International Journal of Science and Research (IJSR)

ISSN (Online): 2319-7064

Index Copernicus Value (2015): 78.96 | Impact Factor (2015): 6.391

Optimization of Styrene Production Process using

Divided Wall Column
Tanmay Kakade1, Niraj Topare2
1, 2
Maharashtra Institute of Technology, Department of Petrochemical Engineering, Pune, Maharashtra 411038, India

Abstract: Styrene which is known to be one of the most expensive monomers is conventionally produced by dehydrogenation of ethyl
benzene which generates a mixture of benzene, toluene and styrene. The separation of this tertiary mixture is done through two column
distillation by first removing benzene from the first column and then separating toluene from styrene in the second column. The
conventional distillation system consumes high-energy and yields low purity of toluene.Therefore to overcome these drawbacks we have
proposed the use of a Divided Wall Column. In this work, we have designed a Divided wall column (DWC) for styrene production and
compared it with the conventional method. By using DWC arrangement we achieved less energy consumption and higher purity of
products compared to the conventional method. The simulation of the DWC was done using four column arrangement in Aspen Plus
software. The results show that, energy consumed when divided wall column was considered is far less as compared to conventional
system used in industry. With the application of DWC column, higher purity toluene was obtained (76.15 % to 96.00 %) and for styrene
purity increased from 99.67 % to 99.99 %.

Keywords: conventional distillation column, Divided wall column, Aspen Plus, high purity, energy saving

1. Introduction internal wall that separates the feed and side stream sides of
the vessel. This is what we call as a Divided-Wall Column
Styrene is one of the most important monomers in modern (DWC). The main advantages of this system are the
petrochemical industry. Approximately 20 million tons of increased the purity of the styrene/toluene and moreover
styrene is produced annually across the globe. The styrene reduction of the energy consumption compared to the
production process was developed in the 1930s conventional distillation system, resulting in lower costs of
independently and simultaneously by BASF in Germany and equipment construction and less energy consumption [1]. As
by Dow Chemical in the USA. It is used for the production of a result, an economical system is obtained, which is superior
many different polymeric materials, the most important being the conventional system in the above-mentioned ways. For
polystyrene, styreneacrylonitrile and acrylonitrile this reason, it is important. For this reason, it is important to
butadienestyrene (ABS). Another important application is in develop distillation equipment such as Divided Wall Column
styrenebutadiene latex. The most important ways of for benzenetoluenestyrene system, as this type of
production of styrene are the catalytic dehydrogenation of technology enhances considerably the purity of product
ethyl benzene (EB) and the oxidation of EB to ethyl benzene associated to conventional separation methods of such
hydro-peroxide. Ethyl-benzene (EB) de-hydrogenation is the system.
main route of styrene production, being among the most
popular and important catalyzed processes. Investigations in 2. Conventional Method
this field have consolidated this process which uses most of
the raw material for styrene production with low levels of by- The Conventional method for styrene production is the
products. Although the by products are just a small dehydrogenation of ethylbenzene, widely used for the
percentage of the raw material, the generated compounds are industrial production of styrene. This method was first
valuable and it is important they have enough degree of devised in mid 1930s. The production of styrene increased
purity to be commercialized. The most common technique to dramatically during the 1940s, when it gained its popularity
obtain each distillation equipment that increases the process as a feedstock for synthetic rubber. The conventional design
energy efficiency has been modest, once the main interest is of the separation section of a benzenetoluenestyrene
on stage of the final stream components is distillation, which system consists of two continuous columns from which
allows the separation of styrene, toluene and benzene as the benzene is extracted first, as it is the most volatile compound.
main reaction products. Distillations is still the best method Then, the styrene stream is purified in the second column
and option available for the separation of compounds with no through removal of toluene. In this case, benzene forms an
azeotropes formation and have a wide temperature range for independent stream after leaving the first column. The
the treatment of output stream coming from the reactor in remaining product continues through the second column,
order to separate the products from the product stream. The where the toluene stream leaves the process with a good
implementation of modern distillation equipment that purity from the top while styrene is collected from the bottom
increases the process energy efficiency has been modest, of the column. Even though, the system is pretty much simple
once the main interest is on stage optimization of catalyzed to understand but making a system giving more purity is need
system reaction. Divided Wall Column is among this type of of hour in this technologically advanced world.
distillation system, consisting of a single distillation column
with bidirectional flow. Instead of using two separate vessels,
a practical implementation is to use a single vessel with an
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Paper ID: ART20172178 311
 International Journal of Science and Research (IJSR)
ISSN (Online): 2319-7064
Index Copernicus Value (2015): 78.96 | Impact Factor (2015): 6.391
conventional systems, we obtain higher purity levels of
Toluene and Styrene, which is one of the main advantages of
the DWC. This way the DWC required energy of
1927.09KW which is around 14.5% less than the
conventional system.

