CHEMICAL REACTION ENGINEERING:

REACTOR DESIGN PROJECT

Caitlin Boyd
Katherine Ross
April 23, 2008
OVERVIEW
Elements of Reactor Design
Reaction of 1-butene to maleic anhydride
Preliminary Plug Flow Reactor Design
Inclusion of Energy Balance
Optimization Process
Optimized Reactor
Conclusions

ELEMENTS OF REACTOR DESIGN
Momentum Balance & Pressure Drop
Reaction Mechanism
Kinetics
Conversion
Production and Selectivity
Energy Balance
Thermodynamic Stability
Optimization
Assumptions
MOMENTUM BALANCE AND PRESSURE DROP
The momentum balance accounts for the pressure
change in the reactor.


where



Pressure drop cannot exceed 10% of initial pressure.




o
T
T
o
o
c c
o
F
F
T
T
P
P
A dW
dP
|
|
) 1 (

=
o
P P 1 . 0 s A
(
(

+

= G
D D
G
p p o
o
75 . 1
) 1 ( 150 ) 1 (
3
|
|
|
|
REACTION MECHANISM
1-butene to maleic anhydride
(1) C
4
H
8
+ 3 O
2
C
4
H
2
O
3
+ 3 H
2
O
(2) C
4
H
8
+ 6 O
2
4 CO
2
+ 4 H
2
O
(3) C
4
H
8
+ O
2
2 C
2
H
4
O
(4) C
4
H
8
+ O
2
C
4
H
6
O + H
2
O

KINETICS
Preliminary Reaction Kinetics (1 Reaction)

r
m
= k
1
* p
B

where p
B
is partial pressure of 1-butene and
k
1
= 3.8075x 10
5
*exp(-11569/T)
[=]
kmol/ kgcat-bar-s






KINETICS
Kinetics for Multiple Reactions from Literature
1



CONVERSION OF REACTANT
The goal conversion of 1-butene found in literature
was 90%.
1
This was used as a basis for all reactor
models throughout the design process.





X stands for conversion, F
BT
0
is the initial flow of 1-
butene and F
BT
is the outlet flow of 1-butene.


PRODUCTION AND SELECTIVITY
Goal Production: 40,000 metric tons/ year

Selectivity of maleic anhydride, the desired product,
was found by the following equation:


Selectivity








O H C O H C CO
MA
F F F
F
6 4 4 2 2
+ +
=
ENERGY BALANCE



where



o This accounts for non- isothermal behavior in the
reactor and allows for the optimization of the
reactor temperature.

=
=
+ A
=
n
i
i io
n
i
i rxn i
Cp F
q H r
dW
dT
1
1
*
*
| | T Ta q =
1000 * 0258826 . 0
4 * 227 . 0
[=] kJ/ kgcat-s
THERMODYNAMIC STABILITY
The reactor gain was analyzed to determine whether
the reactor was thermodynamically stable. The gain
analysis involves raising the coolant fluid temperature
one degree and finding the how much the hotspot
temperature changes.




A gain less than two indicates a thermodynamically
stable reactor.
inlet
Hotspot
T
T
Gain
A
A
=
OPTIMIZATION
Throughout the reactor design project this semester
each memo submission involved a new aspect of
the reactor:
o Volume
o Pressure Drop
o Multiple Reactions
o Energy Balance

The final challenge was to optimize a reactor in
both Polymath and Aspen that would include these
aspects.



INITIAL REACTOR ASSUMPTIONS
90% conversion of 1- butene
Phosphorous and vanadium oxide catalyst
2

Inlet pressure of 2.2 bar
Reactor at 400
o
C
Catalyst bulk density of 1000 kgcat/ m
3
Void fraction: 0.45



REACTOR VOLUME MEMO 2
Catalyst weight was calculated to be 74.473kgcat
Effect of Catalyst Mass on Conversion at Various Temperatures
MOMENTUM BALANCE- MEMO 3
Multi-tubular, 1in. Diameter, Length varies from 1 meter to 1.3 meter
d (meter) # tubes Ac G o length (m) P% P
0.0254 22611.44 11.457 2.380195 18420.58 1.3 11.6 2.54E+04
0.0254 22786.72 11.546 2.361885 18155.67 1.29 11.3 2.48E+04
0.0254 22964.74 11.636 2.343576 17892.67 1.28 11.0 2.42E+04
0.0254 23145.57 11.728 2.325267 17631.57 1.27 10.8 2.37E+04
0.0254 23329.26 11.821 2.306958 17372.39 1.26 10.5 2.31E+04
0.0254 23515.90 11.915 2.288649 17115.12 1.25 10.3 2.26E+04
0.0254 23705.54 12.011 2.270339 16859.76 1.24 10.0 2.20E+04
0.0254 23898.27 12.109 2.25203 16606.31 1.23 9.76 2.15E+04
0.0254 24495.72 12.412 2.197103 15857.42 1.2 9.06 1.99E+04
0.0254 26722.61 13.540 2.014011 13485.29 1.1 6.99 1.54E+04
0.0254 29394.87 14.894 1.830919 11304.2 1 5.28 1.16E+04
Memo 3 Table: Number of Tubes and Pressure Drop for 1 Tubes with Varying Length

