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 polymers 2
Anti-microbial behavior
Biocide in oil well to suppress the growth of bacteria2
100-500 million pounds produced in the U.S. in 2002 2

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 limits 4

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

Species

Feed Rate to Reactor

(kgmol/s)

Change in Reactor
(kgmol/s)

Effluent Rate
(kgmol/s)

Propylene, C3H6

0.05190

-0.04412

0.00779

Oxygen, O2

0.57090

-0.04412

0.52679

Nitrogen, N2

2.14768

2.14768

Acrolein, C3H4O

0.04412

0.04412

Water, H2O (v)

0.04412

0.04412

Total

2.77048

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 atm 6

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 reactors 8

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

V = 8,643 m3

* Pressure drop decreases conversion

C3 H 6 + O 2
H2 O

C2 H4 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

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

r1C

k a c 1B/ 2

r2 H

k a k AC c 1B/ 2 c A
c A n AC k AC n AH k AH n AI k AI n AF k AF

k a c 1B/ 2

k a k AH c 1B/ 2 c A
c A n AC k AC n AH k AH n AI k AI n AF k AF

Symbol
A
B
C
D
E

r3 I

1/ 2
a B

k c

r4 F

k a k AI c 1B/ 2 c A
c A n AC k AC n AH k AH n AI k AI n AF k AF

k a c 1B/ 2

k a k AF c 1B/ 2 c A
c A n AC k AC n AH k AH n AI k AI n AF k AF

F
G
H
I

Species
Propylene
Oxygen
Acrolein
Water
Carbon
Oxides
Acetaldehy
de
Nitrogen
Carbon
Dioxide
Carbon
Monoxide

Chemical
Formula
C3H6
O2
C3H4O
H2O
COx
C2H4O
N2
CO2
CO

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

Temperature
(K)

Acrolein Outlet
Flow (kmol/s)

Carbon Oxides
and
Acetaldehyde
Total
Outlet Flow
(kmol/s)

623

0.04412

0.05937

0.74

633

0.04949

0.05438

0.91

643

0.05401

0.04922

1.10

653

0.05760

0.04430

1.30

663

0.06032

0.03991

1.51

673

0.06227

0.03621

1.72

Acrolein
Selectivity

*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
m

Fj c pj

j 1

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

Coolant
Temperature (K)

Polymath Model
Hotspot
Temperature (K)

Aspen Plus Model

Hotspot
Temperature (K)

658.15

674.12

674.11

659.15

675.24

675.24

GAIN

1.12

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 K 6

10

Feed
Condition
s

Catalyst

Specification

Value

Temperature
Pressure

663.15 K
3 atm

Propylene:Oxygen Ratio

1:11

Propylene Conversion
Bed Voidage

85%
40%

Particle Diameter

5 mm

Bulk Density

1698 kg/m
185047.25
kg
108.98 m3

Bed Weight
Bed Volume
Length
Overall Reactor
Diameter
Tube Diameter
Reactor

FEED

B1

2.40 m
7.60 m
0.0259 m

Number of Tubes
Heat Transfer
Coefficient
Coolant Temperature

86,304
227 W/m2-K

Pressure Drop

9.54%

658.15 K

PRODUCT

Species

Annual Production (Metric

Tons)

Propylene, C3H6

12,363

Oxygen, O2

613,288

Nitrogen, N2

2,269,470

Acrolein, C3H4O

75,008

Water, H2O

36,226

Acetaldehyde, C2H4O

6,783

Carbon Dioxide, CO2

25,779

Carbon Monoxide, CO

2,421

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).
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.
6Dr. Concetta LaMarca
7Reaction Technology. Kirk-Othmer Encyclopedia of Chemical Technology. 4th Edition.
8Perry, Robert. Perry's Chemical Engineers' Handbook. 7th. New York: McGraw-Hill, 1997.
9H.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.
10Cerac Incorporated. MSDS Search 25 March 1994. Accessed: 8 April 2008.
<http://asp.cerac.com/CatalogNet/default.aspx?p=msdsFile&msds=m000443.htm>