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Prediction of Thermodynamic Properties of Industrially important

Polymers





CL 445 Supervised learning II Project report
Submitted By: Rishikesh Awale
Roll No: 10D020009
Project Guide: Professor Jhumpa Adhikari
Submitted on: 28
th
April 2014
Department of Chemical Engineering, IIT Bombay








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Abstract
This project report starts with detailed literature survey of polystyrene and styrene comprising of
all the aspects right from their discovery, various routes of production with all process
considerations & process flow sheets, properties(chemical, physical, mechanical, optical,
thermal and electrical),Product specifications, end uses and Global demand and supply for the
product. The report also briefly emphasises separation of ethylbenzene and styrene by extractive
distillation using sulfolane and Ionic liquid such as 4-methyl-N-butylpyridinium
tetrafluoroborate ([4-mebupy]-[BF4]) and provides VLE data for ethylbenzene and styrene with
both extracting agents mentioned here. The concept of TraPPE-United Atom model is also given
which is used to evaluate total potential energy of system of particles.Lastly introduction to
Gibbs ensemble Monte Carlo simulation technique from statistical thermodynamic point of view
is given where three types of Monte Carlo moves meant to satisfy three conditions of
equilibrium between vapour and liquid of a pure substance / multicomponent mixture namely:
Internal equilibrium within each phase, equality of pressure between the two phases and equality
of Chemical potential of each component in both phases are explained.
















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Certification
Department of Chemical Engineering
Indian Institute of Technology, Bombay
The project report entitled "Prediction of Thermodynamic Properties of Industrially important
Polymers" prepared by Rishikesh Awale (Roll No.10D020009) may be accepted for being
evaluated.

Date: April 28, 2014 Signature of student

Name of the Guide:

Signature of Guide:

















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Index
S. No Topic Page No
1 Chapter 1 - Literature survey of Polystyrene 6
1.1 Introduction 6
1.2 Structure 6
1.3 Production 6
1.4 Polystyrene continuous production PFD(Bulk polymerization process) 7
1.5 Chemistry of free radical polymerisation of styrene 9
1.6 Properties of polystyrene 12
1.7 Uses of polystyrene 14
2 Chapter 2- Literature survey of Styrene 15
2.1 Introduction 15
2.2 Production 15
2.3 Catalytic dehydrogenation of ethyl benzene 15
2.4 PFD of ethyl benzene dehydrogenation process 18
2.5 Process equipments 19
2.6 Process flowsheet description 20
2.7 Ethyl benzene hydroperoxide process 20
2.8 PFD of Propylene oxide process 21
2.9 Process flowsheet description 22



























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S. No Topic Page No
2.10 Ethyl benzene and styrene separation 23
2.11 VLE data for ethyl benzene styrene mixture at different pressures 24
2.12 Antoine equation parameters for ethyl benzene styrene and sulfolane 24
2.13 Worldwide Demand and Scenario of Styrene 25
2.14 Global styrene supply and demand 26
2.15 Styrene global consumption by application 26
2.16 Styrene global supply demand and balance 26
2.17 Uses of styrene 27
2.18 Industrial specifications of styrene 27
3 Chapter 3- Prediction of thermodynamic properties using molecular
simulations
28
3.1 Trappe united atom model 28
3.1 Phase equilibria and coexistence using Gibbs ensemble Monte Carlo method 30
3.2 Particle transfer within a box 31
3.3 Volume exchange among the two phases 31
3.4 Exchange of particles between two boxes 32
35 List of Tables and Figures 33
36 List of references 34













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Literature survey
Introduction
Polystyrene is an important synthetic vinyl polymer widely produced commercially by free
radical vinyl polymerization of monomer styrene, a liquid hydrocarbon produced by
dehydrogenation of ethyl benzene. It is a hard transparent (when not added with colourful
additives) and relatively brittle plastic material used worldwide and finds its applications in
packaging, electric and electronic appliances, construction, automobiles, plastic furnitures.
Historically [1] it is said to be discovered by a German chemist named Eduard Simon when he
first separated it from natural resins. But it was another German organic Chemist, Hermann
Staudinger who found it that polystyrene is made up of long chains of styrene molecules.
Structure
Polystyrene being a polymer of styrene has continuous long chain of styrene (CH
2
=CHC
6
H
5
)
fragments as its repeating unit. The carbon atoms are linked to one another by covalent bonds.
Every alternate carbon atom in the chain has benzene ring attached to it.


Phenyl group present in polymer chain is responsible for some important properties exhibited by
polystyrene and it is only because of these properties polystyrene finds wide range of
applications in our daily life.
The bulky phenyl group attached to polymer chain does not allow rotation about carbon-carbon
single bonds and that is the reason why polystyrene is a hard material.
Another important aspect of presence of phenyl group is that a systematic close packed
crystalline arrangement is not possible because of which polystyrene is a transparent compound.
Production
At commercial scale Polystyrene is manufactured by addition polymerization of styrene in
presence of an inert organic solvent.1, 2- Dichloroethane is one of the most commonly used
solvent for this. There are other alternate organic solvents also such as carbon tetra chloride,
ethyl chloride, benzene, toluene, ethyl benzene methylene dichloride which can be used.
The different methods for production of polystyrene available are [3]:
Fig 1 [2]
7 | P a g e

1. Solution (bulk) polymerization:
Solution (bulk) polymerization is also known as mass polymerization in the industry. Majority
of all polystyrene produced universally follows this method. The common solvents used in this
process are the styrene monomer and ethyl benzene. Mass polymerization process can take place
in two modes, batch and continuous, of which continuous is the most preferred. In batch
polymerization conversion of monomer up to 80% is achievable but the problem of temperature
control, periodic maintenance of reactor vessels is also present. Therefore worldwide,
polymerization of styrene in continuous mode is preferred. From continuous production of
polystyrene conversion up to 85 % is obtained
Feed for the first reactor is 50 weight percent styrene monomer, 100 ppm water (on the basis of
styrene amount in kgs ), 2000 ppm boron trifluoride (gas phase, on the basis of styrene amount
in kgs) and the organic solvent chosen . The initiator solution is prepared by mixing 1.5% by
weight boron trifluoride gas into the organic solvent containing 280 ppm water. This solution is
continuously prepared in a holding vessel and the effluent of this vessel continuously enters in
all the reactors.The polymerization reaction releases heat, not in large amount but still the
temperature must not go beyond 70
o
C , the condition at which average molecular weight of
polymer formed decreases that is why the reactors are jacketed with continuous supply of
cooling agent through them.
The process flow diagram for continuous process of polystyrene:












Initiator
Styrene
Cooling water in
reactor jacket
Cooling water
Separator
Solvent
Polystyrene
Fig 2
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2. Suspension polymerization
Essential requirements for suspension polymerization are:
Initiator, suspending agent, Stabilizing agent, Catalyst and Polymerization Temperature


Initiators: The initiators generally used are benzoyl peroxide and t-butyl hydro peroxide.



