Separation and Purification of Benzene, Toluene and

Xylene
BTX (benzene, toluene, and xylenes) are widely used as the basic chemical intermediates, and
popularly separated from petroleum naphtha, coking naphtha, and pyrolysis gasoline through
solvent purification. These oil fractions contain aromatic and non-aromatic hydrocarbons between
C5 to C8 in which certain components have approximate boiling points and form azeotropes.
Hence, it is difficult and low energy efficiency is needed to separate aromatics from the oil fraction
via regular distillations.

FRACTIONAL DISTILLATION
This method is used to separate the liquids whose boiling points difference is less than 50°C. For
this type of distillation, the fractionating column is vertically inserted between the flask containing
the liquid and condenser.
A fractionating column consists of a long vertical tube through which first the vapour goes up and
then is partially condensed which comes down to the flask. This condensed liquid (having higher
boiling point component) when flows down through the column gets in contact with the ascending
vapours and results in the interchange of heat.
To reach the equilibrium within liquid-vapour system, the vapours get enriched with the more
volatile component at the expense of the liquid. And therefore, ascending vapours become richer
and more volatile i.e. the lowest boiling component while the descending condensate becomes
richer in the highest boiling component. Efficiency of a fractionating column is determined by the
extent of separation.
Apparatus

The apparatus employed for the fractional distillation is shown in the Figure. The impure liquid
is placed in a round bottommed flask of suitable size, one-third to one-half, pumice stones are
added and then the column is fitted absolutely vertical in the position followed by fixing of a water
condenser to the side arm and the distillate is collected in the receiver. The thermometer is placed
in the position such that its bulb should be just below the level of the side arm. The mixture is
heated with a low flame. Care should be taken that the flame should be devoid of draughts so that
uniform heat is supplied (use of an air bath, Figure 1.43 gives better results). Initially heating of
the liquid should be slow so as to avoid the choking of the column [on fast heating, extra
condensation takes place while the column is warming up and so column may be choked with the
liquid]. When once the distillation has started, the flame should be adjusted that about one drop of
the liquid passes in 2-3 seconds so that an efficient fractionation can be obtained. First, the low
boiling point component will be passed over so when it has passed, distillation should cease. Then
heating is slowly increased and a second fraction starts distilling over with a sharp rise in the

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boiling point. A relative large intermediate fraction may be obtained, if the distillation set-up is
inefficient. The distillation should be conducted slowly so as to obtain pure fractions, otherwise
the fractionation has to be repeated.

Fractional distillation of a mixture of benzene and toluene

The boiling point of benzene is 80°C while that of toluene is 110°C and as the b.pt. difference is
30°C (less than 50°C) and so the mixture can be separated by fractional distillation. It is carried
out by using the apparatus shown in Figure and here the lagging of the column is not required. For
about 40 ml of a mixture containing equal volumes of benzene and toluene, about one and a half
hour is needed if distillation is carried out slowly. The flame should have no draughts during the
process. Fractions of boiling points (i) 80-85°C, (ii) 85-107°C and (iii) 107-111°C are collected in
different receivers. The approximate volumes of each fraction are 19, 2 and 17 ml respectively.

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PROCESS FOR PURIFYING BENZENE, XYLENE AND TOLUENE BY
EXTRACTIVE AZEOTROPIC DSTILLATION:
This invention concerns a process for purifying benzene and toluene by extractive distillation.
This invention concerns a process for separating benzene and/or toluene from mixtures containing
the same, together with at least one paraffinic or cyclic saturated hydrocarbon, by extractive
distillation, in a distillation zone, in the presence of an extraction solvent consisting essentially of
an aliphatic N-alkylamide, characterized in that, in order to reduce the solvent losses by
entrainment with the distillate and liquid water is introduced in th portion of the distillation zone
located between the injection point of the extraction solvent and the top of the distillation column,
in an amount and under such conditions that said water vaporizes completely in said portion of the
distillation zone without substantially diluting the solvent, and in that the vapors discharged at the
top are condensed and the condensate is separated into two liquid phases, a first liquid phase
containing essentially saturated hydrocarbons and a second liquid phase containing essentially
condensed water vapor.
According to a preferred embodiment, at least a portion of the second liquid phase is recycled
directly to the distillation zone, to form at least a portion of the liquid water introduced in said
distillation zone. As the alkyl amide, there is preferably used N,N- dimethylformamide and/or
N,N-dimethylacetamide. Water is introduced in the liquid form in an amount and under such
conditions that it is completely vaporized in the distillation column so as to be carried along with
the hydrocarbon vapors evolving from the top of the column, without flowing to a substantial
extent down to the injection point of the extraction solvent. own to the injection point of the
extraction solvent.
It has been observed that when the distillation unit is further heated, for example by means of a
reboiler, and water is introduced in the liquid form, the latter is vaporized by thermal exchange on
a few plates of the column by contact with the ascending vapors. The amount of additional heat so
supplied depends essentially on the amount of injected water which is adapted to each hydrocarbon
mixture to be treated and to the desired specifications for the products.
According to an embodiment of the process, the hydrocarbon mixture to be separated is introduced
into a distillation zone at an intermediary point thereof; the extraction solvent is introduced at a
point of the distillation zone above the point of introduction of the hydrocarbon mixture and water
is introduced, in the liquid form, at a point of the distillation zone above the point of introduction
of the extraction solvent, under such conditions that said water cannot dilute the solvent; the top
product from the distillation zone is condensed; the obtained condensate is separated into two
liquid phases, a first phase containing non-aromatic hydrocarbons and a second phase containing
water; said first and second phases are withdrawn separately, the product from the bottom of said
distillation zone, containing aromatic hydrocarbons and the extraction solvent is discharged and
the solvent is separated, in a known manner, from the aromatic hydrocarbons, to obtain on the one
hand the recovered extraction solvent.

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REFERENCES
Gahee, A. Sotude-Gharebagh, R. and Mostoufi, R., Dynamic optimization of the benzene
extractive distillation unit. Brazilian Journal of Chemical Engineering.
Blöcher, C., Dorda, J., Mavrov, V., Chmiel, H., Lazaridis, N.K. and Matis, K.A. (2003) Hybrid
Flotation—Membrane Filtration Process for the Removal of Heavy Metal Ions from Wastewater.