Background

Styrene is one of the essential reactant that we require for the creation of products we use
day to day. The reason why styrene is so widely used is because it is strong, durable; and can
be used in many things such as foam, cases, appliances, containers and carpets. In 2011, the
demand for styrene was
26,111,000 metric tons[1]
and since this compound is
so versatile the demand for
it will only continue to rise
as the population rises as
well. Styrene began its large
scale production in 1930s
because of new chemical
Figure 1: Styrene Demand 2011 discoveries allowing it to
become readily available.
Today there is no chemical alternative that can compete effective crosslinking and that is
also cheap as well as styrene does. But styrene is a dangerous chemical; it is highly
flammable and it can readily link itself to other styrene molecules when exposed to light and
heat[5]. Polystyrene however, has a major impact to global warming. Because polystyrene
takes 500 years to decompose and is resistant to photolysis meaning it is very difficult to
discard. Burning polystyrene will release Carbon Monoxide and Styrene Monomers into the
environment which is dangerous to our health[2]. Exposure to styrene includes aspiration
into the lung which can cause chemical pneumonitis which can be fatal, it is irritating to skin
and eyes and dangerous to the central nervous system therefore the best solution to control
exposure is incorporate safety practice in the workforce. Styrene is a dangerous molecule
but there are two feasible ways to produce styrene. One of them is responsible for 90% of
today’s styrene production and that is dehydrogenation of ethylbenzene in the presence of
a catalyst. The other process involves the oxidation of ethylbenzene to its peroxide that is
reacted with propylene to produce methylphenyl carbinol which is then dehydrated to form
styrene. But there is also a new process that has emerged such as Toluene Alkynation with
Methanol to from Styrene, because this process has eliminated the ethylbenzene
dehydrogenation unit operating cost would be reduced.
Alternative Process

Dehydrogenation of Ethylbenzene

The dehydrogenation reaction of ethylebenzene is

usually operated at temperatures above 600oC[3]
and is an endothermic reaction which is reversible.
High temperatures and a low benzene partial
pressure are used in the reaction to shift the
equilibrium reaction to favour the production of
styrene because the conversion of ethylbenzene
increases as the reaction temperature increases.[4] Figure 2: Reaction to Form Styrene from Ethylbenzene

Main side reactions include[3]:

Ethylbenzene -> Benzene + C2H4 (Endothermic)

Ethylbenzene + H2 -> Toluene + CH4 (Endothermic)

The side reaction which involves toluene is determined by the temperature of the reactor
that is currently operating. If there is toluene in the reaction, this can be separated by a
distillation column whilst leaving the ethylbenzene and styrene to be recycled and mixed
with fresh ethylbenzene before the reactor.

Ethylbenzene exists as a colourless liquid[10] but is mostly found as a vapour in the

environment, it can move through water and soil because it doesn’t easily bind to soil. But it
can move towards a water supply where it breaks down with the chemicals naturally found
in water. Residential areas close to an underground storage tank of ethylbenzene of landfills
may have some contamination with ethylbenzene due to the leakage from the site. Luckily
ethylbenzene isn’t classified as a hazard
to the environment

One important aspect of the

dehydrogenation of ethylbenzene is its
reactor. The major by-product of the
reaction from ethylbenzene to form
styrene is complex mixtures of aromatics
and well as the formation of coke
therefore in order to minimize these
formations the reactors had to be
adiabatic[6]. These reactors generally had

one circular flow path that entered and Figure 3: Axial Reactor Figure 4: Radial Reactor
then exited the vessel. This circular
design required a low inlet volume to obtain an appropriate distribution of the feed through
 to the catalyst bed compared to an axial flow reactor. These radial reactors also had the
advantages to provide a low pressure drop since its path through the catalyst bed is shorter
than an axial reactor. Because the dehydrogenation of ethylbenzene is an energy
demanding process, many technologies have aimed to decrease this high energy
consumption.[7]

Most styrene plants that involve the dehydrogenation of ethylbenzene to form styrene are
either based on the Lummus Crest/UOP technology or the Fina/Badger process technology
that have adiabatic reactors[6]. Although these processes are very alike there are some key
differences within these
processes such as the
temperature, the reaction
pressure and the amount of
unit operations required to
obtain styrene. However
Lummus Crest undergoes a
Zeolite-base liquid phase
dehydrogenation of
ethylbenzene whilst the
Fina/Badger undergoes a
Figure 5: Fina/Badger Dehydrogenation
vapour-phase
dehydrogenation of
ethylbenzene . Both processes have super-heated steam around 750oC-850oC that is fed
[9]

into the first reactor to prepare the system for a forward reaction. The steam and
ethylbenzene mixture has a ratio of 1.8[8] and is fed into the first reactor at 610oC-650oC
which differs depending on the quality of the catalyst. The reaction mixture cools during
conversion and the then leaves the first reactor at 560oC-570oC. The conversion of
ethylbenzene is about 35%. The process is
repeated into a second reactor which
ethylbenzene is then evaporated by
numerous heat exhangers and mixed with
dilution steam to prevent coke formation
to maximise the conversion to 65%-70%.[6]

