1.

0 INTRODUCTION TO PRODUCTION OF ETHYL BENZENE

1.5 PROCESS SELECTION
In order to produce ethyl benzene as a desired product, there are a few process available which are
by unique process of toluene, super fractionation of mixed aromatic hydrocarbon and alkylation of
benzene with ethylene.The most suitable process for production ethyl benzene is alkylation of
benzene with ethylene. This process produce high purity of ethyl benzene as a main product
compared to other manufacturing process. Less of pure ethylene and benzene has been used in this
process. This process also has low operating condition and the cost of production is lower than
other process.
1.6 REACTION SCHEME THERMODYNAMIC
Ethyl benzene is produced by alkylation of benzene with ethylene, illustrated by the
following chemical reaction:
C6 H6 C2 H4 C6 H5C2 H5 benzene
ethylene ethylbenzene
Benzene alkylation process, for the production of ethyl benzene, consists of three basic steps. The
alkylation reaction takes place at high pressure and low temperature. Typically, ethylene:benzene
molar ratios between 0.15 and 0.2 are used. The reactor inlet temperature is controlled by recycling
a small portion of the reactor effluent. In transalkylation step, in which poly ethyl benzene at
presence of benzene are converted to ethyl benzene on a reverse alkylation process. Transalkylation
takes place in a separate reactor. Then in separation step, in which unreacted benzene, poly ethyl
benzenes and other components enter benzene recovery column and separated from each other. The
bottom for the benzene recovery column is sent to a product column, where ethyl benzene of >
99.9% purity is taken overhead. For this reason 2 distillation columns has been used. The final
product is obtained in liquid phase.

2.1 CHEMICAL DESIGN FOR DISTILLATION COLUMN

2.2 INTRODUCTION
STREAM 17
FLOWRATE : 13,
321.5 kg/hr
COMPONENT :
Benzene ,
Ethylbenzen&
Toulene

STREAM 16
FLOWRATE : 24,345.9
kg/hr
COMPONENT : Benzene,
Ethylbenzene,
1,4-Di Ethylbenzene

STREAM 18
FLOWRATE : 11 024.5
kg/hr
COMPONENT :
Benzene,
Ethylbenzene,
1,4-Di Ethylbenzene

Figure 1: Distillation column T-301

Distillation column is use to produce high purity of liquid product at operating condition. Since
this criteria is crucial, therefore a suitable distillation column need to be chosen wisely since it
will effects the purity and amount of production. The purpose of T-301 is to separate the
ethylbenzene others chemical in stream 18. As a result , ethyl benzene discharged from the top of
T302 as a liquid together with other light component. The bottom outlet of T302 contains no
benzene.

Name

Unit

Vapor fraction
Temperature
Pressure
Molar flow

Feed
(S16)
0
73.6
110
271.4

C
kPa
kmol/h

Top
(S17)
0
81.4
105
170.2

Mass flow
kg/h
24,345.9 13, 321.5
Comp Mole Frac (Benzene)
169.46
169.23
Comp Mole Frac (Ethyl benzene)
91.54
0.92
Comp Mole Frac (1,4 Diethlbenzene)
10.35
0
Table 2.1: Stream summary

Bottom
(S18)
0
145.4
120
101.1
11
024.5

0.17
90.63
10.35

Component Mole fraction

Component
Benzene
Ethylbenzen
e
1,4
Diethlbenzene

Feed, Xf
0.6244
0.3373

Distillate,Xd
0.9943
0.0054

0.0381

Bottom,Xb
1.68e-3
0.8964
0.1024

1.2 DEW AND BUBBLE POINTS

In order to calculate the stages and the condenser and reboiler temperatures, the dew and
bubble points of the feed must be estimated first. Dew point temperature can be defined as
the temperature at which the first bubble of vapor is formed at a given pressure. The
composition of the vapor is at equilibrium with the liquid solution. Bubble point
temperature can be defined as the temperature at which the first dew or condensate forms
from a vapor mixture. The composition of the dew is at equilibrium with the vapor
mixture. By equation, dew and bubble points can defined as follows

Where
xi = concentration of component i in liquid
phase yi = concentration of component i in
vapor phase Ki = equilibrium constant of
component i
The saturated component solved by using the Antoinnes equation as follows :

Where Psat = saturated pressure in mmHg

Component
Xi, f
Psat ( mmHg)
Benzene
0.6244
618.51
E
0.3373
98.02
1.4
0.0381
17.15
Total
1.0

