Professional Documents
Culture Documents
Project Report
Duration:12th Aug, 2014 - 12th Nov, 2014
Table of Contents
1. Acknowledgement3
2. Executive Summary..4
3. Introduction...4
3.1 General Philosophy behind design of chemical processes.4
3.2 Introduction to Ethyl Benzene6
3.3 Ethyl Benzene Reaction System.6
3.4 Reaction Kinetics7
3.5 Commercial methods for production of Ethyl Benzene..8
4. Process Simulation9
4.1 Fluid Property Package...9
4.2 Process Description11
4.3 Process flow diagram.12
4.4 Degrees of freedom13
4.5 Optimization...13
4.6 Idea for heat integration. 17
4.7 Complex Column Configuration17
4.8 Control Structure21
4.9 Controller Performance..24
5. Economics27
5.1 Size of the Heat Exchangers...27
5.2 Size, Capital Costs and Operating Cost of the equipments28
5.3 Objective function(J)..29
6. References29
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Acknowledgement
We are highly indebted to Prof. Nitin Kaistha for making us learn
simulations and then challenging us by giving an open ended design
project which truly tested our skills, patience, team work and
commitment towards a particular task. We would also like to thank Sir
and Mr. Vivek Kumar for their guidance and supervision during the
entire period of project.
We are really grateful to all the Teaching Assistants and Lab staff who
directly or indirectly helped us in completion of our project since it
would not have been possible without their strong support and cooperation.
3|Page
2 Executive Summary
An ethyl benzene plant was designed using the liquid phase alkylation of benzene with ethylene
over zeolite acid catalyst. Fresh ethylene was assumed to have 5% ethane impurity while fresh
benzene had 0.01% toluene impurity. Alkylation reactions, which led to the formation of ethyl
benzene and a side product diethyl benzene and transalkylation reaction in which diethyl
benzene with benzene formed ethyl benzene, were all carried out in the packed bed reactors. To
limit the formation of side products, alkylator was run at high benzene to ethylene ratio.
The separation system consisted of a flash drum and 3 distillation columns. Vapor stream from
the flash drum was separated into ethane from the vent and benzene in the bottoms by first
distillation column. This benzene mixed with the liquid stream from the flash drum and the
combined stream went to second distillation column. Second column separated benzene in the
distillate and mixture of ethyl benzene and diethyl benzene at the bottoms. A part of benzene
from distillate was recycled to the alkylator and rest of it was sent to transalkylator. Third
column took bottoms of the second column as feed and gave ethyl benzene in the distillate and
diethyl benzene in the bottoms which was recycled to the transalkylator.
The dominant design variables were benzene to ethylene excess ratio, split ratio of benzene sent
to the transalkylator and temperature of transalkylator. Each of them were varied with the
objective function (J) which determined the annual profit of the plant. We mostly obtained bell
shaped curves and the values of variables at which the J got maximized were used in the final
flowsheet.
The plant capacity is 84086.64 tonnes of ethyl benzene per annum. The overall capital cost of the
plant came out to be $2.5 million and it consumed yearly raw materials worth $67.2 million and
yearly energy of $4.63 million. The revenue from the plant was calculated to be $89.74 million
per annum and the annual profit was $17.02 million.
3 Introduction
3.1 General philosophy behind design of chemical processes[1]
The chemical process industry is mainly involved in manufacturing of wide range of products
which improves the quality of life of humankind and generates employment. Chemical engineers
deal with a lot of obstacles while designing a process especially when substances involved have
high chemical reactivity, high toxicity, and high corrosivity operating at high pressures and
temperatures.
4|Page
Designing of the plant involves a thorough understanding of the reactions taking place in the
process with the major emphasis on reaction kinetics. Most of the time before starting the
simulation goes in testing the reaction kinetics and choosing a relevant thermodynamic package
which satisfies the experimental vapor liquid equilibrium data and enthalpy data of components.
Douglas[2,3] has proposed a hierarchical approach to the conceptual design in which design
process follows a series of decisions and steps. The decisions are listed as follows:
1.
2.
3.
4.
5.
