Ethyl Benzene Plant Design

Project Report
Duration:12th Aug, 2014 - 12th Nov, 2014
Department of Chemical Engineering
IIT Kanpur
Submitted by :
Rohit Kakkar|Salman Ahmad Khan|Shivang Sharma
Rohan Bishnoi|Himanshu Bareja|Nikhil Kumar
Umang Arora
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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.
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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 impurit
y while fresh
benzene had 0.01% toluene impurity. Alkylation reactions, which led to the forma
tion 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 be
d reactors. To
limit the formation of side products, alkylator was run at high benzene to ethyl
ene ratio.
The separation system consisted of a flash drum and 3 distillation columns. Vapo
r stream from
the flash drum was separated into ethane from the vent and benzene in the bottom
s by first
distillation column. This benzene mixed with the liquid stream from the flash dr
um and the
combined stream went to second distillation column. Second column separated benz
ene in the
distillate and mixture of ethyl benzene and diethyl benzene at the bottoms. A pa
rt of benzene
from distillate was recycled to the alkylator and rest of it was sent to transal
kylator. Third
column took bottoms of the second column as feed and gave ethyl benzene in the d
istillate 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 varie
d with the
objective function (J) which determined the annual profit of the plant. We mostl
y 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 ca
pital 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. Chemic
al engineers
deal with a lot of obstacles while designing a process especially when substance
s involved have
high chemical reactivity, high toxicity, and high corrosivity operating at high
pressures and
temperatures.
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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 st
arting the
simulation goes in testing the reaction kinetics and choosing a relevant thermod
ynamic 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 wh
ich design
process follows a series of decisions and steps. The decisions are listed as fol
lows:
1.
2.
3.
4.
5.
Decide whether the process will be batch or continuous.
Identify the input/output structure of the process.
Identify and define the recycle structure of the process.
Identify and design the general structure of the separation system.
Identify and design the heat-exchanger network or process energy recovery system
.
High efficiency of usage of raw material is a requirement of the majority of che
mical processes.
The extent of recycling of the unused reactants depends on the ease with which t
hey can be
separated from the products and the single pass conversion of the reactors. We c
an 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 proc
esses as well as
economic conditions. The conditions used in the process generally represents a t
rade-off between
process performance and capital and operating cost of the equipment. Final selec
tion of the
operating conditions should be made only after the economic analysis of the proc
ess.
On operating at higher pressure (>10 bar), we would be needing thicker walled mo
re 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, th
us increasing the
cost of equipment.
Several critical temperature limits apply to the chemical processes. At higher t
emperatures, there
is a significant drop in the physical strength of the common construction materi
als (primarily
carbon steel) and it must be replaced by a costly material. There should be a ra
tional explanation
for selecting particular operating conditions which should be supported by econo
mic analysis.
Most of the commercial reactions involve catalysts and the competence of a compa
ny is often the

result of a unique catalyst they use.