Ki
0.749
0.12
0.02

KiXi,f
0.468
0.04
0.000762
0.508

T = Temperature in C
A, B, C =Antoines coefficient
Component

Benzene

7.06437

1296.93

229.916

Ethylbenzene

6.95719

1424.255

213.21

1,4 diethylbenzene

6.9982

1588.31

201.97

Table 2.2 : Antoines coefficient

For bubble point calculation at feed stream which is stream 16
First use Tb = 73.6 oC ( 346.6K)
Pressure
= 110 kPa = 825.1 mmHg
For bubble point calculation at bottom stream which is stream 18
First use Tb = 145.4 oC
Pressure
= 120 kPa = 900.1 mmHg

Component
Benzene
Ethylbenzen
1.4 diethylbenzene
Total

Xi, b
0.00168
0.8964
0.1024
1.0

Psat ( mmHg)
4062.58
967.37
266.37

Ki
0.005
1.075
0.30

Yi, b
0.0000084
0.96363
0.03072
1.00

Component
Xi, t
Psat ( mmHg)
Ki
KiXi,t
Benzene Component 0.9943 Xi, f
791.4Yi, f
1.005Ki
0.9993
E
0.0054
0.00918
Benzene
0.6244132.68
0.468 0.170.745
1.4
0
24.72
0.03
0
Ethylbenzene
0.119
0.3373
0.04
Total
1.0
1.00
1.4 diethylbenzene
0.02
0.0381
0.000762
For
dew
Total
1.0
point
calculation at top stream which is stream 17
First
use Tb
Component
Xi, t
Yi, t
Ki, t
= 81.4
o
Benzene
1.005
0.9943
0.9993
C
Ethylbenzene
1.7
0.0054
0.00918
1.4 diethylbenzene
0
0
0
Total
1.0
1.0
Pressure
= 105 kPa = 787.5 mmHg

2.3 : EQULIBRIUM CONSTANT

The equilibrium constant can be calculated as follows :

Table 1 : Ki value for stream 16

Table 2 : Ki value for stream 17

Table 3 : Ki value for stream 18

2.4

RELATIVE VOLATALITIES
Relative volatility, is the volatility separation factor in vapor-liquid system. In other
words, it is the volatility of one component divided by the volatility of the other. The
greater the value of , the easier will be the desired separation. The relative volatility can

be calculated between any two components in a mixture. Based on K values the relative
volatility can be expressed as belows

which is subscript LK for light key and HK is for heavy key.

The component separated are called light key, which more volatile . The component more
volatile than light key are called light key components and will be present in the bottom
in small amount. The component less volatile than the heavy key are called heavy
component and will be present in the distillate in small amount.(Geankoplis,2014). Light
component is the component of feed mixture which is desired to be kept out of the bottom
product while heavy key component is a component of feed mixture which is desired to
be kept out of the top product. Thus, the selection of key component is as below:
Light key = Benzene
Heavy key = Ethylbenzene
Component

Ki, f

Benzene

0.745

6.26

Ethylbenzene

0.119

1,4 Diethylbenzene

0.02

0.168

Table 4 : value for stream 16

Component

Ki, t

Benzene

1.005

0.59

Ethylbenzene

1.7

1,4 Diethylbenzene

Table 5 : value for stream 17

Component

Ki, b

Benzene

0.005

0.005

Ethylbenzene

1.075

1,4 Diethylbenzene

0.3

0.28

Table 6 : value for stream 18

The following approximation may be used to calculate the average relative volatility :

Where is f

= relative volatility of light key to heavy key at feed of column

= relative volatility of light key to heavy key at top of column

= relative volatility of light key to heavy key at bottom of column

Component

LK,HK

avg

Feed

Top

Bottom

6.26

0.59

0.005

0.447

Ethylbenzene(HK)

1,4 Diethylbenzene

0.168

0.28

0.224

Benzene ( LK )

Table 2.12, average value for all stream

2.5 REFLUX RATIO

The minimum reflux ratio can be estimated by using the method of approximation
evolved by Colburn (1941) and the exact procedure of Underwood (1948). The equation
can be express as belows

