MALAYSIAN INSTITUTE OF CHEMICAL & BIOENGINEERING TECHNOLOGY

UNIVERSITI KUALA LUMPUR

SUBJECT NAME
CHEMICAL PROCESS PRINCPLES

SUBJECT CODE
CLB 10904

PRODUCTION OF STYRENE (80000 MT/year)

GROUP MEMBERS
L01-P2

STUDENT NO. NAME ID

1 MOHAMAD IMAD EL KHEIR 55213117149
2 MUHAMMAD DANIEAL B. LIAKAT ALI 55213117221
3 MUHAMMAD IMRAN AZRIE B. ABU BAKAR 55213117156
4 MUHAMAD HASAN AZANI B. MOHD HALIMI 55213117209
5 MUHAMMAD ZAKWAN B. ZAIDI 55213117161

NAME OF LECTURER
DR. SITI NURUL ATIKAH BT. ABDUL HALIM
1.0 EXECUTIVE SUMMARY

Styrene is a colorless, toxic liquid with a strong aromatic odor. It is used to make rubbers,
polymers and copolymers, and polystyrene plastics. Diethyl benzene (DEB) which is an
intermediate in divinyl-benzene manufacture is the by-product of the process. The demand of
styrene is higher than divinyl benzene, thus the selectivity for our process should favors ethyl
benzene production. In the modern petrochemical industry, styrene is one of the important
monomers. It is approximately 20 million tons of world production of styrene per year. Over the
years, various techniques were investigated for the manufacturing of styrene monomer. After
analysing all the processes, the process selected was catalytic dehydrogenation of ethyl benzene.
This is because the raw materials required are a bare minimum, which consists of ethyl benzene,
catalyst and steam generation. First, the process starts with the fresh batch of ethyl benzene, with
the amount of 241800 MT/year being fed to a mixer. Then, the mixture will continue to Mixer-2
and will mix with about 967200 MT/year of the superheated steam. After that, the effluent of the
reactor will flow through Molten Salt Cooler and Dowtherm Cooler before passing through to the
3-phase Separator where 72545 MT/year of the Vapor Silt, 967200 MT/year of the Waste water
and 169255 MT/year of the Organic Liquid Split will be separated. Next, the organic split then
undergoes distillation process in the distillation column. The styrene is the main product that will
satisfy the demand, and it will be stored into a storage vessel, and is recycled. There are some
improvements that can be made by using toluene and methanol as a catalyst that make the
production of styrene required reaction temperature around 400°C. To produce steam hydrogen
could be burned to help heat product of distillation column. This method will remove the energy-
intensive of the dehydrogenation and make the contaminant cost become lower
2.0 TABLE OF CONTENTS

1.0 EXECUTIVE SUMMARY ............................................................................................................................ 2

2.0 TABLE OF CONTENTS............................................................................................................................... 3

3.0 INTRODUCTION ....................................................................................................................................... 4

4.0 PROCESS SELECTION ............................................................................................................................... 6

4.1 PROCESS DESCRIPTION ....................................................................................................................... 7

4.2 PROCESS BACKGROUND ................................................................................................................... 10

5.0 PROCESS FLOW DIAGRAM .................................................................................................................... 12

6.0 PROCESS EQUIPMENT ........................................................................................................................... 14

7.0 MASS BALANCE ..................................................................................................................................... 16

8.0 ENERGY BALANCE ................................................................................................................................. 26

9.0 PROCESS AND DESIGN IMPROVEMENT ................................................................................................ 36

10.0 REFERENCE .......................................................................................................................................... 37

3.0 INTRODUCTION

Styrene is a type of polystyrene that are used in plastics, protective coatings, resins,
and chemical intermediates. Exophiala jenselmei (the yeast-like fungus) is also been used by
styrene to treat the air that is polluted by styrene. Styrene’s IUPAC names are Vinyl benzene,
Cinnamene, Styrol, Phenylethene, Diarex HF 77, Styrolene, Styropol, Vinylbenzene and also
an organic compound which is the Phenyethylene with a chemical formula C6H5CH = CH2
(Syahiirah, 2016).

The characteristics of Styrene, which is the derivative of benzene, is that it is a

colourless, oily liquid which evaporates easily. Although the high concentrations have a less
pleasant odour, styrene has a sweet smell. Polysterene and also other copolymers are
precursor from styrene. Figure 1 shows the chemical structure of styrene. There is many
equipment that had been used to produce styrene such as reactor (with floating head and
shell tube), reactor feed heating system (3 unit), reactor effluent cooling system (2 unit), 3-
phases separator, pre-separating effluent heat exchanger, column 1, column 2, column 3 and
column intermediate cooling system (Syahiirah, 2016).

Figure 1 Ethyl Benzene Structure

Diethyl benzene (DEB) which is an intermediate in divinyl-benzene manufacture is the

by-product of the process. The demand of styrene is higher than divinyl benzene, thus the
selectivity for our process should favors ethyl benzene production. The production of ethyl
benzene is by coupling ethylene and benzene with an acidic catalyst. Ethylene reacts with
ethyl benzene will form diethyl benzene. The formation of multiply-substituted benzenes is
limited by running the reaction with a large excess benzene (Syahiirah 2016).
The reactions that produce Ethyl Benzene and Diethyl Benzene can be stated ad below:

In which in those formula, the first 1 is the extent reaction. The feed ratio and also
the processing conditions plays important roles in selectivity of these reactions (Syahiirah,
2016).

