Introduction

Benzene, with chemical formula of C6H6 is a colourless liquid with a sweet odor and
can be described as a volatile organic compound comes from both industrial and natural
sources. In industrial, it was first discovered in 1800s. Up till today, benzene has been ranked
as top 20 of most production volume for chemicals produced in United States (retrieved from
http://www.eco-usa.net/toxics/chemicals/benzene.shtml on 29th May 2014). As for natural
sources, benzene can be found in gas emission from volcanoes and forest fires. Benzene is
also present in crude oil and gasoline and cigarette smoke.
Because of its high demand, benzene can be said to be produced by each region in the
world with high production rates. There are few ways or process that can be used in producing
benzene for instance catalytic reforming, toluene hydrodealkylation, toluene
disproportionation and steam cracking.
In doing this project, we chose to use toluene hydrodealkylation process as our process
based on few factors and the further details about this process will be discussed further in this
text.

Process Selection
1

In the early stage of our project, we are needed to choose the best process in producing
benzene. After doing some comparison based on few factors, we chose toluene
hydrodealkylation (HDA) process to be used instead of catalytic reforming process. First of
all, we choose this process because product formed from HDA process almost benzene where
99.6% benzene produced from this process.(F. Rase, Handbook of Commercial Catalysts:
Heterogenous Catalyst) Whereas for catalytic reforming process, benzene being formed
together with toluene and xylene. If this process being used, it will affect the cost of
production. Since benzene is a major product in HDA process, we prefer this process instead
of catalytic reforming process. Plus, HDA process has lower hydrogen consumption compared
to catalytic reforming which will then reduce our cost. (Netzer, Benzene Supply Trends and
Proposed Method for Enhanced Recovery March 29 2005. Web )
On top of that, hydrodealkykation process has a higher conversion which is 70-85% per
pass with ultimate yields of 95-98% of theoretical. (Manufacturing Processes, retrieved on
28th May 2014 from http://www.sbioinformatics.com). Even though HDA required high
operating temperature which is 500 C to 660 C but the catalyst being used is much cheaper
compare to other one. Finally, we chose this process because of its higher reaction efficiencies
and clean operations.
In this process, the main two reactant are toluene and hydrogen. Then, toluene and
Hhydrogen are converted in a reactor packed with catalyst to produce benzene and methane.
This reaction is exothermic and the operating conditions are 500 0C to 660 0C, and 20 to 60
bar of pressure. This process begins with mixing fresh toluene with a stream of recycle
unreacted toluene, and the mixing is achieved in a storage tank. Then, the toluene is pumped
to combine it with a stream of mixed hydrogen and fresh hydrogen gas. The mixture of
toluene and hydrogen is preheated before it is introduce to the heater or furnace. In the
furnace, the stream is heated to 600 0C, then introduced into the reactor. Basically, the main
reactions occurs in the reactor between toluene and hydrogen are as follow :
C7H8 + H2

C6H6 + CH4

Toluene hydrodealkylation process is irreversible process and requires catalyst. The

catalyst used in this process consist of molybdenum oxides or chromium, platinum oxides or
platinum, silica or alumina. Minor reversible side reaction is:
2

2 Benzene

Diphenyl + H2

The catalytic process occurs at lower temperature and offers higher selectivity but
requires frequent regeneration of the catalyst. Then, the products are cooled and introduced
into a pair of separators which separate the unreacted hydrogen. The unreacted hydrogen is
compressed and recycle back to the feed and reactor. The products that leaving the separators
are heated before introduced into a distillation column which the toluene is separated from the
stream and recycle back to the feed. Further fractionation will separates methane and toluene
from the benzene product. The heating requirements are achieved with low, medium and high
pressure steam. The cooling requirements are achieve by cooling water at temperature of 30
0

C and pressure of 1 bar.

The reactor feed preparation is the first phase to begins the process. It begins with

combining of 108.7 kmol/h of a fresh stream of toluene at 1.9 bar and 25 0C with a recycle
stream of unreacted toluene in a storage tank at 2.43 bar and 112 0C. Then, the toluene is
pumped through pump, with discharge pressure of the pump must be 25.5 bar. Next, this will
pumped to a second storage tank where toluene is combined with a combined stream of fresh
and recycle of hydrogen. The new two-phase stream is preheated to 163.9 0C, high pressure
steam at 45 bar is used. This stream exist as the pre-heater as a one-phase stream because the
toluene was vaporized. But then, the stream is introduced to the heater which used air to
combust fuel gas to produce enough heat to raise the temperature of the stream to 600 0C.
Now, the reactor feed is completed as the stream at 24.81 bar of pressure at temperature, 600
0

C which is necessary for reaction to occur.

Then, the stream is introduced into the reactor which packed with catalyst where the

main reaction to produce benzene happens.

C7H8 + H2

C6H6 + CH4

This is exothermic reaction. By injecting hydrogen into reactor, the temperature is

controlled. This hydrogen gas is injected at 40.4 kmol/h, 25.5 bar, and at 44.96 0C. The exiting
stream contains methane, benzene, toluene and hydrogen which exits at 24.81 bar and 671 0C.
The process continues to the separator feed preparation phase. This phase begins with
introducing the stream into a cooling water heat exchanger that cools the products stream to
38 0C which can condenses most of the toluene and benzene in the stream.
3

