Team #2: Kyle Lynch David Teicher Shu Xu

The Partial Oxidation of Propylene to Generate Acrolein

Project Objective Process Background Material Balance Simple Kinetics and Rate Expressions Pressure Drop and Reactor Configuration Multiple Reactions Energy Balance Optimization and Conclusions

Design a Fixed Bed Reactor (FBR) for the production of acrolein by the partial oxidation of propylene Produce 75,000 metric tons acrolein per year Optimize the reactor design to minimize cost

Literature Review Research information on raw materials and products Investigate catalysts and reaction kinetics

Reactor Design Develop mole balances for multiple reactions Implement pressure drop & energy balance equations Optimize reactor

Acrolein Raw material used for the production of pyridine, -picoline, and some essential amino acids1 Used for cleaning irrigation ditches, and other derivatives can be made into rubbers, glues, and polymers2 Anti-microbial behavior Biocide in oil well to suppress the growth of bacteria2 100-500 million pounds produced in the U.S. in 20022

CH2=CH-CHO

Industry produces acrolein by the partial oxidation of propylene using oxygen and steam The reaction is carried out in a catalytic FBR ranging between 350-450 C1 Gaseous products leave and are quenched by cold water, then enter absorption column for product recovery3

CH2=CH-CH3 + O2

CH2=CH-CHO + H2O

Design 1-Preliminary mass and energy balance Design 2-Reactor volume using simple reaction rate expression Design 3-Pressure drop and reactor configuration Design 4-Multiple reactions Design 5-Energy balance on multiple reactions Final Design-Optimization

A total of two weeks each year are allotted for scheduled shutdowns All reactants and products are vapors Air is used as an oxygen source A 1:11 ratio of propylene:oxygen is outside the flammability limits4 The inlet pressure is 1 atm5 Negligible kinetic and potential energy losses Isothermal, T=623.15 K5

 Material balance for annual production rate of 75,000 metric tons CH =CH-CH + O CH =CH-CHO + H O
2 3 2 2 2

Species

Feed Rate to Reactor (kgmol/s)

Change in Reactor (kgmol/s)

Effluent Rate (kgmol/s)

Propylene, C3H6 Oxygen, O2 Nitrogen, N2 Acrolein, C3H4O Water, H2O (v) Total

0.05190 0.57090 2.14768 0 0 2.77048

-0.04412 -0.04412 0 0.04412 0.04412 0

0.00779 0.52679 2.14768 0.04412 0.04412 2.77048

*Design specification for acrolein production rate is 0.04412 kmol/s

All Design 1 assumptions A conversion of 0.85 will be achieved3 1000 kg/m3 is Catalyst bulk density6 Reactor is at steady state Ideal gas law applies Simple kinetics6

To simulate the FBR being designed, a Polymath model was developed. The Polymath reactor was created as a function of catalyst weight Aspen Plus used to examine the relationships between temperature, reactor volume, and conversion

FP = rP W

rA = k C P C

1/ 2 O2

Developed an isothermal reactor model as function of catalyst weight using Polymath and ASPEN

* Higher temperatures require smaller reactors for same conversion V = 167,000 m3

All Design 2 assumptions Inlet pressure is 3 atm6 Catalyst void fraction of 0.46 Particle diameter of 5 mm7 Inlet viscosity is that of pure steam4 Schedule 40 pipe used for multi-tube reactors8

Implemented Ergun pressure drop equation into design Optimized reactor so pressure drop is less than 10%
0 P T F dP = 0 T dW AC (1 ) C P T0 FT0

G (1 ) 0 = 0 D p 3

150 (1 ) + 1.75G Dp

V = 8,643 m3

* Pressure drop decreases conversion

Reactions are carried out in a catalytic FBR with temperatures ranging between 350-390C Acrolein is desired product Major by-products9 Water CO and CO2 Acetadehyde

C3H6+ O2 C2H4O + H2 O C 3 H 6 + 3O2 3CO + 3H 2 O

4C 3 H 6 + 3O2 6C 2 H 4 O
C 3 H 6 + 4.5O2 3CO2 + 3H 2 O

Symbol
r1C = k a c1 / 2 B k a k AC c1/ 2 c A B + c A ( n AC k AC + n AH k AH + n AI k AI + n AF k AF )
k a k AH c 1/ 2c A B + c A ( n AC k AC + n AH k AH + n AI k AI + n AF k AF )

Species Propylene Oxygen Acrolein Water Carbon Oxides Acetaldehyd e Nitrogen Carbon Dioxide Carbon Monoxide

A B C D E

Chemical Formula C3H6 O2 C3H4O H2O COx C2H4O N2 CO2 CO

r2H =

k a c1 / 2 B

r3 I =

k a c 1/ 2 B

k a k AI c 1 / 2 c A B + c A ( n AC k AC + n AH k AH + n AI k AI + n AF k AF )
k a k AF c1 / 2 c A B + c A ( n AC k AC + n AH k AH + n AI k AI + n AF k AF )

F G H I

r4 F =

k a c1 / 2 B

All Design 3 assumptions 2830 kg/m3 is catalyst particle density10 Tan et al. reaction kinetics representative9 CO2 reaction rate independent of temperature

Modified the reactor to include multiple reactions Used approved reaction kinetics to calculate species flow rates

V = 287.5 m3

C / FHI

FC FF + FH + FI
Carbon Oxides and Acetaldehyde Total Outlet Flow (kmol/s) Acrolein Selectivity

Temperature (K) Acrolein Outlet Flow (kmol/s)

623 633 643 653 663 673

0.04412 0.04949 0.05401 0.05760 0.06032 0.06227

0.05937 0.05438 0.04922 0.04430 0.03991 0.03621

0.74 0.91 1.10 1.30 1.51 1.72

*Selectivity of acrolein increases with temperature

All Design 4 assumptions 227 W/m2-K is heat transfer coefficient6 Heat capacities are constant Heats of reactions are constant Coolant temperature is constant at 618.15 K6

An energy balance across the reactor was introduced to further validate the model as a suitable representation of the actual reactor

dT = dW

n Ua ( Ta T ) + i1 rij ( H Rxij ) = bulk

j =1

F j c pj

[ ( )]

Incorporated energy balance into reactor design Compared isothermal reactor and reactor with constant coolant temperature
The Effect of Coolant Temperature on Temperature Profile

*Coolant temperature effects severity of hotspot V = 281.3 m3

Gain measures the dynamic stability of the reactor A Gain< 2 is desired

THS Gain = Tcoolant

Polymath Model Hotspot Temperature (K) Aspen Plus Model Hotspot Temperature (K)

Coolant Temperature (K)

658.15 659.15 GAIN

674.12 675.24 1.12

674.11 675.24 1.13

The catalyst void fraction is 0.46 Catalyst bulk density is 1698 kg/m3 for -Bi2Mo3O12 The inlet pressure is 3 atm6 The inlet temperature is 663.15 K9 The coolant temperature is constant at 658.15 K6
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Specification Value Feed Temperature 663.15 K Conditions Pressure 3 atm Propylene:Oxygen Ratio 1:11 Propylene Conversion 85% Catalyst Bed Voidage 40% Particle Diameter 5 mm Bulk Density 1698 kg/m3 Bed Weight 185047.25 kg Bed Volume Length Overall Reactor Diameter 108.98 m3 2.40 m 7.60 m

FEED

B1

Reactor

PRODUCT

Tube Diameter 0.0259 m Number of Tubes 86,304 Heat Transfer Coefficient 227 W/m2-K Coolant Temperature Pressure Drop 658.15 K 9.54%

Species

Annual Production (Metric Tons)

Propylene, C3H6 Oxygen, O2 Nitrogen, N2 Acrolein, C3H4O Water, H2O Acetaldehyde, C2H4O Carbon Dioxide, CO2 Carbon Monoxide, CO

12,363 613,288 2,269,470 75,008 36,226 6,783 25,779 2,421

1 2

John J. McKetta. Acrolein and Derivatives Encyclopedia of Chemical Processing and Design.

Toxicological Profile for Acrolein, U.S. Department of Health and Human Service, Agency for Toxic Substance and Disease Registry (August 2007).
3 4

Acrylic Acid and Derivatives. Kirk-Othmer Encyclopedia of Chemical Technology. 4th Edition.

Chemical Database Property Constants. DIPPR Database [Online]. Available from Rowan Hall 3rd Floor Computer Lab. (Accessed on 1/26/08). L. D. Krenzke and G. W. Keulks, The Catalytic Oxidation of Propylene: VIII. An Investigation of the Kinetics over Bi2Mo3O12, Bi2MoO6, and Bi3FeMo2O12. The Journal of Catalysis Volume 64 (1980) p. 295302.
5 6 7 8 9

Dr. Concetta LaMarca Reaction Technology. Kirk-Othmer Encyclopedia of Chemical Technology. 4th Edition. Perry, Robert. Perry's Chemical Engineers' Handbook. 7th. New York: McGraw-Hill, 1997.

H.S. Tan, J. Downie, and D.W. Bacon, The Reaction Network for the Oxidation of Propylene Over a Bismuth Molybdate Catalyst, The Canadian Journal of Chemical Engineering Volume 67 (1989) p. 412-417. Cerac Incorporated. MSDS Search 25 March 1994. Accessed: 8 April 2008. <http://asp.cerac.com/CatalogNet/default.aspx?p=msdsFile&msds=m000443.htm>
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