In the modern petrochemical industry, styrene is one of the important monomers. It is

approximately 20 million tons of world production of styrene per year. In 1930, styrene process
was developed independently and simultaneously by BASF in Germany and also by DOW
chemical in America. One of the important application of the production of styrene is butadiene
latex. There are two process that are mainly produced styrene which are dehydrogenation of
ethylbenzene (EB) in presence of steam over iron oxide-based catalyst and also the process
as a by-product in the epoxidation of propene with ethylbenzene hydroperoxide and Mo
complex based catalyst (Syahiirah, 2016).

The process of dehydrogenation of EB accounts more than 90% of worldwide capacity.

In 1957, the catalytic dehydrogenation route in which the potassium promoted iron oxide is
used will typically produce most of the styrene. The process of production of styrene can be
run industrially either isothermally or adiabatically over a fixed bed reactor. The catalysts which
are cobalt, copper, iron and also zinc oxides had been studied and found out that the
potassium promoted iron catalyst is efficient with respect to both selectivity and also activity
(Freie Universitat Berlin, n.d.).

There are a few used of styrene in the industry in which precursor polystyrene is used
for packaging, disposables and low-cost consumer products. For food and beverage industry,
they basically used polystyrene beads for packaging, insulation and cushion packaging.
Styrene is also used as improve the grades of resins in a higher performance application such
as home electronics and appliances (Chevron Phillips, n.d.).
4.0 PROCESS SELECTION

Over the years, various techniques were investigated for the manufacturing of styrene
monomer. After extensive trials and research, the following methods have been used for
commercial production:

1. dehydrogenation of ethyl benzene;

2. oxidation of ethyl benzene to ethyl benzene hydro peroxide, which reacts with propylene
oxide, after which the alcohol is dehydrated to styrene

3. oxidative conversion of ethyl benzene to -phenyl ethanol via acetophenone and

subsequent dehydration of alcohol

4. side-chain chlorination of ethyl benzene followed by dechlorination

5. side-chain chlorination of ethyl benzene, hydrolysis to the corresponding alcohols,

followed by dehydration

6. pyrolysis of petroleum recovery from various petroleum processes.

7. alkylation of benzene with ethylene.

The first and second methods have proven to be the only two commercially utilized routes
to produce styrene. Although, method 3 was practiced by Union-Carbide Corporation, it was
later replaced with the dehydrogenation process. Meanwhile, methods 4 & 5, which involves
chlorine, requires high cost due to the raw materials and from the monomer which contains
chlorinated contaminants. On the other hand, production of styrene directly from petroleum
streams is extremely difficult and quite costly. The two most commercially important methods
to produce styrene are based on ethyl benzene production by alkylation of ethylene and
benzene. There are a few research programs that are trying to replace the expensive benzene
and ethylene feed stocks with a low-cost alternative are being carried out by a lot of
companies.
4.1 PROCESS DESCRIPTION

1. OXIDATION PROCESS
Halcon international’s process is known to be one of the most distinguished oxidation
processes to produce styrene from propylene oxide. The method involved in this process is
the ethyl benzene is oxidized to hydro peroxide, as shown below:

C6H5CH2CH3 + O2 → C6H5CH(OOH)CH3

This reaction undergoes in the liquid phase with the air aerated through the liquid, and
no catalyst is required. Hydro peroxides are unstable compounds, thus exposure to elevated
temperatures must be minimalized to reduce the decomposition rate. Moreover, this method
will produce fewer by-products from the decomposition if the reaction temperature is gradually
reduced during reaction, from 135oC-1600oC during the first half of reaction to 125 oC -1550oC
during the second half. When it is carried out at constant temperature than when the
temperature is gradually reduced, then the reaction will be more selective to produce acid by-
product. This is applicable when the temperature is reduced by a series of reactors, where
each of them is maintained at a progressively lower temperature. The pressure required for
the reaction is not critical; where 800-1500 kPa is adequate to maintain the reactants at liquid
phase. This reaction is as follows:

C6H5CH(OOH)CH3 + CH3CH=CH2 → C6H5CH(OH) CH3 + CH3CH(O)CH2

The catalysts used for this reaction are compounds of metals (molybdenum, tungsten,
vanadium). The epoxidation reaction generally occurs under self-generated pressures at 100
o
C -1300 oC while in the liquid phase. The ethyl benzene hydro peroxide is converted almost
completely, and the selectivity of the reaction in producing propylene oxide is more than 70%.
The alcohol produced can be dehydrated to styrene or, if styrene is not desired, it can be
reduced to ethyl benzene, where it is recycled.
 2. ALKYLATION BENZENE WITH ETHYLENE

In 1958, Universal Oil Products (UOP) developed a new process for alkylation of benzene
with ethylene at presence of aluminium chloride as a catalyst. This is because Aluminium
chloride is highly corrosive, which will lead to the requirement of expensive equipment which
are resistant against acid. This method involves two steps, where first is the Alkylation step,
in which benzene reacts with ethylene. Next is the Trans-alkylation step, in which poly ethyl
benzenes are converted to ethyl benzene on a reverse alkylation process. The final step is
the separation process, in which unreacted benzene, poly ethylbenzenes and other
components are separated from each other and high purity ethyl benzene is produced.

In details, the process begins with acquiring benzene feed from storage tank and is
mixed with recycled benzene. After heating and mixing with ethylene, the mixture will enter
the first reactor and is converted in the reactor. The first reactor warms up the feed of the
second reactor while cooling down and after mixing with ethylene. Next comes the reaction
between poly ethyl benzene with ethyl benzene, where the feed to this reactor is a mixture of
benzene stream taken from benzene tower and recycled poly ethyl benzene stream. Finally,
the outlet stream of trans alkylator reactor is then sent to benzene tower in separation unit.
This process is difficult to apply as it produces a lot of non-processable solid, as well as the
final product is not easy to process nor to transport.