Choosing the best physical method is an extremely important part of any simulati
on. Wrong
property package will lead to incorrect simulation results which could not be tr
usted. Everything
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ranging from volumetric flow rates to energy balances to separation in the equil
ibrium stage
units depends on correct thermodynamic data.
In general, seven steps are involved in simulating any chemical process in a sof
tware. They are
selection of chemical components, thermodynamic models, process topology, feed s
tream
properties, equipment parameters, output options and convergence criteria.
For optimizing a problem, we look for decision variables, objective function, co
nstraints, global
optimum and minimum optimum.
3.2 Introduction to Ethyl Benzene
Ethyl Benzene (EB), compound with a chemical formula of C6H5CH2CH3 is used as an
intermediate in the making of styrene[4]. Styrene is a building block in the man
ufacturing of
polystyrene which is used for producing disposable plastic cutlery and dinnerwar
e, CD jewel
cases, smoke detector housings and so on. EB and styrene units are generally ins
talled together
in order to facilitate the energy economy by integrating energy flows of the two
units.
Ethyl Benzene is mainly manufactured via liquid phase alkylation or a gas phase
alkylation of
benzene. The traditional method used in industries is the liquid phase alkylatio
n of benzene with
ethylene over AlCl3 as the catalyst. It has been observed that in case of liquid
phase alkylation,
temperature is lower while selectivity of ethyl benzene and pressure required is
higher compared
to gas phase alkylation.[5]
A major difficulty faced during manufacturing of EB is that ethyl benzene is mor
e reactive
compared to benzene with respect to ethylene due to lower activation energy and
thus it leads to
the formation of diethyl benzenes (DEBs). To limit the formation of DEBs and oth
er polyethyl
benzene (PEBs) we use a large excess ratio of Benzene to Ethylene in the feed to
the alkylation
reactor. However, large excess ratio leads to higher equipment, separation and r
ecycle cost.
3.3 Ethyl Benzene Reaction System
Ethyl Benzene is produced by reacting benzene with ethylene in liquid phase over
AlCl 3 as the
catalyst. Ethylene contains impurities of ethane while benzene contains slight i
mpurities of
toluene. Ethane does not participate in the reaction while toluene reacts with e
thylene to form
ethyl benzene and propylene but we are assuming only 0.01% toluene in the fresh
benzene and
thus the amount of EB produced using toluene has been considered negligible.
Ethylene on reacting with benzene forms ethyl benzene and ethyl benzene on react
ing further
with ethylene forms diethyl benzene. Diethyl benzene again on reacting with ethy
lene forms
triethyl benzene. The activation energy for the reaction between ethyl benzene a
nd ethylene is
lower than the activation energy of ethylene reacting with benzene and thus if r
eaction is allowed

to proceed without any restriction, we will get more diethyl benzene than ethyl
benzene. Diethyl
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benzene is an undesirable product because most of the ethyl benzene is used in t

he 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 us
e a high benzene
to ethylene ratio in the alkylation reactor. The reactions that take place in th
e 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
Reactions 4 and 5 is basically an equilibrium reaction and is called trans-alkyl
ation reaction.
Reactions 1, 2 and 3 occur in alkylation reactor while 4 and 5 occur in transalk
ylation reactor
both of which are packed bed reactors. Catalysts used for the alkylation reactio
ns are different
from that of the transalkylation reaction and so we can safely ensure that first
three reactions
occur in alkylator while 4 and 5 occur in transalkylator.
3.4 Reaction Kinetics[6,7]
Chemical kinetics is the study of rate of chemical processes. It is one of the m
ost fundamental
thing that is researched out before designing a process. Getting relevant kineti
cs is considered as
one of the major success for designing a process.
During the course of our project, we faced a lot of hardships in finding kinetic
s for ethyl benzene
process. Some papers considered transalkylation as an equilibrium reaction while
some did not,
value of A(Arrhenius constant) in different papers were of different order of ma
gnitudes, and the
one we chose finally also doesnt gives us practical results. The kinetics used is
as follows:
r1 = 0.084*exp(-9502/RT)CE1.0CB0.32
r2 = 0.603*exp(-15396/RT)CE1.3CB0.33
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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 f
or 4th reaction is:
K = XBXDEB/XEB2
At 571.15 K, K is 0.883. At ordinary temperature T, K can be obtained the relati
onship

