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Chemical Reaction Engineering Dr. Robert P. Hesketh Dr.

Concetta LaMarca

Yousef Ghotok Joseph Havelin Wednesday, 23rd April 2008

Outline

Background, Process Reactions, and Rate Expressions Initial Calculations Case I Reactor Volume Using Simple Reaction Rate Expression Case II Pressure Drop and Reactor Configuration Case III Multiple Reactions Case IV Energy Balance for Multiple Reactions Case V Optimization of Reactor Design

Background, Process Reactions, and Rate Expressions

Maleic anhydride is a cyclic organic chemical with formula C4H2O3.

Primary Use: Synthesis of Unsaturated Polyester Resins N-butane is the most common feedstock used in production of maleic anhydride. Bergman and Frisch discovered synthesizing maleic anhydride from n-butane by catalyzing the oxidation reaction. By 1985, all commercial producers of maleic anhydride in the US used n-butane as their feed. Worldwide Production: 1,359,000 tons per year US Production: 273,800 tons per year

Background, Process Reactions, and Rate Expressions


The partial oxidation of n-butane at the surface of the catalyst produces maleic anhydride and water, and side reactions produce carbon monoxide, carbon dioxide and water. Catalyst used is vanadium-phosphorus oxide ((VO)2P2O7). Reactor Type Fixed-Bed Reactor Advantages: easy use and low maintenance demand Disadvantages: hot spots and pockets of diluted butane

Background, Process Reactions, and Rate Expressions

Balanced Stoichiometric Equation: Cases I and II C4H10 + 3.5O2 C4H2O3 + 4H2O Rate Equation: Cases I and II rM = k 1 CB Pseudo-First Order Rate Constant: Cases I and II k1 = 8.1048 106 exp(-15649/T) [m3/kgcat-sec] Reactions From the Oxidation of N-Butane: Cases III, IV, and V

Background, Process Reactions, and Rate Expressions

Reaction Pathway Diagram: Cases III, IV and V

Reaction Rate Expressions: Cases III, IV and V

Rate Constants and Parameters

Initial Calculations

Assumptions: Open system at steady state Negligible changes in kinetic and potential energy Negligible work 14 days worth of downtime per year Inlet gas 1.7 mol% n-butane 80% conversion rate; side reactions not considered in this preliminary stage 25,000 tons/year production rate Reference temperature = 25 C = 298 K

Initial Calculations

Stoichiometric Tables: Molar Stoichiometric Table


Species H2O C4H10 O2 N2 C4H2O3 Total

Initial (kmol/s) 0 0.01051 0.12758 0.47993 0 0.61802

Change (kmol/s) 0.03362 -0.00841 -0.02942 0 .00841 .00042

Final (kmol/s) .03362 .00210 .09816 .47993 .00841 .62222

Mass Stoichiometric Table


Species H2O C4H10 O2 N2 C4H2O3 Total Initial (kg/s) 0 0.61065 4.08231 13.44455 0 18.13751 Change (kg/s) 0.60568 -0.48852 -0.94133 0 0.82417 0 Final (kg/s) .60568 .12213 3.14099 13.44455 .82417 18.13751

Case I

Additional Assumptions: Isothermal Reactor Model to Estimate the Reactor Volume Isothermal Temperature = 673 K Bulk Density = 900 kgcat/m3 Void Fraction = 0.44 Particle Diameter = 5 mm Inlet Pressure = 1.5 bar

Case I

Polymath: Isothermal Packed Bed Reactor Model Results


Variable Conversion Catalyst Wt. Bulk Density VRXTR Value 0.8000043 57675 kg 900 kgcat/m3 64.08333 m3

Aspen Plus: RPLUG Reactor Stream Flows


Substream: MIXED FEED PRODUCT Mole Flow (kmol/sec) VAPOR VAPOR BUTANE 0.0105 2.08E-03 OXYGEN 0.1276 0.0981338 MALEI-01 0 8.42E-03 WATER 0 0.0336756 NITROGEN 0.4799 0.4799

