CHEN 364- Kinetics

Ethylbenzene Production-Course Project

Instructors:
Dr. Nimir Elbashir
Dr. Khaled Elsaid

By: Omar Mansour

Muhammad Farooq Zia
Aisha Al-Kuwari
Maryam Al-Kaabi

“On my honor, as an Aggie, I have neither given nor received

unauthorized aid on this academic work”
Contents
Introduction ................................................................................................................................................. 5
Governing Reactions ................................................................................................................................ 5
Governing Rate Expressions..................................................................................................................... 6
Properties of Selected Compounds .......................................................................................................... 7
Methodology ................................................................................................................................................ 8
Material Balance ...................................................................................................................................... 8
Energy Balance ........................................................................................................................................ 9
Yield, Selectivity, and Conversion ............................................................................................................ 9
Yield ....................................................................................................................................................... 9
Selectivity ............................................................................................................................................ 10
Conversion........................................................................................................................................... 10
Reaction Network ...................................................................................................................................... 10
Reaction Mechanism ................................................................................................................................. 11
.................................................................................................................................................................... 11
Contacting Pattern..................................................................................................................................... 12
Results ........................................................................................................................................................ 13
Non-Isothermal & Non-Adiabatic ........................................................................................................... 14
Adiabatic ................................................................................................................................................. 18
Isothermal ............................................................................................................................................... 21
Comparison of the Three Case Results .................................................................................................... 24
Temperature ........................................................................................................................................... 24
Reactor Volume & Component Flowrates ............................................................................................. 27
Selectivity ................................................................................................................................................ 28
Conversion .............................................................................................................................................. 28
Yield ........................................................................................................................................................ 29
Ethylene to Benzene Ratio ........................................................................................................................ 30
Effect of Inlet Pressure on Ethylene Conversion .................................................................................... 30
Conclusion.................................................................................................................................................. 32
Appendix A ................................................................................................................................................. 33
References.................................................................................................................................................. 35
List of Tables
Table 1: Heat Capacity of Selected Components as Functions of Temperature ........................... 7
Table 2: Heats of Formations of Selected Components. ......................................................................... 7
Table 3: Calculated Heat of Reactions. .......................................................................................................... 9
Table 4: Impact of Temperatures on Each Reaction Rate .................................................................. 25
Table 5: Reactor Volumes and Product Flowrates for each Case .................................................... 27
Table 6: Comparison of Selectivity .............................................................................................................. 28
Table 7: Comparison of Reactant Conversions ....................................................................................... 29
Table 8: Comparison of Overall Yields ....................................................................................................... 29
List of Figures

Figure 1: Reaction Network ........................................................................................................................... 10

Figure 2: Contacting Pattern .......................................................................................................................... 13
Figure 3: The change in molar flowrate of components along the length of PFR. .................... 14
Figure 4: Conversion Profiles of Non-Isothermal Operation ............................................................ 15
Figure 5: Selectivity of Non-Isothermal Case .......................................................................................... 16
Figure 6: The change in temperature with respect to volume for the non-isothermal, non-
adiabatic case....................................................................................................................................................... 18
Figure 7: Flowrate Profiles for the Adiabatic Case................................................................................ 18
Figure 8: Conversion Profiles for the Adiabatic Case. .......................................................................... 19
Figure 9: Selectivity of Adiabatic Case. ...................................................................................................... 20
Figure 10: Adiabatic: Instantaneous Yield ............................................................................................... 20
Figure 11: Temperature Profile within the PFR..................................................................................... 21
Figure 12: Isothermal- Molar Flowrate Profiles .................................................................................... 22
Figure 13: Isothermal - Conversion Profiles ........................................................................................... 23
Figure 14: Isothermal - Selectivity .............................................................................................................. 23
Figure 15: Isothermal Instantaneous Yield.............................................................................................. 24
Figure 16: Comparison of Temperature Profiles ................................................................................... 26
Figure 17: Di-ethylbenzene Production Comparison .......................................................................... 27
Figure 18: Comparison of Ethylene Conversion .................................................................................... 28
Figure 19: Effect of Varying E/B Feed Ratio on Selectivity................................................................ 30
Figure 20: Solubility of Ethylene in Benzene (Holder and Macauley, 1992) .............................. 31
Introduction
The liquid phase alkylation of ethylene and benzene into ethylbenzene is investigated in
this project. This reaction produces the main product, ethylbenzene as well as an undesired
by-product, di-ethyl benzene. Ethylbenzene is a valuable intermediate required for the
production of styrene monomers, and is therefore the desired product in this alkylation
reaction. As reactor engineers, we have been tasked in the CHEN – 364 course to design a
reactor capable of producing 200,000 tons/yr of ethylbenzene. This report will summarize
the methodology and results at which the following tasks have been accomplished.

- Illustrate the reaction network.

- Propose a mechanism for the main reaction which agrees with the given rate
expression.
- Advice on a contacting pattern to improve the reactor performance.
- Determine the size of the reactor to achieve the desired 200,000 tons/yr of
ethylbenzene production.
- Evaluate the conversion, selectivity, and yield at the specified conditions
o Investigate in the case of adiabatic and isothermal.
o Advice on ethylene to benzene ratio.

Governing Reactions
The liquid phase alkylation of ethylene and benzene to produce ethylbenzene and di-
ethylbenzene is governed by the following reactions.

The main reaction is shown in Equation 1.

𝐶6 𝐻6 + 𝐶2 𝐻4 → 𝐶8 𝐻10 Equation (1)

The side reactions are presented in Equations 2-4.

