CHAPTER # 2

MANUFACTURING
PROCESS

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 MANUFACTURING PROCESSES:

FRACTIONAL DISTILLATION:
Straight fractional distillation of petroleum is of value only
in preparing concentrates containing individual aromatics or a narrow boiling
range of aromatics. Benzene forms azeotropes with methylcyclopentane, with
cyclohexane, and with n-hexane. Although toluene does not form azeotropes with
methylcyclohexane, n-heptane or n-octane, the relative volatilities are much
smaller than would be expected from the vapor pressures of the
purehydrocarbons.

EXTRACTIVE DISTILLATION:
The solvent is selected to produce an increase in the
relative volatility of the components to be separated. Azeotropes involving
solvent and feed components must not occur within the extractive distillation
zone. If the solvent is too selective, two liquid phases will occur, and this will
greatly reduce any increase in the volatility ratio.

For the separation of benzene or toluene the extractive agent normally employed
is phenol. But for the separation of xylene , cresol is preferred. The benzene
fraction after extractive distillation and recovery of aromatics from the solvent is
treated with sulphuric acid, washed with sodium hydroxide and dried with
calcium chloride. The toluene fraction is treated with maleic anhydride and
subsequently given sodium hydroxide and water washes. It is finally dried with
calcium chloride.

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AZEOTROPIC DISTILLATION:
The preference for azeotropic distillation rather than
extractive distllation depends upon proportion of aromatics present in the
feedstock, and normallr arises when not less than 40% of aromatics are present in
the feed. In azeotropic distillation the majority of the added agent passes
overhead with the non-aromatics where as in an extractive distillation the major
part of the azeotrop joins the aromatics as column bottoms. The choice of process
is therefore dependent largely upon the most economic heat balance that can be
achieved.

The best azeotroping agents for toluene recovery are aqueous methyl ethyl
ketone, nitromethane, methyl alcohol and dioxin. For benzene recovery, acetone
is the most suitable azeotropic agent, where as methyl alcohol is to be preferred
for toluene recovery. It is possible to use anhydrous methyl ethyl ketone but this
is normally uneconomic.

SOLID ADSORPTION:
This used industriallr in the Arosorb process, which depends
upon the selective adsorption on silica gel. It has been used in one plant that of
sun oil Co., at Marcus hook, for isolating benzene and toluene from the products
of hydroforming of naphthenic feedstock. The product from this process contains
about 27% of benzene and toluene, the remainder being paraffins.

This is fed to a number of silica gel adsorbers in a cyclical operation consisting of

three steps. Introduction of feed to silica gel to give about 70% saturation,
displacement of saturatesfrom the bed with a volatile liquid such as butane or
pentane, and displacement of the benzene and toluenefrom the bed with an
aromatic of higher boiling point, mixed xylenes being used. The xylenes are then
removed by heat and steam. The benzene and toluene, separated from paraffins
of the same boiling range,can then be purified to nitration grade quality by
distillaton.

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For long life silica gel, water, olefins, sulphur and nitrogen compounds must be
absent. With the new catalytic reforming processes, the only problem is the
removal of water.

CRYSTALLIZATION:
This was only used for the isolation of p-xylene from other C 8 aromatics, because
of the similarity of boiling points, p-xylene cannot be separated from m-xylene by
distillation methods, but its relatively high melting point 13.3ºC compared with
that of m-xylene -47.9ºC, and those of other C8 isomers (o-xylene -25.2ºC,
methylbenzene -95.0ºC) is the basis of the technical processes now used.

Petroleum C8 aromatics normally contain about 50% m-xylene, 20% each of p-

xylene and o-xylene and 10% of ethylbenzene, non-aromatics are sometimes left
in as their presence does not obstruct isolation of p-xylene.

SOLVENT EXTRACTION:
The solvents chosen must have a selectivity for aromatics and
must have physical characteristics so that two phases readily separate within a
reasonable range of temperature, say between -30ºC and 150ºC.

UDEX PROCESS:
It is a liquid lquid phase recovery process for the selective extraction
of aromatics from hydrocarbon mixtures through the use of solvent aqueous
diethylene glycol. A recent development has been the addition of a minor
proportion of dipropylene glycol to the diethylene glycol. This is said to improve
the capacity at some sacrifice in selectivity.

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While the addition of water to diethylene glycol increases the selectivity of the
system, it also decreases the solubility of the aromatics. The water content of the
solvent medium is therefore kept down to 8-10%. Because of this low solubility
the temperature is as high as 150ºC. and fairly high solvent ratios (8-15:1) have to
be used. The flow of solvent is counter-current to the feed.

SULFOLANE EXTRACTION (RECOMMENDED PROCESS):

The sulfolane process combines liquid
liquid extraction with extractive distillation to recover high purity aromatics from
hydrocarbon mixtures, such as reformed petroleum naphtha (reformate),
pyrolysis gasoline (pygas), or coke ove light oil (COLO).

Contaminants that are most difficult to eliminate in the extraction section are
easiest to eliminate in the extractive distillation section and vise versa. This
hybrid combination of techniques allows sulfolane units to process feed stocks of
much broader boiling range than would be possible by either technique alone. A
single sulfolane unit can be used for simultaneous recovery of high purity C6-C9
aromatics, with individual aromatics recovered downstream by simple
fractionation.

The sulfolane unit takes its name from the solvent used, tetrahydrothiophene 1,1-
dioxide, or “Sulfolane”. Sulfolane was developed as a solvent by shell oil company
in the early 1960’s and is still the most efficient solvent available for the recovery
of aromatics. Because the sulfolane solvent exhibit higher selectivity and capacity
for aromatics than any other commercial extraction solvent. Sulfolane unit
operates at the lowest available solvent to feed ratio for any given reformate
feedstock. Therefore, for the reformate applications, a sulfolane unit is less
expensive to build and operate than any other type of extraction unit.

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