UEMK4323 PROCESS AND PLANT DESIGN I

MAY 2014


ASSIGNMENT I


TASK II
Name Student ID Year/Trimester
Lee J ian 11UEB02057 Y4/T1
Yang Yew Ren 11UEB02058 Y4/T1
Dieh Hua Loong 11UEB04154 Y4/T1
Kwan Yi An 11UEB01740 Y4/T1
Wah Tee Yan 10UEB01875 Y5/T2

Group 2
Lecturer/Tutor : Dr. Chin Siew Kian


2

Introduction

In the first task of the assignment (Task 1), it was decided that the designed plant will
use the EBOne
TM
Process to produce ethylbenzene (EB) due to its substantially lower
capital cost, along with high yield and less environmental impacts. The EBOne
TM

Process also has comparatively easier process control and instrumentation procedures.
To recap, an overview of the EBOne
TM
Process is briefly discussed in this section.

The EBOne
TM
Process is one of the process that utilises the catalytic alkylation
of benzene with ethylene using zeolite-based catalysts to produce ethylbenzene. The
usage of zeolite-based catalysts (EBZ-500 and EBZ-100) is to replace the conventional
Friedel Crafts catalyst (AlCl3 and HCl) which is highly corrosive to the units of the
plants. Like any other alkylation process, the EBOne
TM
Process consists of two main
processes namely alkylation of benzene with ethylene followed by transalkylation of
di-ethylbenzene with benzene. In general, benzene undergoes an alkylation reaction
with ethylene to form ethylbenzene with a side product of di-ethylbenzene. The di-
ethylbenzene is then separated from ethylbenzene and transalkylated with benzene to
form ethylbenzene. The overall reaction is further illustrated using the figure below.

Figure 2: Reaction Steps in Direct Alkylation of Benzene and Ethylene. Note: From
High Performance Catalyst for Liquid Phase EB Technology by Narsolis, F.,
Woodle, G., Gajda, G. and Gandhi, D.
3

Based on the description of the process, it can be inferred that the types of
materials involved in the plant is benzene, ethylene, ethylbenzene, diethylbenzene and
zeolite catalyst. Thus, it is crucial to compile a preliminary database which includes
the thermophysical properties of the materials, environmental and safety data, prices
and in some cases data obtained from laboratory experiment. All these data are easily
made available from material safety data sheets that were compiled in Task 1. These
data will be summarized in the preliminary database creation section.

Preliminary Process Synthesis
Preliminary Database Creation

Table 1: Summary of relevant thermophysical, environmental and safety and chemical
prices data of reactants, catalyst and products.
Reactants Catalyst Product
Ethylene Benzene Zeolite Ethylbenzene
Formula C2H4 C6H6 - C6H5CH2CH3
Melting point (C) -169 5.5 N/A -94.9
Boiling point (C) -103.8 80 N/A 136
Flash point (C) -136 -11 N/A 15
Density (kg/m
3
) 156.8 880 N/A 867
Environmental and
safety remarks
Extremely
flammable
Highly
toxic
N/A Highly toxic
Price (USD/lb) 0.63 3.45 Varies 0.61






4

Identification of Desired Specifications of Raw Materials and Products

As mentioned in Task 1, ethylbenzene producing plants in the US have capacities
which ranges from 133 to 1440 thousand ton per year which is equivalent to 15.2 to
164.4 ton per hour respectively. Given that the global demand and consumption of
ethylbenzene is increasing annually, it is reasonable to aim to design a plant that has a
capacity within the mentioned range. Thus, it is reasonable to design a start-up plant
that still has a capacity that falls within the range of other well established plants.
Therefore, the capacity of the plant is set to the average the value of the lower and
upper boundary of the range which is approximately 50 ton per hour or 50 000 kg per
hour.

Two raw materials are required to produce ethylbenzene namely ethylene and
benzene. As the raw materials need to undergo a series of reactions to form the desired
product, the plant capacity should be expressed with a molar basis instead of a mass
basis. Since the molecular weight of ethylbenzene is 106.17 kg/kmol, the equivalent
plant capacity on a molar basis is 471 kmol per hour. Due to the stoichiometry, the
minimum amount of benzene and ethylene required to meet the plant capacity is 471
kmol per hour which is conveniently rounded up to 480 kmol per hour. Converting the
flow rate to a mass basis yields 13 464 kg per hour of ethylene and 37 493 kg per hour
of benzene respectively.

Plant capacity : 50 000 kg/h 106.17 kg/kmol =471 kmol/h 480 kmol/h
Minimum ethylene rate : 480 kmol/h 28.05 kg/kmol =13 464 kg/h 13 500 kg/h
Minimum benzene rate : 480 kmol/h 78.11 kg/kmol =37 493 kg/h 38 000 kg/h



5

There is however another side product namely di-ethylbenzene (DEB) which
is produced due to excessive alkylation of benzene in the reaction. Although this
product is recycled in the plant and reacted with benzene in a trans-alkylation process,
the composition of this side product does affect the purity of the desired product.
Furthermore, the determination of the composition of our product is premature in this
step as detailed mass and energy balances around the reactors and distillation units of
the plant is required to determine the purity of our product. Therefore, the total flow
rate of the product of the plant is still uncertain due to the presence of side product
although the flow rate of the desired product by itself is known.