1 1
1
ln (
)=
(
)
571.15
 
571.15
Using the equilibrium constant and forward rate constant, we found out the backw
ard rate
constant. From the above kinetics, we were able to do the reaction with 100% eth
ylene
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. T
hus we
obtained a wide deviation from the experimental data which proved our kinetics t
o be incorrect.
3.5 Commercial Methods for Production of Ethyl Benzene[7]
There are primarily two sources to produce ethylbenzene. The major being alkylat
ion of benzene
and other being superfractionation of C8 aromatic streams. The alkylation of ben
zene is further
carried out commercially by
a) liquid phase alkylation
b) gas phase alkyllation
LIQUID PHASE ALKYLATION:
Alkylation of benzene in liquid phase using aluminium chloride as catalyst is th
e most used
method for ethylbenzene production. Different companies like shell, union carbid
e, Dow
chemicals use this method
The reaction is exothermic in nature (H 114 kJ/mol), kinetically fast and produce
good yields
of ethylbezene. Generally hydrogen chloride or ethyl chloride is used as a catal
yst promoter
which decreases the amount of aluminium chloride needed. Instead of AlCl3 lewis
acids
catalysts, BF3,FeCl3, AlBr3 are also used.
VAPOR PHASE ALKYLATION:
Earlier vapor phase alkylation were not able to compete with liquid phase alkyla
tion. The
alkylation process using boron trifluoride as catalyst had little success and su
ffered drawbacks
like high maintenance costs caused by corrosion from small amount of water.
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However the Mobil Badger process is the most modern and successful vapor phase p
rocess for
production of ethylbenzene. The process uses ZSM 5 synthetic zeolite catalyst.
Zeolites were used earlier for alkylation process but they deactivated quickly b
ecause of coke
formation and low catalytic activity. The catalyst used by Mobil had larger resi
stance 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 Robinso
n, 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. Followi
ng results
were obtained :
Table 4.1.: Root Mean Square difference between the values obtained from 2 data
Package
SRK
Peng Robinson
UNIFAC
Lee Kesler
Root Mean Square Difference
.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 d
ata from Dechema while
Green line represents Y and Purple line represents X of Aspen Plus data. 1(a) Pl
ot for UNIFAC, 1(b) Plot
for Lee Kesler method, 1(c) Plot for SRK, 1(d) Plot for Peng Robinson
4.2 Process Description
Stream containing mostly ethylene with an impurity of ethane (~5%) and stream ha
ving benzene
with a slight toluene impurity (~0.01%) were used as fresh feeds. Fresh feed con
taining ethylene
was passed through compressor to raise the pressure to 50 bars since it was in t
he gas phase
while fresh benzene was passed through a pump which raised its pressure to 50 ba
r. Both these
fresh feeds passed through a valve which reduced their pressure to around 40 bar
s. Pump and
compressor were supplied with the required amount of electricity.
Fresh benzene mixed with recycle benzene and the combined stream along with fres
h ethylene
with some ethane was used as the feed to the alkylation reactor. The feed passed
through a heater
which was used for controlling the temperature before sending to the reactor.
Output of the alkylator reactor mixed that of the transalkylator and the combine
d stream passed
through a cooler followed by a valve to reduce pressure to 1 atm. This stream en
tered the
separator which was used to separate liquid and vapor components of the inlet st
ream. It was
used because ethane in the vapor phase made the separation difficult and if the
inlet stream was
directly send for the distillation, then it would have significantly enhanced th
e reboiler duty of
the column.
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The vapor stream from the separator went through compressor to increase stream p
ressure to
column pressure and cooler to reduce temperature which rose due to compression a
nd finally into
the distillation column. The column gave almost pure ethane in the distillate an
d almost pure
benzene in the bottoms and both these distillate and bottoms which mixed with th
e liquid stream
from separator.
The liquid stream from the separator passed through a valve and finally went int
o 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 c
olumn gave out
almost pure ethyl benzene with slight impurities of benzene and toluene in the d
istillate and
diethyl benzene in the bottoms. The diethyl benzene from the bottoms passed thro
ugh 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 alkylati
on reactor.
4.3 Process Flow Diagram
Figure 4.31 : Process Flow Diagram of the fully optimized flow sheet developed o
n Aspen Hysys
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4.4 Degrees of Freedom

Table 4.4.1 : Degrees of freedom in the flowsheet
Control Degrees of Freedom
Steady State Operating Degrees of Freedom
Steady State Design Degrees of Freedom
43
17
25
4.4 Optimization
Sizing the Reactors
Alkylator
An adjustor block was used to size the reactor for 99% conversion of ethylene. T
his adjustor
block was used during the optimization of other variables, so as to achieve a fi
nal 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 o
n 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 variab
les. 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 enteri
ng the reactor to
the amount of ethylene entering the reactor. On varying the excess ratio, the ma
ximum 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 incre
ases in the
stream, this leads to the production of more diethylbenzene due to the side reac
tion. This causes
more diethylbenzene to enter the second and third columns. Especially, in the th
ird column the
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boilup increases because increase in the amount of diethylbenzene causes the con
centration 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 diethylbenz
ene 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
2.5
1.8 Excess Ratio
3
3.5
4
J vs
4.5
Figure 4.4.1 : Variation of J with Benzene to Ethylene excess ratio in alkylator
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 di
verted to the
transalkylator.
If the split ratio is kept below 90kmol/hr, the Diethyl Benzene in the transalky
lator doesnt get

