GROUP ASSIGNMENT

EP322 CHEMICAL PROCESS SIMULATION AND DESIGN

Title : Production of Styrene

Name and ID : CHAN PEI JING 1001542584

DING SHUAN WEI 1001540160

AINGGARARUBAN A/L GANESHAN 1001642979

TAN CHENG JUN 1001540904

TAN WEI HEN 1001540184

Date of submission : 5/4/2019

Lecturer : Mr Mohd. Fauzi Zanil

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SCHOOL OF ENGINEERING

FACULTY OF ENGINEERING, TECHNOLOGY & BUILT ENVIRONMENT

JAN-APRIL 2019

Table of content

Objective and Introduction

Methodology

Result and summary

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Conclusion

Reference

Appendix

Simulation Design

Youtube link

Objective
1. To determine the amount of styrene produced by using catalytic dehydrogenations of ethyl-
benzene.
2. To determine the simulation of the production process of styrene by using process
simulations.
3. To determine the composition and mass flow rate of each process involve in the production
of styrene.
4. To determine the operating parameter of equipment used in production of styrene via
catalytic dehydrogenations.
Introduction
Styrene known as vinylbenzene, and phenylethane. Styrene is the common name given to the
simplest and most important of unsaturated aromatic monomers family. Styrene is an organic

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compound with the chemical formula C 6H5CH=CH2. Styrene has a molar mass of 104.15
g/mol and it has the density of 0.909g/cm 3. The melting point and boiling point of styrene are
-30 °C (243K) and 145°C (418K) respectively. It is a very important chemical and mostly
used to obtain the daily use plastic materials and items such as toys, jars, bottles, severing
dishes, cups and others. It also used as week as a foam precursor for insulation and
cushioning operations.
Styrene can be obtained at commercial scare through several production processes such as
catalytic dehydrogenation of ethyl-benzene and oxidation of ethyl-benzene. In catalytic
dehydrogenation of ethylbenzene at a high temperature around 630°C (903K) using various
metal oxides as catalysts such as zinc, chromium, magnesium oxides coated on activated
carbon, alumina or bauxite.

Besides, in ethyl-benzene is treated with oxygen to form the ethyl-benzene hydroperoxide.

This hydroperoxides is used to oxidize propylene to propylene oxide. This process will get a
result of 1-phenylethanol is dehydrated and give styrene at relatively low temperatures range
from 180°C to 400°C (453K to 673K) by using an silica gel (SiO2) or titanium dioxide (TiO2)
as a catalyst.

Furthermore, process simulation is defined as the utilization of computer software resources

to develop mathematical models for the construction of an accurate, representative model of a
process (a chemical process, in this case), in order to understand its actual behaviour during
regular plant operations. Process simulation and modelling is the application of a range of
software tools to analyse individual unit operations (or process stages) and their relationships
within the overall process. Process simulation is common use for process mapping, design,
assessment and also cost analysis. By using process simulations, process engineer can identify
the potential problem ahead of time and take corrective actions
Methodology
Identification of Chemical Components

Figure 2.1: Selecting components

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 To begin with, the components involved in the production of styrene are
ethylbenzene, styrene, hydrogen, benzene, ethylene, toluene, methane, and steam (H2O) as an
inert.

Selection of Fluid Package

Once the components are specified, the appropriate fluid package must be selected. The
fluid package contains all the necessary information that is relevant to pure component flash
and physical property calculation. Peng-Robinson (PR) is the recommended property package
for oil, gas and petrochemical application. Hence in the production of styrene, Peng-Robinson
is the most ideal to use since the components are all hydrocarbons, non-polar and gaseous.

Figure 2.2: Selecting fluid packages

Setting Up The Reaction

Styrene in the industry have few production processes to obtain. The most common and easy
to get high yield of styrene is the catalytic dehydrogenation of ethyl-benzene at high
temperature. In this process, there are few reactions that need to consider. The main reaction
is the conversion of ethylbenzene to styrene.

Figure 2.3: Setting up Reaction

The conversion of ethylbenzene to styrene is in the range of 50% to 70% in

commercial. Therefore, 65% of conversion was set in this process. There are 2 side reaction
which is conversion of ethylbenzene to benzene and ethylene (due to the reversible process of
formation of ethylbenzene), and formation of toluene and methane through this process. The
conversion of benzene and ethylene was rated at 21%, while for toluene and methane is 14%.

