Theory:

Plug flow reactor also known as continuous tubular reactor is the type of reactor in which the reactants are
continuously introduced at one end and products continuously removed at the other end. The medium is moved
through the reactor as plug. In an ideal plug flow reactor, it is assumed that there is no mixing of the contents
along the axis of the reactor, although there might be lateral mixing at any point along the axis. Plug flow reactor
describe chemical reactions that are taking place in continuous, flowing systems of cylindrical geometry such as
pipes. They are usually operated at steady state. As the plug flows down the reactor the reaction takes place,
resulting in axial concentration gradient. Products and unreacted reactants flow out of the reactor continuously.
(John Wiley&Sons, 1999)

Figure 1: Typical Plug Flow Reactor

In this reactor type, there is steady movement of materials along the length of the reactor. There is no attempt to
induce mixing of fluid element, thus operating at steady state. At a given position, for any cross-section there is
no pressure, temperature or composition change in the radial direction; no diffusion from one fluid element to
another. As the reaction progresses the number of moles increases, thus at constant pressure, fluid velocity
must increase as conversion increases. [ CITATION Gom15 \l 1033 ]
Under the force of agitation, some fluid particles in the reactor may escape through the exit immediately,
resulting in very short residence times, while some other particles may be agitated back from the exit making
their residence time extremely long. As a result, the residence times of fluid particles in this reactor are very
uneven causing different levels of backmixing. Since the extent of unevenness is related to the force of
agitation, then the stronger the force, the more significant the backmixing. [ CITATION LiS17 \l 1033 ]
The volume necessary to reduce the entering molar flow rate (moles/sec) from initial amount (F AO) to the exit
molar flow rate (FA) is given by the relation below:
FA
d FA
V =∫
F AO
rA

Where:
rA = The rate of reaction in tubular reactor
Common assumptions made in designing tubular low reactor include the steady state operation, reactions take
place in the gaseous phase with constant density, pressure drop along the reactor is negligible (as the vessel is
assumed to be empty and refractory lined).
The production of styrene using ethyl benzene as raw material in plug flow reactor follow the equation below
 C6H5C2H5 → C6H5 – CH = CH2 + H2
(ethyl benzene) (styrene) (hydrogen)
The reaction rate expression is given as:

6
−r A =5.5 ×10 P A e
[ −8500
RT ]
Where:
PA is the partial pressure
R is the universal gas constant
T is the temperature
This reaction is endothermic, in most cases steam is used to supply heat for the reaction. Also, this process is
catalytic, in modern days the common catalyst used in styrene production is unsupported iron (III) oxide
promoted with a potassium compound. 65% of world production of styrene is polymerized to make polystyrene
and other plastics. Also used for elastomers, thermoset plastics and other products. [ CITATION Bry18 \l 1033 ]

The advantages of using plug flow reactor includes:

 Easily maintained since there are no moving parts
 high conversion per unit reactor volume
 Low operating costs
 It mechanically Simple
 Good for large capacity processes
 Low pressure drops
 Continuous operation of the reactor thus no kill time as well
 Good heat transfer.
 Tubes are easy to clean.[ CITATION Cat20 \l 1033 ]

Despite those advantages, plug flow reactors have also disadvantages such as:
 Existence of undesired thermal gradients, hence existence of hot spots for exothermic reactions
 Poor temperature control
 Expensive shutdown and cleaning.
 Difficult to control due to temperature and composition variations. [ CITATION Cat20 \l 1033 ]

Plug flow reactors has several applications, some of them includes:

 Large scale production
 Production of gasoline and oil cracking
 Synthesis of ammonia from its elements
 Oxidation of Sulphur dioxide to Sulphur trioxide
 Fast reactions
 Used as bioreactors for production of products like algae
 Continuous production
 High temperature reactions. [ CITATION Cat20 \l 1033 ]

Discussion:

The concentration of the products in mole fractions after performing simulation in AspenHYSYS software were
found to be 0.4234 for both styrene and hydrogen. For both products, the concentration was same because
according to the stoichiometry of a balanced chemical reaction equation, one mole of ethylbenzene could
produce one mole of styrene and one mole of hydrogen. In other words, the products of the reaction will exit the
reactor in equal amounts.
For both hydrogen and styrene, their mole fraction estimated from the simulation of plug flow reactor, were less
by the amount obtained from laboratory manuals. Styrene is produced by the catalytic dehydrogenation of the
ethyl benzene, the catalyst in this process is used to enhance the complete reaction. Since the effect of catalyst
was not considered during simulation process, then the reaction was not 100% complete. This can be seen
from the product stream where ethylbenzene exist at concentration of 0.1532 mole fraction.

The observed temperature following simulation of the dehydrogenation of ethyl benzene was found to be
214.8oC. This amount was lower than the expected value from the laboratory manuals (425.6 oC). Theoretically,
this reaction is endothermic and hence need supply of heat in which case steam is mostly used, since this
phenomenon was not considered during the design, the product exit at lower temperature than the expected.
[ CITATION Ogo13 \l 1033 ]
 Figure 2: Plot of Temperature versus Length of the Reactor
From figure 2 above, it is shown that, the temperature of the fluid within the plug flow reactor was decreasing
from the inlet towards the exit of the reactor. This is attributed by the fact that, the reaction is endothermic thus it
would be consuming energy along the tube, as a result the temperature of the fluid would be decreasing as
fluids moves towards the exit. This also signify that increasing temperature of the reaction will results in higher
conversion due to faster intrinsic reaction rates. However, there is a limit to how high the temperature can be
raised since side reactions are more likely to occur at these higher temperatures, resulting in decreasing
styrene selectivity. [ CITATION Ogo13 \l 1033 ]
 Figure 3: Plot of Composition versus Length of the Reactor
The behavior of composition throughout the plug flow reactor was plotted as shown in figure 3 above, with
ethylbenzene marked by red color and styrene marked in green color. From the graph, the composition of
ethylbenzene was decreasing towards the exit because it was being dehydrogenated to styrene as product. On
the other hand, the composition of the styrene was increasing along the tubular reactor because it was being
formed. When the fluids reach the exit, more ethylbenzene was dehydrogenated into styrene and thus more
composition.

Conclusion:
The simulation of the production of styrene from ethylbenzene was performed successfully using AspenHYSYS
software package. The results showed that, styrene and hydrogen were formed as products of the reaction at
mole fraction of 0.4234 for each with a deviation of 0.0766 from the laboratory manual value of 0.5 mole fraction
for each product. The discrepancy was accounted by the impacts of catalyst and heat supply that were not
considered during the simulation.
Temperature behavior of the reactor showed that, the temperature of the medium was decreasing along the
reactor from the inlet towards the exit while the composition profile showed that composition of ethylbenzene
was decreasing along the reactor as it was consumed during the reaction while that of styrene was increasing
towards the exit because it was being formed during the reaction in the plug flow reactor. The effects of
temperature, pressure, contact time and catalyst type are to be taken into great consideration as they affect
largely the proceeding of the reaction

References
Catalano, S., Wozniak, A., Kaplan, K. & Plegue, T., 2020. Plug Flow Reactors. s.l.:s.n.

Enekwizu, O. Y., 2013. Performance of a Composite Palladium Membrane Reactor for the Dehydrogenation of
Ethylbenzene to Styrene, s.l.: University of Houston.

Gomez, S. S. et al., 2015. A new perspective on ctalytic dehydrogenation of ethylbenzene: the influence of side-
reactions on catalytic performance. Catalysis Science & Technology, p. 44.

Li, S., 2017. Residence Time Distribution and Flow Models for Reactors. Reaction Engineering.

McCaughey, B., 2018. Catalytic Dehydrogenation of Ethylbenzene to Styrene. s.l.:s.n.

Simulation Result (Screen Shot):

Figure 4: Properties of the Material Streams

Figure 5: Composition of the Streams in mole fraction

Figure 6: Stream Properties after simulation

Figure 7: Simulated Size of the PFR: