ABSTRACT

Styrene is a precursor to many polymer products such as polystyrene,

acrylonitile butadiene styrene (ABS), styrene-acrylonitrile, and various styrene-
butadiene products. These materials are used around the world in a variety of
ways including food storage, packaging, and automobile parts. The market for
styrenics has seen overall growth in the previous decade despite a recent down
year. The market is expected to recover and see large gains in the near future.
Therefore, now is an excellent time to join the market, particularly if current
styrene production cannot meet future demand.
Production of styrene is world-wide, and dates back more than 50 years.
However, new variations on established processes are continually being
developed, and new companies are building plants or buying out older
producers.The feedstock for all commercial styrene manufacture is still
ethylbenzene. This is converted to a crude styrene that requires finishing to
separate out the pure product.
In this project, we are going to construct a model of producing styrene by the
dehydrogenation of ethylbenzene with the purity of 99.9%. Our target of
productivity is 40000 Tons/year with assumption that we operates 7800 hours
per year. We choose this dehydrogenation method since it is less expansive
than other processes applied to product styrene. Moreover, the waste stream
contains only water instead of several chemicals, which are very difficult to
handling, compared to other processes. However, the main disadvantage and
inefficiency of the dehydrogenation process is the lower selectivity on the
comparison with different methods.
 Table of contents

1. Input information............................................................................................4
1.1 Material and product information.............................................................4
1.1.1 Material.............................................................................................5
a. Ethylbenze..........................................................................................5
1.1.2 Product..............................................................................................5
a. Styrene................................................................................................5
1.1.3 By- products......................................................................................5
a. Toluene...............................................................................................5
b. Benzene..............................................................................................6
1.2 Reaction information................................................................................6
1.2.1 Reactions...........................................................................................6
1.2.2 Kinetic Study.....................................................................................8
1.2.3 Catalysts..........................................................................................8
1.3 Process description...................................................................................8
1.4 Cost data.................................................................................................11
2. Decision for Batch Process or Continuous process......................................11
2.1 Definition of Batch Process....................................................................11
2.2 Definition of Continuous Process...........................................................11
2.3 Comparison of two processes.................................................................12
3. Modeling......................................................................................................14
4. Input and Output Structure...........................................................................17
4.1 Material balance.....................................................................................17
4.2 Economic potential.................................................................................21
5. Recycle structure..........................................................................................22
5.1 Number of reactors.................................................................................23
5.2 Reactor configuration.............................................................................24
5.3 Recycle stream.......................................................................................25
6. Separation Structure.....................................................................................25
6.1 Separation configuration........................................................................25
6.2 Separation sequence...............................................................................25
7. Heat integration............................................................................................26
7.1 Pinch analysis.........................................................................................27
7.2 Heat Exchanger Network (HEN)............................................................28
REFERENCES.................................................................................................32
 List of tables

Table 1: Properties of chemical..........................................................................4

Table 2: Prices of material and product............................................................11
Table 3: Comparison between Batch Process vs Continuous Process..............12
Table 4: Equipment in design...........................................................................15
Table 5: Steam data of styrene production design............................................17
Table 6: Molar component of styrene production design.................................19

List of figures

Figure 1: Structure of Ethyl Benzene.................................................................5

Figure 2: Structure of Styrene............................................................................5
Figure 3: Structure of Toluene...........................................................................5
Figure 4: Structure of Benzene...........................................................................6
Figure 5: Information of preliminary design....................................................10
Figure 6: Design modelling of styrene production...........................................14
Figure 7: The input-output structure.................................................................17
Figure 8: Capital cost in Aspen........................................................................21
Figure 9: The recycle structure.........................................................................23
Figure 10: Parameters of reactor......................................................................23
Figure 11: Parameters of reactor......................................................................24
Figure 12: Fixed bed reactors stucture..............................................................25
Figure 13: Configuration Separation................................................................25
Figure 14: Distillation Column T-100..............................................................26
Figure 15: Distillation Column T-101..............................................................27
Figure 16: Composite curve.............................................................................30
Figure 17: Grand Composite curve..................................................................31
1. Input information
1.1 Material and product information
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 compound with the chemical formula
C6H5CH=CH2. Styrene has a molar mass of 104.15 g/mol and it has the density
of 0.909g/cm3. 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.
Table 1: Properties of chemical

Solubiliy
Boiling Melting
Density in water
Chemicals Symbol Characteristics point point
(g/cm3) at 25oC
(oC) (oC)
(g/L)

Benzene C6H6 5.5 80.1 0.8786 1.79

Colorless liquid
Toluene C7H8 110.6 -93.0 0.8669 0.53

Methane CH4 -161.6 -182.5 0.7171 x

Colorless gas
Hydrogen H2 -252.9 -259.2 0.0899 x

Colorless liquid
Ethyl
C8H10 with aromatic 136 -95.0 0.866 4.45x10-3
Benzene
odor