Process Model Development

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 Figure 2.5: Process Flow Diagram

The process was setup as the diagram above. There are only two feed in this process
which is ethyl benzene and the superheated steam. The process consists of two heaters (E-100
and E-101) and one cooler (E-102), two mixers to mix the stream from recycle (MIX-100)
and another one to mix the superheated steam (MIX-101). The feed is flow into the
conversion reactor (CRV-100), two outlet stream from the reactor which is condensate and
the distillate that contain more styrene. A 3-phase separator (V-100) was used after the
conversion reactor to separate multiple components in the stream. The superheated stream
was cooled down and turn into heavy liquid and remove as residual wastewater. Most of the
hydrogen was separated out from the vapour outlet. The light liquid stream is the desire
stream that contain mostly ethylbenzene, styrene and ethylene. Then, the stream is flow into
distillation column (T-101). Benzene as light key removed from the top and styrene from the
bottom. As the bottom stream still contains others components, the stream is flow into second
distillation column (T-102) in order to achieve the desire purity and mass flow rate of the
styrene production.

Simulation of Base Case Operation to Achieve Target Production

Figure 2.6: Equipment used at beginning of step

First of all, pre-heating, mixing and vaporization of ethyl-benzene are required. The
production process starts with ethyl-benzene stream (at STP condition: 25 ºC , 1 bar) is pre-
heated using heater. The initial mass flow rate of the ethylbenzene was set at 10000kg/h. The
temperature was heated to 136 ºC which is the boiling point of ethylbenzene. The pre-heated
stream obtained is then mixed with a recycle stream containing mostly ethyl-benzene and
water, and some traces of styrene and toluene, coming from the top of the Distillation Column
(T-102) which is Styrene Column in a cylindrical, pressurized vessel Streams Mixer,
operating under isobaric conditions. The exit stream leaving the Stream Mixer is completely
vaporized in another heater. The temperature is increased to 250 ºC and the pressure increased
to 2 bar. The vapours obtained are then sent to another pressurized vessel operating also under
isobaric conditions which is in Steam Mixer, at which superheated steam is injected in order
to increase the temperature of the vapor mixture to that of the reaction condition. The amount
of superheated steam to consume in the Steam Mixer should be enough to obtain a gaseous

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stream, prior to being fed to the Conversion Reactor. Since the ratio of the superheated steam
and ethylbenzene that feed into the conversion reactor is approximately in the ratio of 14:1.

Figure 2.7: Conversion reactor setting

After that, catalytic dehydrogenation reaction is included. The ethyl-benzene catalytic

dehydrogenation takes place in a vertical cylindrical shell and tube reactor (Catalytic
Reactor), which operates isothermally. The reacting gaseous mixture flows inside the tubes
over the catalyst bed, while superheated steam is injected in the reactor’s shell to maintain the
reaction temperature in the requested range (580 - 610 °C). The reaction temperature must not
be increased to a value higher than 610 °C since thermal decomposition of both ethyl-benzene
and styrene would occur.

Next, cooling process is necessary the hot gaseous mixture coming from the Catalytic
is pressurized using pressure regulating valves. Then, the mixture is cooled via Cooler, which
uses cooling water as the heat exchanging agent. A two-phase of vapor-liquid stream is
obtained at the exit of the second cooler, which is then sent to the separation and purification
area.

Then, separation and purification process are required after cooling. The styrene
present at the exit stream of the Conversion Reactor must be separated and purified from the
rest of the other chemicals contained on it, for example water, toluene, etc. To accomplish
this, the two- phase stream obtained at the exit of the coolers is sent to a three-phase separator
known as Liquid-Liquid-Vapor Separator. A gaseous mixture primarily composed by
hydrogen, methane and ethylene as well as minor amounts of water and styrene is obtained at
the top of the Liquid- Liquid-Vapor Separator which is light gaseous stream, while a liquid
stream containing water and certain traces of styrene, benzene and ethylene is obtained at the
bottom of this equipment known as wastewater stream. The middle stream contains mainly
styrene, as well as minor amounts of the other chemicals, and is sent to the Distillation
Column (T-101) which is Benzene- Toluene Column in order to recover both the benzene and
toluene contained on it, and also for styrene concentration.

Figure 2.9: Distillation Column

Both the benzene and toluene are obtained at the top of the Distillation Column (T-
101) while a styrene-rich stream is obtained at the column’s bottom, which is sent to the
Distillation Column (T-102) which is Styrene Column to carry out the final purification step.

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At the Styrene Column, the styrene is obtained at the bottom stream, while the stream
obtained at the top of this column is recycled back to the process and mixed with the pure
ethyl-benzene stream which had previously been pre-heated at the first shell and tube heat
exchanger.

To construct distillation column, short-cut distillation column was use initially to

identify the number of actual stages, the inlet stage and the reflux ratio.

