DEPARTMENT OF CHEMICAL ENGINEERING, COLLEGE OF

ENGINEERING

ASSIGNMENT 1

50,000 Metric Tonnes per Annum Production of Cumene from

Alkylation of Benzene

Lecturer Name: Mohd Sabri Bin Mahmud

Section: 01
Date: 2nd April 2020

Name: Mohamad Hatta Aiman Bin Mohd Salleh KA17033

LEVEL 2: INPUT-OUTPUT STRUCTURE
1.1 Feed and Products Destination
The feed materials are:
Components Purity (%) Price
Propylene, C3H6 95.2 $167/kmol
Propane, C3H8 4.8 $0.1/kWh fuel
Benzene, C6H6 99.9 $267/kmol

The products are:

Materials Composition Price
Cumene, C9H12 99.9 $1200/kmol
PDIPB, C12H18 Not necessary $0.1/kWh fuel

1.2 Feed impurities

Propane, C3H8 exist as impurities in feed. These species are inert to the reaction and also will
not cause catalyst fouling. Propane composition is literally low thus it can remain in the feed
to the reactor. However, propane needs to be separated from propylene. Thus, it is decided to
be separate at the product stream along with by-product.

1.3 Output Destination

Output Components Destination
Propylene, C3H6 Recycle to the feed
Benzene, C6H6
Cumene, C9H12 Main Product
PDIPB, C12H18 Side-Product used as fuel for a furnace
Propane, C3H8 Separated as gaseous stream and burnt as fuel

1.4 Input-Output Block Flow Diagram (BFD)

Propane (FC3H8)

Propylene (FC3H6)
Propane (FC3H8)
Cumene (PC9H12)

Process
PDIPB (PC12H18)

Benzene (FC6H6)
1.5 Degree of Freedom
ṅi =ṅ0 + vi ξ 1

Species Inlet Change Outlet

Propylene, C3H6 FC3H6 −ξ 1 -
Benzene, C6H6 FC6H6 −ξ 1−ξ 2 -
Cumene, C9H12 - ξ 1−ξ 2 PC9H12
PDIPB, C12H18 - ξ2 PC12H18

Unknown Variables 4
Independent reaction +2
Equation of extend of reactions -4
Composition of impurities -1
Total 1

1.6 Material Balance

Our production target is 50 000 MT/Annum of Cumene. Thus, continuous reactor
design is suitable for our production. This process consists one reactor that convert Propylene
and Benzene into Cumene (primary) and PDIPB (Side), which is Cumene is our target
product.
To fulfil the materials balance, backward calculation method is used, thus materials
balance of reactor is solved. The reactors are assuming to be isothermal and no significant
pressure drop.
Reactor

Main Reaction: Propylene (C3H6) + Benzene (C6H6)  Cumene (C9H12)

Side reaction: Propylene (C3H6) + Cumene (C9H12)  PDIPB (C12H18)

Assume that 1 year = 8000 production hours

MW of Cumene = 120.19 g/mol

50 000(1 x 106 )
Cumene production per hour = = 52000.99 mol/hr
120.19 x 8000
Rate Law:

r 1=k 1 C p C b

r 2=k 2 C p Cc

*Rate unit is kmol kgcat-1 s-1, Concentration unit in kmol m-3

∆ E1 −1.04 x 105
k 1=A 1 exp ( ) RT
= k 1=3.5 x 104 exp ( 8.314 T )
A1 = 3.5 x 104 m6 kgcat-1 kmol-1 s-1,
Ei= -1.04 x 105 kJ kmol-1
∆ E2 −1.47 x 105
k 2=A 2 exp ( ) RT
= k 2=2.9 x 106 exp ( 8.314 T )
A2 = 2.9 x 106 m6 kgcat-1 kmol-1 s-1,
Ei= -1.47 x 105 kJ kmol-1
Specific Rate Constants unit in m6 kgcat-1 kmol-1 s-1
T = 300 oC + 273 = 573K
R = 8.314 kJ/mol K

Mole balance :
dCp
=r p
dt
d Cb
=r b
dt
d Cc
=r c
dt
d C p dipb
=r p dipb
dt

Stoichiometry:

(r 1−r 2+1 x 10−5 )

Selectivity =
(r 2+1 x 10−5 )

(r 1−r 2+1 x 10−5 )

Yield =
(r 1+r 2+1 x 10−5 )
Cp=(ypo)(Cto)(1-X)

Cb=(ybo)(Cto)(Ꝋ-X)

Cc=(yc)Cto)(X)

Cc=(X)(Cpo)

Graph 1: Graph of Concentration vs Time of ratio Propylene to Benzene 1:2

Graph 2: Graph of Concentration vs Time of ratio Propylene to Benzene 2:1

Graph 3: Graph of Concentration vs Time of ratio Propylene to Benzene 1:1

Graph 4: Graph of Concentration vs Time of ratio Propylene to Benzene 1:4
1.7 Evaluation
From the reaction rate, we can see that with ratio propylene benzene 1:2 will produce higher
concentration of cumene. Beside the selectivity of reaction 1 than reaction 2 also higher
which can be observed through low production of PDIPB. The ratio of 1:2 propylene benzene
is the best which propylene are almost completely converted since benzene easier to separate
with propane than propylene.

conversion vs yield
1.2

0.8

0.6 1
1/2
yield

0.4 1/4
2
0.2

0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
-0.2

-0.4

Conversion of propylene

Graph 5: Graph of Conversion vs Yield

From the Graph 5, its show that with ratio 1:2 propylene benzene conversion can achieve up
to 90% with 99% of yield. it is reasonable to choose the feed ratio in the design process.