Colorless oily
Styrene C8H8 145 -30.0 0.909 0.03
liquid

1.17 x
Ethylene C2H4 Colorless gas -103.7 -169.2 0.131
10-3
1.1.1 Material
a. Ethyl Benzene

Figure 1: Structure of Ethyl Benzene

Ethylbenzene is an organic compound with the formula C 6H5CH2CH3. It is a
highly flammable, colorless liquid with an odor similar to that of gasoline. This
monocyclic aromatic hydrocarbon is important in the petrochemical industry as
an intermediate in the production of styrene, the precursor to polystyrene, a
common plastic material. In 2012, more than 99% of ethylbenzene produced
was consumed in the production of styrene.
1.1.2 Product
a. Styrene

Figure 2: Structure of Styrene

Styrene is an organic compound with the chemical formula C6H5CH=CH2. This
derivative of benzene is a colorless oily liquid, although aged samples can
appear yellowish. The compound evaporates easily and has a sweet smell,
although high concentrations have a less pleasant odor. Styrene is the precursor
to polystyrene and several copolymers.
1.1.3 By - products
a. Toluene

Figure 3: Structure of Toluene

Toluene is an aromatic hydrocarbon. It is a colorless, water-insoluble liquid
with the smell associated with paint thinners. It is a mono-substituted benzene
derivative, consisting of a methyl group (CH₃) attached to a phenyl group. As
such, its IUPAC systematic name is methylbenzene. Toluene is predominantly
used as an industrial feedstock and a solvent.
b. Benzene

Figure 4: Structure of Benzene

Benzene is an organic chemical compound with the molecular formula C 6H6.
The benzene molecule is composed of six carbon atoms joined in a planar ring
with one hydrogen atom attached to each. As it contains only carbon and
hydrogen atoms, benzene is classed as a hydrocarbon.
1.2 Reaction information
1.2.1 Reactions
85% of commercial production of styrene is accounted for dehydrogenation of
ethylbenzene to styrene. The reaction is performed in vapor phase with steam
over a catalyst consisting primarily of iron oxide. The reaction is endothermic
and can either be conducted adiabatically or isothermally. In reality, both
methods can be applied.
The major reaction is the reversible, endothermic conversion of ethylbenzene
to styrene and hydrogen:

(1)
C6H5CH2CH3 ↔ C6H5CH=CH2 ∆H (600°C) = 124.9 kJ/mol
+Ethylbenze(2)
H2 StyreneHydrogen

This reaction proceeds thermally with low yield and catalytically with high
yield. As it is a reversible gasphase reaction producing 2 mol of product from 1
mol of starting material, low pressure favors the forward reaction.
Competing thermal reactions degrade ethylbenzene to benzene, and also to
carbon:

(3)
C6H5CH2CH3 →C6H6 +C2H4 ∆H = 101.8 kJ/mol
Ethylbenze BenzeneEthylene

Styrene also reacts catalytically to toluene:

(4)
C6H5CH2CH3 +H2→C6H5CH3 + CH4 ∆H = – 64.5 kJ/mol
EthylbenzeHydrogen TolueneMethane

The problem with carbon production is that carbon is a catalyst poison. When
potassium is incorporated into the iron oxide catalyst, the catalyst becomes self-
cleaning (through enhancement of the reaction of carbon with steam to
give carbon dioxide, which is removed in the reactor vent gas).