With the flow rates of the raw materials and products determined, other
parameters that needs to be determined include their respective phases, temperature
and pressure. In accordance to the EBOne
TM
process, the raw materials and products
are specified to be in liquid phase. Assuming that both raw materials are pure and
supplied at atmospheric pressure and temperature ranging from 20 to 30C, which is
the average range of temperature in Dalian, China, both benzene and ethylbenzene will
exist in its liquid form (vapour fraction of zero) while ethylene will exist in its gaseous
form (vapour fraction of 1). Hence, the mixture of ethylene and benzene will yield an
outflow of a mixture of liquid and vapour. Therefore, the outflow is typically cooled
using a shell and tube heat exchanger to eliminate the vapour phase in the outflow
before entering the reactors. The table below summarizes the specifications of the raw
materials and products


Table 2: Summary of Specifications of Raw Materials and Products
Name Type Total flow
rate (kg/h)
Composition Phase at 25C
and 1 atm
Ethylene Reactant 13 500 1.0 Gas
Benzene 38 000 1.0 Liquid
Ethylbenzene Product Unconfirmed 0.95 Liquid

6

Eliminating Differences between Molecular Types

The elimination of differences between the molecular types of the raw materials
namely ethylene and benzene is achieved through two main set of reactions namely
the alkylation reaction and the trans-alkylation reaction. In the alkylation part of the
reaction, ethylene is reacted with benzene to form ethylbenzene as shown in the
equations below.
C2H4 +C6H6 C6C5CH2CH3
r
1
=8.4 10
-5
exp (
45.8
RI
)C
L
1.0
C
B
0.32

This is the main reaction that is typically depicted in the alkylation of benzene with
ethylene. However, MacDonald, Roda and Beresford in 2005 suggested that there are
two other reactions that occur simultaneously when the main reaction in the previous
page takes place. The two reactions are listed as follow.
C6H6 +2C2H4 C6C4(CH2CH3)2
r
2
=6.03 10
-4
exp (
61.6
RI
)C
L
1.3
C
B
0.33


C6H5CH2CH3 +C2H4 C6C4(CH2CH3)2
r
3
=8.5 10
-7
exp (
86.4
RI
)C
L
1.77
C
B
0.35


Each reaction is governed by a rate law which is dependent on temperature. Besides
the alkylation set of the reaction, there is another set of reaction that is reversible
namely the trans-alkylation reaction. The equation that governs the reaction is as
follows.
C6H6 +C6C4(CH2CH3)2 C6C5CH2CH3
ln(K
cq
) =
276.6
I
0.3599

7

It is important to note that the alkylation and trans-alkylation reaction utilises different
type of zeolite-based catalyst and hence requires different operating conditions i.e.
different temperatures and pressures.
Distribution of Chemicals

As ethylene is set to be the basis, we first distribute the chemicals in the process under
ideal circumstances by assuming 100% of ethylene fed in is converted in accordance
to stoichiometry i.e. 1 mole of ethylene produces 1 mole of ethylbenzene. Steady state
conditions are also assumed by setting the production rate and the purity of the
products to be constant.

The per-pass conversion of ethylbenzene strongly depends on the reactants
ratio. Based on findings on the EBOne
TM
Process, the Benzene to Ethylene molar ratio
in alkylation reactor is about 4 to 6 at temperature range from 125
o
C to 175
o
C will best
fit the process in terms of overall conversion, product selectivity and yield. Excess
8~10% of fresh benzene is fed into the reaction streams in order to promote the desired
product (EB)s selectivity. However, excess benzene will compromise the final
products purity, although this can be mitigated by the addition of a purge stream,
where it will fulfil the benzene balance and avoid the accumulation of excess benzene
and thus easing the separation between benzene and the final product.

The trans-alkylation reactor recovers the over-alkylised benzene (i.e. poly-
ethylbenzene). It is assumed that only di-ethylbenzene (DEB) is formed without
further alkylisation to higher degree of poly-ethylbenzene as DEB is the major by-
product formed in the process while other over-alkylised products which are known as
tar in this process are of negligible amount. Moreover, to decide the recycling capacity
of unreacted benzene, we further assume that the molar ratio of Benzene to DEB is
about 13.

8

To deviate from ideal assumptions which assumes 100% ethylene conversion,
the overall conversion of the process needs to be determined. According to Zhang, Li,
Fu and Cao in 2003, the overall conversion of ethylene to ethylbenzene is 95% at
minimum. Therefore, attempts were made to vary the overall conversion to 95%. In
such case, there will be an excess of ethylene and benzene that needs to be removed
simultaneously. Again, it is assumed that the production rate and purity is fixed. Since
the overall conversion is lowered, there must be reimbursement at the fresh feed of
ethylene. However, fresh feed of benzene remains unchanged.

Removal of benzene and impurities are essential for EB production process.
Where Stream 13 is the benzene and ethylene (if there is any) mixture that is sent out
from the process circuit to avoid accumulation of reactants. Notably, the composition
and flow rate of such purge are varied while subjecting to the excess amount of fresh
feed of ethylene and benzene. In both cases, it is presumed that some heavy organic
impurities are obtained in the form of tar which can be removed via installation of a
poly-ethylbenzene distillation column as shown. To optimize the products purity, the
high weightage of benzene downstream of the reactors (i.e. Stream 5) has to be
separated by benzene distillation column before entering product distillation column.

