PETROVIETNAM UNIVERSITY

PETROLEUM FACULTY

REACTIVE ADSORPTION

OVERCOMING THE P-XYLENE

EQUILIBRIUM LIMITED REACTION

Members:

1. Xuan Pham Thi Linh

2. Hieu Duong Dinh
3. Trang Nguyen Thi Dai
4. Hieu Bui Duc
1. Introduction
Aromatics and specifically p-xylene are building blocks in the production of a variety of
products used every day. Since worldwide population increases at exponential rate, the demand of
these products will increase as well. The para-Xylene is a valuable raw material for producing
terephthalic acid which in turn is used for the manufacture of polyethylene terephthalate to produce
various fibers and plastic resin.

Fig 1. Integrated UOP aromatics complex

Industrial production of p-xylene consists of a cycle loop where p-xylene separated, and other
isomers sent to an isomerization unit where p-xylene is produced and recycled back to said
separation unit. The raffinate from the separation unit, with a small trace of p-xylene, is fed to the
isomerization unit to produce more p-xylene. Figure 1 shows the process flow of an aromatics
complex based on UOP’s technologies, Parex is the separation unit, whereas Isomar is known as
place where the C8 isomerization reactions occur.
Since xylenes and ethyl benzene form a thermodynamic equilibrium, p- xylene is restricted at
about 22% to 24% in the mixture. In order to overcome this equilibrium constraints, a
multifunctional reactor combining separation and isomerization for producing p-xylene together
with the modification of the existing aromatics complex (Figure 2).
 Fig 2. Block diagrams for single and multifunctional reactor
Based on Le Chatelier’s principle, various ways can be applied to overcome reaction equilibrium
such as changing reaction condition, adding more reactants or removing products. This paper is
aimed to overcome the PX equilibrium limited reaction of 22-24% by combining “reaction with
separation”, which means removal p-xylenes from the mixture of products.
Reactive separation processes are unique in that they combine the unit operations of reaction and
separation process such as distillation, absorption, adsorption, extraction, membranes and so on
into a single, simultaneous operation. There are numerous advantages of reactive separation
processes, overcoming the reaction thermodynamic limitation is the main purpose in this case.
2. Separation and Isomerization Process
Parex (UOP) is the process separates of p-xylene from mixed C8 aromatic isomers based on the
Sorbex principle. This technology simulates the counter-current flow of a liquid feed over a solid
bed of adsorbent without physically moving the solid. It is said that the separation is accomplished
over zeolites adsorbent, from which KY (with toluene desorbent) and BaX (with PDEB desorbent)
zeolite are the most employed. Adsorption in gas phase has also been studied. Gas phase operation
may provide advantages such as better selectivity, nonetheless higher energy costs and axial
dispersion often lead to operation in liquid phase.
The xylene isomerization process is used to maximize the recovery of a particular xylene from a
mixture of C8-aromatic isomers, applied to p-xylene recovery in this case. Xylene isomerization
occurs industrially under gas phase conditions, but xylene isomerization in liquid phase are driven
by the environmental benefits of reduction of energy and pollution. They found that ethylbenzene
cannot be converted in liquid phase because its isomerization to xylenes goes through naphthenes
intermediates, which requires the presence of hydrogen, so the isomerization is separated in two
stages: one in liquid phase for xylenes and one in gas phase for ethylbenzene. Isomar (UOP) are
being made on process intensification by coupling xylenes isomerization and xylenes separation
(both in liquid phase) in a single unit using the Simulated Moving Bed Reactor (SMBR)
technology.
Because the reaction and separation occur in one unit, the process condition should be compatible,
we decided to consider the reactive separation process in two condition: Liquid phase and gaseous
phase.
3. Reactive Adsorption
The general advantages of Reactive Adsorption include improving of the product yield by shifting
the equilibrium in the required direction, compacted reactor and thus reduced cost, increasing the
selectivity of intermediate products. In comparison to other technologies, the biggest advantages
of Reactive Adsorption are low operating temperature and in situ adsorptive separation. However,
applications of adsorptive reactors in industrial-scale still to be seen. The challenges involve
materials development of catalysts/adsorbents and matching of process conditions (same
temperature and pressure) for both reaction and adsorption to achieve high yields and selectivity,
large adsorbent/desorbent requirement and low capacity.
There are different types of adsorptive reactors for screening. Simple reactive chromatography is
discontinuous; Continuous processes can name as rotating cylindrical annulus, the counter-current
moving bed and the simulated moving bed. Besides, based on the properties of adsorption with
respect to pressure, pressure swing adsorptive reactors is also present.
4. Solution for overcoming reaction equilibrium
3.1. Reactive separation process in gas phase
The catalyst used in this unit is bifunctional-type comprising metal and acidic sites. In the
isomerization of xylenes, hydrogen and metal sites are not involved, but they do contribute to
remove the carbonaceous materials from the catalyst surface (Figure 3a). Ethylbenzene converts
to xylenes through intermediates under metal and acid function of isomerization catalysts with the
presence of hydrogen (Figure 3b).