𝐶6 𝐻6 + 2𝐶2 𝐻4 → 𝐶10 𝐻14 Equation (2)

𝐶8 𝐻10 + 𝐶2 𝐻4 → 𝐶10 𝐻14 Equation (3)

𝐶6 𝐻6 + 𝐶10 𝐻14 ↔ 2𝐶8 𝐻10 Equation (4)

As evident from the governing reactions, it is desired to maximize the rate of production of
ethylbenzene by minimizing the rate of production of di-ethylbenzene in Equations 2 & 3,
as well as maximizing the rate of reaction 1. Equation 4 is expressed as an equilibrium
reaction in which in the forward direction, the desired ethylbenzene product is produced,
and however the reverse reaction consumes the product to produce benzene and di-
ethylbenzene.

Governing Rate Expressions

The rate expressions for each reactions have been specified for the main reaction and side
reactions 2 & 3 as expressed in equations 5-7.

−9502
𝑟𝐸𝐵,1 = .084 ∗ 𝐸𝑋𝑃( )𝐶𝐸 𝐶𝐵 0.3 Equation (5)
𝑅𝑇

−15,396
𝑟𝐷𝐸𝐵.2 = .603 ∗ 𝐸𝑋𝑃 ( ) 𝐶𝐸 1.3 𝐶𝐵 .3 Equation (6)
𝑅𝑇

−20,643
𝑟𝐷𝐸𝐵,3 = .00085 ∗ 𝐸𝑋𝑃( )𝐶𝐸 1.77 𝐶𝐸𝐵 .35 Equation (7)
𝑅𝑇

𝑟4 = 𝑘1 𝐶𝐵 𝐶𝐷𝐸𝐵 − 𝑘2 𝐶𝐸𝐵 2 Equation (8)

The equilibrium reaction is treated assumed to be elementary in the formation of its rate
expression as shown in in Equation 8, in which the rate is the sum of the forward and
reverse reactions respectively. This reaction has a specified Kc value of 0.9 at 570K. This
allows for subsequent calculations of the Kc value at different temperatures using Equation
91.

−Δ𝐻𝑟 1 1
𝐾 = 𝐾570 𝐸𝑋𝑃( (𝑇 − 570)) Equation (9)
𝑅

The rate constant of the equilibrium reaction k1 is given by Equation 10.

35,500
𝑘1 = 36602𝐸𝑋𝑃( ) Equation (10)
𝑅𝑇

Which allows for calculations of k2 for the reverse reaction from Equation 11.

𝑘1
𝑘2 = Equation (11)
𝐾
Properties of Selected Compounds
In order to carry our all calculations of temperature, conversion, yield, and selectivity; a
preliminary literature search to determine each materials thermophysical properties was
conducted. For each component, the heat of formation and heat capacities were researched.
Heat capacities are reported as functions of temperature as expressed in Equation 12.
Perry’s Chemical Engineering Handbook was used to obtain the heat capacities of ethylene,
benzene, and ethylbenzene in the units of J/(kmol*K)2. In The heat capacity of di-
ethylbenzene, reported in units of J/(mol*K) and all heats of formations are reported in
Yaws' Handbook of Thermodynamic Properties for Hydrocarbons and Chemicals 3.

𝐶𝑃 = 𝐴 + 𝐵𝑇 + 𝐶𝑇 2 + 𝐷𝑇 3 + 𝐸𝑇 4 Equation (12)

Table 1: Heat Capacity of Selected Components as Functions of Temperature

Component A B C D E
Ethylene2 2.47 *105 4.43 * 103 4.09 * 102 -1.70 * 10-1 2.68 * 104
Benzene2 1.29 * 105 -1.70 * 102 6.48 *10-1 0 0
Ethylbenzene2 1.33*105 4.45*101 3.96*10-1 0 0
Di-ethylbenzene3 152.04 .45 1.11*10-3 1.51*10-6

Heats of formations were also researched for future utilization when determining the heats
of reactions as reported in Table 2.

Table 2: Heats of Formations of Selected Components.

Component Heat of Formation (J/mol)

Benzene 49,100
Ethylene 52,500
Ethylbenzene -12,500
Di-ethylbenzene -72840
Methodology
The software Polymath was used to solve the differential equations required for
investigating the reactor which carries out the liquid phase alkylation of ethylene and
benzene. The system was assumed to be non-isothermal which requires subsequent
evaluation of both material and energy balances.

Material Balance
A material balance was performed for each component based on the reactions in which
they are consumed and are formed. Equations 13-16 summarize the material balance for
each component.

𝑑(𝐹𝐸 ) 𝑑𝐶
= 𝑑(𝑡)𝐸 = −𝑟𝐸𝐵,1 − 2𝑟𝐷𝐸𝐵,2 − 𝑟𝐷𝐸𝐵,3 Equation (13)
𝑑(𝑉)

𝑑(𝐹𝐵 ) 𝑑𝐶
= 𝑑(𝑡)𝐵 = −𝑟𝐸𝐵,1 − 𝑟𝐷𝐸𝐵,2 + 0.5𝑟4,𝑏𝑎𝑐𝑘𝑤𝑎𝑟𝑑𝑠 − 0.5𝑟4,𝑓𝑜𝑟𝑤𝑎𝑟𝑑 Equation (14)
𝑑(𝑉)

𝑑(𝐹𝐸𝐵 ) 𝑑𝐶𝐸𝐵
= = 𝑟𝐸𝐵,1 − 𝑟𝐷𝐸𝐵,3 + 𝑟4,𝑓𝑜𝑟𝑤𝑎𝑟𝑑 − 𝑟4,𝑏𝑎𝑐𝑘𝑤𝑎𝑟𝑑 Equation (15)
𝑑(𝑉) 𝑑(𝑡)