Next, the stream proceeds to the separation known as final phase of process. In this
process, the product is separated from the by-products and unreacted components. Benzene is
separated from unreacted hydrogen, unreacted toluene and the by-products of methane. This
can achieve by introducing the two-phase stream containing hydrogen, benzene, toluene and
methane into a high pressure phase separator. It will separated liquid and vapor. In the
overhead, mainly hydrogen and methane exits but this overhead stream split into two streams.
One stream is compressed to 25.5 bar and is recycle back to the feed and to the reactor. The
other one is the stream that have the portion of fuel gas stream. The separation occurs at a
temperature of 38 0C and 23.9 bar
The partially separated stream is introduced into a second separator where all the
methane and hydrogen is separated in the overhead stream which in low pressure condition.
The liquid exiting the low pressure consist of toluene and benzene and traces of dissolved
methane and hydrogen. The separation completed by heating the stream in heat exchanger and
introduced it to a distillation column. This stream heated at temperature of 90 0C and low
pressure steam is used. Distillation column used to purify benzene product by separated all the
unreacted components and the by-products. Toluene exits as a liquid in the bottom at
temperature of 112 0C and 2.43 bar. The overhead containing benzene, traces of hydrogen and
methane is condensed in condenser at temperature of 112 0C also and a pressure 2.5 bar.
Cooling water is used to condense the vapor exiting column. Remaining methane and
hydrogen are separated in reflux drum where the vapor stream is combined with other gases
streams. The overhead of first and second separator are combined to form fuel gas. The liquid
stream exiting in the bottoms of the reflux drum is pumped at pressure of 3.3 bar for
discharging pressure. The pump stream is separated in two streams. One stream is to feed to
tray one of the column and the other one stream is cooled down to 38 0C in heat exchanger.
Then, the cooled product stream is sent to storage.

CHAPTER TWO
MASS AND ENERGY
BALANCE

Material Balance
Set production rate,m3 to be 30,000 000

tonne
year
6

tonne
year

m3= 30 000 000

m3 =3.42 x10

1000

kg
tonne

kg
hr

Overall Mass Balance

Knowing
min=mout ; thus
m1=m2+m3
CH4 balance
0.215m1 =0.404 m2
0.215 (m2+m3) = 0.404 m2
0.215m2 + 0.215m3 = 0.404 m2
0.215m2 + 0.215( 3.42x106)= 0.404 m2
0.189 m2 = 735 300
kg
m2=3.89 x106 hr
Since
m1=m2+m3
m1= (3.89 x106 +3.42 x106 )

kg
hr

kg
m1= 7.31x106 hr

1 year
365 days x

1 day
24 hour

REACTIVE PROCESS
T=586.293 ,P=24.81atm
REACTOR
m1=7.31X106kg/hr
0.163 C7H8
0.617 H2
0.215 CH4
0.006 C6H6

T=671.075 ,P=24.81atm
m2
0.041
0.495
0.337
0.127

C7H8
H2
CH4
C6H6

Mass Balance
m1=m2
By doing balance on hydrogen
(7.31x106)(0.617) = 0.495(m2)
m2= 9.11 x 106

kg
hr

Energy Balance
References: H2 (g,25 ,1atm) ; C7H8, H2, CH4, C6H6 (g, 586.293 , 24.81atm
Component

C7H8
H2
CH4
C6H6

nin
(kg/hr)
(kJ/kg)
1191530
0
4510270
H1
1571650
0
43860
0

Hin

nout
(kg/hr)
373510

H2

4509450

H3

3070070

H4

1156970

H5

Cp for C7H8= 0.0948+3.8x10-4T 2.786x10-7T2 + 8.033x10-11T3

671.015

586.293

0.0948+3.8x10-4T 2.786x10-7T2 + 8.033x10-11T3

H2=0.0948T +

3.8 X 104 T 2
2

2.786 X 107 T 3
+
3

Hout
(kJ/kg)

8.033 X 1011 T 4
4

H2=(0.0948 (671.015)

8.033 X 1011 (671.015)4

4

8.033 X 10

11

2.786 X 10 ( 671.015)
3

)-(0.0948 (586.293)

2.786 X 10 ( 586.293)
3

3.8 X 104 (586.293)2

2

(586.293)

H2=(63.196 +35.55-28.058+4.071)-(55.217+65.311-15.716+2.378)
H2=124.759-104.185
H2=20.574

kJ
kJ
+ 50.00
mol
mol x

H2=766.03

kJ
kg

1 mol
92.13 g

From table B.8

T(

500

13.83

586.293

16.81

600

By interpolation, find

586.293500
600500
86.293
100

2.572 =

1 ;
113.83
16.8113.83

1 13.83
2.98

1 13.83

3.8 X 10 (671.015)
2

1000 g
1 kg

 1=16.402

kJ
mol

mol
2g

1000 g
kg

kJ
kg

1 = 8201
From table B.8

T(

600

16.81

671.015
700

19.81

3 ;

By interpolation, find

671.015600
700600
71.015
100

3 16.81
3

2.1305 =

316.81
19.8116.81

316.81

3=18.941

kJ
mol

3 = 9470.5

1 mol
2g

1000 g
kg

kJ
kg

671.015

Cp dT

586.293

Cp for CH4 : a + bT + cT2 +dT3

10

= 0.03431 + 5.469 x

10 T + 0.3661 x 10

T2 1.1 x

671.015

0.03431+5.469 105 T + 0.3661108 T

586.293

Cp=

0.03431T +

1.1 x 10^ -11 T3

5.469 10 T 0.366110 T 1.1 10

+

2
3
4

11

671.015

671.015

3
Cp=

671.015

4
5
(5.469 10 )
0.03431 (671.015 )+

586.293

586.293

586.293

4
(5.469 105 )
0.03431 (586.293 )+

Cp=( 23.023+12.312+0.3690.558 )( 20.116 +9.4 +0.2460.325 )

Cp = 29.437

kJ
mol

= 29.437

kJ
kJ
mol
74.85

mol
mol 16.04 g

11

1000 g
kg

11

10

T3

 4 = -2831.23

kJ
kg

671.015

Cp dT

586.293

Cp for C6H6 : a + bT + cT2 + dT3

= 0.07406 + 32.95 x

105 T 25.20 x 108 T 2 + 7.757 x 1011 T 3

671.015

0.07406+ 32.95 105 T 25.20 108 T 2+7.757 1011 T 3

586.293

32.95 10 T 25.20 10 T 7.757 10

0.07406T +

+
2
3
4

12

11

671.015

67.015

671.015

4
586.293

2
Cp=

586.293

586.293

4
5
(32.95 10 )
0.07406 ( 586.293 ) +
(32.95 105)
0.07406 ( 671.015 ) +

kJ
(
49.695+74.1825.379+3.932
)