Typical operating conditions in commercial reactors are ca. 620 °C and as low
a pressure as practicable.
The overall yield depends on the relative amounts of catalytic conversion to
styrene and thermal cracking to byproducts. At equilibrium under typical
conditions, the reversible reaction results in about 80% conversion of
ethylbenzene. However, the time and temperature necessary to achieve
equilibrium give rise to excessive thermal cracking and reduced yield, so most
commercial units operate at conversion levels of 50 – 70 wt%, with yields of
88 – 95 mol%.
Dehydrogenation of ethylbenzene is carried out in the presence of steam, which
has a threefold role:
1. It lowers the partial pressure of ethylbenzene, shifting the equilibrium
toward styrene and minimizing the loss to thermal cracking
2. It supplies the necessary heat of reaction
3. It cleans the catalyst by reacting with carbon to produce carbon dioxide
and hydrogen.
1.2.2 Kinetic study
21.708
= 10.177 × 1011 exp( − )
1 𝑏
RT
7804
= 20.965 exp( )
2 𝑡 ℎ𝑑
RT
49675
= 7.206 × 10 exp( −
11
)
3 𝑏
RT
26857
= 1.724 × 106 exp( − )
4 𝑏 ℎ𝑑
RT
Where p is in bar, T is in K, R = 1.987 cal/mol K, and ri is in mol/m3-reactor
s. The styrene reaction may be equilibrium limited, and the equilibrium
constant is given as below equation:
𝑡ℎ𝑑 P
K = ( 𝑏
)
14852.6
ln K = 15.5408 −
T
1.2.3 Catalysts
Many catalysts have been described for this reaction. One catalyst – Shell 105,
also used in this experiment – dominated the market for many years, and was
the first to include potassium as a promoter for the water-gas reaction. This
catalyst is typically 84.3% iron as Fe2O3 , 2.4% chromium as Cr2O3 , and
13.3% potassium as K2CO3. It has good physical properties and good activity,
and it gives fair yields.
In recent years, the situation has become more complex. The market has
become more competitive, causing manufacturers to seek new catalysts that
produce higher yields without compromising activity or physical properties, or
catalysts that meet specific requirements. A catalyst life of ca. two years is
claimed.
1.3 Process description
The process flow diagram is shown in Figure 5. Ethylbenzene feed is mixed
with recycled ethylbenzene, heated, and then mixed with high-temperature,
superheated steam. Steam is an inert in the reaction, which drives the
equilibrium shown in Equation 1 to the right by reducing the concentrations of
all components. Because styrene formation is highly endothermic, the
superheated steam also provides energy to drive the reaction. Decomposition of
ethylbenzene to benzene and ethylene, and hydrodealkylation to give methane
and toluene, are unwanted side reactions shown in Equations 3 and 4. The
reactants then enter two adiabatic packed beds with interheating. The products
are cooled, producing steam from the high-temperature reactor effluent. The
cooled product stream is sent to a three-phase separator, in which light gases
(hydrogen, methane, ethylene), organic liquid, and water exit in separate
streams. The hydrogen stream is further purified as a source of hydrogen
elsewhere in the plant. The benzene/toluene stream is currently returned as a
feed stream to the petrochemical facility. The organic stream containing the
desired product is distilled once to remove the benzene and toluene and
distilled again to separate unreacted ethylbenzene for recycle from the styrene
product. The separator consists of 2 towers for distillation. Since styrene and
ethyl benzene have very similar boiling points and styrene tends to coincide
easily, the process of separating raw styrene from ethyl benzene must be
performed under these conditions:
- Number of large disks is about 60 and the reflux index is high
- Perform under vacuum to reduce the tower bottom temperature to below
108°C and increase the evaporation temperature
- Have polymerization inhibitors
- Low pressure drop in condenser devices and in disc
The styrene product can spontaneously polymerize at higher temperatures.
Because product styrene is sent directly to the polymerization unit, experience
suggests that as long as its temperature is maintained at less than 125°C, there
is no spontaneous polymerization problem. Because this is less than styrene’s
normal boiling point, and because low pressure pushes the equilibrium in
Equation 1&2 to the right, much of this process is run at vacuum.
1.4 Cost data
Table 2: Prices of chemical and product
Component Cost (USD/ton)
Ethyl benzene 1000
Styrene 7410
Waste water 56
Steam 58
H2 83.33
CH4 100
C2H4 7
Benzene 866.67
Toluene 960

2. Decision for Batch Process or Continuous Process

2.1 Definition of Batch Process
Batch process refers to a process that consists of a sequence of one or more
steps that should be performed in a defined order. A finite quantity of the
product is produced at the end of the sequence, which is repeated in order to
produce another product batch.
Generally, batch is a process that results in the production of limited quantities
of material through subjecting quantities of raw materials to a set of processing
activities over a significant period of time with the use of one of more piece of
equipment. Processing of successive batches must wait until the completion of
the current batch.
2.2 Definition of Continuous Process
A continuous process, on the other hand, refers to a processing that involves
moving a single work unit at a time between every step of the process without
any breaks in time, substance, sequence or extend. As the name suggests, the
flow of product or material is continuous. Every machine operates in a steady
state and performs a certain processing function.
For majority of applications, continuous flow saves costs, energy and time.
When this process is properly implemented, it can reduce waste, improve
quality by making it easier to identify and correct errors, increase productivity
and adapt to the needs of customers more efficiently than batch processing.
2.3 Comparison of two processes
Evaluating the advantage and disadvantages of every type of process is
important to determine which one would work best for you.
When it comes to the cost of equipment, continuous process is more expensive
than the low process. However, when comparing the production rate,
continuous have lower rate than the continuous one. The shut-down times in
continuous process is rare, whereas it happens quite more often in a batch
process.
If you don’t have enough manpower to perform the work, you can benefit more
with a continuous process, as it requires a fewer people than its counterpart. In
terms of ease of automation, batch process is relatively more difficult than the
continuous process.
Both continuous and batch processes are vital in the production of materials or
products. Having a deeper understanding of each of them can help you make an
informed decision in the end.
Table 3: Comparison between Batch Process vs Continuous Process
Batch Process Continuous Process
Definition Batch process refers to a Continuous process
process that involves a refers to the flow of a
sequence of steps single unit of product
followed in a specific between every step of
order. the process without any
break in time, substance
or extend.
Coordination Scheduling is done to Each machine performs
maintain the timing a certain processing
 between move to earth. function and they
operates in a steady
state.
Quantities produced A whole unit of products Large quantities of
are produced. products are obtained.
Fouling Batch process is Continuous process is
involved if the fouling involved if fouling is
expectations are high not considered
Product life span Short, 1-2 years Longer than batch
process
Cost of factory Low cost equipment High cost equipment
equipment
Controlling Batch process can be Control batch process
controlled very easily requires sophisticated
control systems
Shut Down times Often Rare
Workforce Small workforce is Continuous process is
needed generally available in
fully automated plants.
If not, large workforce
will be necessary.
3. Modeling
Table 4: Equipment in design
Abbreviation Equipment Input > Output Parameter