Stabilizing agent: To keep the drops at proper size, a stabilizing agent is added. The stabilizing
agents are often insoluble inorganic such as calcium carbonate, calcium phosphates or bentonite
clay. They are present in small amount than the suspending agents. Their concentration in the
suspension is between 0.01-0.5percent of monomer charged.


Catalyst: A catalyst is used to control the reaction rate. The catalysts are usually Peroxides. The
most common ones are benzoyl, diacetyl, lauroyl, caproyl and tert-butyl. Their concentration
varies from 0.1-0.5% of the monomer charged. The ratio of monomer to dispersing medium is
between 10 and 40%.


Polymerization temperature: Polymerization of styrene occurs at temperature range of 90-95
o
C
In suspension polymerization method we can get polymers of higher average molecular weight.
In this process styrene drops of size range 0.15-0.50 mm in diameter are formed with the help of
an appropriate suspending agent such as partially hydrolysed polyvinyl acetate, inorganic
phosphates or magnesium silicates in aqueous medium. Polymerization reaction takes place in
these small suspended drops providing large surface contact area per unit volume of reactor
solution. Moreover a stabilizing agent for stabilizing size of drops must also be added. Styrene
and water are preheated and then sent as feed into the batch reactor the dispersing and stabilizing
agent and the catalyst without any preheating are charged from top into the reactor. Typical
water to monomer ratios is 1:1 to 3:1.The last and important step is the separation of water from
polystyrene and other organic compounds which is done by physical separation of water from
organic phase in a decanter the organic phase is later dried and passes through devolatilizer so
that the polystyrene gets rid of the volatile compounds in it and is formed in pellets which can be
conveniently stored and packed.
3. Emulsion polymerization- In this method styrene drops of microscopic size are
suspended in aqueous medium with stabilizing and suspending agents added into the mixture.
This method is not commercially used for making polystyrenes is used only when certain
monomeric additives are added along with monomer to make speciality polymer(high impact
grades of polystyrene).
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Chemistry of free radical polymerisation of styrene
In free radical polymerization of styrene ,styrene monomers continuously link to each other
through active centre sites formed after their addition to radicals of initiators (such as Benzoyl
peroxide )and the active centre site subsequently moves to the other side of the polymer
molecules chain with the help of a chain transferring agent such as butyl mercaptan to which
new monomer molecules then links.The polymer chain is terminated when the active chain
centre is detached from it by combination reaction.

The overall process that makes one complete chain of polymer takes place in the following
mentioned stages:
1. Initiation-This is the preliminary step of polymerization in which first free radicals of
initiator are generated either via homolysis in which thermal or any other kind of energy
such as light energy is supplied to break the single bond present in initiator molecule to
give duplicate free radicals or via heterolysis in which reactive free radicals are formed
by electron transfer between initiator and the other ion .These free radicals later add to
monomer molecule as per following scheme:

I R*+R* , I represents Initiator molecule and R* is the free radical of the initiator
R*+MRM* Addition of Free radical to monomer molecule

2. Propagation-In this stage monomer gets attached to the active chain end formed in the
previous step of chain initiation between radical and monomer resulting in the formation
of new active site to which new monomer molecule can link in to ways either in head to
head or head to tail orientation.
Propagation:
R
1
*+M R
2
*
R
2
*+M R
3
*
R
n
*+M R
n+1
*
~CH
2
-CH
*
+ CH
2
=CH ~CH
2
-CH -CH
2
-CH
*
Head to tail
Ph Ph Ph Ph

~CH
2
-CH
*
+CH
2
=CH ~CH
2
-CH -CH-CH
2
*
Head to head
Ph Ph Ph Ph
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3. Transfer-In this step the active polymer chain site is transferred to another molecule to
facilitate further monomer linking at active site of molecule. Chain transfer in case of
styrene polymerization is not feasible without addition of a suitable chain transfer agent
such as Butyl mercaptan.

R
n
* + ZY R
n
Y + Z* ZY is the chain transfer agent

The active chain can be transferred to polymer, monomer, and reaction medium or to the
chain transfer agent itself. The average molecular weight of the polymer increases if the
monomer holds the new active chain site.

4. Termination-This is the last stage in polymerization of polymeric chain carried from the
previous step of chain transfer. Now the active chain centre no longer exists on polymeric chain
and links to new monomer unit. After this the same steps from initiation to termination take
place and several polymeric units (chains) are formed thus. In case of polystyrene termination
via combination reaction is prevalent.

R
n
*+R
m
* P
n+m
Combination reaction
Rn*+Rm* P
n
+ P
m
Disproportionation reaction

Properties of Polystyrene [4]
Chemical properties
1. Polystyrene is an inert and stable chemical.
2. It is soluble in a few organic solvents that contain acetone.
3. It is highly flammable compounds and gives yellowish orange flame on burning.
4. Upon oxidation forms carbon dioxide and water vapour like other hydrocarbons do.
5. Polystyrene polymers get degraded on exposure to sunlight, due to photo oxidation.