(
43.43+56.3116.929+2.291
)
=17.015
Cp=
mol
5 = 17.015

kJ
kJ
mol
1000 g
+ 82.93

mol
mol 78.11 g
kg

5 =1279.54

kJ
kg

Q = out in
=

[ ( 373510 )( 766.03 ) + ( 4509450 )( 9470.5 )+ ( 3070070 )(2831.2 ) +( 1156970 ) ( 1279.54 ) ] [ ( 4510270 ) ( 8201 ) ]

13

-1.224 10

kJ
hr

NON-REACTIVE : COOLER

H2O

2 24.81atm,671.015

38 0C

Cooler

0.041 C7H8 (v)

0.495 H2 (v)
0.337 CH4\(v)

0.127 C6H6 (v)

H 2O (l, 250C, 1atm)
Mass Balance :
14

0.337
24.466
CH4 atm
(v)
0 .127 C6H6
(l)

Since

2 = 9.11 x 10^6 kg/hr

2 = 3
0.4952 = 0.4953

Balance for hydrogen , H2 ,

0.495 ( 9.11 x 10^6 ) = 0.4953

3 = 9.11 x 10^6 kg/hr

Energy Balance :
Reference state : H2 ( g, 250C, 1 atm ) ; C7H8, CH4, C6H6 ( g, 671.0150C, 24.811
atm )

Component

min (kg/hr)

Hin

mout ( kg/hr)

(kJ/kg)

( kJ/kg)

C7H8

3.74x105

H2

4.51 x106

1.16 x106

C6H6

3.74x105

H2

H1

4.51 x106

H3

3.07 x106

H4

1.16 x106

H5

3.07 x106

CH4

Find H1 : assuming that hydrogen, H2, is an ideal gas

From

T ( 0C )

H ( kJ/mol )

600

16.81

671.015

H1

700

19.81

table B.8

Using interpolation :
671.015 - 600 = H1 - 16.81
700 - 600

Hout

19.81 - 16.81
71.015 = H1 - 16.81
15

100

2.1305 = H1 - 16.81
H1 = 18.941 kJ 1 mol 1000g
mol

2g

1 kg

= 9470.5 kJ/kg
Find H2 : from table B.2
State 1 : C7H8( v, 672.0150C, 24.811 atm )
HA
State 2 : C7H8( v, 110.620C, 1 atm )
HB
State 3 : C7H8( l, 110.620C, 1 atm )
HC
State 4 : C7H8( l, 380C, 24.466 atm )

Cp : C7H8
= 0.09418 + 3.8 x 10^-4 T - 2.786 x 10^-7 T2 + 8.033 x 10^-11 T3
110.62

671.015

HA =

Cp ( C7H8 , v ) dT

110.62

671.015

0.09418 + 3.8 x 10^-4 T - 2.786 x 10^-7 T2 + 8.033 x 10^-11 T3 dT

= 0.09418 T + 3.8 x 10^-4 T2/2 - 2.786 x 10^-7 T3/3 + 8.033 x 10^-11 T4/4
110.62
671.015

16

=(10.4182 + 2.32499 - 0.12771 + 3.00713 x 10 ^-3) - ( 63.1962 +

85.5496 -

28.05799 + 4.07143 )

= 12.6205 - 124.75924
= -112.14 kJ 1 mol 1000g
mol 92.13g 1 kg
= -1217.193 kJ/kg
HB = Hv C7H8(110.620C, 1 atm)
= 33.47 kJ

1 mol 1000g

mol 92.13g 1 kg
= 363.291 kJ/kg

38

110.62

HC = P +

Cp( C7H8( l) ) dT

Cp : C7H8(l)
Cp = 0.1488 + 3.24 x 10^-4 T

38

110.62

38

110.62

Cp( C7H8( l) ) dT =

0.1488 + 3.24 x 10^-4 T dT

17

38
110.62

= 0.1488 T + 3.24 x 10^-4 T^2/2

= ( 5.6544 + 0.23393 ) - ( 16.4603 + 1.9824 )
= 5.888 - 18.443
= - 12.555 kJ 1 mol 1000g
mol 92.13g 1 kg

38

110.62

Cp( C7H8( l) ) dT = - 136.275 kJ/kg

SG for C6H6 = 0.866

Density = 0.866 kg/L
P = 1 L

( 1-24.446) atm

92.13g

1kg

0.008314

kJ/mol.K
0.866 kg

1 mol

L.atm/mol.K
= -0.2494 kJ

1 mol 1000g

mol 92.13g 1 kg
= -2.70704 kJ/kg

HC = -2.70704 - 136.275
= - 138.98 kJ/kg

H2 = HA + HB + HC
= -1217.193 + 363.291 - 138.98
= - 99.88 kJ/kg
Find H3 : assuming that hydrogen, H2, is an ideal gas
From table B.8
T ( 0C )

H ( kJ/mol )

25

38

H3

100

2.16

18

1000g

0.08314

By interpolation :
38 - 25 = H3 - 0
100 - 25

2.16 - 0
13 = H3
75

2.16

H3 = 0.3744 kJ
mol

1 mol 1000g
2g

1 kg

= 187.2 kJ/kg

Find H4 : From table B.2

Cp : CH4
= 0.03431 + 5.469 x 10^-5 T + 3.661 x 10^-9 T2 - 1.1 x 10^-11 T3

38

671.015

H4 =

Cp dT

38

671.015

0.03431 + 5.469 x 10^-5 T + 3.661 x 10^-9 T2 - 1.1 x 10^-11 T3 dT

19

= 0.03431 T + 5.469 x 10^-5 T2/2 + 3.661 x 10^-9 T3/3 - 1.1 x 10^-11 T4/4
38
671.015