Table 3: Overall Reaction Summary of EB Production for 0.9999 (approximately 1.00)
Conversion of Ethylene
Flow rate E + B EB
Molecular Weight kg/kmol 28.05 78.11 106.165
Initial (X=1)
kmol/h 480 525 0
kg/h 13500 41000 0
(Round up) kg/h 13500 37500 51000
Converted
kmol/h 480 480 480
kg/h 13464 37492.8 50959.2
9

Remained
kmol/h 0 45 480
kg/h 0 3514.95 50959.2


Excess
Benzene
needs to be
removed

Desired
product with
95.8% purity
obtained

Annual production of EB 51000
kg
h
480
kmol
h


Assume EB at the product stream has purity of 95.8% with 4.2% Benzene.
Since the overall conversion based on ethylene is assumed to be 100%, therefore, for
overall mass balance is as follows.





Figure 1: Overall Mass Balance of EB Production Process

m
p
=n
p
(MW)
p

m
p
=
n
p,LB
X
p,LB
[(X
p,LB
MW
EB
) +(X
p,B
MW
B
)]
m
p
=
480
kmol
h
0.958
(0.958106.165+0.04276.11)
m
p
52600
kg
h


16
Product
EB Production
Process
2
13
1
10


During the alkylation process, assume about 300~500kg/hr of tar is formed
let m
16
=300
kg
h


For 100% conversion of ethylene, the least value of fresh ethylene feed,
n
1,E
=n
p,EB
=480
kmol
h

m
1,E
=480
kmol
h
28.05
kg
kmol
13500
kg
h

About 9% excess of fresh benzene is fed in this process in order to promote the per
pass conversion of the reactors:
n
2,B
=1.09n
p,EB
=1.09_480
kmol
h
] =523
kmol
h

m
2,B
=523
kmol
h
78.11
kg
kmol
41000
kg
h


Overall mass balance:
m
1
+m
2
m
p
m
13
m
16
=0

For alkylation and trans-alkylation reactor:

5
Alkylation
Reactor
Trans-
Alkylation
Reactor
3
4
11
12
78.5mol%
21.5mol%

Separation
Product
Recycle
0.5~1.0 mol%
99.0~99.5mol%
11

Figure 2: Mass Balance on Alkylation and Trans-alkylation Reactors

n
5,EB
=
n
p,EB
0.99
=485
kmol
h

n
4,EB
=0.785n
5,EB
=380
kmol
h

n
12,EB
=0.215n
5,EB
=105
kmol
h



At 125 175C, the reactions equilibrium conversion based on ethylene in the
alkylation reactor is approximately 72.33%.
n
3,E
=
n
4,EB
0.7233
=525
kmol
h


Benzene composition in Stream 3:
According to the EBOne
TM
process, the molar feed ratio of Benzene to Ethylene is
about 4 6, assuming a value of 5, we obtain,
n
3,B
=5n

3,E
2657
kmol
h

where (X
3,E
,X
3,B
) =_
1
6
,
5
6
] (0.17,0.83)

Trans-alkylation conversion based on ethylene is approximately 17.57%
n
4,DEB
=
0.1757(n
3,E
)
2
=46
kmol
h


The unreacted ethylene and benzene at Stream 4:
n
4,E
=n
3,E
(1 0.7233 0.1757) 57
kmol
h

12

During the alkylation process, assume about 300 500 kg/h of tar is formed.
In 100% of conversion from E to EB, it is assumed that 100% of tar is produced from
benzene.
the benzene lost due to the formation of tar =
300
kg
hr
78.11
kg
kmol
=3.84
kmol
kg


n
4,B
=n
3,B
n
4,LB
n
4,LB
bezene loss =2657380 46 3.84
2226
kmol
h


Table 4: Summary of Stream 3

Molecular Weight
(kg/kmol)
Composition,
X
n
(kmol/h)
m
(kg/h)
E 28.05 0.165 525 14700
B 78.11 0.835 2657 207600
EB 106.165 0 0 0
DEB 134.22 0 0 0
Total 3182 222300








13

Table 5: Summary of Stream 4

Molecular Weight
(kg/kmol)
Composition,
X
n
(kmol/h)
m
(kg/h)
E 28.05 0.021 57 1600
B 78.11 0.822 2226 173900
EB 106.165 0.14 380 40300
DEB 134.22 0.017 46 6200
Tar - - - 300
Total 2713 222300

In the trans-alkylation reactor, about 84% of DEB is recovered to EB, to balance the
whole recycle loop of the process, since the recovery rate of DEB in the trans-
alkylation reactor is equivalent to the formation rate of DEB in the alkylation reactor
and the recovery of DEB is approximately 84%,
n
11,DEB
=56
kmol
h

n
12,DEB
=9
kmol
h


The molar ratio of Benzene to DEB in the trans-alkylation reactor is approximately
equals to 13.
n
11,B
=13n
11,DEB
713
kmol
h

And n
11,EB
0.5 mol% EB recycled fromstream 5=0.005(485) 2
kmol
h


14


Figure 3: Ethylene Balance for the Loop
n
8,E
=n
3,E
n
1,E
=525 480=45
kmol
h

n
11,E
=n
6,E
+n
9,E

=n
6,E
+(n
10,E
n
8,E
)
=(n
6,E
+n
10,E
) 45
=n
5,E
45
=n
4,E
+n
12,E
45=n
12,E
+10

