UNIVERSIDAD

AUTONOMA DE
CHIHUAHUA
FACULTAD DE
CIENCIAS QUIMICAS

Control of an Industrial
Ethylbenzene Process
PROCESS SIMULATION

Itzel Espino Favela 311280

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INDEX, TABLE OF CONTENTS
Abstract ............................................................................................................................... 1
1. Introduction .................................................................................................................. 1
1.1 Properties of Ethylbenzene....................................................................................... 1
1.2 Industrial Uses of Ethylbenzene ............................................................................... 2
2. Justification .................................................................................................................. 2
3. Process proposal ......................................................................................................... 3
3.1 Production process description and flowsheet ...................................................... 3
3.2 Description of the chemical reactions involved ...................................................... 4
3.3 Ethyl Benzene Reaction Kinetics ............................................................................. 5
3.4 Phase Equilibrium ..................................................................................................... 6
4. Process simulation ...................................................................................................... 6
5. Conclusion ................................................................................................................. 23
6. Bibliography ................................................................................................................ 24

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Abstract

The work deals with optimization of the process of production of ethylbenzene by liquid
phase benzene alkylation. This process involves the reaction of benzene with ethylene
to form ethylbenzene. Ethylene reacts with ethylbenzene to form undesired product
di-ethyl benzene, if the temperatures of reactor or concentrations of ethylene are high.
Di-ethyl benzene reacts with benzene to form ethylbenzene. Di-ethyl benzene is the
highest-boiling component in the system; it comes out the bottom of two distillation
columns. The recycling benzene is more expensive. Thus it provides a classic
example of an engineering design and optimization of a process. The purpose of this
project is to develop an optimum design for the ethylbenzene process considering
reactor size, benzene recycled. The goal is to simulate a given base case of a vapor
phase reaction ethylbenzene production facility in Aspen Plus simulation software.

1. Introduction

Ethylbenzene is an organic compound with the formula C6H5CH2CH3. The aromatic

hydrocarbon is important in the petrochemical industry and as an intermediate in the
production of styrene, which is used for making polystyrene, it is a common plastic
material. Also present in small amounts in crude oil, ethylbenzene is produced by
combining benzene and ethylene in an acid-catalysed chemical reaction. It is used as
a solvent for aluminum bromide in anhydrous electro deposition of aluminum.
Ethylbenzene is an ingredient in some paints and solvent grade xylene is nearly
always contaminated with a few percent of ethylbenzene.

1.1 Properties of Ethylbenzene

Appearance: Clear, colourless liquid

Molecular formula: C8H10

Molar mass: 106.17 g mol−1

Density: 0.8665 g/mL

Melting point: -95 °C, 178 K, -139 °F

Boiling point: 136 °C, 409 K, 277 °F

Solubility in water: 0.015 g/100 mL (20 °C).

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1.2 Industrial Uses of Ethylbenzene

Industries that use this chemical and how they use it:

Machinery Mfg. and Repair (Solvents - Machinery Manufacture and Repair)

Rubber Manufacture (Solvents - Rubber Manufacture)

Rubber Manufacture (Hydrocarbon Solvents)

Wood Stains and Varnishes (Varnish Solvent)

Paper Coating (Solvents)

Electroplating (Electroplating - Vapors Degreasing Solvents)

2. Justification

Ethylbenzene is produced by the catalytic alkylation of benzene with ethylene, or from

mixed xylenes by isomer separation and catalytic isomerisation, or from 1,3-butadiene
in a two-step process where the butadiene is converted to vinylcyclohexane which is
then dehydrogenated.

Nearly all commercial ethylbenzene is produced by alkylation of benzene with

ethylene.

Studies of this process started with the modelling of the reactor based on the
homogeneous model (Sheel and Crowe, 1969), followed by the heterogeneous model
coupling dusty gas model for axial-flow reactor (Elnashaie et al., 1993) and radial-flow
reactor (Tamsilian et al., 2012). Optimization of operation explored the optimal steam
injection location along the catalytic bed (Clough and Ramirez, 1976) while heuristic
multi-objective optimization algorithms: NSGA (Yee et al., 2003), MODE (Gujarathi
and Babu, 2010) were used to study the problem of maximizing three conflicting
objectives. Plantwide control methodologies were applied in order to maximize
economic profits via control structure designs simulating based on HYSYS
(Vasudevan et al., 2009) and Aspen Plus (Luyben, 2011).

Observe the effect of different variables considered to reach the desired product. The
following points need to be taken care for a proper process design.

✓ Raw material cost reduction. Selectivity of reaction is increased by proper use

of catalysts. Increasing selectivity can reduce separation and recycle costs.

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 ✓ Capital-cost reduction. Better flow sheeting can reduce capital costs effectively
✓ Energy use reduction. Pinch point analysis is used for energy saving.
✓ Increased process flexibility. Process plant should be able to handle a range of
feed compositions.
✓ Increased process safety. Nonlinear analysis can be done to make the process
safer.
✓ Increased attention to quality. Reduction of by products and the effective use
of process control equipment can lead to process safety.
✓ Better environmental performance. Minimization of harmful wastes to the
environment.