𝑑(𝐹𝐷𝐸𝐵 ) 𝑑𝐶𝐷𝐸𝐵
= = 𝑟𝐷𝐸𝐵,2 + 𝑟𝐷𝐸𝐵,3 − 0.5𝑟4,𝑓𝑜𝑟𝑤𝑎𝑟𝑑 + 0.5𝑟4,𝑏𝑎𝑐𝑘𝑤𝑎𝑟𝑑 Equation (16)
𝑑(𝑉) 𝑑(𝑡)

Polymath is used to evaluate each differential equation above. In order to evaluate the
concentrations at different sections in the reactor, the concentrations are evaluated as a
function of the molar and volumetric flowrates. The initial concentration was assumed to
be that of benzene. This is supported by the fact that ethylene, in the gas phase, must
dissolve into the liquid phase to react with benzene to form the products. Therefore, as a
simplifying assumption, the initial concentration is taken to be that of benzene since the
contribution of dissolved ethylene is somewhat negligible and falls within the error
assumed in this preliminary reactor investigation. Equations 17&18 summarize the
methodology in which component concentrations were calculated.

𝐹𝐵𝑜
𝜐= Equation (17)
𝐶𝑡0

𝐹𝑖
𝐶𝑖 = Equation (18)
𝜐
Energy Balance
An energy balance was required to evaluate non-isothermal adiabatic and non-adiabatic
scenarios. This is accomplished by modelling the change in temperature throughout the
reactor volume as expressed in Equation 19.

𝑑(𝑇) (𝑈𝐴 ∗(𝑇𝑎 −𝑇)−Σ(𝑟𝑖 ∗𝐻𝑖 ))

= Equation (19)
𝑑(𝑉) Σ𝐹𝑖 𝐶𝑝,𝑖

Hi denotes the heat of reaction for each respective aforementioned reaction in Equations 1-
4. The heat of reactions were evaluated, using Equation 20, for each reaction as
summarized in Table 3.

𝐻𝑟,𝑖 = Σ𝐻𝑓,𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠−Σ𝐻𝑓,𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠 Equation (20)

Table 3: Calculated Heat of Reactions.

Reaction Heat of Reaction (J/mol)

rEB,1 -101600
rDEB,2 -226940
rDEB,3 -112840
r4 -1260

Yield, Selectivity, and Conversion

The yield, selectivity, and conversion were evaluated by first determining the initial molar
flowrates of ethylene and benzene. This was done by trial and error until the desired
production of 200,000 tons/yr or 65.41 mol/s of ethylbenzene was achieved.

Yield
For the investigated plug flow reactor, the instantaneous yield was defined as the moles of
ethylbenzene formed over the total product formation as seen in Equation 211.

𝑑(𝐶𝐸𝐵 )
𝜑 = 𝑑(𝐶 Equation (21)
𝐸𝐵 )+𝑑(𝐶𝐷𝐸𝐵 )

The overall yield was than determined by plotting the instantaneous fractional yield on excel,
and fitting a polynomial expression to the curve. The overall yield was than obtained by simply
integrating the expression which defines the instantaneous yield according to Equation 22, in
which ethylene has been defined as the limiting reactant 1.

−1 𝐶𝐸,𝑓
Φ𝑃𝐹𝑅 = 𝐶 ∫𝐶 𝜑𝑑𝐶𝐸 Equation (22)
𝐸,𝑜 −𝐶𝐸,𝑓 𝐸,𝑜

Selectivity
The selectivity of ethylbenzene production was also evaluated using data from polymath
exported into Excel. Selectivity is simply defined according to Equation 231.

𝑀𝑜𝑙𝑒𝑠 𝑜𝑓 𝐷𝑒𝑠𝑖𝑟𝑒𝑑 𝑃𝑟𝑜𝑑𝑢𝑐𝑡 𝐹𝑜𝑟𝑚𝑒𝑑

𝑆𝑒𝑙𝑒𝑐𝑡𝑖𝑣𝑖𝑡𝑦 = 𝑀𝑜𝑙𝑒𝑠 𝑜𝑓 𝑢𝑛𝑑𝑒𝑠𝑖𝑟𝑒𝑑 𝑚𝑎𝑡𝑒𝑟𝑖𝑎𝑙 𝑓𝑜𝑟𝑚𝑒𝑑 Equation (23)

Conversion
The conversion of both raw materials, benzene and ethylene was evaluated on Microsoft Excel.
Conversion of both reactants is expressed in Equation 24.

𝐶
𝐶𝑜𝑛𝑣𝑒𝑟𝑠𝑖𝑜𝑛𝑖 = 1 − 𝐶 𝑖 Equation (24)
𝑖𝑜

Reaction Network
The proposed reaction network is presented below in Figure 1.

Figure 1: Reaction Network

This reaction can be classified as a non-homogenous reaction at which benzene reacts in

parallel with ethylene and ethylbenzene to form di-ethylbenzene. Ethylbenzene, the main
desired product can be considered as an intermediate in the series of reactions in which it
may be consumed when reacted with benzene to form di-ethylbenzene.

