CHAPTER 3

MATERIAL BALANCE FOR THE PLANT

3.1 Process Description

Ethylbenzene feed is mixed with recycled ethylbenzene, heated and then mixed with high

temperature superheated stream. Stream is an inert in the reaction, which is used to drive the

equilibrium to ward. Since the formation of styrene is high endothermic, the superheated

steam also provides energy to drive the reaction. Decomposition of ethylbenzene to benzene

and ethylene, and hydrodealkylation to give methane and toluene are unwanted side

reactions. The reactants then enter two adiabatic packed bed reactors (PBR) with inter

heating. The products are cooled and it is sent to a three-phase separator, in which light gas

(H2, C1 and C2), organic liquid, and water exit separate streams. The H2 stream is farther

purified as a source of H2 elsewhere in the plant. The benzene and toluene stream is currently

returned as a feed stream to the petrochemical facilities. The organic stream containing the

desirable product is distilled once to remove benzene and toluene and distilled again to

separate unreacted ethylbenzene for recycle the styrene product

3.1.1 Reactions

Major reaction
C 6 H 5 C 2 H 5 →C 6 H 5 C 2 H 5 + H 2

Styrene formation

Side reaction
C 6 H 5 C 2 H 5 →C 6 H 6 +C 2 H 4

C 6 H 5 C 2 H 5 →8 C +5 H 2

Styrene also reacts catalytically to toluene

C 6 H 5 C 2 H 5 +2 H 2 → C6 H 5 C H 5 +CH 4
Table 3.1: Molecular weight:

COMPOUND MOLECULAR WEIGHT

(kg /kmol )
Ethylbenzene 106.167

Hydrogen 2.015

Benzene 78.11

Toluene 92.14

Methane 16.04

18.015
Steam

Styrene 104.15
3.2 Process Flow Diagram

Figure 3.1 Dehydration of ethylbenzene

3.3 Material Balances Specification for Styrene Plant

Some assumptions were made to help narrow down the feed conditions for design and

simulation, modelling of the styrene production unit and design of the plant. These

assumptions include:

i. Steady-state operation.

ii. Inlet ethylbenzene constitutes of two streams of pure ethylbenzene and a recycle

stream with impurities.

 iii. Steam is charged into the process with flowrate of 8000 k mol /hr and at a temperature

of 800℃ with pressure at 200kPa

3.3.1 Material balance for simulated plant

The classification of unit operations as used in the simulation is as shown below:

Table 3.2: Types and numbers of unit operations used in the simulation

UNIT OPERATIONS MODEL

Reactors  PFR-100
 PFR-101
Separators  V-100

Mixers  MIX-100

Tees
 TEE-100

Column
 T-100
 T-101

Tank
 MIX-101
 MIX-101

Cooler  E-100
 E-101

Pump  P-101

Compressor  k-101
Recycle 1  RCY-1
3.3.2 Determination of feed composition for styrene production

Ethylbenzene stream flowing at 830.3958072 tonnes/day enters the mixer, temperature of

200℃ and pressure of 3.91839 atm is assumed for this process. The feed ethylbenzene is also

assumed to be pure and without Impurities.

Mass flow of the feed inkg /hr is given as:

kg
1
tonnes hr kg
Mass flow=830.3958072 × =34599.8253
day tonnes hr
0.024
day

Average molecular weight is also given as:

Average molecular weight=[ 106.167 × ( 1 ) ]❑

Average molecular weight=106.167 g /mol

For the molar flow, we get:

kg
34599.8253
hr kmol
molar flow= =3 25.9
kg hr
106.167
kmol

Equally, molar flow of is given as:

kmol kmol
molar flow of C 6 H 5 C 2 H 5 =1× 325.9 325.9
hr hr

For the mass flow of C 6 H 5 C 2 H 5, we have:

kg kmol kg
mass flow of N 2=106.167 ×325.9 =34599.8253
kmol hr hr
Recycled ethylbenzene flowing at401.579987468 kg/hr , temperature of 127.7℃ and pressure

of 2.0727 atm enters process. The feed recycled enters the process as im-pure ethylbenzene

composing of 98.85% C 8 H 10 , 1% C 6 H 5 C 2 H 5, 0.15% C 6 H 5 C H 3.

Mass flow of the feed inkg /hr is given as:

kg
1
tonnes hr kg
Mass flow=9 . 637919699232 × =401.579987468
day tonnes hr
0.024
day

Average molecular weight is also given as:

Average molecular weight=[ ( 106.167 ) × ( 0. 9885 ) ] C H +¿+¿92.14

8 10

¿ × ( 0.0015 ) ¿ ¿C 6 H5C H3

Average molecular weight=106.1257895 g/mol

For the molar flow, we get:

kg
401.579987468
hr kmol
molar flow= =3. 784
kg hr
106.1257895
kmol

Equally, molar flow of N2 and O2 is given as:

kmol kmol
molar flow of C 8 H 10=0.9885 ×3.784 =3.740484
hr hr
kmol kmol
molar flow of C 6 H 5 C 2 H 5 =0.01× 3.784 =0.03784
hr hr

kmol kmol
molar flow of C 6 H 5 C H 3=0.0015 ×3.784 =0. 005676
hr hr

For the mass flow of N2 and O2, we have:

kg kmol kg
mass flow of C8 H 10=106.167 ×3.740484 =397.115964828
kmol hr hr
 kg kmol kg
mass flow of C6 H 5 C2 H 5=104.15 × 0.03784 =3.941036
kmol hr hr
kg kmol kg
mass flow of C6 H 5 C H 3=92.14 × 0.005676 =0.52298664
kmol hr hr