Figure 2.10: Parameter setting in short-cut distillation column

For the first column, benzene was used as light key and styrene as heavy key. The
minimum reflux ratio was calculated as 0.717. However, when insert the value into
distillation column, the reflux ratio can be change optimum reflux ratio can be used by trial
and error. The actual number of trays and optimal feed stage was calculated as shown in the
diagram below.

Figure 2.11: Performance setting in short-cut distillation column

Figure 2.12: Parameter setting in second short-cut distillation column

For second distillation column, ethylbenzene is set as light key while styrene, the
desire product set as heavy key. The mole fraction was assuming to be 0.006 for ethylbenzene
and 0.4 for styrene. The minimum reflux ratio is 10.53. As mentioned above, the reflux ratio
will be change according to the process flow.

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 Figure 2.13: Performance setting in second short-cut distillation column

The actual number of trays and optimal feed stage was calculated as shown in the
diagram above. However, the reflux ratio was set a little higher than minimum reflux ratio.
This causes the actual number of trays lower. The reflux ratio does not important as the real
distillation column does not activate the reflux ratio as the specification. From the short cut,
distillation column T-101 and T-102 is then can be construct.

Figure 2.14: Parameter setting in first distillation column

The first distillation column (T-101) only have 4 stages including condenser and
reboiler. In this process, we assume there is no pressure drop in the distillation column. The
pressure of the distillation column was set higher than the minimum requirement and
optimum pressure, which is 100 kPa. Using the monitor system of this equipment, the reflux
ratio is set at 0.5 and the fixed parameter is the distillate temperature which is 113 . The
distillate temperature is the specification that need to activate as 113 is above the boiling point
of the Benzene and toluene. Hence, the distillation column with full reflux was used. The
distillation column was successfully converged.

Figure 2.16: Parameter setting in second distillation column

The second distillation column (T-102) is set up like the first column. The short-cut
distillation column was also used to identify the stages. In this column, 17 stages is used

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including condenser and reboiler. The pressure of this column remain the same as the first
distillation column which is at the optimum pressure 100 kPa. The parameter that need to be
active in this column is mole fraction of the styrene, due to the requirement of the product is
99.7% purity. The temperature of the distillate (ethylbenzene) should be not higher than 136 ,
its boiling point, hence the temperature of the reboiler was set at 133 . Therefore, total
condenser is selected in this column which is different compare to first column.

The purity was successfully get after the purification process using two distillation
column. However, the requirement of the production in this project is 250000 tonne/year,
99.7% purity. The initial mass flow rate of the feed does not meet the requirement.
Calculation was carried out to obtain the best production requirement. Hence, 47000 kg/h of
the ethylbenzene should be used as the flow rate of feed. The changing of the feed flow rate
does not affect any temperature, pressure and the purity of the production.

RESULT & DISCUSSION

Stream Conditions
Initial feed mixture and heating
Temperature (°C) Initial (E-BENZENE) Final (Stream 2)
30° C 135° C
Pressure (kPa) 101.3 kPa

Flowrate (kgmole/hr) 148.413 kgmole/hr

Compositions (mole percentage) 100% ethylbenzene, C8H10

The production of styrene (C8H8) begins with a sole feed stream containing pure volume
(100%) ethylbenzene (C8H10) at 30 °C and approximate atmospheric pressure of 101.3 kPa.
At these parameter conditions, the colourless C8H10 exist in the liquid state and a total of
148.413 kgmole/hr is fed into the system. The first heater, E-100 is put in the flow path to
preheat the C8H10 from 30° C to 135 °C. The duty of heater, E-100 is 16854.41 kW. After
the exiting from the heater (stream 2) is mixed with recycled stream containing mostly of
ethyl-benzene and some traces of styrene, toluene and benzene coming from the top of the
Distillation Column (T-101) which temperature is at 79.74 °C. The heater is chosen rather
than cooler is because, the reaction that will occur in the conversion reactor, CRV-100 which
converts ethylbenzene into styrene and hydrogen (C 8H10 → C8H10 + H2) is an endothermic
reaction. Therefore, providing a heater as an aid to raise the temperature will result in the
highest conversion rate possible.
Mixture with recycled stream and second heating
Recycled Stream Stream 3 after mixer with recycled stream
Temperature 79.75 °C Temperature 120.8 °C
(°C) (°C)
Pressure (kPa) 100 kPa Pressure (kPa) 100 kPa
Flowrate 101.44 kgmole/h Flowrate 176.02 kgmole/hr
(kgmole/hr) (kgmole/hr)
Compositions 0.00 % Composition 84.33 % ethylbenzene
(mole ethylbenzene (mole 0.00 % styrene
percentage) 0.00 % styrene percentage) 0.00% hydrogen
0.00% hydrogen 15.66 % benzene
99.95 % benzene 0.00 % ethylene