Reaction Mechanism
The proposed reaction mechanism is explained in detail below.

k1
𝑎𝐶6 𝐻6 + 𝑏𝐶2 𝐻4 ⇄ 𝐶(6𝑎+2𝑏) 𝐻(6𝑎+4𝑏)
k2

k3
𝐶(6𝑎+2𝑏) 𝐻(6𝑎+4𝑏) ⇄ 𝐶8 𝐻10 + 𝐶6 𝐻6
k4

Two reactions has been considered to form ethylbenzene and benzene from the reaction
“a” moles of benzene and “b” moles of ethylene form an intermediate, such that this
intermediate will form the desired product. The “a” and “b” coefficients were applied in the
mechanism to avoid complications when proceeding in solving for the intermediate
concentration.

𝑟[𝐶(6𝑎+2𝑏) 𝐻(6𝑎+4𝑏) ] = 𝑘1 [𝐶6 𝐻6 ]𝑎 [𝐶2 𝐻4 ]𝑏 − 𝑘2 [𝐶(6𝑎+2𝑏) 𝐻(6𝑎+4𝑏) ] − 𝑘3 [𝐶(6𝑎+2𝑏) 𝐻(6𝑎+4𝑏) ] + 𝑘4 [𝐶8 𝐻10 ][𝐶6 𝐻6 ] = 0

The rate of the intermediate was written based on the reactions that this intermediate is
involved in. Then, the rate of the intermediate was set equal to zero in order to find the
intermediate concentration.

𝑘1 [𝐶6 𝐻6 ]𝑎 [𝐶2 𝐻4 ]𝑏 + 𝑘4 [𝐶8 𝐻10 ][𝐶6 𝐻6 ] = (𝑘2 + 𝑘3 )[𝐶(6𝑎+2𝑏) 𝐻(6𝑎+4𝑏) ]

𝑘1 [𝐶6 𝐻6 ]𝑎 [𝐶2 𝐻4 ]𝑏 + 𝑘4 [𝐶8 𝐻10 ][𝐶6 𝐻6 ]

[𝐶(6𝑎+2𝑏) 𝐻(6𝑎+4𝑏) ] =
(𝑘2 + 𝑘3 )

The reversible reaction of both reactions was assumed to be zero, such that the reaction
will only proceed in the forward direction. As a result, assuming k2=k4=0.
 𝑘1 [𝐶6 𝐻6 ]𝑎 [𝐶2 𝐻4 ]𝑏
𝑟𝐶8 𝐻10 = 𝑘3 [𝐶(6𝑎+2𝑏) 𝐻(6𝑎+4𝑏) ] − 𝑘4 [𝐶8 𝐻10 ][𝐶6 𝐻6 ] = 𝑘3 ( )
𝑘3

The rate equation of ethylbenzene was written, in order to get the rate equation of
ethylbenzene in terms of benzene and ethylene. Based on the rate equations that were
given in the project prompt, ethylene had a coefficient of 1 and benzene had a coefficient of
0.3, as a result, it was applied that a=0.3 and b=1.

𝑟𝐶8 𝐻10 = 𝑘1 [𝐶6 𝐻6 ]0.3 [𝐶2 𝐻4 ]1

Contacting Pattern
In order to determine the desired contacting pattern, the aforementioned rate expressions
were investigated. It is evident that in order to obtain maximum production of
ethylbenzene, the rates of rDEB,2 and rDEB,3 must be minimized. These reaction rates have
higher dependency on ethylene concentration than that of rEB,1. Therefore it is desired to
have high initial concentrations of benzene, and low concentrations of ethylene. This is not
only evident from the rate expressions themselves, but it’s of paramount importance to
ensure that the rate of rDEB,3 is minimized as this consumes ethylbenzene as an
intermediate to form di-ethylbenzene.

It is also desired to have a non-mixed reactor. This is because the maximum amount of
desired product is obtained when fluids of different composition and stages of conversion
are not allowed to mix1. The reactor of choice to achieve maximum conversion of reactants
towards ethylbenzene is a plug flow reactor, in which initial concentrations of benzene are
high, and ethylene is fed slowly into the reactor as shown in Figure 2.
 Figure 2: Contacting Pattern

Results
All subsequent results and discussions are based on the evaluation of the set of differential
equations explained in the introduction. The software Polymath was used to evaluate these
differential equations. Data was extracted from the Polymath software and plotted on excel
to produce more neat and organized graphs. The polymath code used to solve the non-
isothermal case is presented in Appendix A.

From the problem statement it is evident that ethylene is in abundance. However it is

assumed that ethylene is at the same time the limiting reactant, in order to increase the
selectivity towards ethylbenzene production. Ethylene is in the gas phase at the specified
conditions, and because the reaction occurs in the liquid phase, it must dissolve into the
liquid phase prior to any reaction with benzene. Therefore, it may be assumed that
ethylene, although it is in abundance, acts as the limiting reactant since the amount that
dissolves into the liquid phase is limited by the solubility of ethylene and benzene.
Simplifying assumptions were made for this reactor as discussed earlier, however it is
understood that this non-homogenous reaction is not only an issue of reaction kinetics, but
also mass transfer, and heat transfer.

Between each case the initial molar flowrates of reactants ethylene and benzene were kept
constant in order to more accurately evaluate and compare the effect of reactor operation
mode.
Non-Isothermal & Non-Adiabatic
In the non-isothermal and non-adiabatic reactor case, the initial molar flowrates of the
benzene and ethylene were set as 220 mol./s and 145 mol./s, respectively. These flow rates
were used along with the system of equation set on the Polymath, to obtain the results that
are presented below. The trend of molar flowrate for each of the four components,
benzene, ethylene, ethylbenzene and diethyl benzene are shown in Figure 2. The graphs for
conversions of ethylene and benzene, with respect to the change in volume i.e. progression
of the component along the length of the PFR, are generated.