Stream Flows
Species H2O C4H10 O2 N2 C4H2O3 Initial (kmol/s) 0 0.0105 0.1276 0.4799 0 Final (kmol/s) 0.0336 0.0021 0.0982 0.4799 0.0084

Case I

Polymath: Isothermal Packed Bed Reactor Model Effect of Catalyst Weight and Temperature on Conversion
Effect of Catalyst Weight and Temperature on Conversion
1

0.9
0.8

0.7
Conversion of n-butane
0.6 350C 0.5 375C 400C 425C 0.3 450C

0.4

0.2
0.1 0 0 10000 20000 30000 Catalyst Weight (kg) 40000 50000 60000

Case II

Additional Assumptions: Pressure Drop in the Fixed-Bed Reactor Must not Exceed 1/10 the Initial Pressure Pressure drop along the length of the reactor

Case II

Polymath: Isothermal Packed Bed Reactor Model Results


Variable Conversion Catalyst Wt. Value 0.8008841 60500 kg

Aspen Plus: RPLUG Reactor Stream Flows for Single Tube Reactor
Substream: MIXED FEED PRODUCT Mole Flow (kmol/sec) VAPOR VAPOR BUTANE 0.0105 2.02E-03 OXYGEN 0.1276 0.097918 MALEI-01 0 8.48E-03 WATER 0 0.0339223 NITROGEN 0.4799 0.4799

Bulk Density 900 kgcat/m3 VRXTR 67.2222 m3

Stream Flows
Species H2O C4H10 O2 N2 C4H2O3 Initial (kmol/s) 0 0.0105 0.1276 0.4799 0 Final (kmol/s) 0.0336371 0.0020907 0.0981675 0.4799 0.0084093

Stream Flows for Multi-Tube Reactor


Substream: MIXED Mole Flow (kmol/sec) BUTANE OXYGEN MALEI-01 WATER NITROGEN FEED VAPOR 0.0105 0.1276 0 0 0.4799 PRODUCT VAPOR 2.07E-03 0.0981009 8.43E-03 0.0337133 0.4799

Case II

Polymath: Isothermal Packed Bed Reactor Model Effect of Catalyst Weight and Temperature on Conversion
Effect of Catalyst Weight and Temperature on Conversion
1 0.9 0.8 0.7

623K

Conversion of n-butane

0.6 0.5
0.4 0.3 0.2 0.1 0

648K 673K
698K 723K 623K Old 648K Old 673K Old

698K Old 723K Old

10000

20000

30000 Catalyst Weight (kg)

40000

50000

60000

Case II

Polymath: Isothermal Packed Bed Reactor Model Effect of Length on Pressure Drop
Effect of Length on Pressure Drop
90 80 70

Pressure Drop %

60
50

40 30
20

Dp=7mm Dp=14mm

10 0 0 1 2 3 4 5 6 7

Length of Reactor (m)

Case II

Comparison of Three Models


# of Tubes Polymath Aspen Single Tube Aspen Multi-Tube 1 1 37220 Po (Pa) 150000 150000 150000 Pf (Pa) 135500 136543.8 136546.8 T (K) 673 673 673 Pressure Drop % 8.961 8.97 8.97

Case III

Additional Assumptions: Side reactions and byproducts are taken into consideration Polymath: Isothermal Packed Bed Reactor Model Results
Variable Conversion Catalyst Weight Bulk Density VRXTR Value 0.80742 212000 kg 900 kgcat/m3 235.5556 m3
Initial (kmol/s) 0.023 0.2793 1.05065 0 0 0 0 Final (kmol/s) 0.0044292 0.194784 1.05065 0.0084034 0.0884504 0.0219674 0.0187201
Species C4H10 O2 N2 C4H2O3 H2O CO CO2

Aspen Plus: RPLUG Reactor Stream Flows for Multi-Tube Reactor


Species C4H10 O2 N2 C4H2O3 H2O CO CO2 Initial (kmol/s) 0.023 0.2793 1.05065 0 0 0 0 Final (kmol/s) 0.00440171 0.1946573 1.05065 0.00841548 0.0845759 0.0219996 0.0187316