3. DEHYDROGENATION OF ETHYL-BENZENE REACTION:

C6H5CH2CH3 → C6H5CH=CH3 + H2 + (∆HR)

There is numerous licensed process available for the conversion of ethyl-benzene to

styrene. Even though most of the processes share the catalytic dehydrogenation of ethyl
benzene to styrene in the presence of steam, there are two different methods to the reaction
section design, which are the adiabatic process and the isothermal process. Since the
dehydrogenation reaction is an endothermic reaction, heat must be supplied to obtain 1.26-
1.33 MJ/kg of ethyl benzene converted at 250oC. During the adiabatic process, the steam is
superheated to 800 oC -9500oC, where it is then mixed with the preheated ethyl benzene (EB)
feed after being exposed to the catalyst.
 Then, the isothermal process will take place in a PFR and the heat for the reaction is
provided by an indirect heat exchange between the process fluid and a suitable heat transfer
medium. The reactor operating pressure, molar steam to hydrocarbon ratio, reactor operating
temperature and the reactor liquid hourly space velocity (LHSV) affects the dehydrogenation
catalyst, the catalyst life, the molar conversion of ethyl benzene, and the molar selectivity of
ethyl benzene to styrene. There is a compromise between activity for all the catalysts, which
is the EB conversion, and styrene selectivity.

Thus, the most suitable and effective process for large scale production of styrene is
catalytic dehydrogenation of ethyl benzene. This process is the primary, and the most
commercial process for production of styrene, with about 85% of industries worldwide apply
this process. Ethyl benzene will react with a catalyst, in this case, Iron Oxide (Fe3O4), for the
production of styrene.

Figure 2 Dehydrogenation Process

Furthermore, this reaction process is limited in equilibrium, but the process can be
controlled more successfully with the addition of steam. The steam will not react with the ethyl
benzene and catalyst during the process, which will prevent coking. The advantages and
benefits of diluting ethylbenzene with superheated steam are:

1. The partial pressure of ethyl benzene will be lowered, and equilibrium will shift
towards a higher styrene production and reducing the loss due to thermal cracking,

2. The heat needed will be supplied for endothermic reaction,

3. Carbonaceous deposits will be decreased by steam reforming reaction,

4. Prevents reduction and deactivation of catalyst by controlling the iron’s state.

4.2 PROCESS BACKGROUND

After analysing all the processes, the process selected was catalytic
dehydrogenation of ethyl benzene. This is because the raw materials required are a bare
minimum, which consists of ethyl benzene, catalyst and steam generation.

First, the process starts with the fresh batch of ethyl benzene, with the amount of
241800 MT/year being fed to a mixer. After the process is completed, the unreacted ethyl
benzene is recycled back into Mixer-1, where the mixture of both the recycled and fresh ethyl
benzene is approximately about 39295 MT/year. Then, the mixture will continue to Mixer-2
and will mix with about 967200 MT/year of the superheated steam. In this process, the ratio
of steam to feed is 4 : 1. Then, the materials will go the Furnace Heater, Dowtherm Heater
and Molten Salt Heater respectively for the dilution of ethyl benzene, thus enhancing the
conversion of styrene before it is fed to the Isothermal Packed Bed Reactor. Ethyl benzene
converts to styrene in the reactor by mixing the diluted ethyl benzene with the catalyst, Iron
Oxide.

After that, the effluent of the reactor will flow through Molten Salt Cooler and Dowtherm
Cooler before passing through to the 3-phase Separator where 72545 MT/year of the Vapor
Silt, 967200 MT/year of the Waste water and 169255 MT/year of the Organic Liquid Split
(Benzene, Toluene, Ethyl Benzene and Styrene) will be separated. They will then be distillated
to extract and obtain the desired product, which is the Styrene. After the organic split exits the
separator, it will then be fed into the flash tank where the vapor split with an estimate of 18145
MT/year is released.

Next, the organic split then undergoes distillation process in the distillation column
where the Benzene-Toluene mixture and Ethylbenzene-Styrene mixture is separated based
on their respective boiling point. The distillate stream will move to the second
distillation column where Styrene and Ethylbenzene is separated. The styrene is the main
product that will satisfy the demand, and it will be stored into a storage vessel, where the ethyl
benzene that is recovered will be recycled back to Mixer-1.
 1. REACTOR

The root of the feed stream is taken as 241800MT/year of ethylbenzene. The following
assumptions are based on the condition of the reactor to produce 80000MT/year of styrene:

1) Fractional conversion (ethylbenzene to styrene and benzene) = 37.5% of feed

2) Selectivity (styrene / benzene) = 90%
3) Fractional conversion (ethylbenzene to toluene) = 14% of ethylbenzene balance
4) Total conversion (ethylbenzene) = 83.75%.

2. THREE-PHASE SEPARATOR

The production of styrene was performed using steam technology under high
temperature. First, the steam was mixed with the ethylbenzene before it is fed to the reactor.
Thus, water molecule exists at the effluent stream. Since water does not take part in the
reaction (inert), it is disregarded in the calculation. Then, the effluent from the reactor is fed to
the separator in order to remove the gaseous by-product and also most of the water that is
present in the effluent mixture. An assumption was made that the efficiency of the separator
is 80%. Therefore, 80% of the gases by-product is removed, while the waste water is
presumed to be completely removed.