Non-Isothermal: Molar Flowrate Profiles

250

200
F [mol/s]

150
FEB
FDEB
100
FE
FB
50

0
0 500 1000 1500 2000 2500 3000

V [Litres]

Figure 3: The change in molar flowrate of components along the length of PFR.

As seen in Figure 2, the targeted production of ethylbenzene was achieved, at 65.42 mol/s
at a reactor volume of 3005 liters. The di-ethylbenzene production accompanying the
production of ethylbenzene in the case of non-adiabatic and non-isothermal is 36.75 mol/s.
 Non-Isothermal: Conversion Profiles
1.0

0.9

0.8

0.7
X, Conversion

0.6

0.5
XE
0.4 XB

0.3

0.2

0.1

0.0
0 500 1000 1500 2000 2500 3000
V [Litres]

Figure 4: Conversion Profiles of Non-Isothermal Operation

For this non-isothermal case the conversion of both reactants were investigated as seen in
Figure 4. It is evident from the graph of conversion that ethylene is indeed the limiting
reactant. Ethylene and benzene conversion reaches 95.80% and 49.84% respectively in
order to achieve the desired ethylbenzene production in the reactor.
 Non-Isothermal: Selectivity
1.0
0.9
0.8
0.7
Selectivity, SEB

0.6
0.5
0.4
0.3
0.2
0.1
0.0
0 500 1000 1500 2000 2500 3000
V [Litres]

Figure 5: Selectivity of Non-Isothermal Case

Similarly, the graph for the selectivity of ethyl benzene production was generated and is
presented in Figure 5. The selectivity towards ethylbenzene production throughout the
reactor is shown to steadily increase to a maximum point of 86.0% at a reactor volume of
200 liters. This can best be explained by the analyzing the aforementioned rate
expressions. Ethylbenzene production is at is greatest in the beginning of the reaction
where reactant concentration is highest. As the reaction proceeds, more ethylbenzene is
formed which promotes the reaction rDEB,3 and the reverse reaction of r4. This results in a
decrease in selectivity towards ethylbenzene as production of di-ethylbenzene increases.

The instantaneous yield is calculated from the concentration data obtained from the
Polymath results and shown in Figure 6. The area under the curve is also used to calculate
the overall yield which is 0.74.
 Non-Isothermal: Instantaneous Yield
y = -5.27E-04x6 + 1.11E-02x5 - 8.64E-02x4 + 3.00E-01x3 - 3.95E-01x2 + 9.15E-03x + 6.14E-01
1.0

0.9

0.8

0.7

0.6
phi_EB

0.5

0.4

0.3

0.2

0.1

0.0
0.0 1.0 2.0 3.0 4.0 5.0 6.0 7.0 8.0 9.0
Overall yield=0.74 CE

Figure 5: Instantaneous yield of ethylbenzene.

The graph of instantaneous yield corresponds with that of selectivity. At low conversion of
the limiting reactant, ethylene, the fractional yield was as its maximum than slowly
decreases as conversion of ethylene increases. Figure 6 summarizes the non-isothermal
temperature response within the reactor volume. It is seen that the maximum temperature
obtained with simultaneous cooling is 400 K. At a reactor volume of 800 L the temperature
in the reactor begins to decrease. It may be assumed that this is the point where an
appreciable amount of ethylene and benzene have been consumed, thereby decreasing the
rates of reactions which will simultaneously decrease the extent to which heat is released
via the exothermic reactions.
 Non-Isothermal - Temperature Profile
420

400

380
Temperature [K]

360

340

320

300
0 500 1000 1500 2000 2500 3000 3500
V [Litres]

Figure 6: The change in temperature with respect to volume for the non-isothermal, non-adiabatic case.

Adiabatic
Following the non-isothermal investigation, the effect of operating the reactor in adiabatic
conditions was analyzed. The molar flowrate profiles for each reactant are presented below
in Figure 7.

Adiabatic: Flowrate Profiles

250

200

150
F [mol/s]

FEB
FDEB
100
FE
50 FB

0
0 1000 2000 3000 4000 5000
V [litres]

Figure 7: Flowrate Profiles for the Adiabatic Case

In the adiabatic case it is evident that the ethylene and benzene are consumed in a much
more rapid manner than in the non-isothermal case. This results in a lower reactor volume
to achieve the conversion, which is approximately 2160L. However, it is important to note
that for the adiabatic reactor the desired production of ethylbenzene was not achieved.
Ethylbenzene production was limited to 62.63 mol/s due to the increase in di-ethylbenzene
production of 41.06 mol/s. The reasons for these differences will be discussed in later the
report.

The conversion of ethylene and benzene for the adiabatic case are presented in Figure 8. It
is evident that the conversion of ethylene for the adiabatic case is higher at nearly 100%.
The conversion of benzene also increases to 54 %.

Adiabatic: Coversion Profiles

1.0
0.9
0.8
0.7
Conversion

0.6
0.5
XE
0.4
XB
0.3
0.2
0.1
0.0
0 500 1000 1500 2000 2500 3000 3500 4000 4500 5000
Volume [Litres]

Figure 8: Conversion Profiles for the Adiabatic Case.

In Figure 9 the selectivity of ethylbenzene formation is presented. The selectivity reaches a

maximum of 85.7% ethylbenzene formation at 240 L. The selectivity than decreases, for the
same reasons previously discussed, to 60%.
 Adiabatic: Selectivity Profile
1.0
0.9
0.8
Selectivity 0.7
0.6
0.5
0.4
0.3
0.2
0.1
0.0
0 1000 2000 3000 4000 5000
Volume (L)

Figure 9: Selectivity of Adiabatic Case.