= ( 1.30378 + 0.039486 + 6.6962 x 10 ^-5 - 5.7341 x 10^-6 ) - ( 23.0225 +

12.3124 + 0.3687 - 0.55752 )
= 1.34333 - 35.1461
= - 33.803 kJ 1 mol 1000g
mol 16.04g 1 kg
H4 = -2107.42 kJ/kg
Find H5 : From table B.2
State 1 : C6H6( v, 672.0150C, 24.811 atm )
HA
State 2 : C6H6( v, 80.100C, 1 atm )
HB
State 3 : C6H6( l, 80.100C, 1 atm )
HC
State 4 : C6H6( l, 380C, 24.466 atm )

Cp : C6H6
= 0.07406 + 3.295 x 10^-4 T - 2.52 x 10^-7 T2 + 7.757 x 10^-11 T3

80.10

671.015

HA =

Cp dT

80.10

671.015

0.07406 + 3.295 x 10^-4 T - 2.52 x 10^-7 T2 + 7.757 x 10^-11 T3 dT

20

= 0.07406 T + 3.295 x 10^-4 T2/2 - 2.52 x 10^-7 T3/3 + 7.757 x 10^-11 T4/4
80.10
671.015

= (5.932 + 1.05704 - 0.044026 + 7.98296 x 10 ^-4) - ( 49.6954 + 74.1805

- 25.3791 + 3.93154 )
= 6.9458 - 102.42834
= - 95.48 kJ 1 mol 1000g
mol 78.11g 1 kg
HA = -1222.38 kJ/kg
HB = Hv C6H6(80.100C, 1 atm)
= 30.765 kJ

1 mol 1000g

mol 78.11g 1 kg
= 393.87 kJ/kg

38

80.10

HC = P +

Cp( C6H6( l) ) dT

Cp : C6H6 (l)
= 0.1265 + 2.34 x 10^-4 T

38

80.10

38

80.10

Cp( C6H6( l) ) dT =

0.1265 + 2.34 x 10^-4 T d

38
80.10

= 0.1265 T + 2.34 x 10^-4 T^2/2

= ( 4.807 + 0.16895 ) - ( 10.133 + 0.7507 )
= 4.97595 - 10.884
= - 5.908 kJ 1 mol 1000g
21

mol 78.11g 1 kg
= -75.64 kJ/kg
SG of C6H6 = 0.879
Density = 0.879 kg/L
P = 1 L

( 1-24.446) atm

78.11g

1kg

0.008314

kJ/mol.K
0.879 kg

1 mol

1000g

0.08314

L.atm/mol.K

= - 0.2083 kJ

1 mol 1000g

mol 78.11g 1 kg
= -2.667 kJ/kg
HC = -2.667 - 75.64
= -78.307 kJ/kg

H5 = HA + HB + HC
= -1222.38 + 393.87 - 78.307
= -906.817 kJ/kg
Find Q
Q= H

Q=

n
out

HI -

Hi

Q=(3.74x105)( - 99.88)+( 4.51x106 )( 187.2)+( 3.07x106)( -2107.42)+

( 1.16x106)( -906.817)-( 4.51 x106 )( 9470.5)
Q= (-3.47x107) + (8.44x108)+(-6.47 x109)+(-6.47x109) - (4.27 x1010)
Q= -1.213 x1010-(4.27 x1010)
Q= -5.48 x1010

kJ
hr

22

CHAPTER THREE
THERMODYNAMICS

23

Our group had given a task for integrated project which is production of benzene.
Through this draft, we will explain a little bit about our process selection, process flow
diagram and the properties of each unit operation and streams.
In this process, the main two reactant are toluene and hydrogen. Then, toluene and Hydrogen
are converted in a reactor packed with catalyst to produce benzene and methane. This reaction
is exothermic and the operating conditions are 500 0C to 660 0C, and 20 to 60 bar of pressure.
This process begins with mixing fresh toluene with a stream of recycle unreacted toluene, and
the mixing is achieved in a storage tank. Then, the toluene is pumped to combine it with a
stream of mixed hydrogen and fresh hydrogen gas. The mixture of toluene and hydrogen is
preheated before it is introduce to the heater or furnace. In the furnace, the stream is heated to
600 0C, then introduced into the reactor. Basically, the main reactions occurs in the reactor
between toluene and hydrogen are as follow :
C7H8 + H2

C6H6 + CH4

Toluene hydrodealkylation process is irreversible process and requires catalyst. The

catalyst used in this process consist of molybdenum oxides or chromium, platinum oxides or
platinum, silica or alumina. Minor reversible side reaction is:
2 Benzene

Diphenyl + H2

The catalytic process occurs at lower temperature and offers higher selectivity but
requires frequent regeneration of the catalyst. Then, the products are cooled and introduced
into a pair of separators which separate the unreacted hydrogen. The unreacted hydrogen is
compressed and recycle back to the feed and reactor. The products that leaving the separators
are heated before introduced into a distillation column which the toluene is separated from the
stream and recycle back to the feed. Further fractionation will separates methane and toluene
from the benzene product. The heating requirements are achieved with low, medium and high
pressure steam. The cooling requirements are achieve by cooling water at temperature of 30
0

C and pressure of 1 bar.