High efficiency of usage of raw material is a requirement of the majority of chemical processes.
The extent of recycling of the unused reactants depends on the ease with which they can be
separated from the products and the single pass conversion of the reactors. We can recycle the
unreacted raw materials in three ways:
1. Separate and purify unreacted feed material from products and then recycle.
2. Recycle feed and product together and use a purge stream.
3. Recycle feed and product together and do not use a purge stream.
Specifications of streams and process conditions are influenced by physical processes as well as
economic conditions. The conditions used in the process generally represents a trade-off between
process performance and capital and operating cost of the equipment. Final selection of the
operating conditions should be made only after the economic analysis of the process.
On operating at higher pressure (>10 bar), we would be needing thicker walled more expensive
equipment while at pressure lower than ambient tends to make equipment large and may require
special construction techniques to prevent inward flow of outside impurities, thus increasing the
cost of equipment.
Several critical temperature limits apply to the chemical processes. At higher temperatures, there
is a significant drop in the physical strength of the common construction materials (primarily
carbon steel) and it must be replaced by a costly material. There should be a rational explanation
for selecting particular operating conditions which should be supported by economic analysis.
Most of the commercial reactions involve catalysts and the competence of a company is often the
result of a unique catalyst they use.
Choosing the best physical method is an extremely important part of any simulation. Wrong
property package will lead to incorrect simulation results which could not be trusted. Everything
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ranging from volumetric flow rates to energy balances to separation in the equilibrium stage
units depends on correct thermodynamic data.
In general, seven steps are involved in simulating any chemical process in a software. They are
selection of chemical components, thermodynamic models, process topology, feed stream
properties, equipment parameters, output options and convergence criteria.
For optimizing a problem, we look for decision variables, objective function, constraints, global
optimum and minimum optimum.
benzene is an undesirable product because most of the ethyl benzene is used in the making of
styrene and for styrene process, fresh ethyl benzene should have less than 2ppm diethyl benzene.
So to limit the formation of diethyl benzene and other polyethyl benzenes, we use a high benzene
to ethylene ratio in the alkylation reactor. The reactions that take place in the entire process are
as follows:
C6H6
+ C2H4
Benzene
Ethylene
C6H6
Benzene
+ 2C2H4
Ethylene
.1
C6H4 (C2H5)2
Diethyl Benzene
......2
C2H4
Ethylene
C6H4 (C2H5)2
DEB
..3
+ C6H5 (C2H5)2
DEB
2 C6H5C2H5
EB
..........................4
C6H5C2H5
EB
C6H6
Benzene
C6H5C2H5
EB
2 C6H5C2H5
EB
C6H6
+
Benzene
C6H4 (C2H5)2
DEB
......5
7|Page
r3 = 0.00085*exp(-20643/RT)CE1.77CEB0.35
For reaction 4 and 5, we regressed data for CBZ0 and CDEB0 and initial rates and obtained rate
constant of the forward reaction. Alternatively, chemical equilibrium constant for 4th reaction is:
K = XBXDEB/XEB2
At 571.15 K, K is 0.883. At ordinary temperature T, K can be obtained the relationship
1 1
1
ln (
)=
(
)
571.15
571.15
Using the equilibrium constant and forward rate constant, we found out the backward rate
constant. From the above kinetics, we were able to do the reaction with 100% ethylene
conversion even at 60 C but the literature, encyclopaedias and actual plant data tells us that the
temperature should be in the range of 200 C - 300C for 100% ethylene conversion. Thus we
obtained a wide deviation from the experimental data which proved our kinetics to be incorrect.
8|Page
However the Mobil Badger process is the most modern and successful vapor phase process for
production of ethylbenzene. The process uses ZSM-5 synthetic zeolite catalyst.
Zeolites were used earlier for alkylation process but they deactivated quickly because of coke
formation and low catalytic activity. The catalyst used by Mobil had larger resistance to coke
formation and high catalytic activity for transalkylation and alkylation.
Liquid phase alkylation of benzene with ethylene over zeolite acid catalyst has been used in our
project.