The instantaneous yield was plotted for the adiabatic case as presented below in Figure 10.
The instantaneous yield agrees with the aforementioned plot of selectivity, for at low
conversions of ethylene, the maximum instantaneous yield is noted. The overall yield for
the adiabatic case was calculated to be 0.43.

Adiabatic: Instantaneous Yield

y = -1.55E-04x6 + 3.16E-03x5 - 2.32E-02x4 + 7.54E-02x3 - 9.77E-02x2 + 6.96E-02x + 2.09E-01
1

0.9

0.8

0.7

0.6
Yield

0.5

0.4

0.3

0.2

0.1

0
0 1 2 3 4 5 6 7 8 9
CE
Overall Yield: 0.43

Figure 10: Adiabatic: Instantaneous Yield

The temperature profile within the reactor is presented in Figure 11. For the adiabatic case,
there is no cooling at the exterior of the reactor, therefore the temperature rapidly
increases as the heat release from the reaction further propagates the rate at which the
reactions occur. The temperature reaches nearly 500K, and would continue to
exponentially increase if more reactants were available to fuel the reactions.

Adiabatic: Temperature Profile

600

500
Temperature (K)

400

300

200

100

0
0 1000 2000 3000 4000 5000
Volume (L)

Figure 11: Temperature Profile within the PFR.

Isothermal
In the isothermal case, the dT/dV equation in the Polymath code was set at zero as there is
no temperature variation within the reactor. The results were analyzed in a similar manner
as the previous two cases. The molar flowrates of each component throughout the reactor
volume is presented below in Figure 12.
 Isothermal: Molar Flowrate Profile
250

200

150
F [mol/s]

FEB
FDEB
100 FE
FB

50

0
0 500 1000 1500 2000 2500 3000 3500 4000
V [Litres]

Figure 12: Isothermal- Molar Flowrate Profiles

For the isothermal case, as seen in Figure 12, the molar flowrate of desired ethylbenzene
production was achieved at a reactor volume of 3611 L. The corresponding production of
di-ethylbenzene was 29.91 mol/s.

The conversion of ethylene and benzene for the isothermal case are presented in Figure 13.
The conversion of ethylene and benzene reached 86.4% and 43.4% respectively.
 Isothermal:Conversion Profile
1.00
0.90
0.80
0.70
Conversion

0.60
0.50
XE
0.40
XB
0.30
0.20
0.10
0.00
0 500 1000 1500 2000 2500 3000 3500 4000
Volume (L)

Figure 13: Isothermal - Conversion Profiles

The selectivity of ethylbenzene formation throughout the reactor volume is presented

below in Figure 16. The maximum selectivity of ethylbenzene production is 82.7 % is
achieved at a volume of 522 L. The selectivity decreases to 68.1 % at the conclusion of the
reaction.

Isothermal: Selectivity
0.90
0.80
0.70
0.60
Selectivity

0.50
0.40
0.30
0.20
0.10
0.00
0 500 1000 1500 2000 2500 3000 3500 4000 4500
Volume [litres]

Figure 14: Isothermal - Selectivity

The instantaneous yield is presented below in Figure 15. The maximum instantaneous
yield obtained for the isothermal case is roughly 90%. The overall yield for the isothermal
case was calculated to be 30.79 %.

Isothermal Yield
y = -1.92E-04x6 + 3.99E-03x5 - 3.29E-02x4 + 1.36E-01x3 - 2.94E-01x2 + 3.89E-01x + 1.84E-01
1.00
0.90
0.80
0.70
0.60
Yield

0.50
0.40
0.30
0.20
0.10
0.00
0 1 2 3 4 5 6 7 8 9
Overall Yield: 0.77 CE

Figure 15: Isothermal Instantaneous Yield

Comparison of the Three Case Results

The following section will go into detail of the differences reported for each investigated
parameter in the aforementioned section. The reasons for differences will be explained
according to the knowledge learned from reactor kinetics and design.

Temperature
In order to evaluate the effects of increasing temperature for reaction a preliminary
investigation was performed on how the exponential terms of each rate equation are
impacted by a 50 K increase in temperature. Table 4 summarizes the relative impact of
increasing temperature for reaction as well as the impact on the reversible reaction.
Table 4: Impact of Temperatures on Each Reaction Rate

Exponential Term, 𝑒 𝑅𝑇
−𝐸
Reversible Equation

Temperature rEB,1 rDEB,2 rDEB,3 1

k4,forward [𝑚𝑜𝑙.𝑙.𝑠] K k4,backward
[K] 1
[𝑚𝑜𝑙.𝑙.𝑠]
300 0.022 0.002 2.54 × 10−4 6.59 × 10−7 1.14 5.76 × 10−7

350 0.038 0.005 8.30 × 10−4 5.03 × 10−6 1.06 4.73 × 10−6

Ratio 1.72 2.42 3.26 7.64 8.21

−𝐸
The exponential terms i.e. 𝑒 𝑅𝑇 is calculated at two different temperatures of 300 K and 350
K. This allows the comparison of the increase in rate of reaction when there is an increment
of 50 Kelvins. The terms are calculated and then divided to obtain the ratio that is shown in
the last row of Table 4. Among the three irreversible reactions, the third reaction DEB, 3
gives the highest ratio, showing that at higher temperatures, the conversion of
ethylbenzene and ethylene to di-ethylbenzene increases more than the increase in the rate
of production of components in the reactions DEB, 2 and EB, 1.