4. Simulation Model

The simulation of DWC was done using aspen plus software.

The Radfrac column available in the component library of
aspen plus was used. The steady state simulation of aspen
plus was done using Four fictious columns: two absorbers,
Figure 1: Conventional distillation system for styrene rectifier, stripper were used to represent the DWC
production column. In reality there is only one column, but in aspen plus
four columns represent the single DWC column [5]. In this
The stream from a reactor used in styrene production is simulation stream feed is fed into the reactor. Benzene,
analysed in order to compare the energy economy produced Toluene and Styrene are represented by streams Benzene,
with the implementation of a Divided Wall Column and a Toluene and Styrene respectively.
conventional system. The conventional ethyl benzene
dehydrogenation process is the most used production process
of styrene in industrial scale. The stream composition is 85%
styrene, 10% benzene and 5% toluene on mass basis, with a
total mole flow rate of 9667 kgmole/h [2]. This stream was
evaluated by the Aspen Hysys software; a professional
simulation program for chemical processes. The Aspen
Hysys software simulated the conventional separation system
to determine components with adequate purity for
commercialization. From the separation process model the
number of stages used for separation as well as the energy
consumption of the system was obtained. This way, 24 stages
were required by the distillation column for benzene
separation, while, for toluene and styrene removal, 40 stages
were required. The total energy used in the conventional
process was 2199.49 kW, which compares well with the
results reported by other authors for the same separation
process.
Figure 2: Divided Wall Column for Styrene Production
3. Divided Wall Column simulated in Aspen plus.

In the case of a divided wall column, instead of two columns A liquid splitter and vapor splitter are present represented by
(as seen conventionally), there is only one column divided B5and B6 respectively. Pressure is maintained constant
into two parts. The first part of the column is the pre- through the simulation [6]. The variables to be initialized for
fractionator, which helps in separating the stream into two simulation were: number of trays in the column, feed stage,
parts, for example containing Benzene with Toluene, and the vapor/liquid split ratio. Before exporting the file in aspen
other Styrene with Toluene. These two streams are led into dynamics a number of important changes were to be made for
the main distillation, wherein they are purified, separated and the dynamic simulation of the model.
extracted. The partition wall in the middle section of the
column separates the main column from the side column [3]. 5. Mathematical Model
These columns being thermally coupled, the multi-
component feed enters the main column, where a cut between The mathematical model for the simulation of conventional
high and low boiling components takes place. This ensures method and divided wall column was done using
that, taking the example mentioned above, neither low mathematical iterative methods. Two iterative methods were
boiling components of Benzene can pass to the bottom part used. Firstly the Fenske Underwood Gilliland equation
of the side column, nor high boiling components of Styrene method was used followed by a rigorous method. The
can pass through the upper part of the side column, ensuring algorithm for the Fenske Underwood method is shown in the
no contamination of middle boiling fraction of Toluene. This Figure 3 [7]. The minimum numbers of trays were calculated
method is a cost, and energy efficient alternative to the using the Fenske equation. The dew point and the bubble
conventional two column system, due to having one column point temperature were calculated by assuming equilibrium
and one re-boiler and one condenser less [4].From modelling between the liquid and vapour at each tray. To finally design
the divided wall column (DWC) system to obtain the the column it is necessary to calculate the pressure,
products at the same conditions, as those obtained from temperature, composition, stream flows and rates of heat and
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Paper ID: ART20172178 312
 International Journal of Science and Research (IJSR)
ISSN (Online): 2319-7064
Index Copernicus Value (2015): 78.96 | Impact Factor (2015): 6.391
mass transfer in each tray through energy and mass balances. toluene.
These balances require us to solve a lot many equations to 4) In the Figure7, graph (Mole fraction vs Stage number) in
calculate the minimum number of trays required by the the stripper section as the Stage number increases the mole
distillation process. The columns in the aspen plus software fraction of styrene gradually increases till stage 46, that of
are simulated till the required results are obtained which are toluene gradually decreases and that of benzene remains
in comparison with the results obtained from the Fenske approximately zero.
Underwood Gilliland equation. 5) In the Figure 8, graph (Mole fraction vs Stage number) in
the section from which toluene is collected (ABS 2) as the
Stage number increases the mole fraction of toluene
decreases (96%-93%) till stage 24, that of styrene
gradually increases (0.1%-70%) and that of benzene
(approx. 0) remains approximately constant.