MOMENTUM BALANCE- MEMO 3
D
p
= 0.005m D
p
= 0.01m
length (m) P% P P% P
1.3 11.6 2.54E+04 5.24 1.15E+04
1.29 11.3 2.48E+04 5.12 1.13E+04
1.28 11.0 2.42E+04 5.00 1.10E+04
1.27 10.8 2.37E+04 4.89 1.08E+04
1.26 10.5 2.31E+04 4.77 1.05E+04
1.25 10.3 2.26E+04 4.66 1.03E+04
1.24 10.0 2.20E+04 4.55 1.00E+04
1.23 9.76 2.15E+04 4.44 9767.093
1.2 9.06 1.99E+04 4.12 9070.774
1.1 6.99 1.54E+04 3.18 6998.261
1 5.28 1.16E+04 2.40 5277.399
Pressure Drop vs. Reactor Length for D
p
= 0.005m
Pressure Drop vs. Reactor Length for D
p
= 0.01m
Effects of doubling particle
diameter
MULTIPLE REACTIONS- MEMO 4
Assumptions
Isothermal reactor at 623K
Target conversion: 90%
Particle diameter: 0.005m
Bulk density: 1,000 kgcat/m
3
Inlet pressure: 2.2 bar
Void Fraction 0.4

Reactions
(1) C
4
H
8
+ 3 O
2
C
4
H
2
O
3
+ 3 H
2
O
(2) C
4
H
8
+ 6 O
2
4 CO
2
+ 4 H
2
O
(3) C
4
H
8
+ O
2
2 C
2
H
4
O
(4) C
4
H
8
+ O
2
C
4
H
6
O + H
2
O



http://www.bartek.ca/images/chemical.jpg
MULTIPLE REACTIONS- MEMO 4
Reaction constants were found through a
linearization of the ln(K) vs 1/T
Sample Plot of Temperature Dependent K
MULTIPLE REACTIONS- MEMO 4
Species Molar Flows vs. Catalyst Weight
MULTIPLE REACTIONS- MEMO 4
Selectivity
Temperature
o
C Selectivity, S
MA

350 0.04574
330 0.03471
290 0.03482
ENERGY BALANCE- MEMO 5
New assumptions
Inlet temperature: 563 K
Target conversion: 90%
3

Inlet Pressure = 220,000Pa
15

Bulk density = 1000 kgcat/ m
3
rxtr
15

D
p
= 5x10
-3
m
= 0.45
U = 0.227 kJ/ m
2
-s-K
Coolant temperature: 558 K

E.B. used to locate and control reactor hotspot

ENERGY BALANCE- MEMO 5
Constant Feed Temperature of 563K with Varying Coolant Temperatures
Coolant Temperature (K) Selectivity, S
MA

543 0.04004
553 0.04138
563 0.05352
573 0.03831
583 0.03716
ENERGY BALANCE- MEMO 5
Inlet Temperature (K) Selectivity, S
MA

543 0.05305
553 0.05324
563 0.05352
573 0.05398
583 0.05506
Constant Coolant Temperature of 563K with Varying Inlet Temperatures
ENERGY BALANCE- MEMO 5


Aspen Stream Table

INLET OUTLET
Species Flow (kmol/s)
1-butene 0.136882 0.0119
Oxygen 1.77303 1.315
Nitrogen 6.64197 6.642
Maleic Anhydride 0 0.01739
Water 0 0.3051
Carbon Dioxide 0 0.2383
Acetaldehyde 0 0.06663
Methyl Vinyl Ketone 0 0.01471
Pressure (N/m
2
) 220000 202732
Reactor Configuration:
Tubes = 335,867
Catalyst Weight = 792,000 kgcat
Tube Length = 4.481803m