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Physical properties
1. It is transparent, hard and brittle material like glass
2. It is highly elastic
3. Specific gravity of polystyrene is 1.03-1.06 g/cm
3

4. Polystyrene is a non-Newtonian fluid and its viscosity depends on the rate of deformation it
experiences.
Mechanical properties
1. Youngs Modulus 3000-3600 MPa
2. Tensile strength 30-60 MPa
3. Shear Modulus 1400 MPa
4. Crystal form of polystyrene exhibits low impact strength.
Optical Properties
1. Polystyrene when not added with rubber while its processing is transparent plastic
polymer
2. Refractive index is 1.58 to 1.59
3. Transmittance is 88-90%
4. Haze % is 0.1 to 1.1
Thermal properties
1. Polystyrene has glass transition temperature of 100
0
C.
2. Specific heat capacity 1250J/kgK
3. Thermal conductivity 0.14 W/mK
4. Coefficient of thermal expansion(linear) in temperature range 20-100
o
C is 120m/mK
Electrical properties
1. Dielectric strength 20 MV/m
2. Dielectric constant 2.5
3. Resistivity > 10
16
ohm*cm




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Thermodynamic Data of Styrene [5],[6]
CAS Registry Number: 100-42-5
IUPAC name:poly (1-phenylethene-1, 2-diyl)
Chemical Formula: C
8
H
8

Molecular weight: 104.1491
Melting point:-30.6
o
C

Boiling point:145.15
o
C



Gas phase thermochemistry data

Quantity Value Units References
H
f
o
(gas) 146.9+1.0 kJ/mol Prosen and Rossini,
1945
H
f
o
(gas) 151.5 kJ/mol Landrieu, Baylocq, et
al., 1929
H
f
o
(gas) 131.5 +4.0 kJ/mol N/A
H
f
o
(gas) -15.1 kJ/mol Moureu and Andre,
1914


Phase change data
Quantity Value Units Method Reference
Tboil 419. 2. K AVG N/A
Quantity Value Units Method Reference
Tfus 241. 8. K AVG N/A
Quantity Value Units Method Reference
Ttriple 242.47 K N/A Pitzer, Guttman, et al., 1946
Ttriple 242.47 K N/A
Guttman, Westrum, et al.,
1943
Ttriple 242.47 K N/A Guttman, 1943
Quantity Value Units Method Reference
vapH
43.93
0.42 kJ/mol V
Pitzer, Guttman, et al.,
1946, 2
vapH 43.5 kJ/mol N/A Prosen and Rossini, 1945
Table 2



Flammable limits in air = 1.1-6.1 vol %
Flash point = 31.1
o
C
Auto ignition temperature = 490
o
C
Table 1
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Antoine Equation Parameters
log
10
(P)=A(B/(T+C))
P=vapour pressure(bar) &T=Temperature(K)
Temperature
(K) A B C Reference
305.6 - 355.34 4.0593 1459.9 -59.551
Chaiyavech and van Winkle,
1959
303.07 -
417.92 4.21948 1525.1 -56.379 Dreyer, Martin, et al., 1955
Table 3
Enthalpy of fusion
fusH
(kJ/mol)
Temperature
(K) Reference
10.964 242.27 Warfield and Petree, 1961
10.949 242.27
Pitzer, Guttman, et al., 1946,
3
10.95 242.47 Guttman and Westrum, 1943
10.95 242.47
Lebedev, Lebedev, et al.,
1985
10.95 242.3 Domalski and Hearing, 1996
Table 4
Entropy of fusion
fusS
(J/mol*K)
Temperature
(K) Reference
45.32 242.27 Warfield and Petree, 1961
45.16 242.27
Pitzer, Guttman, et al., 1946,
3
45.16 242.47 Guttman and Westrum, 1943
45.2 242.47
Lebedev, Lebedev, et al.,
1985


Condensed phase thermochemistry data
Quantity Value Units Method Reference
fHliquid 103.4 0.92 kJ/mol Ccb Prosen and Rossini, 1945
fHliquid 108 kJ/mol Ccb Landrieu, Baylocq, et al., 1929
fHliquid 87.6 4.0 kJ/mol Ccb N/A
fHliquid -58.6 kJ/mol Ccb Moureu and Andre, 1914
Quantity Value Units Method Reference
cHliquid -4390. 60. kJ/mol AVG N/A
Table 5
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Quantity Value Units Method Reference
Sliquid 240.5 J/mol*K N/A Warfield and Petree, 1961
Sliquid 237.57 J/mol*K N/A Pitzer, Guttman, et al., 1946
Sliquid 237.6 J/mol*K N/A Guttman and Westrum, 1943

Table 6

Constant pressure heat capacity of liquid
Cp,liquid (J/mol*K)
Temperature
(K) Reference
183.2 298.15 Lebedev, Lebedev, et al., 1985
182.6 298.16 Warfield and Petree, 1961
235.6 298 Kurbatov, 1950
182.84 298.15 Pitzer, Guttman, et al., 1946
179.9 298.5 Smith and Andrews, 1931

Table 7
Uses
1. Used for making disposable cutleries
2. Casing of electronic appliances including computers audio and video cassettes are
made from polystyrene
3. Plastic furnitures
4. Essential element of the material used in making soundproof walls
5. Test tubes, petri dishes, trays for conducting tissue cultures are made from polystyrene
6. It is also used in making high impact strength projecting elastomers such as styrene-
butadiene-styrene (SBS) and styrene-isoprene-styrene (SIS) rubber.







15 | P a g e

Styrene
Introduction- It is an aromatic liquid hydrocarbon majorly produced from ethyl benzene in bulk
amounts especially for manufacture of polystyrene an important plastic polymer. It was first
made in mid-1930s by Dow Chemical ltd [7]. It can also be used for manufacture of various
polymers and resins such as Acrylonitrile Butadiene Styrene (ABS), Styrene Butadiene rubber
(SBR), Styrene Butadiene latex and fibreglass.