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 0.00 % ethylene 0.01 % toluene
0.05 % toluene 0.00 % methane
0.00 % methane 0.00 % water
0.00 % water

The pre-heated steam, stream 2 is then mixed with recycled stream at the first mixer, MIX-
100. The recycle stream has a molar flowrate of 101.44 kgmole/hr.
After stream 3, the mixture with stream 2 and recycle stream passed through a second heater
and is heated further from 120.8 °C to 250° C with a pressure of 100kPa and the molar
flowrate of 176.02 kgmole/hr. The duty of the second heater E-102 is 54833.57 kW. As the
incoming superheated steam would not be needed too much in amount to mix it so that it can
increase the temperature of the now a vapor mixture of C8H10, water, a little of toluene and
styrene to that of the main reaction condition.
Mixture with superheated steam and heater
Ultimately, the superheated steam would enter the process flow at 630°C and 200 kPa. The
molar flow rate of this superheated steam is 1000 kgmole/hr. After the mixture at MIX-101,
the total molar flow at this point stream 6 is now 177.5 kgmole/hr. The mixture is then heated
again at the third heater, E-102 from 250.6°C to 600°C (Stream 7) at 100 kPa while
composition and molar flowrate remains unchanged before entering the conversion reactor,
CRV-100.
Conversion, heating and cooling
The conversion reactor, CRV-100 where the conversion reaction ethylbenzene to styrene and
hydrogen takes place, the products are split into 2 streams. The top stream is known as vapour
product (Stream 8) while the bottom stream is the liquid product known as condensate. The
molar flow is discovered to be 0 which means that, after the conversion process, the products
remained only at vapour phase. Regardless, styrene, the desired product has composition
before conversion at 0.00 % has risen to 0.3162%.
Temperature (°C) Vapour product (Stream 8) Liquid product (Condensate)
259.6°C 259.6°C
Pressure (kPa) 100 kPa 100 kPa
Flowrate (kgmole/hr) 305.14 kgmole/hr 0 kgmole/hr
Compositions 5.86 % ethylbenzene, C8H10
(mole percentage) 31.62 % styrene, C8H8
30.66 % hydrogen, H2
19.25 % benzene, C6H6
10.22 % ethylene, C2H4
0.96 % toluene, C7H8
0.95 % methane, CH4
0.49 % water H2O

Stream 8 then entered another heater, E-103 and heated the temperature from 259.6°C to
260°C. The duty of the heater, E-103 is 1164.62 kW. The exiting stream (10) is then fed into
a cooler, E-104. The mixture is then cooled down from 260°C to 50°C with a duty of
70885.78 kW. Since the stream 8 has different components of different volatility and boiling
point, 3 phases is presences vapour, liquid and aqueous. Therefore, a 3-phase separator is put
into use to perform the separation to remove undesired products and the condensed steam as
well.
Three phase separation

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Upon using the 3-phase separator, between 60% to 70% hydrogen constituent as the gaseous
outlet at 520.7 kgmole/hr at 300 kPa (Stream 12), and it is then entered into a compressor, K-
100, with a power of 106.8 kW. As a result, hydrogen exits the compressor at a pressure of
379.5 kPa and temperature of 25°C compared to before 300 kPa and 2.05°C respectively. The
overall process flow continues with pure liquid (Stream 13) carrying about 60.75% of C 8H8, at
the rate of 177.8 kgmole/hr into the first distillation column, T-101.
Distillation columns
First distillation
Inlet 13
Outlet Top: BENZENE,
TOULENE
Bottom: 19
Number of stages 4
Condenser pressure 200 kPa
Reboiler pressure 200 kPa
Reflux ratio 0.5

When the number of stages is set to 4, the inlet stream 13, enters at the second tray from the
condenser, it is possible to produce stable stream at the condenser and reboiler if both
pressure is set to 100 kPa. The distillation function works as well when the reflux ratio is
specified at 0.5.
Temperature (°C) BENZENE/ TOULENE LIQUID PRODUCT (19)
-242.7°C 142.5°C
Pressure (kPa) 200 kPa 200 kPa
Flow rate (kgmole/hr) 87.36 kgmole/hr 154.05 kgmole/hr
Compositios (mole 0.13 % ethylbenzene 1.38 % ethylbenzene
percentage) 3.48 % styrene 69.57 % styrene
0.45 % hydrogen 0.00 % hydrogen
84.42 % benzene 27.06 % benzene
10.46 % ethylene 0.00 % ethylene
0.78 % toluene 2.0 % toluene
0.18 % methane 0.00 % methane
0.1 % water 0.00 % water