3. PRIMARY DISTILLATION COLUMN

After that, the remaining vapor split is completely removed by feeding the effluent of
the reactor to a flash tank. Thus, methane, ethylene and hydrogen gas are no longer available
in the output stream of the tank. The organic split is then separated using distillation columns
by utilizing the differences in boiling point, where the component with the higher boiling point
to the bottom output stream (Ethylbenzene-Styrene), while the lower boing point (Benzene-
Toluene) goes to the overhead output stream. The assumptions on the primary distillation
column are:

1) 98 wt% of Benzene from feed stream @ overhead product stream,

2) 95 wt% of Toluene from feed stream @ overhead product stream,

3) 98 wt% of Styrene from feed stream @ bottom product stream,

4) 95 wt% of Ethylbenzene from feed stream @ bottom product stream.

5.0 PROCESS FLOW DIAGRAM

F-101

Figure 3 Process Flow Diagram (PFD) for Production of Styrene

PROCESS EQUIPMENT LABEL

Table 1 Equipment Label and Equipment

6.0 PROCESS EQUIPMENT

Heater

The equipment that has been used to supply heat for the process or as reactor which
provides heats of reaction, such as an industrial furnace or through fired heater. In production
of styrene, heater is used to supply heat to recycled ethylbenzene that were supplied back to
the feed ethylbenzene.

Mixer

Mixers can be used to complete the processes that need several feed to be properly
mixed before a reaction is started in a reactor. In production of styrene, mixer is used to
efficiently mixed ethylbenzene feed with superheated steam to break down the molecules
before entering the reactor. Then, it is also used to mixed recycled ethylbenzene form from
distillation column back into the feed stream.

Reactor

A chemical reactor is an enclosed volume in which a chemical reaction takes place. In

chemical engineering, it is generally understood to be a process vessel used to carry out a
chemical reaction, which is one of the classic unit operations in chemical process analysis.
The purpose of reactor in the production of styrene is to provide dehydrogenation process on
ethylbenzene feed, so that styrene could be produced.

Cooler / Heat Exchanger

In other to remove heat from the processes or equipment its require the function of
cooling system. Heat removed from one medium is transferred to another medium, or process
fluid. In styrene production process, cooler is used after going through reactor for the
dehydrogenation process, as it will cool the main product formed from vapor to liquid
(ethylbenzene, styrene, benzene, toluene).
Three-Phase Separator

In the three-phase separator, hydrogen and waste water are separated from the
organics split. In styrene production, waste water is all the superheated steam used for
decomposition of ethylbenzene, and hydrogen gas, methane gas and ethylene gas are waste
vapor split. Organic liquid split is the product obtained after the separator that will go to the
distillation column.

Distillation Column

The application and elimination of heat to exploit changes in relative volatility is the
way distillation works. The components with lower boiling points and higher volatility will be
vaporized when heat is applied and leaving less volatile components as liquids. For styrene
production, primary distillation column is used to separate benzene-toluene and ethylbenzene-
styrene mixture, while secondary distillation column is used to separate ethylbenzene and
styrene.

Reboiler

A reboiler is a heat exchanger or a fired heater, providing heat that is required for the distillation
column to complete its function. Reboiler is used in styrene production to ensure that the
product of styrene obtained to be as pure as it would be.

Condenser

A substance can change it form from gaseous to liquid state by using condenser from the
cooling process. Therefore, the latent heat will be transferred to the surrounding environment
and given up on the substance. The purpose of condenser in styrene production is that higher
boiling point substance to be continuously recycled back into the distillation column.
7.0 MASS BALANCE

80000 MT/year styrene is required to be produced.

Ethylbenzene feed →1 Reactor →2 Three-Phase Separator →3 Flash Tank →4 Primary

Distillation Column →5 Secondary Distillation Column →6 Styrene product.

Ethylbenzene feed →1 Reactor

241800 MT/year 241800 MT/year

1.0000 0.1625 Ethylbenzene // 0.3375 Styrene //

REACTOR
Ethylbenzene 0.0375 Ethylene // 0.0375 Benzene //
0.0875 Methane // 0.0875 Toluene //
0.2500 Hydrogen Gas

Ethylene:

Reactor 0.0375 x 241800 MT/year

Ethylbenzene: = 9068 MT/year

0.1625 x 241800 MT/year Benzene:

= 39295 MT/year 0.0375 x 241800 MT/year

= 9068 MT/year

Styrene: Toluene:

0.3375 x 241800 MT/year 0.0875 x 241800

= 81600 MT/year = 21158 MT/year

Methane:

Hydrogen Gas: 0.0875 x 241800

0.2500 x 241800 MT/year = 21158 MT/year

= 60450 MT/year
Reactor →2 Three-Phase Separator

Reactor Feed 1) Water Split 2) Vapor Split

241800 MT/year 1.0000 72545 MT/year

Hydrogen Oxide
0.1625 Ethylbenzene 0.1000 Ethylene

0.3375 Styrene 0.2333 Methane

0.0375 Ethylene 0.6667 Hydrogen Gas

0.0375 Benzene THREE-

PHASE
0.0875 Methane SEPARATOR
3) Organic Liquid Split
0.0875 Toluene
169255 MT/year
0.2500 Hydrogen Gas
0.2321 Ethylbenzene

0.4821 Styrene

0.0107 Ethylene

0.0536 Benzene

0.0250 Methane

0.1250 Toluene

0.0714 Hydrogen Gas

1) Water Split

Superheated steam used in

dehydrogenation process of styrene is
completely removed in this process.
2) Vapor Split Hydrogen Gas:

Ethylene: 0.6667 x 72545 MT/year

0.1000 x 72545 MT/year = 48365 MT/year

= 7255 MT/year

Methane:

0.2333 x 72545 MT/year

= 16925 MT/year

3) Organic Liquid Split

Ethylbenzene: Ethylene:

0.2321 x 169255 MT/year 0.0107 x 169255 MT/year

= 39285 MT/year = 1813 MT/year

Styrene: Methane

0.4821 x 169255 MT/year 0.0250 x 169255 MT/year

= 81600 MT/year = 4233 MT/year

Benzene: Hydrogen Gas:

0.0536 x 169255 MT/year = 0.0714 x 169255 MT/year

= 9072 MT/year = 12085 MT/year

Toluene:

0.1250 x 169255 MT/year

= 21160 MT/year
Three-Phase Separator →3 Flash Tank

1) Vapor Split

18145 MT/year
Separator Feed
0.1000 Ethylene
169255 MT/year
0.2333 Methane
0.2321 Ethylbenzene
0.6667 Hydrogen Gas
0.4821 Styrene

FLASH TANK 2) Organic Liquid Split

0.0107 Ethylene
151110 MT/year
0.0536 Benzene
0.2600 Ethylbenzene
0.0250 Methane
0.5400 Styrene
0.1250 Toluene
0.0600 Benzene
0.0714 Hydrogen Gas
0.1400 Toluene

1) Vapor Split 2) Organic Liquid Split

Ethylene: Ethylbenzene:

0.1000 x 18145 MT/year 0.26 x 151110 MT/year

= 1815 MT/year = 39290 MT/year

Styrene:

Methane 0.5400 x 151110 MT/year

0.2333 x 18145 MT/year = 81600 MT/year

= 4223 MT/year Benzene:

0.0600 x 151110 MT/year

Hydrogen Gas = 9065 MT/year

0.6667 x 18145 Toluene:

= 12107 MT/year 0.1400 x 151110 MT/year

= 21155 MT/year
Flash Tank →4 Primary Distillation Column

1) Benzene/Toluene Split

32540 MT/year

Flask Tank Feed 0.0603 Ethylbenzene

151110 MT/year 0.0501 Styrene

0.2600 Ethylbenzene PRIMARY 0.2727 Benzene

DISTILLATION
0.5400 Styrene COLUMN 0.6169 Toluene

0.0600 Benzene

0.1400 Toluene 2) Organic Liquid Split

118570 MT/year

0.3149 Ethylbenzene

0.6747 Styrene

0.0015 Benzene

0.0089 Toluene

Assume that :

1) 98 wt% of Benzene from feed stream

presence at the overhead product stream,

2) 95 wt% of Toluene from feed stream

presence at the overhead product stream,

3) 98 wt% of Styrene from feed stream

presence at the bottom product stream,

4) 95 wt% of Ethylbenzene from feed

stream presence at the bottom product
stream.
1) Benzene/Toluene Split 2) Organic Liquid Split

Ethylbenzene: Ethylbenzene:

0.0603 x 32540 MT/year 0.3149 x 118570 MT/year

= 1962 MT/year = 37339 MT/year

Styrene: Styrene:

0.0501 x 32540 MT/year 0.6747 x 118570 MT/year

= 1630 MT/year = 80000 MT/year

Benzene: Benzene:

0.2727 x 32540 MT/year 0.0015 x 118570 MT/year

= 8874 MT/year = 178 MT/year

Toluene: Toluene:

0.6169 x 32540 MT/year 0.0089 x 118570 MT/year

= 20074 MT/year = 1055 MT/year

Primary Distillation Column →5 Secondary Distillation Column →6 Styrene product

Organic Liquid Split 38520 MT/year

118520 MT/year SECONDARY 1.00 Ethylbenzene

DISTILLATION
0.325 Ethylbenzene COLUMN
80000 MT/year
0.675 Styrene
1.00 Styrene

1) Styrene 2) Ethylbenzene

0.675 x 118520 MT/year 0.375 x 118520 MT/year

= 80000 MT/year. = 38520 MT/year.

Since the flowrate of toluene and benzene

that flows out from the primary distillation
column is small, it is negligible in the
calculation.

Mass Balance Conclusion

Real production will not give the complete The composition and flowrate of each
separation of the mixture at the distillation substance is rounded off to the nearest
column since efficiency of 100% is number of 1 due to high production
impossible to be achieved. For example, at process. This will slightly result in some
the secondary distillation column, traces of calculation defect, but the amount could be
benzene could still be found in the bottom negligible due to very small amount.
product stream. Therefore, pure styrene is
collected, while pure ethylbenzene is
recycled back to the mixer.
MOLAR FLOWRATE, kmol/hr

REACTOR

Input:

1) Ethylbenzene

= 241800MT/year x 1year/8760hr x
106.17kg/1kmol x 1000kg/1MT

= 2.93 x 106 kmol/hr

Output:

1) Ethylbenzene
5) Benzene
= 39295MT/year x 1year/8760hrs x
= 9068MT/year x 1 year/8760hrs x
106.17kg/kmol x 1000kg/1MT
78.11kg/kmol x 1000kg/1MT
= 4.76 x 105 kmol/hr
= 8.09 x 104 kmol/hr
2) Styrene
6) Toluene
= 81600 MT/year x 1year/8760hrs x
= 21158MT/year x 1year/8760hrs x
104.15kg/kmol x 1000kg/1MT
92.14kg/kmol x 1000kg/1MT
= 9.70 x 106 kmol/hr
= 2.23 x 105 kmol/hr
3) Hydrogen Gas
7) Methane
= 60450 MT/year x 1year/8760hrs x
= 21158MT/year x 1year/8760hrs x
2kg/kmol x 1000kg/1MT
16.04kg/kmol x 1000kg/1MT
= 1.38 x 104 kmol/hr
= 3.87 x 104 kmol/hr
4) Ethylene