enough Benzene to react with, thus the amount of DiethylBenzene in the recycle i
ncreases, this
leads to an increase in the size of the equipment of the second and third distil
lation 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 i
n the recycle
and though the amount of diethyl benzene decreases , the amount of benzene recyc
le increases
and this causes an increase in the size of the distillation column separating be
nzene.
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 t
o total benzene produced
from recycle column
Inlet Temperature of The TransAlkylator
On varying the temperature of the transalkylator, the maximum profit was achieve
d at an inlet
temperature of 1600C.
Below an inlet temperature of 1600C, the profits increase because of an increase
in the
conversion, even though the reaction is mildly exothermic. This happens because
at low
temperatures the reaction doesnt reach equilibrium and kinetically the reaction i
s favored at
higher temperatures. This causes the conversion to increase because of temperatu
re rise. This
leads to more conversion for the same amount of split thus rendering the process
cheaper.
When the temperature is increased beyond 1600C, the reaction having reached equi

librium,
starts to shift backwards because of its exothermicity. This causes the process
to become more
costly for the same split ratio thus decreasing profits.
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1.80E+07
J vs Transalkylator Temperature
J (Economic Function)($)
1.60E+07
1.40E+07
1.20E+07
1.00E+07
8.00E+06
6.00E+06
4.00E+06
100
150
200
Temperature (oC)
250
300
J vs Transalkylator Temperature
Figure 4.4.3: Varitaion of J with the inlet temperature of transalkylator
Benzene Leakage from The Recycle Column
There was no change in the profit as the benzene leakage was changed. So the fin
al value of the
benzene leakage chosen was around 2e 07, so as to always remain in the optimum r
egion for
evwn substantial changes in operating conditions.
J (Economic Function)($)
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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4.5 Ideas for heat integration

Hot Streams: Compressed Ethylene at 267 oC
Liquid flow to reboiler of Product column at 203 oC
Cold Stream: Liquid flow to reboiler of Benzene recycle column at 182.3 oC
The cold stream is first heated using liquid flow to reboiler of product column
by passing
through a heat exchanger. This increases the quality of old stream from 0 to 0.0
5. This is then
heated using compressed ethylene stream with the help of another heat exchanger
to increase the
vapour quality to 0.085.
To get a rough idea of the energy savings, the cold stream is copied from the st
ream entering the
reboiler of Benzene recycle column which is the passed through 2 heat exchangers
, one heated
by liquid flow to reboiler of Product column and another by compressed ethylene.
The rest of
enegry was supplied using an auxillary reboiler. This decreased energy consumpti
on from 6181
kW to 1283 kW, thus saving $2.16 million.
Without Heat Integration
Heat Integration
Energy Consumption Savings
6181kW
1283kW
$2.16 million
0
4.6 Complex Column Configurations
Four complex column configurations were made to show different separation method
s possible
and the reduction in the total reboiler duty as a consequence of using the compl
ex distillation
columns was analyzed.
In the first complex configuration of the columns, the Benzene Recycle Column an
d the Product
Column were replaced. The configuration assembled was, as shown in figure 4.5.1.
The feed was
introduced in a regular column, but with a vapor side draw. Benzene was separate
d at the top,
EthylBenzene was removed at the middle and this stream was subjected to further
distillation in
a side stripper and DiethylBenzene was removed at the bottom.
Reboiler duty of this configuration was 5164 kW while that of conventional confi
guration is
5738 kW. Thus reboiler duty of this configuration is about 10% lower than that o
f the
conventional column
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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 fro
m the bottoms of main
column
For the second complex configuration, a simple Petlyuk column was assembled as s
hown in
figure 4.5.2. This configuration was designed to replace the Ehtane separation a
nd 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 fractionato
r 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 die
thyl 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 vap
or stream at the
bottom from the main column. The main column gives out benzene from the top, eth
yl benzene
from the side draw and diethyl benzene from the bottoms.
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Figure 4.5.2: Petlyuk Column

