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 ºC = 298 K
 Initial Calculations

 Stoichiometric Tables:
 Molar Stoichiometric Table
Species Initial (kmol/s) Change (kmol/s) Final (kmol/s)
H2O 0 0.03362 .03362
C4H10 0.01051 -0.00841 .00210
O2 0.12758 -0.02942 .09816
N2 0.47993 0 .47993
C4H2O3 0 .00841 .00841
Total 0.61802 .00042 .62222

 Mass Stoichiometric Table

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

Bed Reactor Model  Stream Flows
 Results Substream: MIXED FEED PRODUCT
Variable Value
Conversion 0.8000043
Mole Flow (kmol/sec) VAPOR VAPOR
Catalyst Wt. 57675 kg BUTANE 0.0105 2.08E-03
Bulk Density 900 kgcat/m3 OXYGEN 0.1276 0.0981338
VRXTR 64.08333 m3
MALEI-01 0 8.42E-03
WATER 0 0.0336756
 Stream Flows NITROGEN 0.4799 0.4799
Initial Final
Species (kmol/s) (kmol/s)
H2O 0 0.0336
C4H10 0.0105 0.0021
O2 0.1276 0.0982
N2 0.4799 0.4799
C4H2O3 0 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
350°C
0.5 375°C
400°C
0.4
425°C
0.3 450°C

0.2

0.1

0
0 10000 20000 30000 40000 50000 60000

Catalyst Weight (kg)

 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  Aspen Plus®: RPLUG Reactor

Bed Reactor Model  Stream Flows for Single Tube Reactor
 Results Substream: MIXED FEED PRODUCT
Variable Value Mole Flow (kmol/sec) VAPOR VAPOR
Conversion 0.8008841 BUTANE 0.0105 2.02E-03
Catalyst Wt. 60500 kg OXYGEN 0.1276 0.097918
MALEI-01 0 8.48E-03
Bulk Density 900 kgcat/m3
WATER 0 0.0339223
VRXTR 67.2222 m3 NITROGEN 0.4799 0.4799

 Stream Flows  Stream Flows for Multi-Tube Reactor

Initial Final
Substream: MIXED FEED PRODUCT
Species (kmol/s) (kmol/s)
Mole Flow (kmol/sec) VAPOR VAPOR
H2O 0 0.0336371 BUTANE 0.0105 2.07E-03
C4H10 0.0105 0.0020907 OXYGEN 0.1276 0.0981009
O2 0.1276 0.0981675 MALEI-01 0 8.43E-03
N2 0.4799 0.4799 WATER 0 0.0337133
C4H2O3 0 0.0084093 NITROGEN 0.4799 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

648K
0.6
673K
698K
0.5
723K

0.4 623K Old

648K Old
0.3 673K Old
698K Old
0.2
723K Old

0.1

0
0 10000 20000 30000 40000 50000 60000

Catalyst Weight (kg)

 Case II

 Polymath: Isothermal Packed Bed Reactor Model

 Effect of Length on Pressure Drop

Effect of Length on Pressure Drop

90

80

70

60
Pressure Drop %

50

40 Dp=7mm
Dp=14mm
30

20

10

0
0 1 2 3 4 5 6 7

Length of Reactor (m)

 Case II

 Comparison of Three Models

# of Pressure Drop
Tubes Po (Pa) Pf (Pa) T (K) %
Polymath 1 150000 135500 673 8.961
Aspen Single Tube 1 150000 136543.8 673 8.97
Aspen Multi-Tube 37220 150000 136546.8 673 8.97
 Case III
 Additional Assumptions:
 Side reactions and byproducts are taken into consideration

 Polymath: Isothermal Packed  Aspen Plus®: RPLUG Reactor

Bed Reactor Model  Stream Flows for Multi-Tube Reactor
 Results Initial Final
Species (kmol/s) (kmol/s)
Variable Value C4H10 0.023 0.00440171
Conversion 0.80742 O2 0.2793 0.1946573
Catalyst Weight 212000 kg N2 1.05065 1.05065
C4H2O3 0 0.00841548
Bulk Density 900 kgcat/m3 H2O 0 0.0845759
VRXTR 235.5556 m3 CO 0 0.0219996
CO2 0 0.0187316
 Stream Flows
Initial Final
Species (kmol/s) (kmol/s)  Stream Flows for Single Tube Reactor
C4H10 0.023 0.0044292 Initial Final
Species (kmol/s) (kmol/s)
O2 0.2793 0.194784
C4H10 0.023 0.00440319
N2 1.05065 1.05065 O2 0.2793 0.1946679
C4H2O3 0 0.0084034 N2 1.05065 1.05065
H2O 0 0.0884504 C4H2O3 0 0.00841679
CO 0 0.0219674 H2O 0 0.0845672
CO 0 0.0219936
CO2 0 0.0187201
CO2 0 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
623 633 643 653 663 673 683 693 703 713 723

Temperature (K)
 Case III

 Aspen Plus®: RPLUG Reactor

 Effect of Reactor Length on Molar Flows

Effect of Reactor Length on Molar Flows

0.3

0.25

0.2
Molar Flows (kmol/s)

n-butane
Maleic Anhydride
0.15
Water
Carbon Monoxide
0.1 Carbon Dioxide
Oxygen

0.05

0
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5

Reactor Length (m)

 Case III

 Comparison of Three Models

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

Packed Bed Reactor Model  Stream Flows for Multi-Tube Reactor
 Results Initial Final
Species (kmol/s) (kmol/s)
Variable Value
Conversion 0.8091979 C4H10 0.023 0.00438659
Catalyst Weight 173500 kg O2 0.2793 0.1945099
Bulk Density 900 kgcat/m3 N2 1.05065 1.05065

VRXTR 192.7778 m3 C4H2O3 0 0.00840391

H2O 0 0.0846631
CO 0 0.0219706
 Stream Flows
Final CO2 0 0.0188673
Species Initial (kmol/s) (kmol/s)
C4H10 0.023 0.0043884
O2 0.2793 0.1945189
N2 1.05065 1.05065
C4H2O3 0 0.0084033
H2O 0 0.0846545
CO 0 0.0219682
CO2 0 0.0188649
 Case IV

 Aspen Plus®: RPLUG Reactor

 Effect of Varying Ta On Hot Spot

Effect of Varying Ta on Hot Spot

730

720

710

700
Temperature (K)

Ta=673 K
690
Ta=663 K

680 Ta=683 K
Ta=653 K
670

660

650
0 0.5 1 1.5 2 2.5 3 3.5 4

Reactor Length (m)

 Case IV

 Comparison of Isothermal and Real Reactor Models:

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

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

 Optimal Reactor Conditions:  Criteria Met:

To (K) 673  Minimal reactor size
Ta (K) 673  Minimized cost
Po (Pa) 1.70E+05
 Constant selectivity throughout
DOverall (m) 6.95
dIndividual Tube (m) 0.0254
runs
Length (m) 4.158975  Gain < 2
Number of Tubes 74870
 Pressure Drop < 10%
VRXTR (m3) 157.778
Catalyst Wt (kg) 142000
Selectivity 0.204517