The vapour flowrate is lower than the liquid’s flowrate and majority of the top vapour product
of the first distillation column is benzene at 84.42%. The higher the vapour pressure, the
higher the volatility is and therefore, making benzene the low-key components in the first
distillation column. Styrene, would be the heavy-key components would be the majority of
the bottom liquid products.
Second distillation
Inlet 19
Outlet Top: BENZENE
Bottom: STYRENE
Number of stages 12
Condenser pressure 100 kPa
Reboiler pressure 100 kPa

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 Reflux ratio 8.0

When the number of stage is set to 12, the inlet stream 19 enters at the 15 th tray from the
condenser, it is possible to produce a stable stream at the condenser and reboiler when both
the pressure is set at 100 kPa. The distillation functions well when the reflux ratio is set at 8,
unlike the first column. To ensure that styrene reaches the highest purity, specification on
component fraction is added for styrene.
Temperature (°C) BENZENE (Recycle Stream) STYRENE
79.74°C 129.2°C
Pressure (kPa) 100 kPa 100 kPa
Flow rate (kgmole/hr) 101.5 kgmole/hr 465.3 kgmole/hr
Compositions (mole 0.00 % ethylbenzene 1.68 % ethylbenzene
percentage) 0.00 % styrene 84.75 % styrene
0.00 % hydrogen 0.00 % hydrogen
99.98 % benzene 11.15 % benzene
00.00 % ethylene 0.00 % ethylene
0.02 % toluene 2.43 % toluene
0.00 % methane 0.00 % methane
0.00 % water 0.00 % water

As for the second distillation column, the top product 101.5 kgmole/hr, BENZENE stream
has a lower volume than the final styrene 465.3 kgmole/hr contains more benzene due to their
differences of volatility. Benzene and Styrene has vapor pressure of 1.28kPa and 0.667 kPa
respectively so Benzene is more volatile than Sytrene, and readily evaporates. The vapor
product would need to be serve as a recycle stream of the entire process flow and mix with
the preheated feed, S2 at MIX-100 as to maintain the long-term consistency of the many
parameters such as purity and molar flow of the products. Finally, the bottom liquid product is
the ultimate final outlet of the whole process flow. It produced the 84.75% styrene, while the
rest being unreacted benzene, ethylbenzene and toulene, at a pressure of 100 kPa. Although
the final product is not as pure as it could possibly get, it is still acceptable in the industry. In
a nutshell, this plant design can still be improved.
To achieve the 99 % of the yield of styrene, it either can be improved by increase the feed
flow rate and also the distillate rate in first distillation column. Apart from that, in the industry
process the heat required also an important with the investment cost and also lead to pollution
issue. To maximum the heat recovery, the heater can be change to heat exchanger to reducing
the utilities cost.
Conclusion
In conclusion, the superpro designer software was simulating successfully the
production process of styrene via catalytic dehydrogenation of ethyl-benzene. Ethyl-
benzene was preheating and mix with recycle stream in early stage of process. As the
result shown, the styrene composition remains 0%. This also known as pre-treatment.
Next, the reaction takes place in the conversion reactor to convert ethyl-benzene to
styrene and hydrogen. The product was split into vapour product and liquid product.
The composition of styrene was increase to 31.62%. 3-phase separator perform the
separation to remove undesired products and the condensed steam as well. In
distillation column, the vapour flowrate is lower than the liquid flow rate and majority
of the composition is benzene (84.42%).%. The higher the vapour pressure, the higher
the volatility is and therefore, making benzene the low-key components in the first
distillation column. Styrene, would be the heavy-key components would be the
majority of the bottom liquid products. In second distillation, the inlet stream possible

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produce a stable stream at the condenser and boiler. Benzene is more volatile than
styrene and easily to evaporate. Benzene required a recycle stream to mix with the
preheated feed to maintain purity and molar flow of the product and bottom liquid
product was obtained. It produced the 84.75% styrene, the highest purity composition
in the plant.
Reference:
1. Snyder, J. & Subramaniam, B. (1994). A Novel Reverse Flow Strategy for
Ethylbenzene Dehydrogenation in a Packed-Bed Reactor. Chem. Eng. Sci ., 49, 5585-
5601.
2. Auli, N., Sakinah, M., Bakri, A., Kamarudin, H. & Norazian, M. (2013).
Simulation of Xylitol Production: A Review. Australian Journal of Basic and Applied
Sciences, 7(5), 366-372.
3. Speight, J. (2002). Chemical and Process Design Handbook. New York: The
McGraw-Hill Companies, Inc.

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