4 Process Simulation
4.1 Fluid Property Package
Vapor liquid equilibrium data of Benzene and Ethyl Benzene for SRK, Peng Robinson, Lee
Kesler and UNIFAC was obtained in Aspen Plus. Then it was compared with the data obtained
from Dechema, Volume 7 which basically represents the experimental data. Following results
were obtained :
Table 4.1.: Root Mean Square difference between the values obtained from 2 data
Package
SRK
Peng Robinson
UNIFAC
Lee Kesler
.0377
.0392
.0387
.0394
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(a)
(b)
(c)
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(d)
Figure 4.1.1 : Blue line represents Y and red line reprsents X of experimental data from Dechema while
Green line represents Y and Purple line represents X of Aspen Plus data. 1(a) Plot for UNIFAC, 1(b) Plot
for Lee Kesler method, 1(c) Plot for SRK, 1(d) Plot for Peng Robinson
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The vapor stream from the separator went through compressor to increase stream pressure to
column pressure and cooler to reduce temperature which rose due to compression and finally into
the distillation column. The column gave almost pure ethane in the distillate and almost pure
benzene in the bottoms and both these distillate and bottoms which mixed with the liquid stream
from separator.
The liquid stream from the separator passed through a valve and finally went into second
distillation column. This column gave almost pure benzene in the distillate and a mixture of ethyl
benzene and diethyl benzene in the bottoms. The benzene from the distillate was split in two
parts one of which was recycled back to mix with the fresh benzene and served as feed to the
alkylation reactor while second part was send to the transalkylation reactor in which it reacted
with diethyl benzene.
The bottoms from the second distillation column went to the third column. This column gave out
almost pure ethyl benzene with slight impurities of benzene and toluene in the distillate and
diethyl benzene in the bottoms. The diethyl benzene from the bottoms passed through a cooler
followed by a mixer where it mixed with benzene. The mixed stream went through a pump
followed by a heater and finally into a transalkylation reactor. The output from the
transalkylation reactor was recycled to mix with the output stream from alkylation reactor.
Figure 4.31 : Process Flow Diagram of the fully optimized flow sheet developed on Aspen Hysys
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43
17
25
4.4 Optimization
Sizing the Reactors
Alkylator
An adjustor block was used to size the reactor for 99% conversion of ethylene. This adjustor
block was used during the optimization of other variables, so as to achieve a final value of the
volume for which the optimized flow sheet runs, with a 99% conversion. The final value arrived
at was 20m3.
Transalkylator
Using a procedure similar to that of the alkylator, an adjustor block was used on the transalkator
to achieve a conversion of 99% of the equilibrium conversion. The adjustor block was used on
the transalkylator while optimizing the flow sheet for other variables, so as to get the volume of
the transalkylator for the final optimized value of other dominant design variables. The final
volumne arrived at was 7 m3.
The final flowsheet was optimized for 4 dominant design variables.
The final dominant deign variables were chosen to be the following
-Excess Ratio of Benzene to Ethylene
-Split of Benzene sent to the trnasalkylator
-Inlet Temperature of the Transalkylator
-Benzene Leakage down the benzene recycle column
Excess Ratio Of Benzene
The excess ratio of benzene was defined as the ratio of the total benzene entering the reactor to
the amount of ethylene entering the reactor. On varying the excess ratio, the maximum profit
achieved was at a value of 1.8 excess ratio.
When the value of the excess ratio is below 1.8, concentration of ethylene increases in the
stream, this leads to the production of more diethylbenzene due to the side reaction. This causes
more diethylbenzene to enter the second and third columns. Especially, in the third column the
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boilup increases because increase in the amount of diethylbenzene causes the concentration of
ethylbenzene to decrease and this leads to a more difficult separation. Because of this reason the
running and fixed costs of the reboiler end up increasing along with the size of the column.
While on increasing the excess ratio above 1.8, though the amount of diethylbenzene decreases
but the excess benzene leads to a more difficult separation in the first colum, this causes an
increase in the operating and capital in the second column.
J vs Excess Ratio
1.80E+07
J (Economic Function)($)
1.70E+07
1.60E+07
1.50E+07
1.40E+07
1.30E+07
1.20E+07
1
1.5
2.5
3.5
4
J vs
4.5
Split Ratio
This optimization was done after optimizing the excess benzene ratio and setting its value to 1.8.