Stream Flows
Species C4H10 O2 N2 C4H2O3 H2O CO CO2

Stream Flows for Single Tube Reactor


Initial (kmol/s) 0.023 0.2793 1.05065 0 0 0 0 Final (kmol/s) 0.00440319 0.1946679 1.05065 0.00841679 0.0845672 0.0219936 0.0187264

Case III

Polymath: Isothermal Packed Bed Reactor Model

Effect of Reaction Temperature on Selectivity of Maleic Anhydride


Effect of Reaction Temperature on Selectivity of Maleic Anhydride
0.212 0.211 0.21 0.209

Selectivity

0.208 0.207 0.206 0.205 0.204


0.203

623

633

643

653

663

673
Temperature (K)

683

693

703

713

723

Case III

Aspen Plus: RPLUG Reactor Effect of Reactor Length on Molar Flows


Effect of Reactor Length on Molar Flows
0.3

0.25

Molar Flows (kmol/s)

0.2
n-butane 0.15 Maleic Anhydride

Water Carbon Monoxide


0.1

Carbon Dioxide
Oxygen

0.05

0.5

1.5

2.5 Reactor Length (m)

3.5

4.5

Case III

Comparison of Three Models


# of Tubes Polymath Aspen Single Tube Aspen Multi-Tube 1 1 99200 Po (Pa) 150000 150000 150000 Pf (Pa) 137400 137336 137336 T (K) 673 673 673 Pressure Drop % 8.4 8.442666667 8.442666667

Case IV

Additional Assumptions: Non-isothermal Energy Balance taken into consideration Heat exchanger with constant coolant temperature, Ta = 673 K Overall Heat Transfer Coefficient = 105 J/(m2*K*s)

Case IV

Polymath: Non-Isothermal Packed Bed Reactor Model Results


Variable Conversion Catalyst Weight Bulk Density VRXTR Value 0.8091979 173500 kg 900 kgcat/m3 192.7778 m3

Aspen Plus: RPLUG Reactor Stream Flows for Multi-Tube Reactor


Species C4H10 O2 N2 C4H2O3 H2O CO Initial (kmol/s) 0.023 0.2793 1.05065 0 0 0 0 Final (kmol/s) 0.00438659 0.1945099 1.05065 0.00840391 0.0846631 0.0219706 0.0188673

Stream Flows
Species C4H10 O2 N2 C4H2O3 H2O CO CO2 Initial (kmol/s) 0.023 0.2793 1.05065 0 0 0 0 Final (kmol/s) 0.0043884 0.1945189 1.05065 0.0084033 0.0846545 0.0219682 0.0188649

CO2

Case IV

Aspen Plus: RPLUG Reactor Effect of Varying Ta On Hot Spot


Effect of Varying Ta on Hot Spot
730 720 710
700 690

Temperature (K)

Ta=673 K
Ta=663 K

680 670 660


650 0 0.5 1 1.5 2 2.5 3 3.5 4

Ta=683 K

Ta=653 K

Reactor Length (m)

Case IV

Comparison of Isothermal and Real Reactor Models: Polymath


Real Isothermal To (K) 673 673 Ta (K) 673 NA FMAN (kmol/s) 0.0084033 0.0077919 Selectivity 0.2057963 0.206338 Conversion 0.8091979 0.7492456

Aspen
To (K) 673 673 Ta (K) 673 NA FMAN (kmol/s) 0.00840391 0.00780377 FCO (kmol/s) 0.02197067 0.02042879 FCO2 (kmol/s) 0.01886732 0.01739411 Selectivity 0.2057866 0.2063239

Real Isothermal

Case V

Optimal Reactor Conditions:


To (K) Ta (K) Po (Pa) DOverall (m) dIndividual Tube (m) Length (m) Number of Tubes VRXTR (m3) Catalyst Wt (kg) Selectivity 673 673 1.70E+05 6.95 0.0254 4.158975 74870 157.778 142000 0.204517

Criteria Met: Minimal reactor size Minimized cost Constant selectivity throughout runs Gain < 2 Pressure Drop < 10%