[Dimian, 2003]

3. Process proposal

3.1 Production process description and flowsheet

The process considered has two reactors in series, two distillation columns, and two
liquid recycle streams. Thus, it provides a nice example of a multiunit complex process
that is typical of many chemical plants found in industry. An interesting and unusual
feature of the EB process is the recycle to extinction of the DEB by-product. A
significant amount of DEB circulates through the system, and the per-pass EB
selectivity is quite low. But the overall selectivity is essentially 100% since all of the
fresh reactant feeds (ethylene and benzene) end up leaving in the single product
stream as EB. (William L. Luyben, 2011)

Figure 1“Ethyl benzene flowsheet”

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The EB process involves sparging gaseous ethylene into the liquid phase of the first
of two continuous stirred-tank reactors (CSTR) in series. Both reactors operate at high
pressure (20 atm) to maintain liquid in the reactor at the high temperatures required
for reasonable reaction rates (433 K). A large liquid benzene stream is also fed to the
first reactor. The heat of the exothermic reaction is removed by generating 2.5 atm
steam in this reactor. The effluent from the first reactor is fed into the second reactor
along with a recycle stream of DEB. This reactor is adiabatic. The effluent from the
second reactor is fed to a distillation column that produces a distillate that is mostly
benzene, which is recycled to the first reactor along with the fresh feed of makeup
benzene. The bottoms stream is a mixture of EB and DEB. It is fed to a second
distillation column, which produces an EB distillate and a DEB bottoms that is recycled
back to the second reactor. Note that a two-reactor flowsheet is used so that high
conversion of the ethylene can be achieved in the first reactor and conditions are
favorable in the second reactor for the reaction of DEB back to EB (higher
concentration of DEB). (William L. Luyben, 2011)

3.2 Description of the chemical reactions involved

The production of EB involves the liquid-phase reaction of ethylene with benzene

(1)

There are other undesirable reactions that we assume can be represented by the
formation of DEB from the reaction of EB with ethylene.

(2)

A third reaction also occurs, in which DEB reacts with benzene to form EB.

(3)

This reaction makes it possible to recycle the DEB back to the second reactor where
an excess of benzene exists and drives the reaction to the right to produce EB. Thus,
there is essentially no DEB leaving the system despite the fact that a large amount is
produced in the first reactor and passes through the two distillation columns.

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3.3 Ethyl Benzene Reaction Kinetics

Table 1 “Ethyl Benzene Reaction Kinetics”

The activation energy of the undesirable reaction (reaction 2) is larger than that of the
desirable reaction. Therefore, low reactor temperatures improve selectivity. In
addition, selectivity is improved by keeping low concentrations of ethylene and EB in
the reactor. This can be achieved by using a large excess of benzene, but the excess
must be recovered and recycled. A high conversion of ethylene in the first reactor is
desired so that the ethylene concentration is low. This reduces the production of DEB
and results in only a small amount of ethylene that is recycled in the benzene recycle
stream. Ethylene conversion is set at 99% for all the cases considered by adjusting
the temperature of the first reactor.

Figure 2“Per-pass yield.”

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Figure 2 illustrates how the important design optimization variables affect EB yield,
which is defined as the molar flowrate of EB leaving the reactor divided by the sum of
the molar flowrates of EB and DEB. This is per-pass yield, not the overall yield of the
entire process. Yield is increased by increasing the recycle flowrate of benzene or by
increasing reactor size. The larger the reactor, the lower the temperature required for
the fixed ethylene conversion of 99%. The 200 m3 reactor requires temperatures
around 430 K. The 400 m3 reactor requires temperatures around 416 K. The 800 m3
reactor requires temperatures around 403 K. Lower temperature favors EB production
because of the higher activation energy of the DEB reaction.

3.4 Phase Equilibrium

The two separations required are the removal of benzene from EB and the removal of
EB from DEB. The Choa–Seader physical property package is used in the Aspen
simulations. The normal boiling points of these components are 353 K for benzene,
409 K for EB, and 457 K for DEB. The significant differences mean that the two
distillation columns have a fairly small number of trays and required a low reflux ratio
(RR).

4. Process simulation

Simulation is becoming a requirement for all major process designs. By means of

simulation, process engineers can identify potential problems ahead of time and take
corrective actions (Towler & Sinnott, 2008). Common uses for process simulation are
process mapping, design, and assessment, as well as cost analysis (Dimian & Bildea,
2008).

In methods, Aspen suggests that we use CHAO-SEA for steam-liquid balance

modeling.

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Figure 3“Estimation model of thermodynamic properties and L-V balance ratios”

Build the global process, with representative figures like reactors with stirring tank,
columns and pumps.

Figure 4“Global process.”

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Define the feed (benzene and ethylene) with their respective temperatures and
pressures.

Figure 5“Feed.”

Figure 6“Feed.”