Production
There are two major industrial processes by which styrene can be manufactured
1. Catalytic dehydrogenation of ethyl benzene [8]
2. Ethyl benzene hydro peroxide process [9]

1. Catalytic dehydrogenation of ethyl benzene
90% of worldwide production of styrene takes place by employing this process in which the raw
material used are ethyl benzene and steam (not reactant). Ethyl benzene in vaporised from is
used as reactant and the steam should be superheated. Catalyst for this process contains 84.3%
iron as Fe
2
O
3
, 2.4% chromium as Cr
2
O
3
and 13.3% potassium as K
2
CO
3
.Two or three adiabatic
fixed bed reactors connected in series provided with inter stage heating by superheated steam are
employed for the process. The reaction is highly endothermic in nature and thats why large
amount of heat is to be supplied to the reactor for dehydrogenation of ethyl benzene to occur.
Main reaction taking place:
Dehydrogenation of ethyl benzene in presence of superheated steam is the desired reaction
chemical equation for this is as below:
C
6
H
5
CH
2
CH
3
C
6
H
5
CH=CH
2
+ H
2

Besides these there are always other side reactions taking place at higher reactor
temperatures.The dominant side reaction is hydrogenolysis of ethyl benzene producing toluene
and methane:
Fig 3
16 | P a g e

C
6
H
5
CH=CH
2
+ 2 H
2
C
6
H
5
CH
3
+ CH
4
Following are the less dominant side reactions:
C
6
H
5
CH
2
CH
3
C
6
H
6
+ C
2
H
4

C
6
H
5
CH
2
CH
3
8 C + 5 H
2
The last reaction produces carbon which deactivates the catalyst by blocking active catalyst sites
and thereby reduces conversion of ethylbenzene so introduction of superheated steam into the
reactor enables removal of carbon from catalyst because the steam itself reacts with carbon on
surface of catalyst and converts it into CO
2
and H
2
.
Addition of steam offers following advantages [10]
1. Steam added provides heat required for the reaction
2. Steam reduces the partial pressure of ethyl benzene and thus helps in shifting the main
reaction in forward equilibrium direction
3. Steam reduces coke formation by reacting with carbon deposited on catalyst surface formed as
a result of decomposition of methane at higher temperatures and converting it to form carbon
dioxide and hydrogen
Role of steam in enhancing equilibrium conversion of Ethylbenzene can be understood
graphically as follows


The operating conditions for reactor are,
Temperature=600-650
o
C
Pressure<=1bar.
Figure 4
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Steam to ethyl benzene ratio: 10-15
Conversion in the first reactor is around 35% and overall conversion of ethyl benzene up to 65%
is achieved with 90% yield.


Important consideration for process: Since styrene is operated at low temperatures
(~70
0
C) at in the separation process, there is a risk of polymerization. To prevent that,
inhibitors are used in the distillation train. The inhibitors are mainly aromatic compounds
with nitro-, amino- or hydroxyl groups. Since, most of the inhibitors are coloured
compounds; they are not used for the final purification. Instead 4-tert-Butylcatechol
(TBC) is used [9]. Distillations are also carried under vacuum conditions to prohibit
polymerization.









Figure 5
18 | P a g e

Process flow-diagram (Adiabatic process) [9]


Furnace
























Fresh EB














R
e
c
y
c
l
e
d

E
B

Superheated steam
Water







S
t
e
a
m












F
B
R
-
1










F
B
R
-
2

Compressor





H
X
-
1





H
X
-
2





H
X
-
3

C
o
o
l
i
n
g

W
a
t
e
r

Phase
Separator
Compressor
Off-gas









C
o
n
d
e
n
s
a
t
e

Benzene + Toluene
Distillation column
1
EB recovery column Styrene purification column
column
Figure 6
19 | P a g e

Process Equipments
Furnace: The furnace is used to convert steam/water into superheated steam.
Reactors (FBR-1 and FBR-2): For better yields, interaction between reactants and
catalyst must be high. Fluidised beds provide the best solid-gas interaction, but they also
significantly increase the pressure drop. Since the operating pressures are low, high
pressure drop has to be avoided. Hence a fixed bed reactor is used. Commercial catalyst
beds have a radial flow direction, with gases moving outwards. This ensures proper
distribution of gases through the bed and also decreases the pressure drop since the path
followed by gases is shorter as compared to axial flow. Both reactors: FBR-1 and FBR-2
are to be operated at 630C and pressure less than atmospheric as n
g
> 0 (more moles
produced). The FBR-1 is proposed to be operated at 500mmHg and the second reactor,
FBR-2 at 300 mmHg considering the pressure drops after moving through pipes.
HX-1: The first heat exchanger is a typical shell and tube heat exchanger with the
product stream going in the shell side and steam through the tubes.
HX-2: The second heat exchanger is exactly like the first one.
HX-3: The third heat exchanger is a partial condenser that converts with water going
through the tubes and the mixture passing through the shell side.
Phase Separator: A three phase separator is used to remove water and gases from the
product stream. The gas is mainly hydrogen, the by-product of the dehydrogenation
reaction. Hydrogen is removed from the separator and used as a heat source to produce
steam. Some gas is sent back to the separator to maintain the pressure in the separator.
The liquid gets separated into organic and aqueous phases. Water from the separator is
removed as condensate and reused to produce steam. Glass wool is used to remove any
liquids entrained in the vapour phase as the presence of liquids will decrease the
efficiency of gas compressor due to clogging.

Distillation Column: After removing hydrogen and water, the product stream consists
only of SM, EB, benzene, toluene and minor impurities. This stream is then separated
into SM+EB and Benzene + Toluene using a distillation column exploiting the
significant differences in their boiling points which are 145
0
C, 136
0
C, 80.1
0
C and
110.6
0
C respectively.
EB Recovery column: Since the boiling points of SM and EB are close, separation
requires a lot of stages. Perrys Handbook suggests using bubble cap tray column, 2.6
feet diameter and 19.7 in tray spacing. This column would require 34 trays. Hence, most
industrial plants prefer to use a packed column. With a packed column a smaller column
height can provide effective separation equivalent to 70-100 theoretical trays. Structured
stainless steel packing is used in the column. The EB recovered is recycled back to the
reactor. The distillate temperature is to be used as 130
0
C (EB boiling point) and the
raffinate temperature as 146
0
C (Styrene Boiling point). This range is to ensure that EB is
by large in vapour phase and not styrene.
Styrene Purification column: SM is further purified to achieve 99.7% purity as per the
industry standards set by ASTM. The distillate temperature is to be maintained around
146
0
C which is the boiling point of styrene.


20 | P a g e

Process Flow-sheet Description
First of all the fresh and recycled EB are mixed with superheated steam (coming from the
furnace) and the resulting mixture is passed axially through the first reactor labelled as (FBR-
1).The output mixture from FBR- is heated to the requisite temperature by a heat exchanger
(HX-1) because the reaction is endothermic and has brought down temperature of the reaction
mixture. For further conversion of ethylbenzene this mixture is later passed through the second
reactor labelled as (FBR-2).To keep the styrene and ethylbenzene mixture as liquid mixture so
that we can separate them in distillation tower later, it is compressed to a higher pressure so that
none of these two starts boiling. Its now passed through the shell side of a second heat
exchanger labelled as (HX-2) where the output steam from HX-1 is passed through the tubes.
This results in the steam getting heated and the mixture losing heat. This heat exchanger works
as an economizer that produces steam which is sent in the furnace to make superheated steam
and this superheated steam is sent into the first reactor. The mixture which lost heat by making
steam is now sent to the third heat exchanger (HX-3), which is a partial condenser. Cooling
water is used to partially condense the product stream. The mixture loses heat and all the
condensable components (SM, EB, Benzene, Toluene, steam) get condensed into liquid form,
while the non-condensable components (H
2
, CO, CO
2
) remain as is. The 3-phase separator
separates the mixture into gas, organic and aqueous phase. The organic phase is sent forward for
separation by distillation. A series of distillation columns are used to separate Benzene +
Toluene, EB (which is recycled), industrial grade SM and ta

Ethyl benzene hydro peroxide process

This process accounts for less than 10 % worldwide production of styrene. . It produces
propylene oxide (PO) along with Styrene (SM) and the process is called POSM. The global
demand of PO is 2/10 of SM but via POSM 4/10 of PO is produced. Since, the SM production
via this method cant be increased alone, the local PO demand dictates the profitability of this
method. This process is not available for licensing.
There are three steps in the process:
Oxidation Step: Air is bubbled through liquid EB in a series of reactors with decreasing
temperatures from 150 to 130
0
C. This converts EB to EB hydroperoxide.
Epoxidation Step: This reaction is carried out in liquid phase, with temperature ranging
from 100-130
0
C and a catalyst of soluble molybdenum naphthanate/silica gel. This gives
-phenylethanol and Propylene Oxide (PO).
Dehydration Step: The dehydration of -phenylethanol in the presence of a dehydrating
agent like Al
2
O
3
gives SM.



21 | P a g e

Reactions taking place:
Reaction 1: Oxidation of Ethyl Benzene to Ethyl Benzene hydro Peroxide
C
6
H
5
C
2
H
5
+ O
2
C
6
H
5
CH(OOH)CH
3

C
6
H
5
C
2
H
5
+ O
2
C
6
H
5
CH(CH
3
)OH
C
6
H
5
C
2
H
5
+ x O
2
acids + C
6
H
5
CO(CH
3
)

Reaction 2: Reaction of Propylene with EBHP to give Propylene Oxide and MBA
C
6
H
5
CH(OOH)CH
3
+ C
3
H
6
C
6
H
5
CH(CH
3
)OH + C
3
H
6
O

Reaction 3: Hydrogenation of Acetophenone (ACP) to Methyl Benzyl Alcohol [MBA] to enrich
MBA
C
6
H
5
CO(CH
3
) + H
2
C
6
H
5
CH (CH
3
)OH
Reaction 4: Dehydration of Methyl Benzyl Alcohol to give Styrene[SM]
C
6
H
5
CH(CH
3
)OH C
6
H
5
CH = CH
2
+ H
2
O





















22 | P a g e

Process flow diagram of styrene manufacture by Propylene oxide process




























A
i
r

EBHP (90%)
MBA
ACP
EB
13%
conversion
13%
Conversion
Propylene
PO
MBA
ACP
EB
13%
conversi
on
PO
Crude
PO
Purified

Direct Oxidation Catalytic
Epoxidation
Caustic Wash
Ethyl-Benzene
Fresh
Ethyl-Benzene
MBA, ACP, EB
MBA

H
2

Ethyl-Benzene
Recovery Column
MBA
ACP
SM
MBA
ACP
MBA
ACP
Dehydration
Al
2
O
3

SM
refining/Caustic
Wash
Styrene Monomer
ACP Hydrogenation
Figure 7
23 | P a g e

Process flow-sheet description

The raw material ethyl benzene is oxidised at 130
o
C and 0.2MPa pressure to ethyl benzene
hydro peroxide in a series of reactors maintained at temperatures decreasing from 150 to 130
o
C
in which air is continuously bubbled at bottom in liquid column of ethyl benzene fed
continuously inside from top in to the reactor. Later the EBH formed is made to react with
propylene in presence of molybdenum or titanium catalyst to produce -phenyl ethanol and
propylene oxide. This mixture when dehydrated at 250
o
C and low pressures over acidic catalyst
such as Al2O3 produces crude styrene which is finally further purified from oxygenates that act
as poison for catalyst of styrene polymerisation. An additional reaction to convert Acetophenone
(ACP), a side product during the oxidation of EB, is hydrogenated to MBA for better recycling
and higher production of styrene.EB is oxygenated to give the three products at 206-275 kPa and
140C - 150C. The conversion is around 13%. The Selectivity towards EBHP is around 90%
while the other products amount to the remaining 10%. Since, only 13% conversion is achieved,
Ethyl benzene is recovered back for reuse. EBHP is then reacted with Propylene at 95C
130C and 2500-4000 kPa, in presence of titanium catalyst over silica (SiO
2
) support catalyst.
Conversion of around 95% is achieved with selectivity of 92-95% Propylene Oxide. Propylene
Oxide is then separated out from the product stream. The rest of the product stream is treated
with caustic wash to neutralize acids. In the presence of Acids, the Methyl Benzyl Alcohol
[MBA] gets converted to styrene which readily polymerised at the given condition. Ethyl
Benzene is then recovered from the stream as only 13% was earlier converted.The rest of the
stream with MBA and ACP is then carried ahead. MBA from the stream is dehydrated in
presence Al
2
O
3
to give styrene monomer. ACP from the stream is also hydrogenated to MBA in
Reaction set-3 and then fed back to improve overall styrene yield.