P-100 Pump 15 > Wastewater Centrifugal/electric drive

Stainless steel
Outlet pressure = 200 kPa
Efficiency = 80%
Duty: Q8 = 3.542e+004 kJ/h
P-104 Pump 20 > Styrene Centrifugal/electric drive
Stainless steel
Outlet pressure = 200 kPa
Efficiency = 80%,
Duty: Q10 = 828.4 kJ/h
P-105 Pump 19 > 24.1 Centrifugal/electric drive
Stainless steel
Outlet pressure = 200 kPa
Efficiency = 80%,
Duty: Q9 = 73.37 kJ/h
E-100 Heat 25 > 26 & 8 > 9 316 Stainless steel
exchanger A= 226 m2
Boiling in shell, process fluid in
tubes
1 shell – 2 tube passes
Inlet temperature in Tube
= 438.9 oC
Outlet temperature in Tube
= 554.8 oC
Inlet temperature in Tube
= 800 oC
Outlet temperature in Tube
= 464.6 oC
Pressure Drop in Tube
= 10.87 kPa
Pressure Drop in Tube
= 5.186 kPa
E-101 Cooler 6.2 > 6.3 Carbon steel
Inlet temperature = 793.8 oC
Outlet temperature = 450 oC
Pressure Drop = 0.00 kPa
Duty: Q3 = 2.069e+008 kJ/h
E-102 Cooler 10 > 11 Carbon steel
Inlet temperature = 551.2 oC
Outlet temperature = 267 oC
Pressure Drop = 19.1 kPa
Duty: Q4 = 1.641e+008 kJ/h
E-103 Cooler 11 > 12 Carbon steel
Inlet temperature = 267.0 oC
Outlet temperature = 180 oC
Pressure Drop = 5 kPa
Duty: Q5 = 4.721e+007 kJ/h
E-104 Cooler 12 > 13 Carbon steel
Inlet temperature = 180 oC
Outlet temperature = 30 oC
Pressure Drop = 3.7 kPa
Duty: Q6 = 7.424e+008 kJ/h
E-105 Heater HPS > 5 Carbon steel
Inlet temperature = 234 oC
Outlet temperature = 800 oC
Pressure Drop = 500 kPa
Duty: Q1 = 1.12e+009 kJ/h
E-106 Heater 2>3 Carbon steel
Inlet temperature = 134 oC
Outlet temperature = 240 oC
Pressure Drop = 30 kPa
Duty: Q2 = 2.981e+006 kJ/h
MIX-100 Mixer 3 & 6.3 > 7 Pressure drop = 0 kPa
MIX-101 Mixer Ethylbenzene & Pressure drop = 0 kPa
24.2 > 2
TEE-100 Splitter 6 > 1&25 Pressure drop = 0 kPa
K-100 Expander 14 > 23 Carbon steel
Outlet pressure = 140 kPa
Outlet temperature = 67.75 oC
Efficiency = 60%
FPR-100 Reactor 7>8 316 Stainless steel, packed bed
Cylindrical catalyst pellet
(1.6mm x 3.2mm)
Void fraction = 0.4
Height = 9.26 m
Diameter = 1.85 m
FPR-101 Reactor 9 > 10 316 Stainless steel, packed bed
Cylindrical catalyst pellet
(1.6mm x 3.2mm)
Void fraction = 0.4
Height = 9.26 m
Diameter = 1.85 m
VLV-100 Control 6.1 > 6.2 Pressure drop = 2340 kPa
valve Pressure outlet = 160 kPa
Valve opening = 50%
 V-100 3 phase 13 > 14 & 15 & Carbon steel
separator 16 Pressure drop inlet = 0 kPa
Pressure drop vapor outlet = 0
kPa
V= 26.8 m2
X-100 Splitter 16 > 16.1 & 16.2 Carbon steel
& 16.3 Pressure drop = 0 kPa
T-100 Distillation 16.1 > Carbon steel
column Benzene/Toluen Height = 18.6 m
e & 18 Diameter = 3 m
61 sieve trays
54% efficient
Feed on tray 31
T101 Distillation 18 > 19 & 20 Carbon steel
column Height = 24.1 m
Diameter = 6.9 m
158 bubble cap trays
55% efficient
Feed on tray 78