Figure 6: Lummus Crest/UOP Dehydrogenation

Figure 7: Selected Process
 The Picked Process
PRODUCTION OF STYRENE BY
ADIABATIC DEHYDROGENATION
[6]
Fina/Badger Styrene Process

The fresh ethylbenzene is mixed with the

recycled ethylbenzene [P-21] then it is mixed
with steam [P-4] and is fed to the primary and
secondary dehydrogenation reactors. When
steam exits the re-heater as a cool product,
it is then reheated to superheated steam [P-
3] which then enters the primary
dehydrogenation reactor [P-4]. Superheated Figure 8: Styrene Molecule
steam is used for heating the mixture for the
reaction in the secondary dehydrogenation reactor as well [P-6]. These dehydrogenation
reactors [E-2 and E-3] are designed to have low pressure and an even flow distribution. The
dehydrogenation reactors liquid waste is then cooled through a number of heat exchangers
[E-5, E-6 and E-7] which heat the recycled and fresh ethylbenzene[P-9]. The reactors liquid waste is
divided and condensed [P-20] which then enters a vent gas compressor which further
minimized pressure drop.This process has three distillation towers that operate to reduce
polymer formation, to have low temperatures and to operate under vacuum conditions. The
first column [E-13] separates the toluene and benzene by-products from unconverted
ethylbenzene and styrene [P-22], the benzene and toluene is then sent to a different
ethylbenzene plant where it is
further fractionated[P-19]. The
second distillation tower [E-15]
separates the unconverted
ethylbenzene [P-21] that is then
recycled for the feed for the
dehydrogenation reactors. The
temperature of this tower is below
100oC to reduce the polymerisation
of styrene which occurs at
temperatures higher than 100oC.
Figure 9: Selected Process This recovery stream [P-23] is then
fed to the third and final column [E-
16] where styrene itself [P-24] is purified by removing any heavy residue [P-25]. 4-tert-
butylcatechol is injected at the top of the third column to prevent polymerisation during
storage. Preventing polymerisation during storage is maintained by lowering the
temperatures below 20oC and by frequently adding 4-tert-butylcatechol.

Adiabatic dehydrogenation of ethylbenzene processes leads to superheated steam above

600oC which may have dangerous outcomes if not handled properly. However if we based
our selection with an isothermal dehydrogenation of ethylbenzene which was established
by BASF, their reactor is built as a reactor-heat exchanger where ethylbenzene and steam
flow through tubes that are packed with catalysts, the heat however is supplied with hot
flue gas in the outer portion of the reactor, therefore the temperature of the steam is lower
than the adiabatic process[12]. But a disadvantage to this is that the size of the isothermal
reactor that constrains the size limitations of a single-train chemical plant, therefore there
will be an increase of investment costs for chemical
plants[12]. But heat recovery from there flue gas where it
will still enter the atmosphere will have impact on
global warming. Because when fuels are burned
(besides ash and certain gas molecules) their remains
are still there. But it depends on the composition of the
fuel that really has an impact to global warming.
Typically it consists of CO2[11] which is the main
greenhouse gas responsible for global warming which
might conclude to nearby societies protesting against
the chemical plant. This is why an adiabatic process is
more sustainable than the isothermal process. Figure 9: Flue Gas
[1] Jamie Van Fleet. 2010. You Know Styrene. [ONLINE] Available
at: http://youknowstyrene.org/the-styrene-you-know/uses-and-benefits/. [Accessed 15 March 13].

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[3] Byron McCaughey. 2008. Personal Utulsa. [ONLINE] Available

at: http://www.personal.utulsa.edu/~geoffrey-
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[4] Won Jae Lee. 2005. Repository. [ONLINE] Available

at:http://repository.tamu.edu/bitstream/handle/1969.1/4847/etd-tamu-2005C-CHEN-Lee.pdf.
[Accessed 28 March 13].

[5] http://scorecard.goodguide.com/chemical-profiles/html/styrene.html

[6] Guy B. Woodle. 2009. Organica. [ONLINE] Available at: http://organica1.org/ops_85/styrene.pdf

[Accessed 06 April 13].

[7] Wünsch, J.R, 2000. Rapra Review Reports. Expert Overviews covering the Science and Technology
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us+and+Badger+process&source=bl&ots=8kMO0PWwlo&sig=sLgTp_7kEQknj3H1IgNFNttTcGU&hl=e
n&sa=X&ei=LGGkUfnmN4WRigfw7oGQCA&ved=0CDsQ6AEwAw#v=onepage&q=differences%20Lum
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[10] Chris. 1999. Cameo Chemical. [ONLINE] Available at:

http://cameochemicals.noaa.gov/chris/ETB.pdf. [Accessed 15 May 13].

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[Accessed 23 May 13].

[12] James, D.H, 2005. Styrene. Polystyrene and Styrene Copolymers is a separate keyword, [Online].
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