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 c
olumn and the
Benzene recycle column. The column structure is fairly simple, it has a conventi
onal separation
section with a regular reboiler and condenser, with a side draw in the middle. E
thane 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.
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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% decre
ase 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 produ
ct of the first
section being sent to the second. This configuration was meant to replace the Re
cycle 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 se
nds out vapor
stream to the first column from the same stage on which it received the feed. Et
hyl Benzene
comes out in the distillate and Diethyl Benzene from the bottoms of the second c
olumn.
Figure 4.5.4: 2 columns with a single reboiler
Reboiler duty of the configuration is 15% less than the conventional column conf
iguration.
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 c
onfiguration
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 d
uty
4.6 Control Structure
Controls were implemented to control flow rates, temperatures, pressures, compos
itions, levels,
Benzene to ethylene excess ratio and Benzene split ratio at different locations
in the flow sheet.
Controls ensure the safe, stable and economical operation of the chemical proces
ses in a plant.
The designing of the control system involved the identification of appropriate p
ositions at which
the control had to be implemented and the type of the control, which depends on
the variable to
be controlled. Once the positions were identified and controllers were set up, t
hen parameters for
each controller were adjusted and tuned.
In each controller, the process variable and the controlled variable were specif
ied, input values of
Kc, i and d depending upon
he
ype of con
roller were defined i.e. Propor
ion(P),
Propor
ional
In
egral(PI) or Propor
ional In
egral Deriva
ive(PID). Then
he range of
he Pro
cess Varible(PV)
was defined. i.e.
he range around
he se
poin
which
he con
rol can opera
e i
n. Finally
he
con
roller mode was specified i.e. direc
ac
ing or reverse ac
ing.
Reverse mode represen
s
ha

he con
oller ac
ion should be opposi
e
o
he chan
ge in variable.
For example, if we are hea
ing
he componen
s in a hea
er and con
rolling
he
e
mpera
ure of
ou
le
s
ream wi
h
he hea
du
y of
he hea
er. So when
he
empera
ure of
he o
u
le
s
ream
increases beyond
he se
poin
,
hen we need
o reduce
he hea
du
y in order
o
bring
he

empera
ure close
o se
poin
and
hus
here will be reduc
ion in
he con
rol v
alve opening which
21 | P a g e

would res
ric

he amoun
of hea
ing fluid
o flow. This kind of con
roller ac
i
on is called reverse
ac
ion.
If we are cooling
he sys
em and
empera
ure of
he ou
le
s
ream rises, we will
increase
he
amoun
of coolan
flowing
hrough
he valve by increasing
he valve opening. So
wi
h increase in

empera
ure, valve opening increases and
hus
he con
roller is in
he direc
mo
de.
Propor
ional con
rollers were used
o con
rol level and Propor
ional In
egral co
n
rollers for res

of
he variables. Af
er defining
he con
rollers,
here came
he
ask of
uning

hem. Af
er running

he simula
ion in
he dynamic mode, all
he con
rollers were carefully observed
and
he
performance of each of
hem was analyzed by observing
he varia
ions in
he PV a
nd opening
percen
of
he valve (Ou
pu
%) wi
h
ime.
If PV was far away from
he se
poin
and fluc
ua
ing rapidly wi
h
ime or ou
pu

% was close
o
0 or 100 or fluc
ua
ing wi
h
ime,
hen
his was an indica
ion
ha

he con
roll
er was no
working
properly and
here was a need
o
une i
. For
uning,
he values of Kc and i were
varied un
il all
con
rollers became s
able wi
h PV close
o se
poin
and Ou
pu
% away from
he
ex
remes of 0
and 100.
22 | P a g e