60% of ethylene is converted into EB in Transalkylation Reactor:
1
n
12,E
n
11,E
=0.60
_
n
12,E
n
11,E
=0.40
n
11,E
=n
12,E
+10

n
11,E
=13
kmol
h
,n
12,E
=5
kmol
h

The unreacted benzene at Stream 12:
n
12,B
=n
11,B
(n
11,E
n
12,E
) (n
11,DEB
n
12,DEB
)
n
12,B
=713 (135) (569)
n
12,B
=657
kmol
h



5
14
6
1 3
8
7 9 11
12

Reaction
10
4
15

Table 6: Summary of Stream 11
Molecular Weight (kg/kmol) Composition, X n (kmol/h) m (kg/h)
E 28.05 0.017 13 400
B 78.11 0.908 713 55700
EB 106.165 0.003 2 200
DEB 134.22 0.072 56 7500
Total 784 63800

Table 7: Summary of Stream 12
Molecular Weight (kg/kmol) Composition, X n (kmol/h) m (kg/h)
E 28.05 0.007 5 200
B 78.11 0.846 657 51300
EB 106.165 0.135 105 11100
DEB 134.22 0.012 9 1200
Total 776 63800

Table 8: Summary of Stream 5
Molecular Weight (kg/kmol) Composition, X n (kmol/h) m (kg/h)
E 28.05 0.018 62 1700
B 78.11 0.826 2883 225100
EB 106.165 0.14 485 51500
DEB 134.22 0.016 56 7500
Total 3486 285800

16

Table 9: Overall Reaction Summary of EB Production for 95% Conversion of
Ethylene
Flow E + B = EB
Molecular Weight kg/kmol 28.05 78.11 106.165
Initial (X=1)
kmol/h 505 525 0
kg/h 14200 41000 0
(Round Up) Kg/h 13500 37500 51000
Converted
kmol/h 480 480 480
kg/h 13464 37492.8 50959.2
Remained
kmol/h 25 45 480
kg/h 701.25 3514.95 50959.2

95%
conversion
of ethylene.
Excess
ethylene
needs to be
removed.
Unchanged
excess
benzene.
Needs to be
removed.

Desired
product with
purity of
95.8% is
obtained

Eliminating Differences in Composition

1. Benzene Distillation Column
With the aid of the spreadsheet provided by ChemSOF, as a preliminary process
synthesis, we assume the separation is a binary system consisting of the dominant keys
in the separation process. In benzene distillation, based on the summary of Stream 5,
the dominant keys are Benzene (14%) and Ethylbenzene (82.6%). Apart from ethylene
and DEB, the binary composition of E and EB are:
X
(F)E,bInary
=
0.14
0.826+0.14
=0.145
X
(F)B,bInary
=
0.826
0.826+0.14
=0.855
17

Type equation heie.And the desired distillate composition of light key, B is:
X
(D)B,bInary
=0.99

Similary, desire bottom composition of light ke, B is:
X
(B)B,bInary
=0.05
General reflux ratio 1.5
Feed temperature=107
o
C

Through Antoine Equation, we obtained the saturated pressure of B and EB at
107 C as follows.
ln[P
sat
(mmHg)] =A
B
I(K) +C
P
sat,B
=1584.09mmHg ,P
sat,EB
=322.97 mmHg
Relative volatility of B and EB,o =
P
sut,B
P
sut,LB
=4.9047

The values above are plugged into the spreadsheet to generate a McCabe Thiele
diagram in order to show the approximate number of stages and its feed stage location.
However, such diagram only indicates the fine separation between B and EB,
regardless of the presence of E and DEB. Considering the existence of E and DEB in
the column, it is estimated that the minor light key, ethylene would be distillated and
the minor heavy keys, DEB and Tar would be liquefied. Such diagram indicates that
the separation of benzene from ethylene is relatively easy, and we predict that Stream
6 and 14 has the approximate composition as shown below.






18


Table 10: Summary of Stream 6
Molecular Weight (kg/kmol) Composition, X n (kmol/h) m (kg/h)
E 28.05 0.020 58 1600
B 78.11 0.976 2860 223100
EB 106.165 0.002 7 700
DEB 134.22 0 0 0
Total 2925 226500



Table 11: Summary of Stream14
Molecular Weight (kg/kmol) Composition, X n (kmol/h) m (kg/h)
E 28.05 0.001 4 100
B 78.11 0.051 26 2000
EB 106.165 0.848 480 50900
DEB 134.22 0.1 56 7500
Tar - - - 300
Total 566 60800



19


Figure 4: Mc-Cabe Thiele Diagram of Binary System at 107
o
C of Ethylbenzene and
Benzene

2. Ethylbenzene Distillation Column
Similarly, as a preliminary process synthesis, we assume the separation is a binary
system of the dominant keys in the separation process, for EB distillation, based on
Stream 14, the dominant keys are Ethylbenzene (84.8%) and Di-ethylbenzene (10.0%).
Apart from ethylene and benzene, the binary composition of EB and DEB are:
X
(F)EB,bInary
=
0.848
0.848+0.1
=0.8945
X
(F)B,bInary
=
0.1
0.848+0.1
=0.1055