= 9068 MT/year x 1year/8760hrs x

28.05kg/kmol x 1000kg/1MT

= 2.90 x 104 kmol/hr

PRIMARY DISTILLATION COLUMN

Input:

1) Ethylbenzene 3) Benzene

= 39290 MT/year x 1year/8760hr x = 9065 MT/year x 1 year/8760hrs x

106.17kg/1kmol x 1000kg/1MT 78.11kg/kmol x 1000kg/1MT

= 4.76 x 105 kmol/hr = 8.08 x 104 kmol/hr

2) Styrene 4) Toluene

= 81600 MT/year x 1year/8760hrs x = 21155 MT/year x 1year/8760hrs x

104.15kg/kmol x 1000kg/1MT 92.14kg/kmol x 1000kg/1MT

= 9.70 x 105 kmol/hr = 2.23 x 105 kmol/hr

Output:

1) Ethylbenzene 3) Benzene

= 37339 MT/year x 1year/8760hrs x = 178 MT/year x 1 year/8760hrs x

106.17kg/kmol x 1000kg/1MT 78.11kg/kmol x 1000kg/1MT

= 4.53 x 105 kmol/hr = 1.58 x 103 kmol/hr

2) Styrene 4) Toluene

= 80000 MT/year x 1year/8760hrs x = 1055 MT/year x 1year/8760hrs x

104.15kg/kmol x 1000kg/1MT 92.14kg/kmol x 1000kg/1MT

= 9.51 x 105 kmol/hr = 1.11 x 104 kmol/hr

SECONDARY DISTILLATION COLUMN

Input = Output

1) Ethylbenzene 2) Styrene

= 38520 MT/year x 1year/8760hr x = 80000 MT/year x 1year/8760hrs x

106.17kg/1kmol x 1000kg/1MT 104.15kg/kmol x 1000kg/1MT

= 4.67 x 105 kmol/hr = 9.51 x 105 kmol/hr

8.0 ENERGY BALANCE

FLOW DIAGRAM

REACTOR HEAT
136.2℃ 650℃ EXCHANGER

50℃

SECONDARY PRIMARY
DISTILLATION DISTILLATION
142.5℃ COLUMN 128.8℃ COLUMN
REACTOR
136.2℃ 650℃
Reactor

• Ethyl Benzene
• Ethyl Benzene
• Styrene
• Hydrogen Gas
• Ethylene
• Benzene
• Toluene
• Methane

Process Flow:
Reference state :( 136.2℃, l)

SUBSTANCE INLET OUTLET

n (kmol/hr) H in (kJ/kmol) n (kmol/hr) H out (kJ/kmol)
Ethyl Benzene (l) 2.93 x 106 0(ref) 4.76 x 105 H1

➢ Ethyl Benzene
Ethyl Benzene (l, 136.2℃)

1
2
Ethyl Benzene (v, 136.2℃) Ethyl Benzene (v, 650℃)

1 ∆Ĥ1 = ∆Ĥ v, Ethyl Benzene = 35.98 kJ/kmol

∆Ĥ22 = ∫ CpdT
650
= ∫136.2(−43.1 x 10-3 + 0.7072 x 10-5 T – 4.811 x 10-12 T2 + 1.301 x 10-19 T3) dT

= 20.72 kJ/kmol

H1 = ∆Ĥ1 + ∆Ĥ2 = 56.7 kJ/kmol

Q = (56.7 kJ/kmol x 4.76 x 105 kmol/hr) = 26.99 x 106 kJ/ hr

HEAT EXCHANGER

650℃ 50℃
Heat Exchanger

• Ethyl Benzene • Ethyl Benzene

• Styrene • Styrene
• Hydrogen Gas • Hydrogen Gas
• Ethylene • Ethylene
• Benzene • Benzene
• Toluene • Toluene
• Methane • Methane

Process Flow:
Reference state: (650℃, l)

SUBSTANCE INLET OUTLET

n (kmol/hr) H in (kJ/kmol) n (kmol/hr) H out (kJ/kmol)
Ethyl Benzene (l) 4.76 x 105 0(ref) 4.76 x 105 H1
6 6
Styrene 9.70 x 10 0(ref) 9.70 x 10 H2
Hydrogen Gas 1.38 x 104 0(ref) 1.38 x 104 H3
Ethylene 2.90 x 104 0(ref) 2.90 x 104 H4
Benzene 8.09 x 104 0(ref) 8.09 x 104 H5
5 5
Toluene 2.23 x 10 0(ref) 2.23 x 10 H6
4 4
Methane 3.87 x 10 0(ref) 3.87 x 10 H7

➢ Ethyl Benzene
Ethyl Benzene (v, 650℃) Ethyl Benzene (l, 50℃)

1 3
2
Ethyl Benzene (v, 136.2℃) Ethyl Benzene (l, 136.2℃)

∆Ĥ11 = ∫ CpdT
136.2
= ∫650 (−43.1 x 10-3 + 0.7072 x 10-5 T – 4.811 x 10-12 T2 + 1.301 x 10-19 T3) dT

= -21.80 kJ/kmol

∆Ĥ22 = ∆Ĥ v, Ethyl Benzene = -35.98 kJ/kmol

∆Ĥ33 = ∫ CpdT
 50
=∫136.2(0.161) dT

= -13.88 kJ/kmol

H1 = ∆Ĥ1 + ∆Ĥ12+ ∆Ĥ3 = -71.66 kJ/kmol

➢ Styrene
Styrene (v, 650℃) Styrene (l, 50℃)

1 3
2
Styrene (v, 145℃) Styrene (l, 145℃)