Figure 4.6.1: Fully Op
imized flowshee
wi
h con
rols

Table 4.6.1 : The following con
rols were implemen
ed in
he flowshee
OBJECT TO
CONTROL
CONTROLLER
TYPE
PROCESS
VARIABLE
To Con
rol Flow of
E
hylene
Flow
0.5
0.5
0-200
100
Reverse
Flow
Inle
Flow Ra
e
Fresh benzene Flow
ra
e
0.1
0.5
1.5-2
1.8
Reverse
Tempera
ure
Inle
Feed Tempera
ure
0.5
5
35-55
45
Reverse
Tempera
ure

Ou
le
Tempera
ure of
Alkyla
or
4
1
30-80
65
Direc

Tempera
ure
Level
Inle
S
ream Temp
Level
0.5
2
5
0
40-60
0-100%
50
50%
Direc

Direc

Pressure
Inle
Pressure
0.5
5
700-850
770
Reverse
Tempera
ure
Inle
Tempera
ure
0.5
5
40-100
70

Direc

Pressure
Pressure of Vessel
12
0.8
550-800
670
Direc

Excess Ra
io
To Con
rlol Inle

Tempera
ure of
Alkyla
or
Con
rol Exi


empera
ure from
alkyla
or
Tempera
ure of Inle

S
ream
o Separa
or
Separa
or Level
E
hane Column Inle

Pressure
E
hane Column Inle

Tempera
ure
E
hane Column
Condensor Pressure
23 | P a g e
RANGE SET
Kc Ti OF PV POINT MODE

E
hane Column
Condensor Level
E
hane Column
Condensor Tempera
ure
E
hane Column Reboiler
Level
E
hane Column Tray
Tempera
ure
Recycle Column
Condensor Pressure
Recycle Column
Condensor Level
L/F Ra
io Con
roller of

he Recycle Column
Recycle Column
Reboiler Level
Recycle Column Tray
Tempera
ure
Produc
Column
Condensor Pressure
Produc
Column
Condensor Level
Produc
Column Tray
Tempera
ure
Produ
Column
Condensor Reboiler
Level
Spli
Ra
io Con
roller(
Benzene Spli
)
Transalkyla
or Inle

Tempera
ure
Level
Tempera
ure
Level
2
0
0-100
85%
Direc

0.1
40
20-60
40
Reverse
1
0

0-100%
50%
Direc

Tempera
ure
Level
Tray Tempera
ure
(Tray 4)
0.5
15
140-180
157
Reverse
Pressure
Condensor Pressure
5
1
140-300
240
Direc

Level
Level
2
0
0-100
50%
Direc

Flow
Reflux Ra
e
0.5
0.5
.2-.8

0.5425
Reverse
Level
Level
2
0
0-100
50%
Direc

Tempera
ure
Temp of 18
h Tray
0.5
30
110-150
135
Reverse
Pressure
Condensor Pressure
4
1
110-140
120%
Direc

Level
Level
2
0
0-100
50%
Direc

Tempera
ure
Temp of Tray 27
0.5
8
160-195
172
Reverse
Level
2
0
0-100%
64%
Direc

Flow
Level
Flow Ra
e of Bz
o
Transalkyla
or
0.5
0.5
0-200
100%
Reverse
Tempera
ure
Inle
Tempera
ure
0.4
10
140-180
160
Reverse
4.7 Con
roller Performance
Varia
ion of Throughpu

24 | P a g e

Level
Tempera
ure of
Condensor

Figure 4.7.1 : Varia
ion of EB produc
ion Ra
e wi
h 10% change in
hroughpu

Figure 4.7.2: Varia
ion of e
hane ven
ra
e wi
h 10% change in
hroughpu

25 | P a g e

Figure 4.7.3 : Vari
ion of DEB recycle ra
e wi
h change in
hroughpu

Figure 4.7.4: Vari
ion of EB puri
y in
he produc
wi
h change in
hroughpu

26 | P a g e

Figure 4.7.5 : Vari
ion of Benzene flow in
he recycle wi
h change in
hroughpu

Varia
ion of E
hane Percen
age in
he feed
Figure 4.7.6 : Varia
ion of E
hyl Benzene puri
y wi
h changes in mole percen
of
e
hane in e
hylene feed
27 | P a g e