Fig 3. Reactions for a) xylenes isomerization, b) ethylbenzene isomerization

The process flow of an isomerization and separation unit is described in Figure 4. The feed is first
combined with hydrogen-rich recycle gas then heated and vaporized in the heater to achieve the
reactor operating temperature. The hot feed gas stream is then sent to the reactor. Adsorbent flows
from the regenerator to the top of the reactor and adsorbs all p-Xylene from the reaction. Because
p-xylene adsorption occurs immediately, the equilibrium balance of the xylene fractions is broken.
The adsorbent and adsorbate are withdrawn from the bottom of the reactor and sent to the
desorption column, in which p- Xylene is separated and adsorbent is sent back to the top of the
reactor. Since the adsorption is in gas phase, desorption can be done by the swing on Temperature
or Pressure.

Fig 4. Adsorptive reaction unit

The idea for the reactor comes from the Methanol synthesis
process, where Gas–solid–solid trickle-flow reactor GSSTFR (in
which fine adsorbent trickles through the fixed bed of catalyst) is
used (Figure 5).
The improvement of the GSSTFR is the structured trickle-bed
reactor where adsorbent flows through a monolithic catalyst,
similar to the one shown in Figure 6. It is said that monoliths is
low-pressure-drop and low-energy-consuming.

Fig 5. Gas–solid–solid trickle-flow reactor

 Fig 6. Monolith structure packed with catalyst particles
3.2. Reactive separation process in liquid phase
Ghislain Bergeot carried out experiments for producing high-purity p-xylene by coupling a step of
selective p xylene adsorption and a step of xylene isomerization from an aromatic C8 mixture
through Reactive Simulated Moving Bed. The adsorbent for p-xylene separation is BaLSX with a
Si/Al ratio of about one, the author claimed that BaLSX presented better selectivity compared to
that of BaX, specifically on ethylbenzene; the desorbent is toluene; and the isomerization catalyst
is HZSM-5 type, which is industrially used in xylene isomerization in gas phase. The adsorption
is carried out at preferably 200-220ºC and less than 4 MPa, and the reactions are preferably 180-
300ºC and 2-3 MPa at liquid phase, which means that an optimum compromise will exist. To
suppose, adsorption and catalysis operate at the same temperature and pressure.
W
Figure below introduce a new type of reactor based on the principle of Simulated Moving Bed :
 Fig 7. Adsorptive reaction device.

Fig 8.
The main column is divided into four equal parts like four zones in Simulated Moving Bed, each
is filled with catalyst and adsorbent. First, the material stream is a mixture of C8 fractions including
o, m, p-xylene and ethylbenzene go to the Adsorption zone from the top. Here the isomerization
reaction produces a balanced mixture of 22-24% p-xylene, o, m-xylene and ethylbenzene isomers;
p-xylene produced will mainly adsorbed in this section. Purification zone is place where undesired
components is stripped from the selective poor volume. Desorption zone located between
desorbent and extract nodes, in which the solid is regenerated by desorption of the p-xylene by
using the desorbent. The mixture of p-xylene and desorbent is withdrawn to recover p-X and
regenerate the desorbent. Buffer zone located between the raffinate and desorbent nodes, in which
the desorbent before being recycled, is regenerated.
Since p-xylene adsorption immediately, the p-xylene recovery efficiency was enhanced, and the
thermodynamic equilibrium of the xylene fractions was also broken.
In order to move the fluid, we need a fluid moving device and a rotary device to replace the position
of the zones. So that, with this model, we may need more energy than normal SMB.
 Fig. 9. Scheme for a classical SMBR
5. Conclusion
In this report, my group had been shown our knowledge about Adsorptive Reaction Process
applied on overcoming p-xylene isomerization equilibrium and given new ideas with the desire to
solve the problem. However, it still has many limitations so that our team are looking forward for
giving advices from the professionals to improve this idea and give us chance to widen
knowledges.
References

[1]. Santi Kulprathipanja, Reactive Separation Process, 2002

[2]. Jonathan Carlos Gonçalves da Silva, Hybrid Separations and Adsorption/Reaction Processes:
The Case of Isomerization/Separation of Xylenes, April 2015

[3]. Alírio E. Rodrigues, SIMULATED MOVING BED TECHNOLOGY Principles, Design and
Process Applications, 2015

[4]. Andrzej Stankiewicz & Jacob A. Moulijn, RE-ENGINEERING THE CHEMICAL

PROCESSING PLANT Process Intensification, 2004