Inlet steam flowing at1 44000 kg /hr , temperature of 800℃ and pressure of 1.974 atm is

assumed for this process. The feed composes of purely 100% H2O.

kg
1
tonnes hr kg
Mass flow=3 .4 56 × =1 44000
day tonnes hr
0.024
day

For the molar flow, we get:

kg
1 44000
hr kmol
molar flow= =8000
kg hr
18
kmol

Equally, molar flow of H2O is given as:

kmol kmol
molar flow of H 2 O=1 ×8000 =8000
hr hr
For the mass flow of H2O, we have:

kg kmol kg
mass flow of H 2 O=18 × 8000 =1 44000
kmol hr hr

Table 3.3. Composition of steam for Process Simulation

COMPONENTS MOL COMPOSITION MOL MASS
WEIGHT (kg / (%) FLOW FLOW
kmol ) (kmol /hr ) (kg /hr )
H2 O 18 100 8000 144000

TOTAL 100 8000 144000

Table 3.4. Composition of Pure Ethylbenzene for Process Simulation
COMPONENTS MOL COMPOSITION MOL MASS
WEIGHT (kg / (%) FLOW FLOW
kmol ) (kmol /hr ) (kg /hr )
C6 H5 C2 H5 106.167 100 325.9 34599.825

TOTAL 100 325.9 34599.825

3.3.3 Modelling of a plug flow reactor

Accumulation=Input−Output +Generation

V
dCA
dt
=F A ↓ Z + F A ↓ Z+ ∆ Z +V r A
[ ]
mol
s

0=F A ↓ Z + F A ↓ Z+∆ Z + ∆ Z AC r A

F A↓ Z + F A↓ Z+ ∆ Z
lim (0= ¿+ A C r A )¿
∆ Z→ 0 ∆Z

−d F A
0= + A C r A … … … … ..( A)
dz

where V =∆ Z A C

Expressing∈terms of conversion
 ( )( )
1−X T0
r A =−K 0 C AO
1+ X T

Amount reated F A0 −F A
X= =
inlet feed F A0

F A0 X=F A0 −F A

F A=F A0 (1−X )

Substituting for the value of F A into eqn ( A )

−d (F A 0 ( 1−X ) )
0= + AC r A
dz

−dF A 0 d (F A0 X )
0= + + AC r A
dZ dZ

dx
0=F A 0 + AC r A
dZ

( )( T )
F A 0 dx 1−X T0
=−r A= K 0 C AO
AC dZ 1+ X

solving for reactor volume

dF A 0
dv =
rA

F A1
d FA
v= ∫
F AO
rA

where V =∆ Z A C
Table 3.5: Composition of feed for Reactor Modelling

COMPOSITIONS MOL MOL FLOW

FRACTION (kmol /hr )

C6 H5 C2 H5 0.1954 1627.682

H2 O 0.8046 6702.318

TOTAL 1 8330

The table above shows the compositions, fractions and flow rates of reactor feed for

modelling of the reactor only. For design and simulation of the plant, the composition of

reactor feed is based on 19.54% C 6 H 5 C 2 H 5 and 80.46% H2O only.

3.3.4 Material Balance for styrene reactor

Table 3.6: Summary of material balance for the styrene reactor input
COMPONENTS MOL COMPOSITION INPUT
WEIGHT ( (%)
kg /kmol )

MASS MOLAR
FLOW (kg FLOW (kmol /
/hr ) hr )
C6 H5 C2 H5 106.167 19.54 172806.115 1627.682

H2 O 18.015 80.46 120742.258 6702.318

TOTAL 100 49.597 8330

 Table 3.7: Summary of Material Balance for the styrene glycol reactor output

COMPONENTS MOL COMPOSITION (%) OUTPUT

WEIGHT (
kg /kmol )
MASS MOLAR
FLOW (kg / FLOW (kmol /
hr )
hr )
C2 H4 28.05 0.0011 0.0727 9.3253
C6 H6 78.11 0.0011 0.2023 9.3252
C6 H6 C2 H4 104.15 0.0181 4.4547 153.9774
C6 H5 C2 H5 106.167 0.0015 0.3737 12.6733
2 0.0181 0.6850 153.7170
CH4
H2 O 18.015 0.9420 40.0336 8000.0008
2.015 0 0.0001 0.2319
H2

C6 H5 C H5 92.14 0.0181 3.9343 153.7170

TOTAL 1 49.75650 8493

3.3.5 Material balance for cooler (E-100)

Table 3.8. Summary of Material Balance for cooler (E-100)

COMPONENTS INPUT OUTPUT

MASS MASS MASS MOLAR

FLOW (kg / FRACTION FLOW (kg / FRACTION
hr ) hr )

C2 H4 0.0757 0.0011 0.0757 0.0011

C6 H6 0.2107 0.0011 0.2107 0.0011
C6 H6 C2 H4 4.4717 0.0182 4.4717 0.0182
C6 H5 C2 H5 0.3271 0.0013 0.3271 0.0013
CH4 0.6877 0.0182 0.6877 0.0182
H2 O 40.0336 0.9418 40.0336 0.9418
H2 0.0001 0.0000 0.0001 0.0000
C6 H5 C H5 3.9500 0.0182 3.9500 0.0182
TOTAL 49.7565 1 49.7565 1