On varying the Split ratio, a maximum profit was achieved at a split of 90 kmol/hr. i.e. out of the
total benzene coming out as distillate from the second column, 90 kmol/hr was diverted to the
transalkylator.
If the split ratio is kept below 90kmol/hr, the Diethyl Benzene in the transalkylator doesnt get
enough Benzene to react with, thus the amount of DiethylBenzene in the recycle increases, this
leads to an increase in the size of the equipment of the second and third distillation columns,
namely the reboiler duty and the size of the reboiler.
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And on increasing the amount of benzene split, the amount of benzene increases in the recycle
and though the amount of diethyl benzene decreases , the amount of benzene recycle increases
and this causes an increase in the size of the distillation column separating benzene.
J vs Split Ratio
1.75E+07
J (Economic Function)($)
1.70E+07
1.65E+07
1.60E+07
1.55E+07
1.50E+07
1.45E+07
1.40E+07
1.35E+07
1.30E+07
40
65
90
115
Split Ratio
140
165
190
J vs Split Ratio
215
Figure 4.4.2 : Variation of J with the ratio of benzene sent to transalkylator to total benzene produced
from recycle column
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1.80E+07
J vs Transalkylator Temperature
J (Economic Function)($)
1.60E+07
1.40E+07
1.20E+07
1.00E+07
8.00E+06
6.00E+06
4.00E+06
100
150
200
Temperature (oC)
250
300
J vs Transalkylator Temperature
J (Economic Function)($)
1.72E+07
J vs Benzene Leakage
1.70E+07
1.68E+07
1.66E+07
1.64E+07
1.62E+07
1.60E+07
1.58E+07
1.56E+07
1.54E+07
0.00E+00 2.00E-07 4.00E-07 6.00E-07 8.00E-07 1.00E-06 1.20E-06
J vs Benzene
Benzne Leakage
Figure 4.4.4 : Variation of J with benzene leakage from the recycle column
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17 | P a g e
Figure 4.5.1: First complex column configuration showing main column with a side rectifier. Mostly
Benzene in distillate, Ethyl Benzene from side rectifier and Diethyl Benzene from the bottoms of main
column
For the second complex configuration, a simple Petlyuk column was assembled as shown in
figure 4.5.2. This configuration was designed to replace the Ehtane separation and Benzene
Recycle Columns. The feed is first partially distilled in the pre-fractionator. This tray section
separates benzene from diethylbenzene. The exit streams form the pre-fractionator are fed to the
main separation section. Benzene is removed at the top, Ethylbenzene is removed at middle and
a mixture of diethyl benzene and ethyl benzene was removed at the bottoms.
The pre-fractionator gives out mostly benzene, ethyl benzene and very little diethyl benzene as
vapor from the top and very little benzene, ethyl benzene and diethyl benzene as liquid from the
bottom to the main column. It also receives the liquid stream at the top and vapor stream at the
bottom from the main column. The main column gives out benzene from the top, ethyl benzene
from the side draw and diethyl benzene from the bottoms.
18 | P a g e
Reboiler duty of petlyuk column came out to be around 5738 kW, which is only a 1.7 % decrease
from the initial reboiler duty. This column doesnt prove to be much efficient in terms of
reduction of total reboiler duty.
The purpose of the third assembled column was to replace the Ethane Separation column and the
Benzene recycle column. The column structure is fairly simple, it has a conventional separation
section with a regular reboiler and condenser, with a side draw in the middle. Ethane is vented
out at the top, benzene is removed at middle and a mixture of ethyl benzene and diethyl benzene
was removed at the bottom.
19 | P a g e
Figure 4.5.3: Column with a side draw. Benzene at the top, ethyl benzene in the middle and diethyl
benzene in the bottoms
Reboiler duty of this configuration came out to be 4481 kW, which is a 23% decrease from the
conventional reboiler duty.
The final configuration assembled is shown in figure 4.5.3.