For the reversible reaction, the rate constant for the forward reaction at the two
temperatures is calculated first. Then the equilibrium constant K and the backward rate
constants are calculated. The ratio of the backward rate constant for the two temperatures
is higher than the ratio for the forward rate constants. This indicates that at the higher
temperature, the backward rate increases by a greater factor than the increase in the
forward rate. Therefore, the formation of diethyl benzene is favored at higher
temperatures.
 Comparison of Temperature Profiles
600

500

400
T [K]

300 Non-Isothermal
Adiabatic
200 Isothermal

100

0
0 500 1000 1500 2000 2500 3000
V [Litres]

Figure 16: Comparison of Temperature Profiles

From the temperature profile in Figure 16 of the three types of reactor conditions, it can be
seen that for the non-isothermal case, the temperature approaches a maximum value of
398 K as the heat from the exothermic reactions is released. However, as the reactants are
used up, the rate of reactions decrease, owing to the decrease in concentration of the
reactants. This causes the temperature to decrease and plateau, approaching the value of
300 K at increasingly larger volume, or at a further point in the PFR.

For the adiabatic case, the temperature profile can be seen to increase along the length of
the PFR. However, at certain point of around 1900 liters, the temperature plateaus off to a
value of 482 K. This is because the reactants have been consumed at this point and the
concentration of ethylene becomes a limiting factor. This stabilizes the rate of reaction
which makes the net heating effect zero. In the isothermal case, the dT/dV expression has
been equated to zero, hence the horizontal line showing constant temperature throughout
the length of the reactor.
Reactor Volume & Component Flowrates
The reactor volumes and molar flowrates of the products are summarized in Table 5.

Table 5: Reactor Volumes and Product Flowrates for each Case

Non-Isothermal Adiabatic Isothermal

Reactor Volume (L) 3005 2160 3611
Ethylbenzene (mol/s) 65.42 62.63 65.42
Diethylbenzene (mol/s) 36.75 41.06 29.91

As seen in Table 5, the non-isothermal and isothermal cases both achieved the desired
ethylbenzene production. However in the adiabatic case, the molar flowrate target was not
achieved. This can be best explained by the temperature variations in each case. In the
adiabatic case, temperature rapidly increases. As seen in Table 4, the rate for rDEB,3 is
heavily impacted by increases in temperature. Therefore, in the adiabatic case the rate of
rDEB,3 is greatly increased resulting in the ethylene and ethylbenzene consumption to form
di-ethylbenzene.

Comparison of DEB Molar Flowrate

45
40
35
30
FDEB [mol/s]

25
Non-Isothermal
20
Adiabatic
15
Isothermal
10
5
0
0 500 1000 1500 2000 2500 3000 3500 4000 4500
V [litres]

Figure 17: Di-ethylbenzene Production Comparison

This is supported by also analyzing the di-ethylbenzene production within the three cases.
As seen in Figure 17, the di-ethylbenzene production increases between the isothermal,
and adiabatic cases due to the relative changes in reactor operating temperature

Selectivity
The selectivity for ethylbenzene production is summarized in Table 6.

Table 6: Comparison of Selectivity

Case Maximum Selectivity Final Selectivity

Non-Isothermal 86 64.2
Adiabatic 85.7 60
Isothermal 86.4 68.1

As expected the selectivity of the each case is directly related to the temperature profiles.
The isothermal case has the highest selectivity, in which lower temperatures results in
higher production of ethylbenzene. The isothermal case had a selectivity of 68.1 % whereas
the adiabatic case had a selectivity of 60.0%. As the temperature increases the production
of di-ethylbenzene is promoted resulting in lower selectivity.

Conversion
The comparison for conversions of the limiting reactant, ethylene are presented below in
Figure 18.

Comparison of Ethylene Conversion in 3 Cases

1.20

1.00

0.80
XE

0.60 Non-Isothermal
Adiabatic
0.40
Isothermal
0.20

0.00
0 500 1000 1500 2000 2500 3000 3500 4000 4500
Volume [Litres]

Figure 18: Comparison of Ethylene Conversion

It is evident that as the temperature increases, the respective conversions also increase.
This is due to the direct dependence of the rate expressions on temperature. Increasing the
temperature simultaneously increases the rate of the reaction and thereby the
consumption of ethylene and benzene. Table 7 summarizes the respective changes in
ethylene and benzene conversions for each case.

Table 7: Comparison of Reactant Conversions

Case XB (%) Xe (%)

Non-isothermal 49.8 95.8
Adiabatic 54 100
Isothermal 43.4 86.4

Yield
Table 8 summarizes the different overall yields obtained for each case.
Table 8: Comparison of Overall Yields

Case Overall Yield (Φ)

Non-isothermal 0.74
Adiabatic 0.43
Isothermal 0.77

As seen in Table 8, the overall yields are greatest in the cases in which temperature
remains relatively low. This is similar to previous reasons mentioned in which high
temperatures favor di-ethylbenzene production, thereby reducing the yield of
ethylbenzene.
Ethylene to Benzene Ratio
The effect of varying the ethylene to benzene feed ratio between 0.707 and 0.902 is
depicted below in Figure 19.