4. Input and Output structure

Figure 7: The input and output stucture

4.1 Material balance
Based on the Aspen Hysys App, we have calculated the molar flow rate of the
feed stream and the product stream
Table 5: Stream data of the styrene production design
Unit EB 2 3 HPS 5
Vapour
fraction 0 0 1 0 1
Temperature ℃ 136 134.0412 240 234 800
Pressure kPa 200 200 170 3000 2500
Molar flow Kmol/h 51 53.38435 53.38435 20000 20000
 Mass flow Kg/h 5393.425 5646.49 5646.49 360302 360302
Liquid
m3/h 6.198485 6.489351 6.489351 361.0291 361.0291
volume flow
Heat flow kJ/h 585920.2 588548.4 3569445 -5.4E+09 -4.3E+09

Unit 6.1 6.2 6.3 7 8

Vapour
1 1 1 1 1
fraction
Temperature ℃ 800 793.7503 450 445.3972 438.8702
Pressure kPa 2500 160 160 160 150
Molar flow Kmol/h 15000 15000 15000 15053.38 15085.21
Mass flow Kg/h 270226.5 270226.5 270226.5 275873 275873.1
Liquid
m3/h 270.7718 270.7718 270.7718 277.2612 277.9432
volume flow
Heat flow kJ/h -3.2E+09 -3.2E+09 -3.4E+09 -3.4E+09 -3.4E+09

Unit 9 10 11 12 13
Vapour
1 1 1 1 0.003492
fraction
Temperature ℃ 554.8269 551.1692 267 180 30
Pressure kPa 139.1344 129.1344 110 105 101.325
Molar flow Kmol/h 15085.21 15103.23 15103.23 15103.23 15103.23
Mass flow Kg/h 275873.1 275873.1 275873.1 275873.1 275873.1
Liquid
m3/h 277.9432 278.3296 278.3296 278.3296 278.3296
volume flow
Heat flow kJ/h -3.3E+09 -3.3E+09 -3.5E+09 -3.5E+09 -4.3E+09

Unit 14 15 16 16.1 16.2

Vapour
1 0 0 0 0.77139
fraction
Temperature ℃ 30 30 30 30 99.95989
Pressure kPa 101.325 101.325 101.325 101.325 101.325
Molar flow Kmol/h 52.74409 14997.8 52.68524 52.64023 0.028079
Mass flow Kg/h 215.228 270186.7 5471.216 5470.676 0.50585
Liquid
m3/h 1.560544 270.7324 6.036687 6.035691 0.000507
volume flow
Heat flow kJ/h -423521 -4.3E+09 5207418 5214400 -6984

16.3 Benzene/ 18 19 20
Unit
Toluen
Vapour
1 0 0 0 0
fraction
Temperature ℃ 30 69.3735 138.5715 90.15187 147.0447
Pressure kPa 101.325 45 85 25 105
Molar flow Kmol/h 0.016933 1.003419 51.63681 2.384354 49.25246
Mass flow Kg/h 0.034306 87.85987 5382.816 253.0644 5129.752
 Liquid
m3/h 0.000489 0.100452 5.935239 0.290866 5.644373
volume flow
Heat flow kJ/h 2.722857 33080.03 6246968 2554.872 6307141

Unit Styrene Wastewater 23 24.1 24.2

Vapour
fraction 0 0 1 0 0
Temperature ℃ 147.0957 30.00918 67.75158 90.23216 90.23216
Pressure kPa 200 200 140 200 200
Molar flow Kmol/h 49.25246 14997.8 52.74409 2.384354 2.384354
Mass flow Kg/h 5129.752 270186.7 215.228 253.0644 253.0644
Liquid
m3/h 5.644373 270.7324 1.560544 0.290866 0.290866
volume flow
Heat flow kJ/h 6307966 -4.3E+09 -363561 2628.244 2628.243

Unit 25 26
Vapour
fraction 1 1
Temperature ℃ 800 464.5895
Pressure kPa 2500 2494.814
Molar flow Kmol/h 5000 5000
Mass flow Kg/h 90075.5 90075.5
Liquid m3/h
volume flow 90.25728 90.25728
Heat flow kJ/h -1.1E+09 -1.1E+09