Ethyl benzene and styrene separation [11]
The relative volatility for VLE mixture of styrene and ethyl benzene has value ~ 1.3-1.4 because
boiling points of these two compounds are quite close. Therefore fractional distillation for
separating out these compounds from each other either requires large reboiler duty or vaccum
conditions inside distillation column. Either of these are high energy/power consuming options
but are still in practice at commercial scale. Besides these the distillation towers are required to
have around 100 trays to achieve higher purity of styrene as finished product. Current Research
on extractive distillation of styrene-ethyl benzene mixture reveals that sulfolane can be added to
this mixture and can increase the value of relative volatility from 1.3 -1.4 to 2.2 thereby easing
the separation of components. A further research study shows that sulfolane can be replaced with
Ionic liquid such as 4-methyl-N-butylpyridinium tetrafluoroborate ([4-mebupy]-[BF
4
]).This new
extracting agent increases the value of relative volatility of styrene ethyl benzene VLE mixture
24 | P a g e

up to 2.7-2.8 .The advantages of ILs are that they are chemically and thermally stable at
temperatures close to 100
o
C and have low vapour pressure at these temperatures.
VLE data for styrene ethyl benzene mixture at different pressures [12]
5 kPa 10 kPa 20 kPa
T x
1
y
1
T x
1
y
1
T x
1
y
1

332.3 0.026 0.037 348.2 0.026 0.037 366 0.026 0.036
332.1 0.051 0.074 347.9 0.051 0.073 365.7 0.05 0.07
331.5 0.089 0.126 347.6 0.084 0.118 365.4 0.084 0.114
330.5 0.181 0.245 346.6 0.178 0.239 364.5 0.176 0.233
329.5 0.264 0.346 345.7 0.281 0.36 363.5 0.279 0.35
329.1 0.349 0.44 344.7 0.376 0.466 362.5 0.374 0.455
327.9 0.475 0.569 344 0.478 0.565 361.8 0.476 0.558
327 0.571 0.658 343.2 0.574 0.656 360.9 0.575 0.653
326.3 0.676 0.752 342.4 0.67 0.739 360 0.667 0.735
325.5 0.784 0.841 341.5 0.775 0.828 359.2 0.774 0.824
325 0.877 0.91 341.1 0.834 0.874 358.8 0.834 0.871
324.5 0.938 0.953 340.3 0.937 0.951 358 0.937 0.949
Table 8


Table 8









Antione Equation Parameters for Styrene, Ethyl-benzene and Sulfolane
Component T(K) Ai Bi Ci
Ethyl-benzene 324-364
20.8051 3211.78 -63.05
Styrene 332-373
21.1275 3453.58 -58.5
Sulfolane 391.2-559.2 21.9503 5193.41 -61.76
Table 9

P
i
sat
represents saturation pressure of component i at temperature T
25 | P a g e

Worldwide Demand and Supply Scenario of styrene[13]
The demand for styrene has since shifted towards the manufacture of polystyrene. In 2010, the
worldwide consumption of styrene was approximately 25 million tonnes, of which more than
half was for the production of polystyrene .The demand for styrene is expected to grow at 0.8%
in Asian markets.


The global consumption for styrene monomer is driven by polystyrene demand. The global
demand for styrene in 2010 was approximately 25million tonnes/year, 61% of which was for
polystyrene production. Since the Asia-Pacific region (not including China) is a net importer of
styrene, it would be profitable to establish a plant in this region. The demand for styrene in Asia-
Pacific was 7.3million tonnes/year in 2010 and has been growing at 0.8%/year. The total
capacity achievable by plants in Asia-Pacific is 9million tonnes. However, in recent years the
demand for styrene has seen steady increase due to higher production of polystyrene and EPS.
The global utilization rate is predicted to increase from 80% in 2010 to as high as 93% by 2017.

Figure 8
26 | P a g e






Based on the annual consumption growth rate of 0.8%, the consumption of styrene in Asia-
Pacific will be 7.71millon by the year 2017. So to balance this 0.41million tonne increase in
consumption, the total capacity needs to be increased by 0.5million tonnes assuming that the
plant operates at 80% utilization. Hence, a plant capacity of 100,000-500,000 tonnes/year is a
feasible option.
IOCL has set up a 220,000 tonnes/year capacity SBR plant in Panipat and a recently closed
BASF plant in Thane had a capacity 100,000 tonnes/year. Hence, we set the plant capacity to
200,000 tonnes/year.
Figure 9
Figure 10
27 | P a g e


Uses
Styrene based products are used extensively in rubber, plastic, insulation, fibreglass and
packaging
Polystyrene - It is the main polymer of styrene. It is a thermoplastic- thus making it
mouldable above a temperature and solidifies when cooled. They are used for packaging
of several goods example: CD-covers, jewellery cases etc.

ABS (Acrylonitrile Butadiene Styrene) - It mainly is known for its strength and shock
absorbing nature. Used in golf club heads, car bumper heads, protective gears,
refrigerator liners, medical devices, small household appliances and luggage etc.

SBR (Styrene Butadiene Rubber) - On account of its elastic properties, it is used in
making vehicle tires, shoe heels and soles etc.