Desired distillate composition of light key, B is
X
(D)B,bInary
=0.999


20

Similary, desired bottom composition of light key, B is:
X
(B)B,bnu
=0.005
General reflux ratio 1.5l
Feed temperature=195
o
C
Through Antoine Equation we obtained the saturated pressure of B and EB at 195 C
ln[P
sat
(mmHg)] =A
B
I(K) +C
P
sat,EB
=2938.11mmHg ,P
sat,DEB
=993.43 mmHg
Relative volatility of B and EB,o =
P
sat,EB
P
sat,DEB
=2.9575

The values above are plugged into the spreadsheet to generate a McCabe Thiele
Diagram in order to show the approximate number of stages and its feed stage location.
However, such diagram only indicates the fine separation between EB and DEB,
regardless of the presence of E and B. Considering the existence of E and B in the
column, it is estimated that both the minor light keys, ethylene and benzene would be
distillated and the minor heavy key, tar would be liquefied. In addition, the amount of
ethylene from the feed stream is significantly small and can be negleted. Such diagram
indicates that the separation of ethylbenzene from di-ethylbenzene is relatively easy.
However, it is difficult to remove the remained benzene in Stream 14 as the previous
benzene distillation already had its maximum distillation limit to remove benzene.
Thus, we predict that the Product Stream and Stream 15 has the approximate
composition as shown:
Table 12: Summary of Product Stream
Molecular Weight (kg/kmol) Composition, X n (kmol/h) m (kg/h)
E 28.05 0 0 0
B 78.11 0.042 201 1600
EB 106.165 0.958 480 51000
DEB 134.22 0 0 0
Total 501 52600
21

Table 13: Summary of Stream 15
Molecular Weight (kg/kmol) Composition, X n (kmol/h) m (kg/h)
E 28.05 0 0 0
B 78.11 0 0 0
EB 106.165 0.007 1 100
DEB 134.22 0.993 50 6700
Tar - - - 300
total 51 7100



Figure 5: Mc-Cabe Thiele Diagram of Binary System at 195
o
C of Ethylbenzene and
Diethylbenzene
3. Poly-Ethylbenzene Distillation Column
The poly-ethylbenzene is estimated as a perfect separator between Tar and Poly-
ethylbenzene, as the Tar is comparatively heavier than the distillati
22


Figure 6: Distribution of Chemicals throughout the Proces
23

Eliminating Differences in Temperature, Pressure and Phase

At the beginning of the process both raw materials are feed into the stream under
surrounding temperature and pressure which are 25C and 101.325 kPa. When it
comes to stream 3, the pressure of mixture of benzene and ethylene is rapidly increased
to 1500-2000kPa by compressor to change gas phase of benzene into liquid phase.
Therefore, gas phase of ethylene will dissolve in benzene and feed into the alkylation
reactor.

The temperature of effluent from alkylation reactor is increased to the range of
125C - 175C by supplying heat to the reactor. In this condition, reactants still remain
in liquid phase. The reason why temperature is increased is because under that
condition we can get the highest conversion of ethylbenzene compare to other
temperature.

However, in stream 5 the temperature and pressure is decreased to 107C and
470kPa respectively which is the condition of bubble point then feed into distillation
column. The bottom product comes out from first distillation column with higher
temperature and lower pressure due to the reboiler supplies heat during the operation
and a minor pressure drop commonly occur when pass through a distillation column.
Both top and bottom column of product will still remain in liquid phase. Same theory
applied to second and third distillation column.

The effluent from third distillation column will pass through a shell-and-tube
heat exchange first then only feed into alkylation reactor. Therefore, temperature
decreases to 40C. Same condition and reason to alkylation reactor, effluent from the
transalkylation with 125C- 175C temperature and 1500-2000kPa

24


Figure 7: Changes in Temperature, Pressure and Phase in the Plant
25

Task Integration

1. Alkylation Reactor
The first reactor that will be used in this plant design is alkylation reactor. This is because
the ethylbenzene plant consists of a benzene and ethylene alkylation reactor assembly
which forms the product compound of ethylbenzene and other by-products such as di-
ethylbenzene. This reactor is to facilitate a reaction to produce ethylbenzene at the highest
yield and level of safety as possible.

2. Benzene Distillation Column
Benzene distillation column will be used in ethylene benzene production. The main
purpose of this benzene distillation column is used to separate benzene and ethylbenzene
from the main process stream. The benzene which had already separated will be recycled.

3. Ethylbenzene Distillation Column
The ethylbezene and di-ethylbenzene at bottom part of benzene distillation column will
be flowed to another distillation column which is ethylbenzene distillation column. The
main function of this distillation column is to separate the main product (ethylbezene) and
byproduct (di-ethylbenzene) from the process.

4. Polyethylbenzene Distillation Column
Polyethlybenzene distillation column will be used in this process because to separate
diethylbenzene and tar. Moreover, diethylbenzene will be proceeding to trans-alkylation
reactor to form ethylbenzene.


26

5. Flash Drum
A portion of the distillated from benzene distillation column will proceed to flash drum.
Flash drum is used for gas and liquid mixture separation. The vapour travels through the
gas outlet at a design velocity which minimizes the entrainment of any liquid droplets in
the vapour as it exits the vessel. In this plant design project, flash drum is used to separate
benzene into two streams. One of the streams will be flow to storage tank and another one
stream will be proceeding to trans-alkylation reactor for trans-alkylation process. This is
accomplished by invoking high pressure drop allowing some of the process stream to flash
off.