Table 6: Molar component of the styrene production design

Unit EB 2 3 HPS 5
Benzene kgmole/h 0.5 0.5 0.5 0 0
E-Benzene kgmole/h 50 52.37895 52.37895 0 0
Ethylene kgmole/h 0 0 0 0 0
H2O kgmole/h 0 0 0 20000 20000
Hydrogen kgmole/h 0 0 0 0 0
Methane kgmole/h 0 0 0 0 0
Styrene kgmole/h 0 0.000238 0.000238 0 0
Toluene kgmole/h 0.5 0.505164 0.505164 0 0

Unit 6.1 6.2 6.3 7 8

Benzene kgmole/h 0 0 0 0.5 0.500016
E-Benzene kgmole/h 0 0 0 52.37895 20.55804
Ethylene kgmole/h 0 0 0 0 4.70E-05
H2O kgmole/h 15000 15000 15000 15000 15000
Hydrogen kgmole/h 0 0 0 0 31.82091
Methane kgmole/h 0 0 0 0 2.32E-05
Styrene kgmole/h 0 0 0 0.000238 31.82114
Toluene kgmole/h 0 0 0 0.505164 0.505158
 Unit 9 10 11 12 13
Benzene kgmole/h 0.500016 0.500139 0.500139 0.500139 0.500139
E-Benzene kgmole/h 20.55804 2.530042 2.530042 2.530042 2.530042
Ethylene kgmole/h 4.70E-05 0.000471 0.000471 0.000471 0.000471
H2O kgmole/h 15000 15000 15000 15000 15000
Hydrogen kgmole/h 31.82091 49.84888 49.84888 49.84888 49.84888
Methane kgmole/h 2.32E-05 7.95E-05 7.95E-05 7.95E-05 7.95E-05
Styrene kgmole/h 31.82114 49.84906 49.84906 49.84906 49.84906
Toluene kgmole/h 0.505158 0.505108 0.505108 0.505108 0.505108

Unit 14 15 16 16.1 16.2

Benzene kgmole/h 0.072175 0 0.427963 0.427963 0
E-Benzene kgmole/h 0.046166 0 2.483877 2.483877 0
Ethylene kgmole/h 0.000465 0 6.41E-06 0 0
H2O kgmole/h 2.185623 14997.79 0.028079 0 0.028079
Hydrogen kgmole/h 49.8138 0.018157 0.016926 0 0
Methane kgmole/h 7.92E-05 0 2.51E-07 0 0
Styrene kgmole/h 0.600779 0 49.24829 49.24829 0
Toluene kgmole/h 0.025002 0 0.480105 0.480105 0

Unit 16.3 Benzene/ 18 19 20

Toluen
Benzene kgmole/h 0 0.427963 0 0 0
E-Benzene kgmole/h 0 0.099999 2.383877 2.378952 0.004925
Ethylene kgmole/h 6.41E-06 0 0 0 0
H2O kgmole/h 0 0 0 0 0
Hydrogen kgmole/h 0.016926 0 0 0 0
Methane kgmole/h 2.51E-07 0 0 0 0
Styrene kgmole/h 0 0.000515 49.24777 0.000238 49.24753
Toluene kgmole/h 0 0.474942 0.005164 0.005164 0

Unit Styrene Wastewater 23 24.1 24.2

Benzene kgmole/h 0 0.072175 0.072175 0 0
E-Benzene kgmole/h 0.004925 0.046166 0.046166 2.378952 2.378951
Ethylene kgmole/h 0 0.000465 0.000465 0 0
H2O kgmole/h 0 2.185623 2.185623 0 0
Hydrogen kgmole/h 0 49.8138 49.8138 0 0
Methane kgmole/h 0 7.92E-05 7.92E-05 0 0
Styrene kgmole/h 49.24753 0.600779 0.600779 0.000238 0.000238
Toluene kgmole/h 0 0.025002 0.025002 0.005164 0.005164

Unit 25 26
Benzene kgmole/h 0 0
E-Benzene kgmole/h 0 0
Ethylene kgmole/h 0 0
H2O kgmole/h 5000 5000
 Hydrogen kgmole/h 0 0
Methane kgmole/h 0 0
Styrene kgmole/h 0 0
Toluene kgmole/h 0 0

4.2 Economic potential

- TOTAL CAPITAL COST: 17332800 USD
- TOTAL OPERATING COST: 11158800 USD/ year
- EQUIPMENT COST: 6678900 USD
- TOTAL INSTALLED COST: 10916800 USD
- TOTAL UTILITIES COST: 7839890 USD/year

Figure 8: Captital cost in Aspen

Calculation
OPERATION LABOR:
NOL = (6.29 +31.7P2 +0.23Nmp)0.5
Where NOL is the number of per shift, P is the number of processing steps
involving the handling of particulate solids-for example, transportation and
distribution, particulate size control, and particulate removal. N np is the number
of nonparticulate processing steps and includes compression, heating, cooling,
mixing and reaction. In general, for the process considered in this text, the
value P is zero, and the value of Nnp is given by

