CONCEPTUAL DESIGN ANALYSIS FOR STYRENE PRODUCTION

The following concept covers the alternatives process design concepts for production of styrene.
Each concept is explained in detail, including chemical equations and a block flow diagram.

SELECTED DESIGN CONCEPTS

1. Catalytic Dehydrogenation of Ethylbenzene (Adiabatic Process)

Direct dehydrogenation of ethylbenzene to styrene take place of 85% of commercial production,
and can be achieved either adiabatically or isothermally, both methods are used in plants but
over 75% of all operating styrene plants perform the dehydrogenation reaction adiabatically.
(Lee, 2005)

Styrene reaction:

C6H5CH2CH3 ↔ C6H6CHCH2 + H2

∆H (600 C) = 124.9 kJ/mol (Lee, 2005)

This process involves the dehydrogenation of ethylbenzene (EB) to styrene (ST) in an adiabatic
reactor. Steam is mixed with the feed to lower the partial pressure of EB, favoring conversion.
The reaction is endothermic and reversible, requiring high temperatures to achieve desirable
yields.

Furthermore, there are some undesirable by-products that are produced by other side
reactions occurring in the reactor increasingly with temperature and partial pressures, which
are benzene, toluene, ethylene and carbon dioxide.

The major variables must be considered in the design optimization are the steam-to-EB ratio,
reactor inlet temperature, reactor size and EB recycle flowrate. High reactor temperature
energizes the side reaction, but it will not require more EB recycle to achieve the desired
styrene production rate as if the reactors run at low temperature. The side reactions could be
suppressed by increasing steam-to-EB ratio but that will increase the furnace fuel cost and
steam supply cost.

The production of styrene is done by the dehydrogenation of ethylbenzene in a high-

temperature, gas-phase adiabatic reactor. The reaction is reversible and endothermic, and as it
is a reversible gas-phase reaction producing 2 mol from 1 mol of starting material, low
pressure favors the forward reaction to shift equilibrium of the reversible reaction towards the
products.

There are several other side reactions that consume EB and produce undesirable by-products.

Benzene/ethylene reaction:

C6H5CH2CH3 → C6H6 + C2H2

Toluene/methane reaction:

C6H5CH2CH3 + H2 → C6H5CH3 + CH4

Carbon monoxide reactions:

2H2O + C2H4 → 2CO + 4H2

H2O + CH4 → CO + 3H2

Carbon dioxide reaction:

H2O + CO → CO2 + H2
Figure 1: Styrene process flow diagram (Vasudevan, Suraj. et al., 2009)

2. Styrene/Propylene Oxidation Process

This process is for co-production of propylene oxide and styrene monomer and it’s concerned in
to improve the recovery of 1-phenyl ethanol and the styrene from heavy residual stream by the
acid treatment and cracking. Also uses different distillation steps to separate unreacted reagents
and caustic treatment to reduce the acidic characteristics of the streams.

The patents issued to ARCO and Shell but the first development of the process was by ARCO
and this process that will be explain in detail is ARCO’s and about 15% of the world uses this
process to produce styrene.
Figure 2: Styrene / propylene oxidation process. (Vasudevan, Suraj. et al., 2009)
As shown is Figure 2, reactor 1 is fed with ethylbenzene via line 1 and oxidized occurs to form
ethylbenzene hydro peroxide by reaction with molecular oxygen fed via line 2 with Oxidation
conditions in reactor 1 are 135°-145 ℃. and 50-55 psig.

The reaction mixture from reactor 1 contain of unreacted ethylbenzene, ethylbenzene hydro
peroxide, 1-phenyl ethanol, acetophenone and heavies carried via line 4 to be fed into
epoxidation Reactor 2 where the ethylbenzene hydro peroxide is catalytically reacted at range 95
℃ to 115 ℃ and 600 psia with propylene via line 4 to form propylene oxide (line 5).

The epoxidation reaction mixture (reactor 2) is treated with aqueous caustic to neutralize acidic
materials and to remove the epoxidation catalyst (not shown) and the treated epoxidation
reaction mixture comprised of unreacted propylene, propylene oxide, ethylbenzene, 1-phenyl
ethanol, acetophenone and heavy materials flowing via line 7 to distillation 1. In distillation 1,
the overhead is the unreacted propylene and product propylene oxide is separated via line 6.

The bottoms fraction contained of ethyl benzene, 1-phenyl ethanol, acetophenone and heavies is
removed from distillation 1 via line 7 into distillation 2. the overhead ethyl benzene stream is
separated from distillation 2 via line 8 and can be recycled to reactor 1.

The bottoms stream from distillation 2 contained of 1-phenyl ethanol, acetophenone and heavies
flowing via line 9 to distillation 3. The overhead fraction from distillation 3 contained of 1-
phenyl ethanol and acetophenone is separated via line 10 the combined streams from distillation
2 and evaporator unit are reacted in dehydration and cracking zone 16 at 200°C-230 ℃. and 100
-300 mmHg and passed to dehydration unit where 1-phenyl ethanol is converted to styrene
monomer which is recovered via line 18.

The bottoms stream from distillation 3 flowing via line 11 to mixing unit where it is mixed with
aqueous sulfuric acid which is fed via line 12.

The admixture from mixing unit exiting via line 13 to decantation 24 where the immiscible
phases are separated. The aqueous sodium-containing phase is separated by means of line 14 and
may be further treated or discarded. The organic phase reduced in sodium is removed via line 15
and passes to wiped film evaporator unit where up to 40% by weight of the stream is separated
as a distillate fraction via line 17 a vapor stream is separated at 175 ℃. and 50 mmHg.

This fraction contains various 1-phenyl ethanol condensation products, some 1-phenyl ethanol,
esters and the like. In this embodiment, the distillate fraction passes to dehydration unit wherein
components of the distillate are cracked and/or dehydrated to provide supplemental styrene
monomer values. The heavy bottoms from wiped film evaporator unit are recovered via line 16
and represents an upgraded stream suitable as heavy fuel. (Lee, 2005)
.
PROCESS SELECTION

A table below shows a comparison between the two process of styrene production by
dehydrogenation of ethylbenzene and propylene oxide depending on simplicity,
economics and using

Table 1: Comparison between two different process of styrene processes used world-
wide.

Criteria Dehydrogenation of Propylene oxide

ethylbenzene

Using Uses by around 85% of Around 15 % of styrene

styrene production production

Economic Need high number of utilities Requires high capital cost

Simplicity One stage to produce styrene PO>EBHP>MPA>Styrene

According to this comparison, the best process is dehydrogenation of ethylbenzene.

Direct dehydrogenation of ethylbenzene to styrene accounts for 75% of commercial

production, and it was chosen for this project mainly for the following reasons:

1. It accounts for 75% of commercial production of styrene and it has proved its
effectiveness.

2. Its relatively better for environmental and economic considerations.

3. Availability of the process information and description is more than the other
processes.

4. Possibility to sell benzene and toluene as by-products.

REFERENCES
Lee, W. J. (2005). Ethylbenzene dehydrogenation into styrene: kinetic modeling and
reactor simulation. Industrial & Engineering Chemistry Research.

Vasudevan, Suraj. et al. (2009, October 13). Application and Evaluation of Three
Methodologies for Plantwide Control of the Styrene Monomer PlantE.
Engineering, Chemistry Industrial & Engineering Chemistry Research.