∆Ĥ11 = ∫ CpdT
145
= ∫650 (−28.25 x 10-3 + 0.6159 x 10-5 T – 4.023 x 10-12 T2 + 9.935 x 10-20 T3) dT

= -13.03 kJ/kmol

∆Ĥ22 = ∆Ĥ v, Styrene =-43.50 kJ/kmol

∆Ĥ
3 3 = ∫ CpdT
50
=∫145(0.1299) dT

= -10.24 kJ/kmol

H2 = ∆Ĥ1 + ∆Ĥ12+ ∆Ĥ3 = -66.32

➢ Hydrogen Gas 1
Hydrogen Gas (v, 650℃) Hydrogen Gas (v, 50℃)
H3 1= ∫ CpdT
50
= ∫650(28.84 x 10-3 + 0.00765 x 10-5 T + 0.3288 x 10-8 T2 – 0.8698 x 10-12 T3) dT

= -17.58 kJ/kmol

➢ Ethylene
1
Ethyl Benzene (v, 650℃) Ethyl Benzene (v, 50℃)

H4 1= ∫ CpdT
50
= ∫650(40.75 x 10-3 + 11.47 x 10-5 T – 6.891 x 10-8 T2 + 17.66 x 10-12 T3) dT

= - 43.02 kJ/kmol

➢ Benzene
Benzene (v, 650℃) Benzene (l, 50℃)

1 3
2
Benzene (v, 80.10℃) Benzene (l, 80.10℃)

∆Ĥ11 = ∫ CpdT
80.10
= ∫650 (74.06 x 10-3 + 32.95 x 10-5 T – 25.20 x 10-8 T2 + 77.57 x 10-12 T3) dT

= -91.19 kJ/kmol

∆Ĥ22 = ∆Ĥ v, Benzene =-30.77 kJ/kmol

∆Ĥ33 = ∫ CpdT
50
= ∫80.10(126.5 x 10-3 + 23.4 x 10-5 T) dT

= -4.27 kJ/kmol

H5 =∆Ĥ1 + ∆Ĥ12+ ∆Ĥ3 = - 126.23 kJ/kmol

➢ Toluene
Toluene (v, 650℃) Toluene (l, 50℃)

1 3
2
 Toluene (v, 110.62℃) Toluene (l, 110.62℃)

∆Ĥ11 = ∫ CpdT
110.62
= ∫650 (94.18 x 10-3 + 38.00 x 10-5 T – 27.86 x 10-8 T2 + 80.33 x 10-12 T3) dT

= - 106.95 kJ/kmol

∆Ĥ22 = ∆Ĥ v, Toluene = -33.47 kJ/kmol

∆Ĥ33 = ∫ CpdT
50
= ∫110.62(148.8 x 10-3 + 32.4 x 10-5 T)dT

= -10.60 kJ/kmol

H6 = ∆Ĥ1 + ∆Ĥ12+ ∆Ĥ3 = -151.02 kJ/kmol

➢ Methane
1
Methane (v, 650℃) Methane (v, 50℃)

H71= ∫ CpdT
50
= ∫650(34.31 x 10-3 + 5.469 x 10-5 T + 0.3661 x 10-8 T2 – 11.00 x 10-12 T3) dT

= -31.92 kJ/kmol

Q = ((4.57 x 105 kmol/hr) (-71.66 kJ/kmol) + (9.70 x 106 kmol/hr) (-66.32 kJ/kmol) +
(1.38 x 104 kmol/hr) (-17.58 kJ/kmol) + (2.9 x 104 kmol/hr) (-43.02 kJ/kmol) +
(8.09 x 104 kmol/hr) (-126.23 kJ/kmol) + (2.23 x 105 kmol/hr) (-151.02 kJ/kmol) +
(3.87 x 104 kmol/hr) (-31.92 kJ/kmol))

= -72.27 x 107 kJ/hr

PRIMARY DISTILLATION COLUMN
50℃ 128.8℃
Primary Distillation
Column

• Ethyl Benzene
• Ethyl Benzene • Styrene
• Styrene • Benzene
• Hydrogen Gas • Toluene
• Ethylene
• Benzene
• Toluene
• Methane

Process Flow:
Reference state: (50℃, l)

SUBSTANCE INLET OUTLET

n (kmol/hr) H in (kJ/kmol) n (kmol/hr) H out (kJ/kmol)
Ethyl Benzene (l) 4.76 x 105 0(ref) 4.53 x 105 H1
5 5
Styrene 9.70 x10 0(ref) 9.51 x10 H2
Benzene 8.08 x 104 0(ref) 1.58 x103 H3
Toluene 2.23 x 105 0(ref) 1.11 x 104 H4

➢ Ethyl Benzene 1
Ethyl Benzene (l, 50℃) Ethyl Benzene (l, 128.8℃)

H1 = ∫ CpdT
1
128.8
=∫50 (0.161) dT

= 12.69 kJ/kmol

➢ Styrene
1
Styrene (l, 50℃) Styrene (l, 128.8℃)

H21= ∫ CpdT
128.8
=∫50 (0.1299) dT

= 10.24 kJ/kmol

➢ Benzene
 Benzene (l, 50℃) Benzene (v, 128.8℃)

1 3
2
Benzene (l, 80.10℃) Benzene (v, 80.10℃)

∆Ĥ11 = ∫ CpdT
80.10
= ∫50 (126.5 x 10-3 + 23.4 x 10-5 T) dT

= 4.27 kJ/kmol

∆Ĥ22 = ∆Ĥ v, Benzene =30.77 kJ/kmol

∆Ĥ33 = ∫ CpdT
128.8
= ∫80.10 (74.06 x 10-3 + 32.95 x 10-5 T – 25.20 x 10-8 T2 + 77.57 x 10-12 T3) dT