SB latex - It is a water emulsion of styrene-butadiene co-polymer Particles. Mainly used
for paper coating, carpet backing, wood lamination


Product Industrial specifications [14]

Content Unit Specification
Purity wt% Min. 99.70
Benzene Content wt% Max. 1
Ethylene Benzene ppm 500 max.
Colour Pt-Co Haze units Max. 10
Inhibitor Content mg/kg 10-20
Polymers Content mg/kg Max. 10
Aldehydes (Benzaldehyde) wt% Max 0.32
Peroxides Content (as H
2
O
2
) mg/kg Max. 100
Table 10







28 | P a g e

Prediction of Thermodynamic properties using molecular simulations
Styrene of high purity as finished product cannot be obtained unless the efficient ways of
separating it from unconverted reactants and side products of the process are known.Styrene has
to separated from ethylbenzene in plants producing styrene. The difference in boiling points of
these chemicals is only 9
o
C and therefore direct fractional distillation will require large no of
trays and high reboiler duty therefore extractive distillation if adopted will make separation
process more economic. Knowledge of VLE data and activity coefficients is essential for
designing and operating distillation process as it reveals nature of interactions among the species
in liquid and vapour phases to be separated and deviations from ideality.

Molecular simulations are the better means for estimating thermodynamic properties
comparatively more accurately experimentally for systems containing multiple phases of pure or
multicomponent mixture in equilibrium. The overall interaction energy of system of molecules
of pure or multicomponent mixture is described in terms of an appropriate conservative force
field.

TraPPE UA [16]
TraPPE refers to transferable potentials for phase Equilibria.Phase equilibrium behavoir,
deviation from ideality of solutions are all attributed to the nature of intermolecular interactions
(forces) among atoms/molecules in solution.These intermolecular ineteractions can be described
by conservative force fields one which is widely used for molecular modelling and simulation is
United atom force field model. TraPPE United atom force models groups carbon and hydrogen
atoms bonded to it together as a pseudo atom i.e. C, CH, CH
2
, CH
3
and CH
4
are all one
interaction site in the system. By 'transferable' we mean that the force field parameters such as
epsilon and sigma in LJ potential model for a given interaction site (pseudo atom)should be
same when used for different molecules (e.g., identical parameters should be used for the methyl
group present in, say, n-hexane, 1-hexene, or 1-hexanol) and that the force field should be same
for different state points (e.g., pressure, temperature, or composition) and for different
properties (e.g., thermodynamic, structural, or transport).
The total potential energy of the system is divided into two parts:
1. Bonded - This accounts for intramolecular interactions between pseudo atoms within a
molecule itself.
2. Non-bonded- This accounts for intermolecular interactions between pseudo atoms present on
different molecules and pseudo atoms within a molecule if these are separated by four or more
bonds.

29 | P a g e







Bonded interactions are further of 3 types
(i) 1-2 interaction in which interaction sites connected through a common bond are
considered, the bond length is assumed to be fixed.
There are 7 such interactions which exist between pseudo atoms located at 1 and 2,2 and
3,3 and 4,4 and 5,5 and 6,6 and 1,1 and 7 & 7 and 8.Schematic of 1-2 interaction is as below:
A B

(ii) 1-3 interaction in which interaction sites separated by two bonds at the two ends of V-
shaped network which bends about the location of central pseudo atom are considered.
There are 9 such V shaped network under harmonic bonding potential formed by pseudo atoms
located at 1,2,3; 2,3,4; 3,4,5; 4,5,6; 5,6,1; 6,1,2; 6,1,7; 2,1,7; and 1,7,8 locations
A C
B
(iii) 1-4 interactions also called dihedral interactions in which the interaction sites separated
by three chemical bonds forming a network (shown below) which is under torsion about central
bond are considered.
A D
B C


The angle between the planes containing pseudo atoms A, B, C and B, C, D is called dihedral
angle and this angle changes by virtue of interaction between pseudo atoms A and D.


Pseudo atoms located at 2, 3, 4, 5 & 6 are CH groups in benzene ring
Pseudo atom located at 1 is Carbon atom in benzene ring
Pseudo atom located at 7 is CH group of substituted alkene group
Pseudo atom located at 8 is CH
2
group of substituted alkene group

Figure 11
Figure 12
30 | P a g e

Phase equilibria and coexistence using Gibbs ensemble Monte Carlo method [15]
Gibbs ensemble method is one of the computationally most efficient and simple systematic
method used for obtaining VLCCs (Vapour liquid coexistence curves) from VLE data obtained
from simulation results for pure substances or multicomponent mixtures helpful in predicting
their important thermodynamic properties.

The macroscopic system which consists of liquid and its vapour is checked for equilibrium by
first taking out two microscopic regions from each phase in separate fictional boxes and
applying acceptance criteria for following mentioned moves which are meant for satisfying
conditions for Vapour liquid equilibrium:
1. Trial move to displace a randomly selected particle in one of the boxes from its initial
location to new coordinates. This trial move is intended for condition of internal
equilibrium within each box
2. Trial move to exchange volume among the two boxes in such a way that the total volume
of the two boxes remains fixed. This trial move is intended for condition of equality of
pressure between two phases.
3. Trial move to transfer a particle from one box to the other. This trial move is intended for
condition of equality of chemical potentials of each component in all phases

Let the Temperature, Total Volume and Total Number of particles in a system of pure substance
present partially in liquid and vapour phase be T, V and N respectively.

Then the expression for partition function [15] for the overall system is as follows:
QNVT=

)]

)]

is the thermal de Broglie wavelength given as =

,
1
and
2
are the scaled coordinates of the particles in vapour and liquid phase
respectively and U
1
(N
1
) and U
2
(N
2
) represent potential energy of vapour and liquid phase

If V
1
and N
1
are the volume and number of particles of vapour phase then volume and number of
particles of liquid phase will be V-V
1
and N-N
1
respectively.

The probability of finding configuration of system [15] in above mentioned state is:
P (N
1
, V
1
; N, V, T)

exp (N
1
lnV
1
+N
2
lnV
2
- U
1
(N
1
)-U
2
(N
2
))
Keeping this expression in mind we will later see the acceptance criterias in Gibbs ensemble
method for ascertaining conditions of vapour liquid equilibrium.


