Tatory Process

An aromatics complex is a combination of process units which are used to convert petroleum naphtha and
pyrolysis gasoline to the basic petrochemical intermediates: benzene, toluene, and xylenes (BTX).
The Tatoray process is integrated between the aromatics extraction and xylene recovery sections of the plant.
Toluene (A7) is fed to the Tatoray unit rather than being blended into the gasoline pool or sold for solvent
applications. If the goal is to maximize the production of PX from the complex, the C9 aromatic (A9) by-product
can also be fed to the Tatoray unit rather than blending it into the gasoline pool. Processing A 9-A10 in a Tatoray
unit shifts the chemical equilibrium in the unit toward decreased benzene production and increased production
of xylenes.
The Tatoray process provides an ideal way of producing additional mixed xylenes from low-value toluene and
heavy aromatics. The Tatoray process produces an equilibrium mixture of xylenes plus ethylbenzene. The
xylenes are recovered and isomerized to PX while the ethylbenzene can also be converted to xylenes.
The two major reactions in the Tatoray process are disproportionation and transalkylation. The conversion of
toluene alone to an equilibrium mixture of benzene and xylenes is called disproportionation. The conversion of
a blend of toluene and A9 to xylenes through the migration of methyl groups between methyl-substituted
aromatics is called transalkylation.

The Tatoray process uses a very simple flow scheme consisting of a fixed-bed reactor and a product separation
section. The fresh feed to the Tatoray unit is first combined with hydrogen-rich recycle gas, preheated by
exchange with the hot reactor effluent, and then raised to reaction temperature in a fired heater. The combined
feed vapor is then sent to the reactor where it is processed downflow over a fixed bed of catalyst. The reactor
effluent is then cooled by exchange with the combined feed and a product condenser and is sent to a product
separator. Hydrogen-rich gas is taken off the top of the separator, where a small portion of it is purged to
remove accumulated light ends from the recycle gas loop. It is then mixed with makeup gas and recycled to the
reactor. The pelleted catalyst is used in a fixed-bed reactor in the presence of hydrogen. Typical operating
conditions are: 350–530°C, 1–5 MPa (10–50 atm), and H2/ hydrocarbon ratio of 5–12:1. Toluene per pass
conversion is about 40–50%. Per pass conversion can be increased by increasing pressure or temperature,
although this also reduces yield and increases the rate of catalyst deactivation. The product typically contains <
2 mol% EB.
Parax Process
The Parex process provides an efficient means of recovering para-xylene by using a solid zeolitic adsorbent that
is selective for para-xylene. Parex units are designed to recover more than 97 wt % of the para-xylene from the
feed in a single pass at a product purity of 99.9 wt % or better. The Parex design is energy-efficient,
mechanically simple, and highly reliable.
Before the introduction of the Parex process, para-xylene was produced exclusively by fractional crystallization.
In crystallization, the mixed-xylenes feed is refrigerated to a point where the para-xylene isomer precipitates as
a crystalline solid. The solid is then separated from the mother liquor by centrifugation or filtration. Final
purification is achieved by washing the para- xylene crystals with either toluene or a portion of the para-xylene
product. The principal advantage of the Parex adsorptive separation process over crystallization technology is
the ability of the Parex process to recover more than 97 percent of the paraxylene in the feed per pass.
Crystallizers must contend with a eutectic composition limit that restricts para-xylene recovery to about 65
percent per pass.
In a typical Parex unit is the separation takes place in the adsorbent chambers. Each adsorbent chamber is
divided into a number of adsorbent beds. Each bed of adsorbent is supported from below by specialized
internals that are designed to produce highly efficient flow distribution. Each internals assembly is connected to
the rotary valve by a “bed line.” The internals between each adsorbent bed are used to inject or withdraw liquid
from the chamber and simultaneously collect liquid from the bed above and redistribute the liquid over the bed
below.
The Parex process has four major streams that are distributed to the adsorbent chambers by the rotary valve.
These net streams include
● Feed in: mixed-xylenes feed
● Dilute extract out: para-xylene product diluted with desorbent
● Dilute raffinate out: ethylbenzene, meta-xylene, and ortho-xylene diluted with desorbent
● Desorbent in: recycle desorbent from the fractionation section
At any given time, only four of the bed lines actively carry the net streams into and out of the adsorbent
chamber. The rotary valve is used to periodically switch the positions of the liquid feed and withdrawal points
as the composition profile moves down the chamber. A pump provides the liquid circulation from the bottom of
the first adsorbent chamber to the top of the second. A second pump provides circulation from the bottom of the
second adsorbent chamber to the top of the first. In this way, the two adsorbent chambers function as a single,
continuous loop of adsorbent beds. The dilute extract from the rotary valve is sent to the extract column for
separation of the extract from the desorbent. The overhead from the extract column is sent to a finishing
column, where the highly pure para-xylene product is separated from any toluene that may have been present in
the feed.
The dilute raffinate from the rotary valve is sent to the raffinate column for separation of the raffinate from the
desorbent. The overhead from the raffinate column contains the unextracted C8 aromatic components:
ethylbenzene, meta-xylene, and ortho-xylene, together with any nonaromatics that may have been present in the
feed. The raffinate product is then sent to an isomerization unit, where additional para-xylene is formed, and
then recycled to the Parex unit. The desorbent from the bottom of both the extract and raffinate columns is
recycled to the adsorbent chambers through the rotary valve. Any heavy contaminants in the feed accumulate in
the desorbent. To prevent this accumulation, provision is made to take a slipstream of the recycle desorbent to a
small desorbent rerun column, where any heavy contaminants are rejected. During normal operation, mixed
xylenes are stripped, clay-treated, and rerun prior to being sent to the Parex unit. Thus, few heavy contaminants
need to be removed from the bottom of the desorbent rerun column.

Isomar Process
The yield of o- and p-xylenes can be maximized by using catalytic conversion processes. The Isomar process
enriches the p-xylene in the Parex raffinate by re-establishment of the equilibrium. The acidic metal-containing
Zeolite catalyst used here also isomerizes ethylbenzene selectively to xylene isomers in their equilibrium ratio.
Since hydrogenolysis (Hydrogenolysis is a catalytic chemical reaction that breaks a chemical bond in an
organic molecule with the simultaneous addition of a hydrogen atom to the resulting molecular fragments) on
the metal components must be guaranteed to maintain the activity of this bifunctional catalyst, the Isomar
process is operated with a certain partial pressure of hydrogen in the catalytic reactor.