Nmp = ∑ Equipment

Compressors
Towers
 Reactors
Heaters
Exchangers
NOL= (6.29 + 31.7 × 02 + 0.23 × 12)0.5 = 3 𝑆
Nmp is 12 because our process includes 7 heat exchangers, 2 reactors, 2 tower, 1
compressor
Operating labor = 4.5 × 3 = 13.5 = 14
Labor Costs = 14 × 59580 = 834 100 USD/yr

Component Mass flow rate Cost Total cost

(ton/hr) USD/ton (USD/yr)
Ethyl Benzene 5308.30× 10−3 1000 46500708
Styrene 5129.23× 10−3 7410 332946526
Hydrogen 100.42× 10−3 83.33 73303.67
Methane 0.001271× 10−3 100 1.11
Ethylene 0.013043× 10−3 7 0.80
Benzene 33.43× 10−3 866.67 253801.5362
Toluene 43.76× 10−3 960 368004

∑ 𝑎𝑡𝑎𝑙 𝑜𝑡 = Cost of Ethyl Benzene = 46500708 USD/yr

∑ 𝑜𝑑𝑡 + − 𝑜𝑑𝑡 𝑜𝑡 = Cost of Styrene + Cost of Benzene +
Cost of Toluene + Cost of Methane + Cost of Hydrogen + Cost of Ethylene
= 332946526 + 253801.5362 + 368004 + 1.11 + 73303.67 + 0.80
= 333641637 USD/yr
Profit =
∑ 𝑜𝑑𝑡 + − 𝑜𝑑𝑡 𝑜𝑡 - ∑ 𝑎𝑡𝑎𝑙 𝑜 - Capital -
Equipment cost - Operation labor cost - Installed cost - Operation cost -
Utilities cost
17332800+6678900+10916800
= 333641637 - 46500708 - -
10 834100 - 11158800
7839890 = 263815289 USD/yr
5. Recycle structure

Figure 9: The recycle structure

5.1 Number of reactors
The process uses two reactors in order to meet two requirements of the process.
The first reason of using two reactors in the process is to maintain temperature
of reaction is always at constant, do not have any fluactions. The second reason
is to increase the effeciency of the reaction so that the product of process is
purer and have at least impurities as possible.

Figure 10: Parameters of reactor

 Figure 11: Parameters of reactor
5.2 Reactor configuration
Fixed bed reactors are the simplest type pf reactor to design, and consist of
solid catalyst particles being loaded and packed into the bed. Within the
chemical industry, fixed-bed reactors are used as standard in heterogeneously
catalyzed gasphase reactions, and only if special conditions such as rapid
catalyst deactivation or operation in the explosive regime have been taken into
account, is the alternative of fluidized-bed operation considered.
With regards to reactor application and construction, it is convenient to
differentiate between fixed-bed reactors for adiabatic operation and those for
non-adiabatic operation. Since temperature control is one of the most important
methods to influence a chemical reaction, adiabatic reactors are used only when
the heat of reaction is low, or where there is only one major reaction pathway;
in these cases no adverse effects are expected on selectivity or yield due to the
adiabatic temperature development. The characteristic feature of an adiabatic
reactor is that the catalyst is present in the form of a uniform fixed bed (Fig.3)
which is surrounded by an outer, insulating jacket.
 Figure 12: Fixed bed reactors stucture
5.3 Recycle stream
Due to the presence of reactant (Ethylene Benzene) exist, we construct the
recycle stream to collect Ethylene Benzene and send it back to Reactor 1 to
restart the chemical reaction. At the same time, the “Fuel Gas” stream, the
“Benzene/Toluene” stream and the “Styrene” stream are being collected at the
end of the process.
6. Separation stucrure
6.1 Separation configuration

Figure 13: Configuration Separation

6.2 Separation sequence
Boiling
Molar flow
Component Formula point
(kmole/h)
(oC)
Benzene (B) C6H6 0.427963 80.09
Toluene (T) C7H8 0.480105 110.6
E-Benzene (E) C8H10 2.483877 136.2
 Styrene (S) C8H8 49.24829 145.2

CES 0.427963
TES
B = 0.480105 + 2.483877 + 49.24829 × 110.6 − 80.09 = 0.24

→ Second split
0.480105 + 2.483877
CES T = × 136.2 − 110.6 = 0.45
ES 2.483877 + 49.24829

→ First split

2.483877 + 0.480105 + 2.483877

CESES = 49.24829 × 145.2 − 136.2 = 0.62
→ Last split because ∆T = 9𝑜 𝑡𝑜𝑜 𝑚𝑎𝑙𝑙

Figure 14: Distillation Column T-100

 Figure 15: Distillation Column T-101
7. Heat integration
7.1 Pinch analysis
∗ ∗
∆ = 𝟏℃ (/℃. ) (℃) (℃)