31 | P a g e

Particle transfer within a box

When a particle in vapour phase initially at location for which total potential energy of the
vapour phase is U
i
is randomly picked and located to new coordinates for which total potential
energy of the vapour phase is say U
f
then the change in potential energy of the vapour system
is U= U
f
-U
i
.
Using the probability density function [15] which we had mentioned earlier:
P (N
1
, V
1
; N, V, T)

exp (N
1
lnV
1
+N
2
lnV
2
- U
1
(N
1
)-U
2
(N
2
))
Probability distribution of initial configuration given above is:
P
i

exp (N
1
lnV
1
+N
2
lnV
2
- U
1i
(N
1
)-U
2i
(N
2
)) (1)
Similarly Probability distribution of final configuration given above is:
P
f

exp (N
1
lnV
1
+N
2
lnV
2
- U
1f
(N
1
)-U
2i
(N
2
)) . (2)
Dividing equation (1) with equation (2) we get relative probability for transition from initial
configuration to final configuration as:

= [exp (-(U
1f
(N
1
)- U
1f
(N
1
))]

= [exp (-(U)]
If sign of U is positive then a random number is generated in [0,1] and the move is accepted
only if random number generated is less than exp(-U) otherwise not accepted. In case U is
negative the probability of transition of particle to new location is 1 as exponent of a negative
number is always greater than or equal to 1 and probability can at max be equal to 1.

Volume Exchange among the two boxes

Let us assume that the initial and final volumes of vapour phase are V
i
and V
f
respectively then
the change in volume is V= V
f
-

V
i

Let total potential energy of the vapour phase before and after volume change is E
i
and E
f
then
change in potential energy of vapour phase is U= U
f
-U
i


Using the probability density function [12] which we had mentioned earlier:
P (N
1
, V
1
; N, V, T)

exp (N
1
lnV
1
+N
2
lnV
2
- U
1
(N
1
)-U
2
(N
2
))
Probability density corresponding to initial configuration where volume of vapour phase is V
i

and energy E
i
is:
32 | P a g e

P
i

exp (N
1
lnV
1
+N
2
lnV
2
- U
1i
(N
1
)-U
2i
(N
2
)) [U
1i
(N
1
) + U
2i
(N
2
) =U
i
]
.(1)

Similarly for final configuration where volume of vapour phase is V
f
and total energy E
f

probability density is:
P
f

exp (N
1
lnV
1
+N
2
lnV
2
- U
1f
(N
1
)-U
2f
(N
2
)) [U
1f
(N
1
) + U
2f
(N
2
)=U
f
]
.(2)
Dividing equation (1) with equation (2) we see relative probability for transition from initial
configuration to final configuration as:

= [

]
N1
[

]
N-N1
exp[-(E
f
-E
i
)]

Particle exchange between two boxes
In this last trial move of Gibbs ensemble Monte Carlo simulation a particle is randomly picked
and transferred to another box after randomly picking the box from which particle will be
transferred. For transfer of particle from vapour phase to liquid phase the relative probability for
occurrence of this event is:

(

)

)
(

)
(

)((

))

exp[-(E
f
-E
i
)]
Therefore the probability that particle from vapour phase will go to liquid phase is

)
(

exp[-(E
f
-E
i
)] if E
f
-E
i
is positive and 1 if its negative
Similarly for transfer of particle from liquid to vapour phase the probability is
(

)(

)
(

)(

)
exp[-(E
f
-E
i
)] if E
f
-E
i
is positive and 1 if its negative









33 | P a g e

List of Figures and Tables in report
Fig 1-Chemical structure of polystyrene
Fig 2-Flow sheet of solution polymerization of styrene
Fig 3-Chemical structure of styrene
Fig 4-Effect of presence of steam on equilibrium conversion of ethylbenzene versus
Temperature
Fig 5- Equilibrium conversion of ethylbenzene versus Temperature for two different pressures
Fig 6- Process flow diagram for catalytic dehydrogenation of ethylbenzene
Fig 7- Process flow diagram for propylene oxide process
Fig 8 -Yearly global styrene demand and capacity variation
Fig 9-Styrene global consumption by application
Fig 10-Styrene global supply demand and balance
Fig 11- Location of pseudo atoms in styrene molecule
Fig 12 - Four molecule dihedral network in styrene

Table 1 Gas phase thermochemistry data of styrene
Table 2 Phase change data
Table 3 Antoine equation parameters for styrene
Table 4 Enthalpy of fusion
Table 5-Entropy of fusion
Table 6-Condensed phase thermochemistry data
Table 7-Constant pressure heat capacity of liquid styrene
Table 8-VLE data for styrene ethylbezene mixture at different pressures
Table 9-Antione Equation Parameters for Styrene, Ethyl-benzene and Sulfolane
Table 10-Industrial specifications for styrene




34 | P a g e


List of References:
[1] http://inventors.about.com/od/pstartinventions/a/styrofoam.htm
[2] http://www.nature.com/srep/2013/130826/srep02502/fig_tab/srep02502_F1.html
[3] Polystyrene: Synthesis Production and Application by J.R. Winsch
[4] http://www.boedeker.com/polyst_p.htm
[5] http://webbook.nist.gov/chemistry/
[6] http://www.styrenemonomer.org/2.2.html &
http://www.chemicalbook.com/ChemicalProductProperty_EN_CB3415111.htm
[7] Ullmann's Encyclopedia of Industrial Chemistry
[8] Arno Behr, Styrene Production from Ethylbenzene. Universitat Dortmund
[9] http://www.sbioinformatics.com/design_thesis/Styrene/Styrene_Methods-2520of-
2520Production.pdf
[10] Chemical process technology 2
nd
edition Jacob A Moulin et al
[11] Journal of chemical and engineering data Mark T. G. Jongmans et al
[12] Journal of chemical and engineering data Isobaric Low-Pressure VaporLiquid Equilibrium
Data for Ethylbenzene + Styrene + Sulfolane and the Three Constituent Binary Systems By
Mark T. G. Jongmans et al
[13] Styrene: 2013 World Market Outlook and Forecast up to 2017, merchant research
and consulting ltd.
[14] ASTM, Designation: D2827 13 Standard Specifications for Styrene Monomer
[15] Introduction to Molecular Simulation and Statistical Thermodynamics by Berend Smit
Daan Frenkel.
[16] https://www.chem.umn.edu/groups/siepmann/trappe/united_atom.php