= relative volatility of component i with respect to some reference

Rm

= minimum reflux rati

Xi,d

= concentration of component i in the tops at minimum reflux

is the root of the following equation

xi,f = concentration of component i in the feed

q = depends on the condition of the feed
The value of q is given by

Hv,feed = Latent heat of the feed

Cp,feed = Specific heat of the feed

73.6 C

Tbubble

73.6 C

Specific heat

133.5 J/gmol.K

Component

xi,f

Latent Heat of
Vaporization, j/mole

Benzene

0.6244

33 200

Ethylbenzene

0.3373

38 600

1,4-Diethylbenzene

0.0381

55 000

Table : Data for calculation q at feed stream

Latent heat of the feed is therefore

= 33 200(0.6244) +38 600(0.3373) + 55 000(0.0381)

= 35 845.36 J/mole
The q value is
q=

133.5 ( 73.673.5 ) +35 845.36

35 845.36
= 1.0004

Apply the value of q into the equation below

x

ii ,f =1q=11.0004=0.0004
i

ii ,f
i

By using Goal Seek operation in Microsoft Office Excel the satisfactory value of is
1.079937
Component

Xi, f

Benzene

i Xi

i xi , f
i

6.26

3.91

0.75

0.3373

-4.2196

0.168

0.006

-0.007

0.6244
Ethylbenzene
0.3373
1,4 Diethylbenzene
0.0381
1.00

Total

Table : , data for calculation at feed stream

The value of is then substitute into the equation as below
x

ii ,d =R m +1
i

Component

Xi, d

i Xi

ii ,d
i

Benzene

0.59

0.59

1.204

0.0054

0.068

0.9943
Ethylbenzene
0.0054
1,4 Diethylbenzene
Total

0
1.00
Table : data for calculation Rm at stream 19
Rm + 1 = 1.272
Rm = 0.272

R = 1.5Rm
=1.5(0.272)
=0.408

2.6 MINIMUM AND THEORETICAL NUMBER OF STAGES

Minimum stages

L,av

2 (6.26)(0 .56)(0.005)

= 2.83
X LK
X HK

X HK
X LK

b
log
N m=
0.9943
0.0054

0.8964
0.00168

b
log

2 LF LD LW

Nm = 11.76 stages
Theoretical stages
R
0.408
=
=0.29
R+1 0.408+1
Rmin
0.272
=
=0.213
Rmin+1 0.272+ 1
Nm
=0.49
N
11.76
=0.49
N
N=24 theoretical stages(23 trays+1 reboiler)

LOCATION OF FEED TRAY

Ne
B
log
=0.206 log [
Ns
D

( )(

xf , HK
xf , LK

)(

Xb , LK 2
]
Xd , HK

Where XLK,D = mol fraction of light key in distillate

XHK,D = mol fraction of heavy key in distillate
XHK,B = mol fraction of heavy key in bottom
XLK,B = mol fraction of light key in bottom
a = average relative volatility of light key

log

Nr
101.1
=0.206 log [
Ns
170.2

)(

0.6244
0.3373

)(

0.8964 2
]
0.00168

Nr
=0.47
Ns
Nr + Ns=2 4
0.47Ns + Ns= 24
Ns= 16.32
This mean feed tray is 16 trays from top

2.8 COLUMN EFFICIENCY

The prediction of overall column efficiency can be obtained from the correlation given
by OConnell below:

Where
a = the molar average liquid viscosity, mNs/m2
a = average relative volatility of the light key = 3.462
The molar average liquid viscosity is given by

Where VISA,
VISB= constant in the liquid velocity equation
Temperature at dew point (top) = 81.4 c
Temperature at bubble point (bottom) = 145.4 c
Average temperature = 113.4 C/386.4 K

Component

VIS A

VIS B

XF

Mean viscosity

Viscosity

(mNs/m2)

(mNs/m2)

Benzene

328.49

182.48

0.6244

0.22

0.137

Ethylben

410.58

219.67

0.3373

0.15

0.051

1,4

0.0381

3.6

0.137

Thus the average a can be calculated as below

a

0.137 + 0.051 + 0.137

= 0.325

Overall efficiency is
E0

=51 - 32.5 log(0.325x 3.462)

= 49.34 %

2.9 NUMBER OF ACTUAL STAGES

by using eq of overall tray efficiency,
Eo number of ideal tray / number of actual tray
Number of actual tray = 23 / 0.4933 46.62 = 46 tray

DENSITY AND RELATIVE MOLAR MASS

Component

feed

Distillate

bottom

Molar weight
(g/mol)

