Partial Oxidation of Benzene to

Maleic Anhydride
Derek Becht
Mike Raymond
Eric Nette
Matt Hunnemeder
Overview
Project Description

Background

Assumptions

Solution Methodology

Final Design

Overall Comparison
Project Description
Reaction: Partial oxidation of benzene

Reactor: Fixed bed reactor

Production: 50000 M tons/year maleic
anhydride

Step by step modeling process






Fogler H.S. Elements of Chemical Reaction Engineering; Pearson Education: New Jersey, 2006.
Maleic Anhydride
Feed stocks
1

Benzene

N-Butene

N-Butane
Major Uses
2

Resins

Oil Additives

Copolymers
Financial Considerations
Market Price
3,4

Maleic Anhydride: $1.54/kg - $ 1.70/kg


Benzene: $929.99/m
3
$940.55/m
3

Financial Earnings
$20,922,183/yr neglecting all cost, except feed


Standard Assumptions
Open system + steady state

Negligible potential and kinetic energy

No mechanical or shaft work

Turbulent flow
Uniform temperature, pressure, and concentration
within the control volume

2 weeks downtime

Benzene Specific Assumptions
1.1 mol % inlet benzene
5


Conversion, X
B
, is 0.76
6


Dry air


Negligible CO
2
in air



A. Bielanski, M. N. (1997). V2O5-MoO3 Catalysts for Benzene Oxidation. Applied catalysts , 223-261.
Reactor and Particle Properties
Bulk Density
7
= 930 kg
cat
/m
3

V
2
O
5
-MoO
3
Particle Diameter
8
= 0.006m

Void Fraction = 0.4 m
3
gas
/m
3
rxtr

Heat Transfer Coefficient
8
= 202.4 W/m
2
-K

Coolant Temperature
8
= 653 K




Solution Methodology
Ideal Reactor -> Realistic Reactor

Considerations:
Pressure drop

Side reactions

Temperature rise/drop
Case 1: Ideal Reactor
Assumptions Reaction Kinetics
Isothermal
One reaction
Isobaric


Inlet Conditions Feed Rates
658 K Benzene: 0.02122 kmol/s
1.5 atm Oxygen: 0.4177 kmol/s
1.1 mol% benzene Nitrogen: 1.577 kmol/s



Conversion Profile
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
20000 40000 60000 80000 100000 120000 140000 160000 180000 200000
C
o
n
v
e
r
s
i
o
n

X
B

Catalyst Weight kg
cat
350
360
370
380
410
390
400
385
420
430
440
Heat Duty Profile
y = -32.191x
R = 1
-35.00
-30.00
-25.00
-20.00
-15.00
-10.00
-5.00
0.00
0.00 0.20 0.40 0.60 0.80 1.00
H
e
a
t

D
u
t
y

(
M
W
)

Conversion (Mol Reacted/Mol Fed)
Case 2: Pressure Drop
Additional Assumptions Momentum Equations
Ideal Gas

Constant Density




Additional Property
Viscosity
9
= 3.2197E-5 PaS




Conversion Profile
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
20000 50000 80000 110000 140000 170000 200000
C
o
n
v
e
r
s
i
o
n

X
B

Catalyst Weight kg
cat
350 with Pressure Drop
360 with Pressure Drop
370 with Pressure Drop
380 with Pressure Drop
390 with Pressure Drop
400 with Pressure Drop
410 with Pressure Drop
420 with Pressure Drop
430 with Pressure Drop
440 with Pressure Drop
385 with Pressure Drop
Particle Diameter
0
2
4
6
8
10
12
0 0.5 1 1.5 2 2.5 3
P
r
e
s
s
u
r
e

D
r
o
p

%

Length (m)
.006m Particle Diameter
.012m Particle Diameter
Case 3: Multiple Reactions
Mechanism Rate Expressions