The reactor feed preparation is the first phase to begins the process. It begins with

combining of 108.7 kmol/h of a fresh stream of toluene at 1.9 bar and 25 0C with a recycle
stream of unreacted toluene in a storage tank at 2.43 bar and 112 0C. Then, the toluene is
pumped through pump, with discharge pressure of the pump must be 25.5 bar. Next, this will
pumped to a second storage tank where toluene is combined with a combined stream of fresh
24

and recycle of hydrogen. The new two-phase stream is preheated to 163.9 0C, high pressure
steam at 45 bar is used. This stream exist as the pre-heater as a one-phase stream because the
toluene was vaporized. But then, the stream is introduced to the heater which used air to
combust fuel gas to produce enough heat to raise the temperature of the stream to 600 0C.
Now, the reactor feed is completed as the stream at 24.81 bar of pressure at temperature, 600
0

C which is necessary for reaction to occur.

Then, the stream is introduced into the reactor which packed with catalyst where the

main reaction to produce benzene happens.

C7H8 + H2

C6H6 + CH4

This is exothermic reaction. By injecting hydrogen into reactor, the temperature is

controlled. This hydrogen gas is injected at 40.4 kmol/h, 25.5 bar, and at 44.96 0C. The exiting
stream contains methane, benzene, toluene and hydrogen which exits at 24.81 bar and 671 0C.
The process continues to the separator feed preparation phase. This phase begins with
introducing the stream into a cooling water heat exchanger that cools the products stream to
38 0C which can condenses most of the toluene and benzene in the stream.
Next, the stream proceeds to the separation known as final phase of process. In this
process, the product is separated from the by-products and unreacted components. Benzene is
separated from unreacted hydrogen, unreacted toluene and the by-products of methane. This
can achieve by introducing the two-phase stream containing hydrogen, benzene, toluene and
methane into a high pressure phase separator. It will separated liquid and vapor. In the
overhead, mainly hydrogen and methane exits but this overhead stream split into two streams.
One stream is compressed to 25.5 bar and is recycle back to the feed and to the reactor. The
other one is the stream that have the portion of fuel gas stream. The separation occurs at a
temperature of 38 0C and 23.9 bar
The partially separated stream is introduced into a second separator where all the
methane and hydrogen is separated in the overhead stream which in low pressure condition.
The liquid exiting the low pressure consist of toluene and benzene and traces of dissolved
methane and hydrogen. The separation completed by heating the stream in heat exchanger and
introduced it to a distillation column. This stream heated at temperature of 90 0C and low
pressure steam is used. Distillation column used to purify benzene product by separated all the
unreacted components and the by-products. Toluene exits as a liquid in the bottom at
25

temperature of 112 0C and 2.43 bar. The overhead containing benzene, traces of hydrogen and
methane is condensed in condenser at temperature of 112 0C also and a pressure 2.5 bar.
Cooling water is used to condense the vapor exiting column. Remaining methane and
hydrogen are separated in reflux drum where the vapor stream is combined with other gases
streams. The overhead of first and second separator are combined to form fuel gas. The liquid
stream exiting in the bottoms of the reflux drum is pumped at pressure of 3.3 bar for
discharging pressure. The pump stream is separated in two streams. One stream is to feed to
tray one of the column and the other one stream is cooled down to 38 0C in heat exchanger.
Then, the cooled product stream is sent to storage.

PFD FOR TOLUENE HYDRODEALKYLATION

26

PROPERTIES OF UNIT OPERATION AND STREAMS

SUBSTANCE

PROPERTIES

TOLUENE

Molecular formula

VALUE
C7 H 8

Molecular weight

92.13 g/mol

SG

0.866

Density

0.87 g/mL @ 20 C

Boiling point

110.62 C @ 1 atm

Melting point

-94.99 C @ 1 atm

Critical temperature

593.9 K

Critical pressure

40.3 atm

Appearance

Colorless liquid

Odor

Sweet, pungent smell

Cp

Cv

Liquid
155.96 J/(mol.K) @ 25 C,
1 atm
Gas
103.7 J/(mol.K) @ 25 C, 1
atm
Liquid
147.646 J/(mol.K) @ 25 C,
1 atm
Gas
95.386 J/(mol.K) @ 25 C,

1 All the other properties from Felder, R.M. & Rousseau, W.R. (2005), Elementary
Principles of Chemical Processes, 5th ed, United State, America, John Wiley &
Sons, Inc.
2 http://en.wikipedia.org/wiki/Toluene
3 http://en.wikipedia.org/wiki/Toluene
4 Toluene-physical properties http://www.epa.gov/ttn/atw/hlthef/toluene.html
5 http://en.wikipedia.org/wiki/Toluene_(data_page)

27

1 atm

Hv

33.47 kJ/mol @ 110.62 C

Hm

6.619 kJ/mol @ -94.99 C

SUBSTANCE

PROPERTIES

VALUE

HYDROGEN

Molecular formula

H2

Molecular weight

2.016 g/mol

Density

0.0899 g/L @ 0 C, 1 atm

Boiling point

-259.19 C @ 1 atm

Melting point

-252.76 C @ 1 atm

Critical temperature

33.3 K

Critical pressure

12.8 atm

Appearance

Colorless

Odor

Odorless

Cp
Cv

10

28.82 J/(mol.K) @ 25 C, 1
atm 9
10.183 kJ/(kg.K) @ 300K

6 Gases-Densities http://www.engineeringtoolbox.com/gas-density-d_158.html
7 http://en.wikipedia.org/wiki/Hydrogen
8 http://en.wikipedia.org/wiki/Hydrogen
9 http://www.webelements.com/hydrogen/thermochemistry.html
10 Boles, M.A. & Cengel, Y.A. (2013), Thermodynamics, 7 th ed, New York, Mc Graw
Hill
28

 Hv

0.904 kJ/mol @ -252.76 C

Hm

0.12 kJ/mol @ -259.19 C

SUBSTANCE

PROPERTIES

VALUE

METHANE

Molecular formula

CH 4

Molecular weight

16.04 g/mol

Density

0.656 g/L at 25 C, 1 atm

11

Boiling point

-161.5 C @ 1 atm

Melting point

-182.5 C @ 1 atm

Critical temperature

190.70 K

Critical pressure

45.8 atm

Appearance

Colorless

12

Odor

Odorless

13

Cp

11 http://en.wikipedia.org/wiki/Methane
12 http://en.wikipedia.org/wiki/Methane
13 http://en.wikipedia.org/wiki/Methane
29

14

Liquid
52.93 J/(mol.K) @ 25 C, 1
atm

 Hv

Gas
35.69 J/(mol.K) @ 25 C, 1
atm
Gas
1.7354 kJ/(kg.K) @ 27 C
8.179 kJ/mol @ -161.5 C

Hm

0.94 kJ/mol @ -182.5 C

Cv

15

SUBSTANCE

PROPERTIES

VALUE

BENZENE

Molecular formula

C6 H 6

Molecular weight

78.11 g/mol

SG

0.879

Density

0.8765 g/ c m

@ 20 C,

Boiling point

1 atm 16
80.10 C @ 1 atm

Melting point

5.53 C @ 1 atm

Critical temperature

562.6 K

14 http://en.wikipedia.org/wiki/Methane_(data_page)
15 Boles, M.A. & Cengel, Y.A. (2013), Thermodynamics, 7 th ed, New York, Mc Graw
Hill
16 http://www.sabic.com/me/en/productsandservices/chemicals/benzene
30

Critical pressure

SUBSTANCE
1) CHROMIUM

48.6 atm
17

Appearance

Colorless liquid

Odor

Aromatic, gasoline-like

Cp

19

Cv

20

18

Hv

Liquid
134.8 J/(mol.K) @ 25 C, 1
atm
Gas
82.44 J/(mol.K) @ 25 C, 1
atm
Gas
0.949 kJ/kg.K @ 25 C, 1
atm
30.765 kJ/mol @ 80.10 C

Hm

9.837 kJ/mol @ 5.53 C

PROPERTIES
Symbol

VALUE
Cr

21

17 http://en.wikipedia.org/wiki/Benzene
18 http://en.wikipedia.org/wiki/Benzene
19 http://en.wikipedia.org/wiki/Benzene_(data_page)
20 Boles, M.A. & Cengel, Y.A. (2013), Thermodynamics, 7 th ed, New York, Mc Graw
Hill
21 All the properties from http://www.lenntech.com/periodic/elements/cr.htm
31

(catalyst)

Atomic mass
Density

7.19 g/ c m

atm
2672 C @ 1 atm

Melting point

1907 C @ 1 atm

Appearance

Hard metal, silver-gray

color
24

PtO2

Atomic formula
Atomic mass
Density

10.2 g/ c m

@ 20 C, 1

atm
N/A

Melting point
Appearance

22

211.077 g/mol

Boiling point

3) PLATINUM
(catalyst)

@ 20 C, 1

Boiling point

Atomic number

2) PLATINUM OXIDE
(catalyst)

51.996 g/mol

450 C @ 1 atm

23

Symbol

Crystalline solid, black or

brown
Pt 24

Atomic mass

211.077 g/mol

Density

10.2 g/ c m

@ 20 C, 1

Boiling point

atm
3825 C @ 25 C

Melting point

1768.3 C @ 25 C

Appearance

Crystalline solid, black or

violet-black

22 All the properties from http://www.americanelements.com/ptox.html

23 http://www.espimetals.com/index.php/msds/621-platinum-oxide
24 All the properties from http://en.wikipedia.org/wiki/Platinum
32

4) SILICA(silicon dioxide)
(catalyst)

Symbol

SiO 2

Molecular weight

60.09 g/mol

Density

5) ALUMINA
(aluminium oxide)
(catalyst)

2.648 g/ cm

25

26

@ 25 C

Boiling point

2230 C @ 1 atm

Melting point

1701 C @ 1 atm

Appearance

Transparent crystal

Symbol

Al 2 O3

Molar mass
Density

28

101.96 g/mol
3.95 g/ cm

@ 25 C

Boiling point

2980 C @ 25 C

30

Melting point

2040 C @ 25 C

31

Appearance

White solid

Odor

Odorless

25 http://en.wikipedia.org/wiki/Silicon_dioxide
26 Felder, R.M. & Rousseau, W.R. (2005), Elementary Principles of Chemical
Processes, 5th ed, United State, America, John Wiley & Sons, Inc.
27 http://en.wikipedia.org/wiki/Silicon_dioxide
28 http://en.wikipedia.org/wiki/Aluminium_oxide
29 http://www.azom.com/article.aspx?ArticleID=3382
30 http://www.gcsescience.com/imeltcompak.htm
31 http://www.gcsescience.com/imeltcompak.htm
32 http://en.wikipedia.org/wiki/Aluminium_oxide
33 http://en.wikipedia.org/wiki/Aluminium_oxide
33

27

32

33

29

CHAPTER FOUR
HYDROCARBON

34

CHEMICAL AND PHYSICAL PROPERTIES OF BENZENE

Based on IUPAC name, an organic chemical compound with the molecular formula
C6H6 is called benzene. The systematic name for benzene is Cyclohexa-1,3,3-triene while the
other names for benzene is 1,3,5-Cyclohexatriene, Benzol and Phene. The molecule of
benzene is composed of 6 carbon atoms joined in a ring, with 1 hydrogen atom attached to
each carbon atom.

Figure 1 The molecular structure of benzene

The molar mass for benzene is 78.11 g mol-1. The density of benzene is 0.8765(20)
g/cm3. Melting and boiling point of benzene are 5.53 C and 80.1 C respectively. Benzene is a
chemical that is a colorless or light yellow liquid at room temperature. It has a sweet odor and
is highly flammable. Evaporation of benzene into air is very quickly. Since its vapour is
heavier than air and may sink into low-lying area. Besides, benzene dissolves only slightly in
water and will float on top of water. Benzene is more soluble in alcohol, CHCl3, CCl4, diethyl
ether, acetone and acetic acid.
Table 1.1 Chemical properties of benzene
Chemical Properties

Value (Unit)

Index of refraction

1.5011 (20 C)

Specific gravity

0.87

pKa

2.13

35

Dissociation enthalpy

9.9 kJ/mol at 5.42 C

Table 1.2 Physical properties of benzene

Physical Properties

Value (Unit)

Melting point

5.53 C

Boiling point

80.1 C

Density

0.8765 (20)

g/cm 3

pH

Molecular weight

78.11 g/mol

Specific heat

0.1348

36

kJ
kg . K

PROCESS DESCRIPTION (toluene hydrodealkylation)

1.1 RAW MATERIAL
Material/

Toluene

Hydrogen

Bonding

Hydrogen bond,

Properties

double bond
Molecular

Molecular weight :

weight :

1.00794 u

92.13 g/mol

Boiling point :

Boiling point :

-252.879 oC

110.3 oC

Melting point :

Melting point :

-259.16 oC

-94.8 oC

Density :

Density :

0.07g/cm3

0.865 g/cm3

Physical and chemical

Physical and

properties :

chemical

colorless, odorless, tasteless,

properties :

non-toxic, nonmetallic,

clear, water-

highly combustible diatomic

insoluble liquid

gas with the molecular

with the typical

formula H2

terms
Chemical
structure

37

smell of paint
thinners

1.2 DESCRIPTION PROCESS

Hydrodealkylation of toluene is used though heavier aromatics are used as well. The
reaction that takes place is as follows:
C6CH3 + H2 C6H6 + CH4
The reaction with more alkylated benzenes is:
C6H4(CH3)2 + H2 C6H5CH3 C6H6 + CH4
Hydrodealkylation of toluene can be operated under catalytic or thermal conditions.
Toluene is mixed with heavier aromatics or paraffins from the benzene fractionation column.
They are then heated with a gas containing hydrogen at a specific pressure. The stream is then
moved past a dealkylation catalyst contained in the reactor. Here, the toluene reacts with the
hydrogen, and benzene and methane are produced. Benzene is then separated from the
methane using a separator, which operates at high pressures. Here the gas containing the
methane is removed. The product is then sent to a fractionalization column where distillation
is used to recover the benzene. The benzene is then sent to be stored. Unreacted toluene and
other heavier aromatic by-product are recycled back to the feed. There is a 70 to 85 percent
conversion rate of toluene to benzene through this process.

38

1.3TYPE OF REACTION, REACTION MECHANISM AND RULES APPLIED

A number of possible reactions are reported in addition to the primary reaction (1).

C6H5CH3 + H2 C6H6 + CH4

These include hydrogenation of benzene and toluene to cycloparaffins, hydrocracking of
paraffins and reaction of benzene and toluene to various diphenyls.
A free-radical mechanism has been suggested (2).

1) Initiation:
In this process, H2 is convert into 2 hydrogen radical.
2) Propagation:
The hydrogen radical then attack toluene and form methane and phenyl radical. Phenyl
radical then attack hydrogen and form benzene and hydrogen radical.
3) Termination:
Two hydrogen radicals form hydrogen atom again by sharing electron.
Saturated hydrocarbons if present are thermodynamically favoured to hydrocrack to CH4 and
those of C6 and above do so very rapidly wit high heat effects. Success of the process depends
on preventing hydrogenation of benzene to cyclohexane and high heat effects of
hydrocracking which could occur with saturated impurities or cyclohexane produced in the
reactor. Cyclohexane if not hydrocracked will contaminate the benzene product because of its
close boiling point to benzene (1).

39

1.4 ADVANTAGES AND DISADVANTAGES

By using catalyst in this process, there are several advantages we can get. The catalytic
processes employ one or more catalysts that promote the conversion of the alkyl aromatic
compounds to benzene and the remaining alkyl. The said catalysts can be employed as usual
in the form of powders, blacks or gauzes and also as partitions, for example as membranes,
films, foils and tubes perm-selective to hydrogen, for carrying out the hydrogenation, and
hydrodealkylation processes. The introduction of molybdenum into the alloy improves the
heat-resistance of the catalyst, which is important in the heat-treatment when regenerating the
catalyst.
The catalytic processes, however, are not always suitable for the commercial
conversion of alkyl aromatic compounds to benzene and the remaining alkyl. In particular, the
activity, selectivity and conversion rate of such catalysts are not always suitable for large scale
hydrodealkylation at the temperatures and pressures suitably employed. If the reaction
temperature or pressure is increased, side reactions such as hydrocracking of the aromatic ring
is promoted.
Furthermore, some catalysts tend to deactivate with use, presumably due to coke
formation on the catalyst surface. In this regard, it is believed that active sites promote
polymerization of either hydrogenolysis products or aromatic hydrocarbons resulting in
hydrocarbon condensation on the catalyst surface. Under the conditions of the process, these
condensed species are dehydrogenated forming coke. The result of these reactions is a
reduction in activity of the catalyst since the coke is strongly adsorbed onto the sites which
promote dealkylation. In other words, this coke or carbon build-up either blocks or poisons
the active catalyst sites causing deactivation.
Additionally, some catalysts tend to deactivate with use, due to the presence of sulfur
and in particular thiophene sulfur in the process feed. Thus, catalysts such as certain noble
metal catalysts deactivate over time due to the presence of sulfur in the feed. These catalysts
must be replaced or regenerated when sulfur reduces the activation to an extent low enough to
prevent suitable conversion of the feed. In view of the disadvantages associated with utilizing
catalytic hydrodealkylation processes, non-catalytic hydrodealkylation processes have been
developed. Mainly, such processes employ the use of heat and pressure to convert
alkylaromatic compounds to benzene and the disassociated alkyl compounds.

40

1.5 REASON CHOOSING THE METHOD

There are some reasons why we chose this process. Toluene hydrodealkylation can be
done by catalytic or thermal processes. Both are quite similar. Toluene is heated to 590-650 C
and 25-40 atm for catalytic hydrodealkylation or to as high as 760 C in the thermal processes.
The catalytic process has the advantage of lower heat loads but they have catalyst costs.
Hence, here catalytic hydrodealkylation process is taken and chromium oxide, Cr2O3, is
selected as the catalyst in order to make it more reasonable since it has been the most widely
used. Up to 3-12 % Cr2O3 being use in form of spheres or tablets for this process. Supplier of
this catalyst is United Catalyst, Engelhard.
The severe conditions cause a rapid coke laydown that must be removed periodically
by regeneration. Long catalyst life is reported when careful control of regeneration
temperatures is practiced. Excessive temperatures, about 650 C, can convert Cr2O3 to an
inactive form and reduce the surface area of alumina. Like many other oxide catalysts, it is
resistant to poisons, but water vapour is a temporary poison.

Environment
41

Benzene is dangerous to human being because it has been listed as human carcinogen
(retrieved from 12th Report on Carcinogens on June 10, 2011 on 25th May 2014; web) and can
cause cancer. Long- to high levels of term exposure benzene can cause leukemia.
At Australia for example, benzene is one of the toxic emitted into the atmosphere and
being track by their National Pollutant Inventory (NPI) from time to time. (Benzene
Retrieved May,29, 2014 from http://www.npi.gov.au/resource/benzene.) This shows that
benzene have the potentially cause problem for our health and health of the environment.
Benzene can be found from many sources. The main source of benzene are from
vehicle exhaust and other combustion processes and from industry producing or using it.
Benzene is also released naturally from volcanoes and forest fires, but the amounts released
are insignificant in comparison to those emitted by man's activities. (retrieved on 26th May
2014 from http://apps.sepa.org.uk/spripa/Pages/SubstanceInformation.aspx?pid=21 ). Other
than that, it can also be found from common products containing benzene like include glues,
cigarettes, cleaning products, paint strippers and some art supplies such as ink and paint.
Humans being can be exposed to benzene through many ways because benzene can be
found anywhere; air, water and soil.You can be exposed to small amounts of benzene
outdoors, where the air can contain low levels from tobacco smoke, automotive service
stations, vehicle exhaust, and industrial emissions. You can be exposed to higher levels of
benzene near gas stations, hazardous waste sites, or industrial facilities.
You can even be exposed to benzene indoors at home, where the air can contain higher
levels of benzene than outdoor air, from products such as glue, paint, furniture wax, and
detergent. Not just that, by drinking or eating foods that has been contaminated even in small
amount is also a way that can cause human to be exposed to benzene.
You can be exposed to higher than normal levels of benzene at work if you work at a
facility that makes or uses benzene, including petroleum refining sites, pharmaceutical plants,
petrochemical manufacturing facilities, rubber tire manufacturing facilities, or gas stations.
You may be exposed if you are a steel worker, printer, shoemaker, laboratory technician, or
firefighter.
Breathing very high levels of benzene, or eating or drinking foods contaminated with
high levels of benzene, can cause death. Eating or drinking foods contaminated with high
levels of benzene can also cause vomiting and stomach irritation. Small amounts of benzene,
which are not harmful, can be found in fruit, fish, vegetables, nuts, dairy products, beverages,
and eggs. Short-term exposure to high levels of benzene by breathing or eating affects the
central nervous system and can cause paralysis, coma, convulsions, dizziness, sleepiness,
rapid heart rate, tightness of the chest, tremors, and rapid breathing.
In women, it can shrink ovaries and cause menstrual irregularity. Spilling benzene on
your skin can cause redness, sores, scaling, and drying of the skin. If benzene contacts the
42

eyes, it can cause irritation and damage to the cornea. Long-term exposure to benzene can
decrease red blood cells, leading to anemia. It can also cause excessive bleeding and affect the
immune system, increasing the chance of infection.
In term of environment, , benzene can react with other chemicals to create smog. This
could break down naturally but it might also attach to rain and snow and be carried to the
ground to contaminate water and soil.When aquatic life, like fish, shellfish and other creatures
in our rivers, lakes and oceans, is exposed to benzene, it makes them sick and can stop them
from having babies. It can alter their behaviour, change their appearance and shorten their
lives.While for plants, when plants are exposed to benzene in the soil their growth can be
slowed and they may even die.

Conclusion
Two type of process for benzene production have been presented ; catalytic process and
hydrodealkykation of toluene process. Each processes have their own pros and cont which have been
discussed earlier. However, hydrodealkylation being chose because of its main factor ; higher
conversion rate and was found to be more economical of both manufacturing and running costs.
The importance of benzene in worlwide can be seen through the increase of market demand
from times to times and its presence as reactant in most of our daily utensils. It is then important for
us to be extra careful in dealing with benzene products or by product as benzene has been classifies as
carcinogenic to humans, based on sufficient evidence that benzene causes acute myeloid leukemia.
Steps like reducing benzene- product are important in protecting ones health and environment.

References
43

Book
1

Howard F. Rase ( 2000 ) Handbook of Commercial Catalyst; Heterogenous Catalyst.

Inbuden

Article
1

David Netzer, Benzene Supply Trends and Proposed Method for Enhanced
Recovery March 29 2005. Web )

Web
1

Manufacturing Processes retrieved from

http://www.sbioinformatics.com/design_thesis/Benzene/Benzene_Methods-2520of-

2
3

2520Production.pdf on May 27th 2014.

Benzene retrieved from http://www.npi.gov.au/resource/benzene on May 29th 2014.
Benzene retrieved from
http://apps.sepa.org.uk/spripa/Pages/SubstanceInformation.aspx?pid=21 on May 29th
2014.

Report
1) 12th Report on Carcinogens on June 10, 2011 on 25th May 2014

44