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Implement pumps to increase or equalize pressure, even if they are not present in the
diagram

Figure 7“Auxiliary equipment: Pressure changers.”

Figure 8“Auxiliary equipment: Pressure changers.”

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Figure 9“Auxiliary equipment: Pressure changers.”

Connect the feed currents and define the operating conditions of the reactors

Figure 10“Reactors.”

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Figure 11“Auxiliary equipment: Pressure changers.”

Add RadFrac columns, connect them, and define the stages and operating conditions
of the condenser and the reboiler

Figure 12“Column 1.”

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Figure 13“Column 1.”

Figure 14“Column 1.”

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Figure 15“Column 2.”

Figure 16“Column 2.”

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Figure 17“Column 2.”

Decrease heat load to adjust outlet flows. It also helps to increase the reflux ratio.

Figure 18“Outlet flows from reactor R1 and R2.”

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Figure 19“Outlet flows from reactor R1 and R2.”

Figure 20“Outlet flows from reactor R1 and R2.”

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Figure 21“Dome and bottom flows (c1).”

Figure 22“Dome and bottom flows (c1).”

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Figure 23“Dome and bottom flows (c1).”

Figure 24“Condenser and rehervitor data (c1).”

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Figure 25“Dome and bottom flows (c2).”

Figure 26“Dome and bottom flows (c2).”

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Figure 27“Dome and bottom flows (c2).”

Figure 28“Condenser and rehervitor data (c2).”

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The composition profiles show how the composition of the compound evolves along
the column in the different phases.
Block C-1: Composition Profiles
1.00

0.90

0.80

0.70
Liquid mole fraction BENCENO
0.60
Mole fraction

Liquid mole fraction ETILENO

0.50 Liquid mole fraction ETILBENZ
Liquid mole fraction DIETILBZ
0.40

0.30

0.20

0.10

0.00
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21
Stage

Figure 29“Liquid phase and steam composition profiles (c1).”

Block C-1: Composition Profiles

1.00

0.90

0.80 Vapor mole fraction BENCENO

0.70 Vapor mole fraction ETILENO

Vapor mole fraction ETILBENZ
0.60
Mole fraction

Vapor mole fraction DIETILBZ

0.50

0.40

0.30

0.20

0.10

0.00
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21
Stage

Figure 30“Liquid phase and steam composition profiles (c1).”

Block C-2: Composition Profiles

1.00

0.90 Liquid mole fraction BENCENO

Liquid mole fraction ETILBENZ
0.80 Liquid mole fraction DIETILBZ
0.70

0.60
Mole fraction

0.50

0.40

0.30

0.20

0.10

0.00
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25
Stage

Figure 31“Liquid phase and steam composition profiles (c2).”

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 Block C-2: Composition Profiles
1.00
Vapor mole fraction BENCENO
0.90
Vapor mole fraction ETILBENZ
0.80 Vapor mole fraction DIETILBZ

0.70

0.60
Mole fraction

0.50

0.40

0.30

0.20

0.10

0.00
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25
Stage

Figure 32“Liquid phase and steam composition profiles (c2).”

Figure 33“Diameter (c1).”

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Figure 34“Height (c1).”

Figure 35“Diameter (c2).”

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Figure 36“Height (c2).”

5. Conclusion

Process simulation has been extensively used in recent years to design, evaluate or
optimize processes, systems and specific operations of the chemical industry and its
related disciplines. Currently, Aspen Plus constitute one of the most used process
simulators because of the great number of chemical and petrochemical processes that
can be simulated.

In the optimization process, the main emphasis was given on saving cost of raw
materials rather than saving energy and capital costs. The ethylbenzene process
exhibits an interesting design feature in terms of the engineering trade-offs. The basic
components of the ethylbenzene process are the reactor and the distillation column.
Optimization in the reactor section was conducted and it was found that increase in
the reactor size lower reactor temperatures, better EB selectivity, and lower DEB
recycle flow rates. Increasing benzene recycle give better ethylbenzene selectivity and
lower Di-ethyl benzene recycle, but separation cost is increase. Therefore depending
on the requirement of a particular industry it could be modified to provide the desired
result.

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6. Bibliography

Luyben, W. L., 2011. Design and control of the ethyl benzene process. AIChE journal,
57, 655-670

Luyben, W. L. Distillation Design and Control Using Aspen Simulation, John Wiley &
Sons, Hoboken, NJ, 2006.

Douglas, J. M. Conceptual Design of Chemical Processes, McGraw-Hill, New York,

1988

Chachuat, B., Srinivasan, B., Bonvin, D., 2009. Adaptation strategies for real-time
optimization. Computers & Chemical Engineering, 33, 1557-1567

Luyben WL. Plant wide Dynamic Simulators in Chemical Processing and Control New
York: Marcel Dekker, (2002).

McCabe.W.L, Smith.J.C, Harriott.P, Unit Operations of Chemical Engineering, Sixth

Edition, McGraw-Hill Higher Education (2001).

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