1.8 Economical Potential

EP2 = Revenue – Materials cost
Raw materials Product Price Flow Rate Cost
(mol/h)
Propylene, C3H6 - $167/kmol 52000.9980 8684.16
Benzene, C6H6 - $267/kmol 104001.996 27768.53
- Cumene, C9H12 $1200/kmol 46800.8982 56161.07
- PDIPB, C12H18 $0.1/kWh fuel 520.0100
- Propane, C3H8 $0.1/kWh fuel 2621.8991

56161.07−27768.53−8684.16
EP 2=
46800.89
= 0.35 USD/kmol Cumene
Appendix

Polymath calculation
#mole balance
#proppylene
d(Cp)/d(t) = rp
Cp(0) = 209.911 #mol/m3
# benzene
d(Cb)/d(t) = rb
Cb(0) = 419.822 #mol/m3
#cumene
d(Cc)/d(t) = rc
Cc(0) = 0 #kmol/m3
#PDIPB
d(Cpdib)/d(t) = rpdib
Cpdib(0) = 0 #kmol/m3

#rate law
r1=k1*Cp*Cb
r2=k2*Cp*Cc
rp=-r1-r2
rb=-r1
rc=r1-r2
rpdib=r2
t(0)=0
t(f)=3600
k1=3.5e4*exp(-1.04e5/R/T)
k2=2.9e5*exp(-1.47e5/R/T)
R=8.314
T=573.15 #K

#selectivity and yiled

S=(r1-r2+0.00001)/(r2+0.00001)
Y=(r1-r2+0.00001)/(r1+r2+0.00001)
Xp=1-Cp*N*P0/(Cp0*N0*P)
Xb=delta-Cb*N*P0/(Cp0*N0*P)
N=(Cp+Cb+Cc+Cpdib)*V
V=1
N0=(Cp0+Cb0)*V
P0=(Cp0+Cb0)*R*T
Cp0=209.911
Cb0=419.822
delta=Cb0/Cp0
P=(Cp+Cb+Cc+Cpdib)*R*T
Data of polymath calculation

Calculated values of DEQ variables

  Variable Initial value Minimal value Maximal value Final value
1 Cb 419.822 210.0077 419.822 210.0077
2 Cb0 419.822 419.822 419.822 419.822
3 Cc 0 0 209.7335 209.7335
4 Cp 209.911 0.0158365 209.911 0.0158365
5 Cp0 209.911 209.911 209.911 209.911
6 Cpdib 0 0 0.0808476 0.0808476
7 delta 2. 2. 2. 2.
8 k1 1.163E-05 1.163E-05 1.163E-05 1.163E-05
9 k2 1.161E-08 1.161E-08 1.161E-08 1.161E-08
10 N 629.733 419.8378 629.733 419.8378
11 N0 629.733 629.733 629.733 629.733
12 P 3.001E+06 2.001E+06 3.001E+06 2.001E+06
13 P0 3.001E+06 3.001E+06 3.001E+06 3.001E+06
14 R 8.314 8.314 8.314 8.314
15 r1 1.024884 3.868E-05 1.024884 3.868E-05
16 r2 0 0 0.0001273 3.857E-08
17 rb -1.024884 -1.024884 -3.868E-05 -3.868E-05
18 rc 1.024884 3.864E-05 1.024884 3.864E-05
19 rp -1.024884 -1.024884 -3.872E-05 -3.872E-05
20 rpdib 0 0 0.0001273 3.857E-08
21 S 1.025E+05 4.845294 1.025E+05 4.845294
22 t 0 0 3600. 3600.
23 T 573.15 573.15 573.15 573.15
24 V 1. 1. 1. 1.
25 Xb 0 0 0.9995394 0.9995394
26 Xp 0 0 0.9999246 0.9999246
27 Y 1. 0.998032 1. 0.9984166

Differential equations
1 d(Cp)/d(t) = rp
2 d(Cb)/d(t) = rb
3 d(Cc)/d(t) = rc
4 d(Cpdib)/d(t) = rpdib

Explicit equations
1 R = 8.314
2 T = 573.15
  K

3 k1 = 3.5e4*exp(-1.04e5/R/T)
4 r1 = k1*Cp*Cb
5 rb = -r1
6 k2 = 2.9e5*exp(-1.47e5/R/T)
7 r2 = k2*Cp*Cc
8 rp = -r1-r2
9 rc = r1-r2
10 rpdib = r2
11 S = (r1-r2+0.00001)/(r2+0.00001)
12 Y = (r1-r2+0.00001)/(r1+r2+0.00001)
13 Cb0 = 419.822
14 P = (Cp+Cb+Cc+Cpdib)*R*T
15 V = 1
16 N = (Cp+Cb+Cc+Cpdib)*V
17 Cp0 = 209.911
18 P0 = (Cp0+Cb0)*R*T
19 N0 = (Cp0+Cb0)*V
20 Xp = 1-Cp*N*P0/(Cp0*N0*P)
21 delta = Cb0/Cp0
22 Xb = delta-Cb*N*P0/(Cp0*N0*P)

General
Total number of equations 26
Number of differential equations 4
Number of explicit equations 22
Elapsed time 0.000 sec
Solution method RKF_45
Step size guess. h 0.000001
Truncation error tolerance. eps 0.000001