= 5.15 kJ/kmol

H3 = ∆Ĥ1 + ∆Ĥ12+ ∆Ĥ3 = 40.19 kJ/kmol

➢ Toluene
Toluene (l, 50℃) Toluene (v, 128.8℃)

1 3
2
Toluene (l, 110.62℃) Toluene (v, 110.62℃)

∆Ĥ3 = ∫ CpdT
1
110.62
= ∫50 (148.8 x 10-3 + 32.4 x 10-5 T)dT

= 10.60 kJ/kmol

∆Ĥ22 = ∆Ĥ v, Toluene =33.47 kJ/kmol

∆Ĥ1 = ∫ CpdT
3
128.8
= ∫110.62(94.18 x 10-3 + 38.00 x 10-5 T – 27.86 x 10-8 T2 + 80.33 x 10-12 T3) dT
 = 2.47 kJ/kmol

H4 = ∆Ĥ1 + ∆Ĥ12+ ∆Ĥ3 = 46.54 kJ/kmol

Q = ((4.53 x 105 kmol/hr) (12.69 kJ/kmol) + (9.51 x 105 kmol/hr) (10.24 kJ/kmol) +
(1.58 x 103 kmol/hr) (40.19 kJ/kmol) + (1.11 x 104 kmol/hr) (46.54 kJ/kmol)

=16.07 x 106 kJ/hr

SECONDARY DISTILLATION COLUMN

128.8℃ Secondary 142.5℃
Distillation Column

• Ethyl Benzene • Ethyl Benzene

• Styrene • Styrene
• Benzene
• Toluene

Reference state: (128.8℃, l)

SUBSTANCE INLET OUTLET
n (kmol/hr) H in (kJ/kmol) n (kmol/hr) H out (kJ/kmol)
Ethyl Benzene (l) 4.67 x 105 0(ref) 4.67 x 105 H1
5 5
Styrene 9.51 x10 0(ref) 9.51 x10 H2

➢ Ethyl Benzene
Ethyl Benzene (l, 128.8℃) Ethyl Benzene (v, 142.5℃)

1 3
2
Ethyl Benzene (l, 136.2℃) Ethyl Benzene (v, 136.2℃)

∆Ĥ1 = ∫ CpdT
1
136.2
=∫128.8 (0.161 ) dT
 = 1.19 kJ/kmol

∆Ĥ22 = ∆Ĥ v, Ethyl Benzene =35.98 kJ/kmol

∆Ĥ33 = ∫ CpdT
142.5
= ∫136.2 (−43.1 x 10-3 + 0.7072 x 10-5 T – 4.811 x 10-12 T2 + 1.301 x 10-19 T3) dT

= 0.27 kJ/kmol

H1 = ∆Ĥ1 + ∆Ĥ12+ ∆Ĥ3 = 37.44 kJ/kmol

➢ Styrene
1
Styrene (l, 128.8℃) Styrene (l, 142.5℃)

H21= ∫ CpdT
142.5
=∫128.8 (0.1299) dT

= 1.78 kJ/kmol

Q = ((4.67 x 105 kmol/hr) (37.44 kJ/kmol) + (9.51 x 105 kmol/hr) (1.78 kJ/kmol)

=19.18 x 106 kJ/hr

9.0 PROCESS AND DESIGN IMPROVEMENT

Styrene is a chemical that is flammable liquid, colourless and has sweet odour and is
highly volatile. Styrene is usually used to make many products such as plastic, synthetic
rubber, and polystyrene. Styrene is made by ethylbenzene-based technology. The reaction
can be performed in various methods such as vapour or liquid phase. The normal process of
styrene production, which is the dehydrogenation of ethylene benzene while using an iron
oxide catalyst, which requires the temperature of 600 °C. The cost of styrene production is
very high and consume a lot of energy. Thus, some adjustment must be made to improve the
energy economy of this process.

There are some improvements that can be made by using toluene and methanol as a
catalyst that make the production of styrene required reaction temperature around 400°C.By
using toluene and methanol the ratio of the desired product quantity to the total quantity of
products increase almost 80%. Other than that, to reduce the composition of methanol and
improve the efficiency the design of the reactor should be improved. To produce steam
hydrogen could be burned to help heat product of distillation column. This method will remove
the energy-intensive of the dehydrogenation and make the contaminant cost become lower.

.
Production Of Styrene With Catalyst Production Of Styrene Without Catalyst

Temperature = 400 °C Temperature = 600 – 900 °C

Energy : Low Energy : High
Cost : Low Cost : High
10.0 REFERENCE

Chevron Phillips, (n.d.) Styrene Monomer [Online]. [Acessed 10th MAY, 2018] Available from
World Wide Web: http://www.cpchem.com/bl/aromatics/en-
us/Pages/StyreneMonomer.aspx.

Syahiirah N., (2016) Plant Design For Production Of Styrene [Online] [Acessed 10th May,
2018] Available from World Wide Web:
https://www.academia.edu/29247967/CHE231__Final_Year_Report_Plant_Design_P
roduction_Of_Styrene_2016_

Freie Universitat Berlin, (n.d.) Chapter 1: Introduction (Styrene Synthesis) [Online].

[Accessed 10th May, 2018] Available from World Wide Web:
http://www.diss.fuberlin.de/diss/servlets/MCRFileNodeServlet/FUDISS_derivate_000
000001287/1_Kapitel-1.pdf?hosts= .

Geankoplis, C. J. (2014). Vapour-Liquid Separation Process. Pearson Education Limited, 741-752.