The assembly in Figure 4.5.5 consists of two tray section, with the bottom product of the first
section being sent to the second. This configuration was meant to replace the Recycle Column
and the Product Column.
The initial tray section was used to separate benzene from the feed. The bottoms product of the
first column was introduced as feed into the second column. The second column sends out vapor
stream to the first column from the same stage on which it received the feed. Ethyl Benzene
comes out in the distillate and Diethyl Benzene from the bottoms of the second column.
Reboiler duty of the configuration is 15% less than the conventional column configuration.
Table 4.5.1 : Summary of reboiler duty reduction on implementing complex column
Configuration
Power Consumed(kW)
% Saving
1
5164
10
2
5738
1.7
3
4481
23.23
4
4961
15
20 | P a g e
Then the complex column whose reboiler duty was 23% less than the conventional configuration
was implementd in the flowsheet and got it converged. The new flowsheet appeared as follows :
Figure 4.5.5 : Flowsheet with the above complex column showed minimum reboiler duty
would restrict the amount of heating fluid to flow. This kind of controller action is called reverse
action.
If we are cooling the system and temperature of the outlet stream rises, we will increase the
amount of coolant flowing through the valve by increasing the valve opening. So with increase in
temperature, valve opening increases and thus the controller is in the direct mode.
Proportional controllers were used to control level and Proportional Integral controllers for rest
of the variables. After defining the controllers, there came the task of tuning them. After running
the simulation in the dynamic mode, all the controllers were carefully observed and the
performance of each of them was analyzed by observing the variations in the PV and opening
percent of the valve (Output%) with time.
If PV was far away from the set point and fluctuating rapidly with time or output % was close to
0 or 100 or fluctuating with time, then this was an indication that the controller was not working
properly and there was a need to tune it. For tuning, the values of Kc and i were varied until all
controllers became stable with PV close to set point and Output % away from the extremes of 0
and 100.
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OBJECT TO
CONTROL
CONTROLLER
TYPE
PROCESS
VARIABLE
To Control Flow of
Ethylene
Flow
0.5
0.5
0-200
100
Reverse
Flow
0.1
0.5
1.5-2
1.8
Reverse
Temperature
0.5
35-55
45
Reverse
Temperature
Outlet Temperature of
Alkylator
30-80
65
Direct
Temperature
Level
0.5
2
5
0
40-60
0-100%
50
50%
Direct
Direct
Pressure
Inlet Pressure
0.5
700-850
770
Reverse
Temperature
Inlet Temperature
0.5
40-100
70
Direct
Pressure
Pressure of Vessel
12
0.8
550-800
670
Direct
Excess Ratio
To Contrlol Inlet
Temperature of
Alkylator
Control Exit
temperature from
alkylator
Temperature of Inlet
Stream to Separator
Separator Level
Ethane Column Inlet
Pressure
Ethane Column Inlet
Temperature
Ethane Column
Condensor Pressure
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RANGE SET
Kc Ti OF PV POINT MODE
Ethane Column
Condensor Level
Ethane Column
Condensor Temperature
Ethane Column Reboiler
Level
Ethane Column Tray
Temperature
Recycle Column
Condensor Pressure
Recycle Column
Condensor Level
L/F Ratio Controller of
the Recycle Column
Recycle Column
Reboiler Level
Recycle Column Tray
Temperature
Product Column
Condensor Pressure
Product Column
Condensor Level
Product Column Tray
Temperature
Produt Column
Condensor Reboiler
Level
Split Ratio Controller(
Benzene Split)
Transalkylator Inlet
Temperature
Level
Temperature
Level
0-100
85%
Direct
0.1
40
20-60
40
Reverse
0-100%
50%
Direct
Temperature
Level
Tray Temperature
(Tray 4)
0.5
15
140-180
157
Reverse
Pressure
Condensor Pressure
