach as clear as possible bottom product in water compound in order to few distillate product has to be burned. Two slightly different constructions of separations are examined. It can be concluded the computer simulations and experimental verification are proved the separation efficiency of EHAD in first case of maximal boiling azeotrope mixture.