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

Fogler H.S. Elements of Chemical Reaction Engineering; Pearson Education: New Jersey, 2006.

Production: 50000 M tons/year maleic anhydride Step by step modeling process

Maleic Anhydride

Feed stocks1

Major Uses2

Benzene
N-Butene

Resins
Oil Additives

N-Butane

Copolymers

Financial Considerations
Market Price3,4
Maleic Anhydride: $1.54/kg - $ 1.70/kg Benzene: $929.99/m3 $940.55/m3

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 benzene5

Conversion, XB, is 0.76 6

Dry air Negligible CO2 in air
A. Bielanski, M. N. (1997). V2O5-MoO3 Catalysts for Benzene Oxidation. Applied catalysts , 223-261.

Reactor and Particle Properties

Bulk Density7 = 930 kgcat/m3

V2O5-MoO3 Particle Diameter8 = 0.006m

Void Fraction = 0.4 m3gas/m3rxtr Heat Transfer Coefficient8 = 202.4 W/m2-K

Coolant Temperature8 = 653 K

Solution Methodology
Ideal Reactor -> Realistic Reactor

Considerations:
Pressure drop

Side reactions
Temperature rise/drop

Case 1: Ideal Reactor

Assumptions
Isothermal One reaction Isobaric

Reaction Kinetics

Inlet Conditions
658 K 1.5 atm 1.1 mol% benzene

Feed Rates
Benzene: 0.02122 kmol/s Oxygen: 0.4177 kmol/s Nitrogen: 1.577 kmol/s

Conversion Profile
1 0.9 0.8 350 360 370 380 410 390 400 385 420 430 440 40000 60000 80000 100000 120000 140000 160000 180000 200000

Conversion XB

0.7 0.6 0.5 0.4 0.3 0.2 0.1 0 20000

Catalyst Weight kgcat

Heat Duty Profile

-35.00 -30.00 y = -32.191x R = 1

Heat Duty (MW)

-25.00 -20.00 -15.00 -10.00 -5.00 0.00 0.00

0.20

0.40

0.60

0.80

1.00

Conversion (Mol Reacted/Mol Fed)

Case 2: Pressure Drop

Additional Assumptions
Ideal Gas Constant Density

Momentum Equations

Additional Property
Viscosity9 = 3.2197E-5 PaS

Conversion Profile
1 0.9 0.8 360 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 50000 80000 110000 140000 170000 200000 440 with Pressure Drop 385 with Pressure Drop 350 with Pressure Drop

Conversion XB

0.7 0.6 0.5 0.4 0.3 0.2 0.1 0 20000

Catalyst Weight kgcat

Particle Diameter
12 10

Pressure Drop %

.006m Particle Diameter .012m Particle Diameter

0 0 0.5 1 1.5 2 2.5 3

Length (m)

Case 3: Multiple Reactions

Mechanism Rate Expressions

2 C6H6 + 6 O2 -> 3 C4H2O3 + 3 H2O C6H6 + 6 O2 -> 3 CO + 3 CO2 + 3 H2O

Molar Flow Rates

0.05 0.045

Flow Rate (kmol/s)

0.04 0.035 0.03 0.025 0.02 0.015 0.01 0.005 0 0 0.5 1 1.5 2 Benzene Maleic Anhydride Water Carbon Dioxide Carbon Monoxide

Reactor Length (m)

Selectivity
1.0 0.9

Selectivity of MA

0.8

0.7
0.6 0.5 0.4 0.3 0.2 0.1 0.0 590 600 610 620 630 640 650 660 670

Temperature (K)

Case 4: Energy Balance

Additional Assumptions
Constant heat capacity Constant coolant temperature Multi-tube reactor

Coolant Temperature
690

685
680

Temperature (K)

675 670 665 660 655 650 651 K 660 K 640 K 670 K

645
640 0 0.5 1 1.5 2 2.5 3

Reactor Length (m)

Inlet Temperature
675 670

Temperature (K)

665 660 658 K 655 650 645 640 635 0 0.5 1 1.5 2 2.5 3 650 K 670 K 640 K

Reactor Length (m)

Final Design: Optimization

Pressure
Pressure (bar) Conversion Pressure Drop % Selectivity Hot Spot (K)

1.5 1.75

0.764 0.823

9.33 7.95

0.319 0.313

671.0 674.0

0.867

6.93

0.308

676.9

Temperature
Inlet Temperature (K) Conversion Selectivity Flow Maleic Anhydride (kmol/s)

648 653 658 668

0.7598 0.7625 0.7597 0.7417

0.3036 0.3037 0.3035 0.3028

1.686E-02 1.692E-02 1.685E-02 1.644E-02

Overall Comparison
Property Temperature (K) Inlet Benzene (kmol/s) Catalyst Weight (kg) Reactor Length (m) Diameter (m) Volume (m3) Potential Earnings ($/yr) Initial Design 658 0.02122 139,750 97.4 7.2 150 20,822,183 Final Design 653 0.02684 76,400 2.476 6.5 82.2 8,901,617

Pressure Drop Selectivity Coolant Gain Inlet Gain

9.95% 0.3036 1.008 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?