Effect of varying E/B on Selectivity of Ethylbenzene

0.9

0.8

0.7

0.6
E/B=0.707
0.5
SEB

E/B=0.756
0.4
E/B=0.805
0.3
E/B=0.854
0.2
E/B=0.902
0.1

0
0 500 1000 1500 2000 2500 3000 3500 4000
V (L)

Figure 19: Effect of Varying E/B Feed Ratio on Selectivity

Figure 19 shows the effect of varying the ethylene to benzene feed ratio on selectivity of
ethylbenzene. The base case considered 145 mol/s of ethylene along with 205 mol/s of
benzene. This has a ratio of 0.707, and has the highest selectivity of ethylbenzene. However,
as the ratio is increased, the selectivity decreases because the formation of di-ethylbenzene
is favored. This can be further corroborated by the rate equations expressed in Equation 6
and Equation 7. These reaction rates show that the rate of di-ethylbenzene is more strongly
dependent on the concentration of ethylene than the main reaction expressed in Equation
5. Therefore, minimizing the feed ratio of ethylene, will result in the greatest selectivity
towards ethylbenzene production.

Effect of Inlet Pressure on Ethylene Conversion

The effect of ethylene feed pressure on solubility of ethylene in benzene is presented below
from a paper by Holder et. al in Figure 20.
 Figure 20: Solubility of Ethylene in Benzene (Holder and Macauley, 1992)

The ethylene feed is in gaseous phase whereas the reaction is happening in the liquid
phase. Therefore, a mass transfer process occurs at the gas-liquid interface, where the
gaseous ethylene dissolves in the benzene and participates in the reactions. As shown in
Figure 20, as the pressure of the inlet ethylene stream increases, the mole fraction of the
ethylene in benzene also increases [4]. This means that more ethylene is transferred from
gaseous phase to liquid phase per unit time, thus increasing the rate of reactions, in which
ethylene is a reactant. The conversion of ethylene increases at higher pressures, because
higher mole fraction dissolves and reacts with benzene in the main reaction (or
ethylbenzene and diethyl benzene in the side reactions).
Conclusion
The production of 200,000 tons/yr of ethylbenzene was investigated in this report. The
process can be described by four reactions to signify the production of ethylbenzene and
di-ethylbenzene side product. Three different scenarios were investigated in this reported
in which the reactor operates in isothermal, non-isothermal, and adiabatic conditions. This
allowed for the analysis of how temperature impacts different investigated variables such
as yield, conversion, and selectivity. For each case, the suggested reactor volume was
specified. The results found that in order to produce high yields of ethylbenzene, it is
desirable to operate at lower temperature, although it may be desired to operate with high
temperatures if selectivity is not of consider and one wants to minimize the reactor
volume.

In conclusion, this project was effective in ensuring that the students properly understood
the different aspects of material and energy balances as they relate to reactor design. The
interpretation and comparison of data results for each case was effective in ensuring
students properly understood the relative effects of temperature and concentration on
reaction rates and production of either the desired or undesired products.
Appendix A

FBo=205
FEB(0)=0.00001
FDEB(0)=0.00000001

FE(0)=145
FB(0)=205

CEB=FEB/v

CDEB=FDEB/v
CE=FE/v
CB=FB/v
v=FBo/Cto

reac1=(kreac1*exp(-9502/(R*T))*CE*CB^0.3)
reac2=(kreac2*exp(-15396/(R*T))*(CE^1.3)*CB^0.3)
reac3=(kreac3*exp(-20643/(R*T))*CE^1.77*CEB^0.35)
reac4f=k1*CB*CDEB
reac4b=k2*CEB^2
reac4=reac4f-reac4b
k1=(36602*exp(-35500/(R*T)))
k2=k1/K
K=0.9*exp((-h4/R)*((1/T)-(1/570)))

d(FEB)/d(V)=reac1-reac3+reac4f-reac4b
d(FDEB)/d(V)=reac2+reac3-0.5*reac4f+0.5*reac4b
d(FE)/d(V)=-reac1-2*reac2-reac3
d(FB)/d(V)=-reac1-reac2+0.5*reac4b-0.5*reac4f

R=8.314
kreac1=0.084
kreac2=0.603
kreac3=0.00085

To=300
Cto=11.3
CpB=((1.2944*10^5)-(1.695*10^2)*T+(6.478*10^-1)*(T^2))/1000
CpE=((2.4739*10^5)-(4.428*10^3)*T+(4.0936*10)*(T^2)+(-1.697*10^(-
1))*(T^3)+(2.6816*10^-4)*(T^4))/1000
CpEB=((1.3316*10^5)+(4.4507*10^1)*T+(3.9645*0.1)*(T^2))/1000
CpDEB=152.0449+.45487*T+-.00111*(T^2)+1.51066*10^-6*(T^3)

sum2=(FEB*CpEB)+(FDEB*CpDEB)+(FE*CpE)+(FB*CpB)
sum1=(reac1*h1)+(reac2*h2)+(reac3*h3)+(reac4*h4)

h1=-101600
h2=-226940
h3=-112840
h4=-1260

d(T)/d(V)=((Ua*(Ta-T))-sum1)/sum2

T(0)=300
Ta=298
Ua=75
V(0) =0
V(f) = 3005

XE=1-(CE/7.992683)
XB=1-(CB/11.3)
SEB=FEB/FDEB
References

[1] Levenspiel, Octave. Chemical Reaction Engineering. 3rd ed., Wiley India, 2007.

[2] Perry, Robert H., et al. Perry's Chemical Engineers' Handbook. 7th ed., McGraw-Hill,
1999.

[3] Yaws, Carl L. Yaws Handbook of Thermodynamic Properties for Hydrocarbons and
Chemicals. Knovel, 2009.

[4] Holder, G. and Macauley, D. (1992). Solubility of ethylene in benzene at pressures to 9

MPa and temperatures from 353 to 433 K. Journal of Chemical & Engineering Data, 37(1),
pp.100-104.