Benzene

0.6244

0.9943

0.0016

,liqu id
(kg/m3)

78.11

876

8
Ethylben

0.3373

0.0054

0.8964

106.17

866

1,4

0.0381

0.1024

134.22

862

Relative Molar Mass, RMM

RMM = ( Component mole fraction x Molecular weight)

RMM at feed =(0.6244x78.11) + (0.3373x106.17) + (0.038x134.22) =85.09

kg/kmol

RMM at Distillate(Top Product)

=(0.9943 x78.11) + (0.0054 x106.165) + (0 x134.2181) =78.23 kg/kmol

RMM at Bottom Product

=(0.00168 x78.11) + (0.08964 x106.17) + (0.1024 x134.22) =23.39 kg/kmol

Density top

Liquid density, L = (0.9943x876) + (0.0054x866) + (0x862)

= 874.06 kg/m3

Vapor density, V = (78.23 kg/kmol / 22.4 m3/kmol)(273 K / 354.4 K)

(1.05 bar / 1bar)

= 2.82 kg/m3

2.11 COLUMN DIAMETER

The important factor that affects the column diameter is vapor flowrate.
The vapor velocity should be below than which would cause excessive
liquid entrainment or high pressure drop. To estimate the maximum
allowable superficial vapor velocity, we use Lowenstein (1961) equation:

For diameter column above than 1 m, plate spacing of 0.3 to 0.6 m will
normally be used, and 0.4 m (15 in.) can be taken as an initial estimate.

(Coulson & Richardon, 2003) In this design, taking plate spacing as 0.3 m,
the allowable superficial vapor velocity, calculated is:

lv 2

v
Uv=(0.171l 2t +0.27 l
t 0.047 )

874.062.82 2

2.82
Uv=(0.171(0.3)2 + 0.27(0.3)0.047 )

=0.327

The column diameter, Dc can be determined from the equation :

Dc
=

Where V = the maximum vapor rate,kg/s

Above the feed point,

Vapor flowrate,
Vn = D (R + 1)

Vn = 13 321.5 kg/h (0.408+ 1)

Liquid flowrate,
= 18 756.67 kg/h

Ln = Vn D

Below the feed point,

Ln = 18 756.67 - 13 321.5 =5435.17kg/h

Liquid flowrate,
Lm = Ln + F

Lm = 5435.17+ 24 345.9

= 29 781.07 kg/h

= 29 781.07 kg/h x (1 h / 3600 s)

= 8.27 kg/s

Vapor flowrate,
Vm = Lm W

Vm = 29 781.07 11 024.5

= 18 756.57 kg/h

= 18 756.57 kg/h x (1 h / 3600 s)

= 5.21 kg/s

Dc=

4 (5.21)
(2.82)(8.27)
= 0.53 m

Column area,Ac can be calculated using:

Ac=

( 0.53 )2
4

= 0.22 m2

2.12 COLUMN HEIGHT

Without considering the skirt or any support, the column height can be
calculated using the equation below:
by knowing:
the plate thickness is 5mm
tray spacing is 0.3m
Column height = (No. stage )(tray spacing) + (tray spacing x 2) + (No. stage 1)
(plate thickness) Column height = (46)(0.3) + (0.3 x 2) + (46-1)(0.005) = 14.625
m
= 16.09 m (including 10% safety factor)

2.12 COLUMN HEIGHT

Without considering the skirt or any support, the column height can be
calculated using the equation below:

by knowing:

the plate thickness is 5mm tray spacing is 0.4m

Column height = (No. stage )(tray spacing) + (tray spacing x 2)

+ (No. stage 1)(plate thickness)

Column height = (63)(0.4) + (0.4 x 2) + (63-1)(0.005)

= 26.31 m

= 28.94 m (including 10% safety factor)

2.13 SUMMARY OF CHEMICAL DESIGN

In chemical design, it focuses on the internal part of distillation column which specifically
about the packing, feed location stages of column and others.

Dew point Temperature (top)

81.4C

Bubble point Temperature (bottom)

145.4C

Bubble point temperature (feed)

73.6 C

Minimum number of stages

11.76 stages

Reflux ratio
0.408

Feed point location

Tray 26

Number of theoretical stages

24 stages

Overall tray efficiency

0.4934

Number of actual trays

46 trays

Column diameter
0.53m

Column height
16.09m