140-300
240
Direct
Level
Level
0-100
50%
Direct
Flow
Reflux Rate
0.5
0.5
.2-.8
0.5425
Reverse
Level
Level
0-100
50%
Direct
Temperature
0.5
30
110-150
135
Reverse
Pressure
Condensor Pressure
110-140
120%
Direct
Level
Level
0-100
50%
Direct
Temperature
Temp of Tray 27
0.5
160-195
172
Reverse
Level
0-100%
64%
Direct
Flow
Level
Flow Rate of Bz to
Transalkylator
0.5
0.5
0-200
100%
Reverse
Temperature
Inlet Temperature
0.4
10
140-180
160
Reverse
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Level
Temperature of
Condensor
Figure 4.7.2: Variation of ethane vent rate with 10% change in throughput
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26 | P a g e
Figure 4.7.5 : Varition of Benzene flow in the recycle with change in throughput
Figure 4.7.6 : Variation of Ethyl Benzene purity with changes in mole percent of ethane in ethylene feed
27 | P a g e
Figure 4.7.7 : Varition of ethane vent rate with changes in mole percent of ethane in ethylene feed
Figure 4.7.8 : Varition of Benzene flow in the recycle with change in mole percent of ethane in feed
Figure 4.7.9 : Varition of DEB in the recycle with change in mole percent of ethane in feed
5 Economics
5.1 Sizing of the Heat Exchangers
Sizing of the equipments play a major role in the economics of the plant. Designers are always in
the search of reducing the size keeping the overall performance safe, stable and efficient. There
is always a question at the back of the mind that can we reduce volume of the reactors? Is there a
way to reduce the number of trays in the column? What should be the heat transfer rates across
heaters and coolers that could limit their size? and so on.
28 | P a g e
For heat exchangers such as heaters, coolers, condensers and reboilers areas were found using
the following formula :
Q = UATlm
eq (5.1)
(1 2)
..eq(5.2)
1
)
2
ln(
Table 5.2.1 : Size, Capital Cost and Operating Cost of all the major equipments
Equipment
Cooler before Alkylator
Heater before Transalkylator
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Size
19.55 m
10.68 m2
2.397E+04
3481
4868
3.987E+04
Transalkylator
.35 m2
71.57 m2
No of Tubes = 50
Length = 10m
Volume = 20 m3
D= 0.22 m
Length = 20m
Volume = 5m3
D = .56m
No. of Trays = 5
Height = 3.048 m
.75 m2
.48 m2
No of Trays = 34
Height = 20.73 m
161.3 m2
196.3 m2
No of Trays = 35
Height = 21.34 m
33.55 m2
105.4 m2
997
8.492E+04
3.677E+06
350.1
5683
2.923E+04
2.534E+04
9162
7242
None
1565
2.087E+05
6.3E+05
122
8478
None
1.868E+05
1.592E+05
2.851E+05
4.991E+05
2.918E+06
None
3.762E+04
1.149E+05
2.246E+04
1.080E+06
$4.635E+06
$2.534E+06
3 years
$51.25 per kmol
$33.66 per kmol
$113.3 per kmol
$6.724E+07
$8.974E+07
$1.702E+07
6 References
[1] : Turton, Richard, et al. Analysis, synthesis and design of chemical processes. Pearson
Education, 2008.
30 | P a g e
[2] : Douglas, J. M., Conceptual Design of Chemical Processes (New York: McGraw-Hill,
1989).
[3] : Douglas, J. M., A Hierarchical Design Procedure for Process Synthesis, AIChE
Journal, 31 (1985): 353.
[4] : Ebrahimi, Ali Nejad, et al. "Modification and optimization of benzene alkylation process for
production of ethylbenzene." Chemical Engineering and Processing: Process
Intensification 50.1 (2011): 31-36.
[5] : Ganji,
Hamid, et al. "Modelling and simulation of benzene alkylation process reactors for
production of ethylbenzene." Petroleum and Coal 46 (2004): 55-63.
[6] : Qi, Zhiwen, and Ruisheng Zhang. "Alkylation of benzene with ethylene in a packed reactive
distillation column." Industrial & engineering chemistry research 43.15 (2004): 4105-4111.
[7] : Tiako Ngandjui, L. M., D. Louhibi, and F. C. Thyrion. "Kinetic analysis of diethylbenzenebenzene transalkylation over faujasite Y." Chemical Engineering and Processing: Process
Intensification 36.2 (1997): 133-141.
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