Figure 4: Purity vs Reflux Ratio

Figure 3: Algorithm of the Fenske Underwood Gilliland

Equation

6. Data Analysis
Based on the simulation performed, the divided wall column
system is analysed and compared with the conventional
distillation system. The system structure is presented by the
four graphs (Fig.4, Fig.5, Fig6, Fig.7, Fig.8).
Figure 5: Purity vs Distillate Rate
1) In Figure 4, graph (Purity vs reflux ratio) we compare the
purity of each product against the variation of reflux ratio.
As seen from the graph(Fig.3) we observe that as the reflux
ratio increases the purity of all 3 components decreases .
We get higher purity of all components when simulated at
reflux ratio equals to 1.97.
2) In Figure 5, graph (Purity vs Distillate rate) compares the
purity of each product against the variation of distillate
rate. From the graph, we observe that purity of benzene,
toluene and styrene is maximum for distillate rate equals to
739.9 kgmol/h. Generally as we decrease the distillate rate,
the purity of styrene remains unchanged but the purity of
benzene and toluene increases considerably.
3) In the Figure 6, graph(Mole fraction vs Stage number) in
the rectifier section as the Stage number increases the mole Figure 6: mole fraction vs Stage number in rectifier block
fraction of styrene remains constant (approximately zero), (Aspen Plus)
toluene increases gradually up to stage 11, increases
exponentially upto stage 21 and then becomes gradual till
stage 24 and that of benzene decreases up to stage 13,then
decreases exponentially up to stage 21 and then remains
constant. General observation is the Stage number does not
have not much effect on the mole fractions of Benzene and
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Paper ID: ART20172178 313
 International Journal of Science and Research (IJSR)
ISSN (Online): 2319-7064
Index Copernicus Value (2015): 78.96 | Impact Factor (2015): 6.391
cost of the DWC is also less as compared to the conventional
system as the use of one condenser and one reboiler is
eliminated. Also in DWC the purity of Toluene increased
from 76.15 % to 96.00%, while the purity of styrene
increased from 99.67% to 99.99%.

References
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[2] Jonathan J. Parra Santiago,Carlos Alberto Guerrero
Figure 7: Mole fraction vs Stage number in stripper block Fajardo,Jose Ricardo Sodre, Distillation process
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not only saves energy but also gives us a better purity of over binary FeOx-MeOy/Mg(Al)O catalysts derived from
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saving [8].

8. Conclusion
The Divided Wall Column system presents an advantage in
comparison with the Conventional System as it not only
reduced the energy consumption but also improved the purity
of the final products. From the results obtained, it was
observed that a considerable energy saving of approximately
272.4KW was obtained when using the DWC. The energy
consumed by the Divided Wall Column was observed as
1927.09KW, while the energy consumption of the
Conventional System was 2199.49 KW. The construction

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