Figure 4.7.7 : Vari
ion of e
hane ven
ra
e wi
h changes in mole percen
of e
ha
ne in e
hylene feed
Figure 4.7.8 : Vari
ion of Benzene flow in
he recycle wi
h change in mole perce
n
of e
hane in feed
Figure 4.7.9 : Vari
ion of DEB in
he recycle wi
h change in mole percen
of e
h
ane in feed
5 Economics
5.1 Sizing of
he Hea
Exchangers
Sizing of
he equipmen
s play a major role in
he economics of
he plan
. Design
ers are always in

he search of reducing
he size keeping
he overall performance safe, s
able and
efficien
. There
is always a ques
ion a

he back of
he mind
ha
can we reduce volume of
he re
ac
ors? Is
here a
way
o reduce
he number of
rays in
he column? Wha
should be
he hea

ransfe
r ra
es across
hea
ers and coolers
ha
could limi

heir size? and so on.
28 | P a g e

For hea
exchangers such as hea
ers, coolers, condensers and reboilers areas wer
e found using

he following formula :
Q = UATlm
eq (5.1)
Q : Power supplied
o
he hea
er
U : Overall hea

ransfer ra
es ob
ained from li
era
ure[4]
A : Area of hea
er or cooler
Tlm : Log Mean Tempera
ure Difference(LMTD)
For finding LMTD we assumed
empera
ure of s
eam
o remain cons
an
for hea
er a
nd

empera
ure of cold wa
er rose from 30C
o 40C for cooler. Using
hese assump
ions
and inle

and ou
le

empera
ure, we found T1 and T2 and calcula
ed Tlm from
he following fo
rmula :
 =
(1 2)
..eq(5.2)
1
)
2
ln(
5.2 Size, Capital Cost and Operating Cost of the equipments
For finding capital cost of the equipments, we first obtained purchased cost(Cp)
using formula :
log10Cp = K1 + K2log10(A) + K3[(log10A)2]
..eq(5.3)
where A is the capacity or size parameter and K1, K2 and K3 are constants
Then Pressure factor(Fp) was found using :
log10Fp = C1 + C2log10(P) + C3[(log10P)2]
eq(5.4)
where unit of P is bar gauge (barg) and C1, C2 and C3 are constants.
Pressure factor is used in the overall capital cost because in purchase cost, it
is assumed that the
equipment operates at the atmospheric pressure.Material factor(Fm) for different
materials are
obtained since purchase cost assumes that the material is made up of carbon stee
l.
Then we obtained Bare Module Cost Factor(FBM) which accounts for direct and indi
rect costs
associated with the purchased cost(Cp). Final capital cost or bare module cost o
f the equipment is
calculated using :
FBM = (B1 + B2FMFP)
eq(5.5)
CBM = CPFBM
.eq(5.6)
where CBM is the bare module cost of the equipment
Table 5.2.1 : Size, Capital Cost and Operating Cost of all the major equipments
Equipment

Cooler before Alkylator

Heater before Transalkylator
29 | P a g e
Size
Capital Cost($) Operating Cost($/yr)
2
19.55 m
10.68 m2
2.397E+04
3481
4868
3.987E+04

Cooler before Ethane Column

Heater before separator
Alkylator
Transalkylator
Ethane Column (Vessel + Trays)
Ethane Column condenser
Ethane column reboiler
Recycle column(Vessel + Trays)
Recycle column condenser
Recycle column reboiler
Product column(Vessel + Trays)
Product column condenser
Product Column Reboiler
.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
5.3 Objective Function(J)
Objective Function(or J function) is defined as follows :
 =      
 
 
Table 5.3.1 : J function calculations
Total Energy Cost
Total Capital Cost
Payback Period
Cost of Benzene
Cost of Ethylene
Selling Price of Ethyl Benzene
Total Raw Material Cost per annum
Revenue per annum
J(Profit per annum)
$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 process
es. 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 alky
lation 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 f
or
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 a
nd Processing: Process
Intensification 36.2 (1997): 133 141.
31 | P a g e