Puianu Monica

IIPCB , 2017

Styrene production

Contents
1. Short description of the
process......................................................................................................... 2
2.
Simulations.....................................................................................................................
.....................3

2.1. Aspen Plus

V8.6.........................................................................................................................................
4
2.1.1. Model of the
process........................................................................................................................ 4
2.1.2. Simulation
results.............................................................................................................................. 4
2.1.3. Model
validation.............................................................................................................................
..6
2.1.4. Sensitivity
analysis.............................................................................................................................6
2.1.5.
Conclusions.........................................................................................................................
................8

3.References..................................................................................................................
..........................9

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1. Short description of the process
Styrene, also known as phenylethylene, vinylbenzene, styrol or cinnamene, is
an important industrial unsaturated aromatic monomer. It occurs naturally in small
quantities in some plants and foods. It is a colorless liquid with an aromatic odor, is
infinitely soluble in acetone, carbon tetrachloride, ether, n-heptane and ethanol [1]
[2]. Other important properties of styrene are listed in Table 1.
Table 1. Physical properties of styrene monomer [1]

Property Value Unit

C at
Boiling point 145 1atm
Freezing point -30.6 C
Autoignition
temperature 490 C
Explosive limits in
air 1.1-1.6 %
Heat of
polymerization 74.48 kJ/mol

There are two process routes commercially used for the manufacture of
styrene: dehydrogenation and coproduction with propylene oxide. Both routes use
ethylbenzene as an intermediate. Styrene is a commodity chemical, traded in large
volumes domestically and internationally. The product specifications are largely
dictated by the market. The minimum purity is usually 99.8% which can be easily
met in a well-operated plant of modern design. Styrene is the monomer used to
make polystyrene which has multiple uses, the most common being in packaging
and insulated Styrofoam beverage cups.
In this work the production of styrene from dehydrogenation of ethylbenzene
was studied. The process flow diagram is shown in Figure 1.

2
 Figure 1. Reference styrene production process flow-sheet

Ethylbenzene feed is mixed with recycled ethylbenzene, heated and then mixed
with high-temperature superheated steam. Steam is used in the process in order to
drive the equilibrium reaction shown in

3
 Reaction 1 to the right by reducing the concentration of all components.
Because styrene production is highly endothermic, the superheated steam also
provides energy to drive the reaction. Decomposition of ethylbenzene to
benzene and ethylene(Reaction 2) and the hydrodealkylation reaction resulting
in methane and toluene (Reaction 3), are unwanted side reactions.

Reaction 1

Reaction 2

Reaction 3

The reactants enter a two adiabatic packed bed with inter-heating. The products
are cooled, producing steam from the high-temperature reactor effluent. The
cooled product stream in then sent to a three phase separator where the light
gases, organic liquid and water are separated in different streams. The gas
stream is further purified and used as a source of hydrogen elsewhere in the
plant. The benzene-toluene stream is returned as a feed stream to a
petrochemical facility. The organic stream containing the desired product is
distilled once to remove the benzene and toluene and again to separate the
unreacted ethylbenzene from the styrene product and recycled.
The styrene product can spontaneously polymerize at higher
temperatures and for this reason is necessary to maintain the temperature less
than 125C. Because this is less than styrene's normal boiling point and
because low pressure pushes the equilibrium to the right, much of this process
is run at vacuum [3].

2. Simulations
Styrene production process was modeled using the simulation
softwareand AspenPlus V8.6. The SRK (Soave-Redlich-Kwong) thermodynamic
package was chosen for the simulations. The inlet stream of the raw materials
as taken from literature as presented in Table 2.
Table 2. Inlet streams
characterization

Stream 1 4 List of equipments used

Number (Ethylbenz (High Pressure in the
ene) Steam) simulation:
Temperature
[C] 136 253.7
Pressure [bar] 2 42.37 compressors: 1
Vapor mole heat exchangers:
fraction 0 1 5
Total flow
[kmol/h] 123.42 4016.3 fired heater: 1
Component flowrates
[kmol/h] pumps: 4
Water 0 4016.3 reactors: 2
Ethylbenzene 121 0 towers: 2
Styrene 0 0 vessels: 2

4
 Hydrogen 0 0
Benzene 1.21 0
Toluene 1.21 0
Ethylene 0 0
Methane 0 0

2.1. Aspen Plus V8.6

2.1.1. Model of the process

The flowsheet build in Aspen Plus that describes the styrene production
process can be found in APENDIX 2. In this case too, an additional separator was
added to further separate the organic phase from the light gases and water.

The reactors were modeled as adiabatic stoechiometric reactors, in the same way
as in
CHEMCAD.
For the three-phase separator a V-DRUM1 was selected from the
Separators Palette and for parameterization the temperature, pressure and valid
phases: Vapor-Liquid-DirtyWater, was specified.
In case of the towers, two distillation columns were chosen and
parameterized as it can be seen in Figure 10.

