Extractive and azeotropic distillation

Extractive distillation and azeotropic distillation share as a common characteristic,

in that an auxiliary solvent is added to the crude aromatics fraction to achieve better
separation by distillation. Extractive distillation takes place in the presence of
an extractive material with high solvent power for aromatics, which has relatively
low volatility compared with the compounds which are to be separated, and is
constantly added at the top of the fractionation column. The purpose of the auxiliary
solvent is to change the vapor pressures of the hydrocarbon components in
such a way that they can be more easily separated by distillation; e.g. the vapor
pressure of benzene is lowered to the point when the accompanying non-aromatics
can be distilled off as an overhead fraction.

Figure 4.11: Flow diagram for production of aromatics by extractive distillation

In azeotropic distillation, on the other hand, the additive and the component to
be separated form an azeotrope i. e. a mixture boiling at a given temperature and
with a constant composition. Azeotropic distillation can only be used to refine
highly-enriched mixtures of aromatics, such as occur in coke-oven benzole,
whereas extractive distillation can also be used to separate aromatics which are
present in low concentrations. As early as World War I toluene used in the
production
of explosives was obtained by extractive distillation, using phenol as the
extractive material.
The main methods of extractive distillation employed today to recover aromatics
(Figure 4.11) use dimethylformamide, N-formylmorpholine (Krupp-Koppers),
N-methylpyrrolidone (Distapex/ Lurgi) and sulfolane (Shell/ UOP) as extractive
agents.
The Morphylane process, which operates with N-formylmorpholine, can also
be run in conjunction with benzene predistillation, allowing low energy
consumption
rates to be achieved through optimized heat recovery. The largest plant of this
kind is operated by Redestillationsgemeinschaft in Gelsenkirchen, West-Germany
and has a capacity of 336,000 tpa of hydrorefined benzole (Figure 4.12).
Operating the rectification columns under pressures up to 18 bar gives the
overhead
vapors a greater heat content; these are used to heat the distillation feed. The
yield of benzene is over 99%.

1 Predistillation column; 2 Extractive distillation column; 3 Stripping column; 4 Raffinate

Column
Figure 4.12: Flow diagram for production of aromatics by the Morphylane process with optimum
heat economy

Azeotropic distillation is only of minor importance in the production of BTX

aromatics; the most important azeotropic entrainers are methyl ethyl ketone and
methanol. Figure 4.13 shows the production of toluene by azeotropic distillation

with methanol.

1 and 2 Azeotropic distillation columns; 3 Extraction column; 4 Methanol column

Figure 4.13: How diagram for azeotropic distillation for the production of toluene