REACTOR SIMULATIONS
Memo 2 Memo 3 Memo 4 Memo 5
Single Tube Multi- tube
Reactor Volume (m
3
) 0.074473 14.8946 14.8946 5.03 792
Catalyst Weight (kgcat) 74.473 14894.6 14894.6 5030 792,000
Inlet Flows
1-butene (kmol/s) 0.0149 0.0149 0.0149 0.149 0.136882
Oxygen (kmol/s) 0.193 0.193 0.193 0.193 1.77303
Maleic Anhydride (kmol/s) 0 0 0 0 0
Carbon Dioxide (kmol/s) N/A N/A N/A 0 0
Acetaldehyde (kmol/s) N/A N/A N/A 0 0
Methyl Vinyl Ketone (kmol/s) N/A N/A N/A 0 0
Outlet Flows
1-butene (kmol/s) 0.00149 0.001583 0.001669 0.001488 0.013683
Oxygen (kmol/s) 0.15277 0.15305 0.03969 0.1502 1.3284
Maleic Anhydride (kmol/s) 0.01341 0.01332 0.01323 0.001469 0.01731
Carbon Dioxide (kmol/s) N/A N/A N/A 0.021165 0.22945
Acetaldehyde (kmol/s) N/A N/A N/A 0.008581 0.06733
Methyl Vinyl Ketone (kmol/s) N/A N/A N/A 0.0023614 0.01486
Pressure (Pa) 220,000 220,000 220,000 220,000 220,000
Inlet Temperature (K) 673.15 673.15 673.15 623 563
Maximum Temperature (K) 673.15 673.15 673.15 623 566.08
Coolant Temperature (K) N/A N/A N/A N/A 558
Length (m) N/A 1 1.24 0.400275 4.481803
Diameter (m) N/A 4.35 0.0254 0.0258826 0.0258826
Number of Tubes 1 1 23,706 23,884 335,867
Pressure Drop (%) N/A 5.3 10 0.18 7.97
Hotspot Location (m) N/A N/A N/A N/A 0.3924
Gain N/A N/A N/A N/A 1.73
Conversion of 1-butene 90% 89.40% 88.80% 90% 90%
OPTIMIZED REACTOR
An inlet temperature of 563K, a coolant
temperature of 558K and an inlet pressure 2.4 bar
produce a gain under two.




Other conditions gave a thermodynamically
unstable reactor. With these conditions the reactor
volume and catalyst weight were changed to give a
90% conversion and optimal selectivity of maleic
anhydride.
Coolant
temperature
(K)
Inlet
Temperature
(K)
Hotspot
Temperature
(K) Gain
559 563 568.593818 1.935906
558 563 566.657912
557 563 564.86977 1.788142
OPTIMIZED REACTOR
Optimized Reactor
Reactor Volume (m
3
) 723.4
Catalyst Weight (kgcat) 723400
Inlet Flows
1-butene (kmol/s) 0.136882
Oxygen (kmol/s) 1.77303
Maleic Anhydride (kmol/s) 0
Carbon Dioxide (kmol/s) 0
Acetaldehyde (kmol/s) 0
Methyl Vinyl Ketone (kmol/s) 0
Outlet Flows
1-butene (kmol/s) 0.011874
Oxygen (kmol/s) 1.328376
Maleic Anhydride (kmol/s) 0.172473
Carbon Dioxide (kmol/s) 0.228121
Acetaldehyde (kmol/s) 0.07038
Methyl Vinyl Ketone (kmol/s) 0.015541
Pressure (Pa) 240,000
Inlet Temperature (K) 563
Maximum Temperature (K) 566.65
Coolant Temperature (K) 558
Length (m) 4.09
Diameter (m) 0.025883
Number of Tubes 335,900
Pressure Drop (%) 6.05%
Hotspot Location (m) 0.3275
Gain 2
Conversion of 1-butene 0.9
F1
REACTOR1
REACTOR2
F2
SPLITER
MIXER
O2
O1
INLET
OUTLET
REACTOR3
F3
O3
REACTOR4
F4
O4
CONCLUSIONS
Overall the selectivity from the reaction scheme is
not optimal for producing maleic anhydride
When the reaction temperature is above 563K the
reaction becomes a runaway
The reactor is too large to be cost effective
After 1983 nothing was published because it was
found that butane was a better feedstock

REFERENCES
1
Cavani, F., Trifiro, F.; Oxidation of 1-Butene and
Butadiene to Maleic Anhydride. Industrial
Engineering Chemical Product Research and
Development. 1983. Vol 22. No. 4, 570-577

2
Varma, R. L.; Saraf, D. N.; Journal of Catalysis;
[online] 1978, 55, 351-272