6. Condenser
The condenser will be used in this plant design. The purpose of the condenser is to cool
down the temperature of the cool water after flowed through the shell-and-tube heat
exchanger and so it can be re-used back.

7. Valves
Valves are used as safety relief device and also to decrease the pressure of a liquid stream
in the process.

8. Trans-alkylation Reactor
Trans-alkylation reactor will be used in this plant design. The main function of this reactor
is to produce ethylbenzene at low temperature from benzene and polyethylbenzene. The
trans-alkylation process is independent of pressure, and as such there is no reason to lower
the pressure when it will need to be increased again for the recycle loop.


27

9. Cooling Water System
Cooling water at 22C and 100 psig enters the upper header and exits the plant at 55C
and 100 psig. The outlet temperature was determined to be below 60 - 70C to avoid
scaling issues (MacDonald et. al.). An inlet temperature of 22C was selected based on an
average seasonal temperature.

10. Shell-and-tube Heat Exchanger
Shell-and-tube heat exchanger will be used in this ethylbenzene production plant design.
The heat exchanger is simulated with a complex shell and tube heat exchanger. The
process stream flows on the tube side of the exchanger and the cooling water passes
through the shell ride.

11. Centrifugal Pump
Centrifugal pump is to pump require component in liquid phase at high pressure into the
reactor. In this plant design, the fresh benzene is pumped to the reactor at about 1.8MPa
(Zhang et. al., 2003).









28

Base Case Design
Process Flow Diagram(PFD)

Figure 8: Process Flow Diagram(PFD) of Ethylbenzene Production Plant
29

Heuristics

1. Raw material and chemical reactions
Heuristic 1: Select raw materials and chemical reactions to avoid, or reduce, the
handling, and storage of hazardous and toxic chemicals.
In recent years, there is rising awareness in the handling and storage of toxic and
hazardous raw materials. This is to protect the environment and to avoid evident safety
problems. Lesson was learnt from the accident occurrences especially from the 1984
accident in Bhopal, India, where water was accidentally mixed with the active
intermediate, methyl isocyanate. Thus, selection of raw materials and chemical reactions
is vital in reducing and minimising the loss of live and cost.
In spite of that, the usage of benzene and ethylene cannot be avoided as our raw
materials in ethylbenzene manufacturing since the benzene group is a major part of
ethylbenzene chemical structure. Benzene is widely used as an industrial raw material to
produce ethylbenzene. In fact, every industrial process reviewed in the previous task (Task
1) uses benzene as a main raw material. Although there is an experimental process that
attempts use lignin and toluene as the raw materials to produce ethylbenzene, the lignin is
still ultimately converted to benzene while toluene is converted to ethylene in that process.
Furthermore, the yield is significantly lower than other processes with low product purity
and fluctuating lignin prices. Hence, we must use benzene and ethylene as our raw
materials and cannot avoid the handling of these hazardous raw materials as benzene is
toxic and ethylene is flammable.





30

2. Distribution of Chemicals
Heuristic 2: Use an excess of one chemical reactant in a reaction operation to
completely consume a second valuable, toxic, or hazardous chemical reactant.
According to this heuristic, we have to use ethylene as the excess chemical reactant to
completely consume benzene, since benzene is more valuable and more toxic based on
the MSDS.
But, to prevent over alkylation of benzene to di-ethylbenzene and tri-ethylbenzene,
we decided to make benzene as the excess chemical reactant. The over alkylation of
benzene will produce more di-ethylbenzene and tri-ethylbenzene than our desired product,
ethylbenzene which are side products that are not valuable. Furthermore, by adjusting the
temperature and pressure will not help in avoiding the usage of benzene as an excess
material as the alkylation process is more sensitive to the molar ratio of benzene to
ethylene. Therefore, we have no choice but to use benzene as the excess chemical reactant.

Heuristic 7: For competing series or parallel reactions, adjust the temperature, pressure,
and catalyst to obtain high yields of the desired products. In the initial distribution of
chemicals, assume that these conditions can be satisfied- obtain kinetics data and check
this assumption before developing a base-case design.
According to the collision theory, the rate of reaction can be increased if the collisions
between molecules are increased. Thus, by increasing the temperature, kinetic energy is
increased allowing the molecules to move faster and collide more frequently. The
temperature adjusted for the both alkylation and trans-alkylation reactions are in the range
of 125 175C but the catalyst used in alkylation and trans-alkylation are EBZ-500
TM
and
EBZ-100
TM
respectively. A catalyst is a substance which speeds up a reaction but is
chemically unchanged at the end of the reaction. In other words, after the reaction we can
obtain the same mass of catalyst as the beginning of reaction. Catalyst will provide an
alternative pathway for the reaction with lower activation energy while ensuring a higher
successful collision rate between molecules. Hence, an approximated 99.6% yield of the
desired products will be obtained from EBOne
TM
process.
31