C1 439 555 595192 444 560

C2 234 800 1979153 239 805

C3 134 240 28133 139 245

H1 800 465 205764 795 460

H2 551 260 564546 546 255

H3 177 30 5056514 172 25

H4 794 450 601769 789 445

H5 260 177 564465 255 172

From there, we can sketch the temperature interval diagram and the cascade
diagram:
Qaccumulated (kJ/hr) Qadjusted (kJ/hr)
0 740157866
 -19791530 720366336
-30431864 709726002
-298732844 441425022
-323468212 416689654
-426863088 313294778
-447983538 292174328
-449993337 290164529
-717354060 22803806
-731500940 8656926
-740157866 0
-704223622 35934244
-538287049 201870817
38155547 778313413

Hot pinch = 244℃

Tpinch = Cold pinch = 234℃
Qhot utility = 740157866 (kJ/hr)
Qcold utility = 778313413 (kJ/hr)

7.2 Heat exchanger network (HEN)

Above pinch (CNC ≥ CNH)

Stream Load ( kJ/h )

1
68997539.32
2
1120200591
3
168798
4
68997539.32
5
164129878.8
7
206858424.5
8
9031440
→ QHot Ultility = 740157866 (kJ/hr)

Below pinch (CNH ≥ CNC)

Stream Load ( kJ/h )

3 2813300
6 1120200591
8 37819155

→ QCold Ultility = 778313413 (kJ/hr)

Figure 6: Composite curve
Figure 17: Grand Composite curve
 REFERENCES

1. “Ethylene Benzene”, Wikipedia, Wikimedia Foundation, 2020.

https://en.wikipedia.org/wiki/Ethylbenzene

2. “Benzene”, Wikipedia, Wikimedia Foundation, 2020.

https://en.wikipedia.org/wiki/Benzene

3. “Styrene”, Wikipedia, Wikimedia Foundation, 2020.

https://en.wikipedia.org/wiki/Styrene

4. “Toluene”, Wikipedia, Wikimedia Foundation, 2020.

https://en.wikipedia.org/wiki/Toluene

5. Richard Turton, “Formalin Hints”, Analysis, Synthesis, and design of

chemcial process, 2012.

6. Prof. Dr. Arno Behr, “ Catalytic Dehydrogenation of Ethylbenzene”,

Experiment: Styrene Production from Ethylbenzene, 2016.

7. Austin , G.T. Shreve, Chemical Process Industries, 5th Edition McGraw-

Hill,1986.

8. Octave Levenspiel, Chemical Reaction Engineering, 3rd Edition, John

Wiley & Sons, Inc, United States of America, 1999, p72.

9. Mark E. Davis and Robert J. Davis, Fundamentals of Chemical Reaction

Engineering, Mc Graw-Hill, New York, 2003, p65 and p84.

10. Max S. Peters Klaus D. Timmerhaus, PLANT DESIGN AND ECONOMICS

FOR CHEMICAL ENGINEERS, Fourth Edition, McGraw-Hill, Inc, 1991.

11. N.ILAKKIYA, Project report “SIMULATION AND OPTIMIZATION OF

AN EXISTING ETHYLBENZENE DEHYDROGENATION REACTOR”,
2012.

12. Ullmann´s Encyclopedia of Industrial Chemistry, 5th Edition, Vol. A25,

chapter “Styrene”, page 329 – 344, VCH, Weinheim 1994, 6th edition as
electronic release (available from the University of Dortmund via the
homepage of the university library); also printed as: “Industrial organic
chemicals: starting materials and intermediates, an Ullmann´s
encyclopedia” 1th Edition, Vol. 7, chapter “Styrene”, page 4417 – 4441,
 Vol. 4, chapter “Ethylbenzene”, page 2207 – 2220, Wiley-VCH, Weinheim
1999.

13. Kirk-Othmer, Encyclopedia of Chemical Technology, 4th Edition,

Vol.22,chapter “Styrene”, page 956 – 994, Wiley-Interscience, New York
1992.

14. Shiou-Shan Chen, “Styrene,” Kirk-Othmer Encyclopedia of Chemical

Technology, online version (New York: John Wiley and Sons, 2006).

15. “Styrene,” Encyclopedia of Chemical Processing and Design, Vol. 55, ed.
J. J. McKetta, (New York: Marcel Dekker, 1984), 197–217.

16. Snyder, J. D., and B. Subramaniam, “A Novel Reverse Flow Strategy for
Ethylbenzene Dehydrogenation in a Packed-Bed Reactor,” Chem. Engr. Sci.
49 (1994): 5585–5601.