2 C
6
H
6
+ 6 O
2
-> 3 C
4
H
2
O
3
+ 3 H
2
O
C
6
H
6
+ 6 O
2
-> 3 CO + 3 CO
2
+ 3 H
2
O
Molar Flow Rates
0
0.005
0.01
0.015
0.02
0.025
0.03
0.035
0.04
0.045
0.05
0 0.5 1 1.5 2
F
l
o
w

R
a
t
e

(
k
m
o
l
/
s
)

Reactor Length (m)
Benzene
Maleic Anhydride
Water
Carbon Dioxide
Carbon Monoxide
Selectivity
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
590 600 610 620 630 640 650 660 670
S
e
l
e
c
t
i
v
i
t
y

o
f

M
A

Temperature (K)
Case 4: Energy Balance
Additional Assumptions
Constant heat capacity

Constant coolant temperature

Multi-tube reactor


Coolant Temperature
640
645
650
655
660
665
670
675
680
685
690
0 0.5 1 1.5 2 2.5 3
T
e
m
p
e
r
a
t
u
r
e

(
K
)

Reactor Length (m)
651 K
660 K
640 K
670 K
Inlet Temperature
635
640
645
650
655
660
665
670
675
0 0.5 1 1.5 2 2.5 3
T
e
m
p
e
r
a
t
u
r
e

(
K
)

Reactor Length (m)
658 K
650 K
670 K
640 K
Final Design: Optimization
Pressure




Temperature
Pressure
(bar)
Conversion
Pressure
Drop %
Selectivity
Hot Spot
(K)
1.5 0.764 9.33 0.319 671.0
1.75 0.823 7.95 0.313 674.0
2 0.867 6.93 0.308 676.9
Inlet
Temperature (K)
Conversion Selectivity
Flow Maleic
Anhydride
(kmol/s)
648 0.7598 0.3036 1.686E-02
653 0.7625 0.3037 1.692E-02
658 0.7597 0.3035 1.685E-02
668 0.7417 0.3028 1.644E-02
Overall Comparison
Property Initial Design Final Design
Temperature (K) 658 653
Inlet Benzene (kmol/s) 0.02122 0.02684
Catalyst Weight (kg) 139,750 76,400
Reactor Length (m) 97.4 2.476

Diameter (m) 7.2 6.5
Volume (m
3
) 150 82.2

Potential Earnings ($/yr) 20,822,183 8,901,617
Pressure Drop 9.95%
Selectivity 0.3036
Coolant Gain 1.008
Inlet Gain 0.051
References
1) Barone et al., United States Patent 4018709. Patent Issued 1977.

2) Maleic anhydride - Chemical Profile. <http://www.the-innovation-group.com/ChemProfiles/Maleic%20Anhydride.htm>. (accessed
01/24/2008).

3) William Lemos. US Price Report Maleic Anhydride. <http://www.icis.com/v2/chemicals/9076024/maleic-anhydride/pricing>.
(accessed 01/25/2008).

4) Americas Market Summary Benzene. http://www.icis.com/articles/2008/01/29/9096633/NOON-SNAPSHOT. (accessed 01/24/2008).

5) Sharma R.K. et al. (1984). Selective Oxidation of Benzene to maleic anhydride at Commercially Relevant Conditions. Institution of
Chemical Engineers Symposium Series, 353-360.

6) Americas Market Summary Benzene. http://www.icis.com/articles/2008/01/29/9096633/NOON-SNAPSHOT. (accessed 01/24/2008).

7) U.S. Patents. (1996). Oxide catalyst and process for producing maleic anhydride by oxide catalyst (No. 266510 filed on 1994-06-27).

8) U.S. Patents. (1978). Process for the Manufacture of Maleic Anhydride (No. 4070379 filed on 10/21/1976).
http://www.freepatentsonline.com/4070379.html

9) Chemical Database Property Constants. DIPPR Database [Online]. Available from Rowan Hall 3rd Floor Computer Lab. (Accessed on
1/24/2008).



Questions and Comments?