Heuristic 8: For reversible reactions, especially, consider conducting them in a
separation device capable of removing the products, and hence, driving the reactions to
the right. Such reaction - separation operations lead to very different distribution of
chemical.
A reversible reaction proceeds in both directions i.e. reactant will react and form products,
while the product will also react and reform into reactants. Reversible reactions will reach
an equilibrium point which equalizes the concentrations of reactants and products. In the
ethylbenzene production process, there is one reversible reaction that occurs in trans-
alkylation reaction.
C6H6 +C6H4(C2H5)2 2C6H5C2H5
If a reversible reaction occurred during the process, it will cause a lower
conversion of desired amount that we want. Thus, we must drive the reaction to the right
to optimise the conversion. In order to solve this problem, there are two ways that can be
used to shift the reaction to the right i.e. by using an excess of benzene and by removing
ethylbenzene from the feed stream before entering into the trans-alkylation reactor.
Le Chteliers principle states that the position of equilibrium point will change
and shift to counteract the change to re-establish an equilibrium if the dynamic equilibrium
is influenced by changing the condition. With excess benzene, the concentration of
benzene will increase and thus follow the principle of Le Chtelier the reaction will tend
to shift to right. Same principle apply to second method we used, the concentration of
ethylbenzene will remain minimum as possible thus the reaction will tend to shift to right.
If we distillation ethylbenzene out after transalkylation, the concentration of ethylbenzene
will become higher and thus the reaction will reverse back and lead to a lower conversion.





32

3. Separation
Heuristic 9: Separation liquid mixture using distillation and stripping towers, and
liquid-liquid extractors, among similar operations
Heuristic 10: Attempt to condense vapour mixtures with cooling water. Then follow
the previous heuristic (heuristic 9).
When we separate a mixture of component, the first things we must do is to determine the
phase of mixture enter the separator. With the different phase of mixture we used different
type of separator. For liquid phase of mixture, we can use distillation, enhanced distillation,
stripping towers, liquid-liquid extraction and so on. However for vapour phase of mixture,
we can use partial condensation, cryogenic distillation, absorption and absorption
membrane. So, after determined the phase of mixture entering the separator, the second
step we need to do is determine which type of separator we need to use.
In the whole process we total have three distillation columns and one flash drum.
The three distillation columns are actually in series order. First distillation column is
installed connect to the shell-and-tube heat exchanger (E-2) which receive the effluent of
alkylation reactor. In this distillation column, the main purpose is wanted to separate
excess benzene out from top column of separator with other substances. Part of the excess
benzene will recycle back to feed stream of benzene and ethylene. However, another part
of excess benzene will flow through flash drum. Other substances like ethylbenzene, di-
ethylbenzene and small amount of benzene in liquid phase will connect and feed into the
second distillation column.
In the second distillation column is wanted to extract our desire product,
ethylbenzene from the process. Ethylbenzene is extracted out in this step because we want
to reduce the amount of reversible reaction occur in the transalkylation section after that.
So ethylbenzene will extract out from top column and other substances leftover in liquid
phase will go through bottom stream and connect to third distillation column.
The last distillation column is connected with the transalkylation reactor. The
purpose of this distillation is wanted to purge the unwanted side product, tar out from the
process. If we do not purge the tar out from the process, it will accumulate and damage to
33

our equipment. Di-ethylbenzene and benzene will combine with the feed from flash drum
and feed into transalkylation reactor to futher react become ethylbenzene that we wanted.

4. Heat Transfer in Reactors
Heuristic 12: To remove a highly-exothermic heat of reaction, consider the use of
excess reactant, and inert diluents, and cold shoots. There affect the distribution of
chemicals and should be inserted early in process synthesis.
In our process, we are involving two reactors for alkylation and transalkylation reaction.
Both of the reactors are high exothermic reaction. So this becomes an important issue on
our process. To handle this problem, we using excess of benzene to cover out it. So,
heauristic 12 is applied.

5. Heat Exchangers and Furnaces
Heuristics 16: Unless required as part of the design of the separator or reactor,
provide necessary heat exchange for heating or cooling process fluid streams, with or
without utilities, in an external shell-and-tube heat exchanger using counter-current
flow. However, if a process stream requires heating above 750F, use a furnaces
unless the process fluid is subject to chemical decomposition.
Heuristics 27: When using cooling water to cool or condense a process stream,
assume a water inlet temperature of 90F (from a cooling tower) and a maximum
water outlet temperature of 120F.
To cool the mixture of fresh feed and recycle stream to the reactor, we have design a heat
exchanger E-1 to cool the feed before it entering alkylation reactor. We have to cool the
feed to around 40C to make sure that it is in liquid form at applied presssure. This
condition is required for the benzene alkylation.

34

Moreover, there is another heat exchanger E-2 to cool down the stream before
entering distillation column C-1. This heat exchanger will cool the stream from around
290-310C to around 102C, which a temperature suitable for distillation process. Besides
these, heat exchanger E-3 is designed to cool the stream before it enters the trans-
alkylation reactor R-2 as well.
These heat exchangers are external shell-and-tube heat exchangers using counter-
current flow. They have higher efficiency as compared to parallel flow heat exchanger.
Besides, we also make sure that the inlet temperature of cooling water is at 90F (32.2C)
and the outlet is at 120F (48.89C). This can be done by adjusting the flow rate of cooling
water. So, we applied heuristics 16 and 27.