Figure 10. Distillation columns parameterization in Aspen Plus

2.1.2. Simulation results

The most important results obtained with Aspen Plus simulation software, are
presented below. The results from the three-phase separator are presented in
Figure 12. In this case too, the

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separator does not perform an ideal separation and for this reason another
component separator is added in order to separate all the light gases and water
from the organic mixture as water forms azeoptropes with all of the organic
components: benzene, toluene, styrene and ethylbenzene:

Figure 11. Azeotropes search results from Aspen Plus

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 Figure 12. Three-phase separator results from Aspen Plus

2.1.3. Model validation

Data used for validation was taken from reference [3]:

Table 4. Validation of Aspen Plus model

21 26 23 22
(Benzene+Tolu (Wastewater
Stream Number (Styrene) ene) (Hydrogen) )
Mod Mode Mode
Ref el Ref Model Ref l Ref l
Temperature
[C] 123.8 124.3 70 75.8 202.2 150.9 65 33.1
Pressure [bar] 2 2 2 2 1.4 1.4 2 2
Vapor mole
fraction 0 0 0 0 1 1 0 0
Total flow
[kmol/h] 120.08 98.943 3.34 2.746 120.2 193.673 3000 2936.75

Component flowrates
[kmol/h]

Water 0 0 0 0 0 63.352 3000 2936.65

Ethylbenzene 0.05 0 0.1 0.679 0 10.989 0 0.054
Styrene 120.03 98.943 0 0 0 9.601 0 0.001
Hydrogen 0 0 0 119.38 107.924 0 0.033
Benzene 0 1.37 0.711 0 0.638 0 0.006
Toluene 0 1.86 1.356 0 0.438 0 0.003
Ethylene 0 0 0 0.16 0.144 0 0.001
Methane 0 0 0 0.65 0.586 0 0.001

As it can be seen from Table 4, there are small differences between the
simulated and the literature data, thus the can say that the model can be
used successfully to describe the styrene production process.

2.1.4. Sensitivity analysis

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 A sensitivity analysis was performed in Aspen Plus to see the effect
of the pressure change inside the three-phase separator. The pressure
was changed between 0.65 bar and 1 bar and the flow variation of the
outputs was investigated. The results are presented in
Figure 13 to Figure 16 .

SENSIT1 - Results
Summary
2950
H2O KMOL/HR

2945

2940

2935
RKMOL/H

2930

2925

2920

2915
0.65 0.66 0.67 0.68 0.69 0.70 0.71 0.72 0.73 0.74 0.75 0.76 0.77 0.78 0.79 0.80 0.81 0.82 0.83 0.84 0.85 0.86 0.87 0.88 0.89 0.90 0.91 0.92 0.93 0.94 0.95 0.96 0.97 0.98 0.99 1.00
VARY1 B29 PARAM PRES BAR

Figure 13. Water flow variation in the outlet of the three-phase at various
pressures

SENSIT1 - Results
Summary
113.5
H2 KMOL/HR
113.0

112.5

112.0

111.5

111.0
KMOL/HR

110.5

110.0

109.5

109.0

108.5

108.0

107.5
0.65 0.66 0.67 0.68 0.69 0.70 0.71 0.72 0.73 0.74 0.75 0.76 0.77 0.78 0.79 0.80 0.81 0.82 0.83 0.84 0.85 0.86 0.87 0.88 0.89 0.90 0.91 0.92 0.93 0.94 0.95 0.96 0.97 0.98 0.99 1.00
VARY 1 B29 PARAM PRES BAR

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 Figure 14. Hydrogen flow variation in the outlet of the three-phase at
various pressures

SENSIT1 - Results
Summary
1.60
BEN
1.55 Z KMOL/HR
1.50 TOL KMOL/HR
1.45
1.40
1.35
1.30
1.25
1.20
KMOL/HR1.1
0

1.15

1.05
1.00
0.95
0.90
0.85
0.80
0.75
0.70
0.65 0.66 0.67 0.68 0.69 0.70 0.71 0.72 0.73 0.74 0.75 0.76 0.77 0.78 0.79 0.80 0.81 0.82 0.83 0.84 0.85 0.86 0.87 0.88 0.89 0.90 0.91 0.92 0.93 0.94 0.95 0.96 0.97 0.98 0.99 1.00
VARY 1 B29 PARAM PRES BAR

Figure 15. Benzene and toluene flow variation in the outlet of the three-phase at various
pressures

SENSIT1 - Results
Summary
110.5
110.0 STYR KMOL/HR
109.5
109.0
108.5
108.0
107.5
107.0
KMOL/HR

106.5
106.0
105.5
105.0
104.5
104.0
103.5
103.0
102.5
102.0
0.65 0.66 0.67 0.68 0.69 0.70 0.71 0.72 0.73 0.74 0.75 0.76 0.77 0.78 0.79 0.80 0.81 0.82 0.83 0.84 0.85 0.86 0.87 0.88 0.89 0.90 0.91 0.92 0.93 0.94 0.95 0.96 0.97 0.98 0.99 1.00
VARY 1 B29 PARAM PRES BAR

Figure 16. Styrene flow variation in the outlet of the three-phase at

various pressures

As it can be seen from the sensitivity analysis results, with the increase of
the pressure at a constant temperature of 65C, a better separation of the
phases present in the three-phase separator takes place.

2.1.5. Conclusions

The results obtained using process simulator Aspen Plus to describe the
styrene production process are in line with literature data and proved to be
satisfying.
The sensitivity analysis conducted showed that when increasing the
pressure at a constant temperature, in the three-phase separator, a better
separation can be obtained.

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3. References

[1] K. Othmer, "Styrene," in Encyclopedia of Chemical Technology, New York, John

Wiley & Sons, 2006.

[2] D. H. James and W. M. Castor, "Styrene," 2000.

[3] R. Turton, R. C. Bailie, W. B. Whiting, J. A. Shaeiwitz and D. Bhattacharyya,

"Styrene Production," in
Analysis, synthesis, and design of chemical processes 4th Edition, Michigan,
Pearson, 2012, pp. 1116-1124.

APENDIX 1

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