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.
dP o Po T FT

dW Ac (1 ) c P T o FTo
where
G (1 ) 150(1 )
o 3
1.75G
o D p Dp

Pressure drop cannot exceed 10% of initial pressure.

P 0.1Po
REACTION MECHANISM

1-butene to maleic anhydride

(1) C4H8 + 3 O2 C4H2O3 + 3 H2O

(2) C4H8 + 6 O2 4 CO2 + 4 H2O

(3) C4H8 + O 2 2 C2H 4O

(4) C4H8 + O 2 C 4 H6 O + H 2 O
KINETICS

Preliminary Reaction Kinetics (1 Reaction)

rm = k 1 * pB

where pB is partial pressure of 1-butene and

k1 = 3.8075x 105 *exp(-11569/T) [=] kmol/ kgcat-bar-s
KINETICS
Kinetics for Multiple Reactions from
Literature1
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, FBT0 is the initial flow of

1-butene and FBT 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:

FMA
Selectivity
FCO2 FC 2 H 4 O FC 4 H 6 O
ENERGY BALANCE
n

dT r * Hi rxn i q
i 1
n
dW
F
i 1
io * Cpi

where
0.227 * 4
q Ta T [=] kJ/ kgcat-s
0.0258826 *1000

o This accounts for non- isothermal behavior in the

reactor and allows for the optimization of the
reactor temperature.
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.

THotspot
Gain
Tinlet

A gain less than two indicates a thermodynamically

stable reactor.
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 catalyst2

Inlet pressure of 2.2 bar

Reactor at 400oC

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
Memo 3 Table: Number of Tubes and Pressure Drop for 1 Tubes with Varying Length
Multi-tubular, 1in. Diameter, Length varies from 1 meter to 1.3 meter
d (meter) # tubes Ac G o length (m) P% P
2.3801 18420.5 2.54E+0
0.0254 22611.44 11.457 95 8 1.3 11.6 4
2.3618 18155.6 2.48E+0
0.0254 22786.72 11.546 85 7 1.29 11.3 4
2.3435 17892.6 2.42E+0
0.0254 22964.74 11.636 76 7 1.28 11.0 4
2.3252 17631.5 2.37E+0
0.0254 23145.57 11.728 67 7 1.27 10.8 4
2.3069 17372.3 2.31E+0
0.0254 23329.26 11.821 58 9 1.26 10.5 4
2.2886 17115.1 2.26E+0
0.0254 23515.90 11.915 49 2 1.25 10.3 4
2.2703 16859.7 2.20E+0
0.0254 23705.54 12.011 39 6 1.24 10.0 4
2.2520 16606.3 2.15E+0
0.0254 23898.27 12.109 3 1 1.23 9.76 4
2.1971 15857.4 1.99E+0
0.0254 24495.72 12.412 03 2 1.2 9.06 4
2.0140 13485.2 1.54E+0
0.0254 26722.61 13.540 11 9 1.1 6.99 4
1.8309 1.16E+0
0.0254 29394.87 14.894 19 11304.2 1 5.28 4
MOMENTUM BALANCE- MEMO 3
Effects of doubling particle
diameter

Pressure Drop vs. Reactor Length for Dp = 0.005m

Pressure Drop vs. Reactor Length for Dp = 0.01m

MULTIPLE REACTIONS- MEMO 4
Assumptions
Isothermal reactor at 623K
Target conversion: 90%
Particle diameter: 0.005m
Bulk density: 1,000 kgcat/m3
Inlet pressure: 2.2 bar
Void Fraction 0.4
http://www.bartek.ca/images/chemical.jpg

Reactions
(1) C4H8 + 3 O2 C 4H2O3 + 3 H 2O
(2) C4H8 + 6 O2 4 CO2 + 4 H2O
(3) C4H8 + O2 2 C2H4O
(4) C4H8 + O2 C4H6O + H2O
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 Selectivity,
o
C SMA
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 = 220,000Pa15
Bulk density = 1000 kgcat/ m3rxtr15
Dp = 5x10-3 m
= 0.45
U = 0.227 kJ/ m2-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 Selectivity,
Temperature (K) SMA
543 0.04004
553 0.04138
563 0.05352
573 0.03831
583 0.03716
ENERGY BALANCE- MEMO 5
Constant Coolant Temperature of 563K with Varying Inlet Temperatures

Inlet
Temperature Selectivity,
(K) SMA
543 0.05305
553 0.05324
563 0.05352
573 0.05398
583 0.05506
ENERGY BALANCE- MEMO 5

Aspen Stream Table

INLET
OUTLE
T
Reactor Configuration:
Species Flow Tubes = 335,867
(kmol/s) Catalyst Weight = 792,000 kgcat
0.13688
1-butene 2 0.0119 Tube Length = 4.481803m
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/m2) 220000 202732
REACTOR SIMULATIONS
Memo 2 Memo 3 Memo 4 Memo 5
Single Tube Multi- tube
Reactor Volume (m3) 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.
Coolant Inlet Hotspot
temperatur Temperatur Temperature
e (K) e (K) (K) Gain
1.9359
559 563 568.593818 06
558 563 566.657912
1.7881
557 563 564.86977 42

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.
 OPTIMIZED REACTOR
Optimized Reactor
Reactor Volume (m3) 723.4
Catalyst Weight (kgcat) 723400
Inlet Flows REACTOR1

1-butene (kmol/s) 0.136882

Oxygen (kmol/s) 1.77303
Maleic Anhydride (kmol/s) 0 O1

Carbon Dioxide (kmol/s) 0 F1

REACTOR2

Acetaldehyde (kmol/s) 0
Methyl Vinyl Ketone (kmol/s) 0 F2 MIXER
Outlet Flows SPLITER OUTLET

1-butene (kmol/s) 0.011874 INLET

O2

F3
Oxygen (kmol/s) 1.328376 REACTOR3

Maleic Anhydride (kmol/s) 0.172473

Carbon Dioxide (kmol/s) 0.228121
Acetaldehyde (kmol/s) 0.07038 O4
F4
Methyl Vinyl Ketone (kmol/s) 0.015541 O3
REACTOR4

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
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