6. Pressure Reduction
Heuristics 21: For liquid flow, assume pipeline pressure drop of 2psi/100ft of pipe and
a control valve pressure drop of at least 10psi. for each 10-ft rise in elevation, assume
a pressure drop of 4psia.
We have included a control valve in our process designing. The valve is located right after
the alkylation reactor. This valve helps to reduce the pressure from around 1700kPa to
around 470kPa. According to heuristics 21, a control valve pressure drop of at least 10psi
(68.95kPa). Since our pressure drop across the control valve is much greater than 10psi,
we applied heuristics 21.

Heuristics 20: For heads up to 3,200 ft and flow rates in the range of 10 to 5,000 gpm,
use a centrifugal pump. For high heads up to 20,000 ft and flow rates up to 500 gpm,
use a reciprocating pump. Less common are axial pump for heads up to 40 ft for flow
rates in the range of 20 to 100,000 gpm and rotary pumps for heads up to 3,000 ft for
flow rates in the range of 1 to 1,500 gpm.

35

In fact, we have three pumps in our PFD. The first one is located right at the inlet
of benzene feed, which it used to pump benzene feed to the alkylation reactor. The second
pump is used to pump the recycle benzene to mix with the fresh feed. The third pump is
to pump outlet stream of trans-alkylation reactor to recycle back for distillation process.
All the pumps are centrifugal pumps. This is because the difference in pressure of
streams in our operation is lower than 3,200 ft of head and the flow rates is within the
range of 10 to 5,000 gpm. Hence, we have chosen centrifugal pump to be included in our
operation. We follow the heuristics 20.

List of Major Equipment and Required Specifications
Table 14: List of Major Equipment and Required Specifications
Equipment Type Required specification
Reactor Temperature
Pressure
Flow rate
Height
Diameter

Sizing of Reactor
Type of reactor
Material used to
build reactor

Heat Exchanger Temperature
Pressure
Flow rate
Sizing
Diameter
Type of heat
exchanger
Duty
Material used to
build heat exchanger

36

Distillation
Column
Temperature
Pressure
Flow rate
Type of
distillation
column
Number of
tray
Height
Diameter
Material used to
build heat exchanger

Valve Temperature
Pressure
Flow rate
Valve type
Sizing
Material used to
build valve
Number of port

Pump Temperature
Pressure
Flow rate
Horsepower

Type of pump
Material used to
build pump



Condenser Temperature
Pressure
Flow rate
Type of
condenser

Sizing
Entering feed phase
Horsepower
Material used to
build condenser

Flash Drum Temperature
Pressure
Flow rate

Entering feed phase
Material used to
build flash drum

37

Additional Data
Table 15: Summary of Additional Data of equipment
Component


Equipment
Sizing Height Diameter
Power
needed
efficiency
Tray
efficiency
Tray
number
Number of
tray feed
(count from
top)
Pressure drop
Centrifugal
pump
(P-2)
*TBM *TBM *TBM
10.5
kW
75% - - - -
Alkylation
reactor (R-1)
250m
3
*TBM *TBM *TBM - - - - 0
Benzene
distillation
column (C-1)
*TBM 16.3m 3.4m 21kW - 60% 27 11 70kPa
EB distillation
column (C-2)
*TBM 20.3m 2.3m 21kW - 60% 33 19 70kPa
Transalkylation
(R-2)
30m
3
*TBM *TBM *TBM - - - - 0
Control valve
(VLV-100)
*TBM *TBM *TBM *TBM *TBM - - - 1200kPa
Note: *TBM =To be measured.
The data above are further details regarding conditions of the equipment used in the construction of the plant. For the data which is not inserted at
the above table, it will be generated in task 3 when the stimulation is constructed out.
38

Conclusion
In Task 2, the preliminary process synthesis and base-case is created and designed. A
summary of all relevant data regarding raw materials, products, unit operations and
equipment used are provided and summarized in this task. This serve as a detailed
guideline for the team to initiate a pilot plant to test and verify the conditions given in
this task.
There are limitations encountered in the performance of this task. Much of the data
required such as the sizing of each unit used as well as detailed kinetic and transport
data can only be obtained through a thorough HYSYS simulation which will be carried
out in Task 3. Therefore, certain aspects of the PFD and values of parameters such as
the conversion of the reactors and temperature and pressure of the distillation columns
are pending with respect to the simulation. Therefore, all data and values mentioned
in this task are preliminary and should only serve as a guideline as they will be
finalized only in task 3 after a thorough mass and energy balance is carried out coupled
with a steady state simulation of the plant.

References
J irui, Z., Dongfeng, L., Jiquan, F., & Gang, C. (2003). US 6,504,071 B2. Process and
Apparatus for Preparation of Ethylbenzene by Alkylation of Benzene with Dilute
Ethylene Contained in Dry Gas by Catalytic Distillation. Retrieved from
http://www.google.com/patents/US6504071
MacDonald, J., Roda, R., & Beresford, M. (2005). Liquid Phase Alkylation of
Benzene with Ethylene. Retrieved from www.scribd.com/mobile/doc/106876722
Seider, W. D., Seader, J. D. & Levin, D. R. (2003). Product & Process Design
Principles. (2nd ed.). U.S: Wiley.
Narsolis, F., Woodle, G., Gajda, G. & Gandhi, D. (n.d.) High Performance Catalyst
for Liquid Phase EB Technology. Retrieved from
http://www.digitalrefining.com/data/articles/file/271533368.pdf


39