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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 acids
1


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 bacteria
2


100-500 million pounds produced in the U.S. in 2002
2


CH
2
=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 C
1


Gaseous products leave and are quenched by cold water, then
enter absorption column for product recovery
3

CH
2
=CH-CH
3
+ O
2
CH
2
=CH-CHO + H
2
O
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 atm
5


Negligible kinetic and potential energy losses

Isothermal, T=623.15 K
5

Species
Feed Rate to Reactor
(kgmol/s)
Change in Reactor
(kgmol/s)
Effluent Rate
(kgmol/s)
Propylene, C
3
H
6
0.05190 -0.04412 0.00779
Oxygen, O
2
0.57090 -0.04412 0.52679
Nitrogen, N
2
2.14768 0 2.14768
Acrolein, C
3
H
4
O 0 0.04412 0.04412
Water, H
2
O (v) 0 0.04412 0.04412
Total 2.77048 0 2.77048
Material balance for annual production rate of 75,000 metric tons
*Design specification for acrolein production rate is 0.04412 kmol/s
CH
2
=CH-CH
3
+ O
2
CH
2
=CH-CHO + H
2
O
All Design 1 assumptions

A conversion of 0.85 will be achieved
3


1000 kg/m
3
is Catalyst bulk density
6

Reactor is at steady state

Ideal gas law applies

Simple kinetics
6

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
P
P
r
W
F
=
c
c
2 / 1
2
O P A
C C k r =
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 m
3
All Design 2 assumptions Inlet pressure is 3 atm
6


Catalyst void fraction of 0.4
6


Particle diameter of 5 mm
7


Inlet viscosity is that of pure steam
4


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
0
0 0
1
T
T
C C
F
F
T
T
P
P
A dW
dP

=
|
|
( ) ( )
(
(

+

= G
D D
G
p p
75 . 1
1 150 1
3
0
0
|
|
|
|
V

= 8,643 m
3
* Pressure drop decreases conversion
Reactions are carried out in
a catalytic FBR with
temperatures ranging
between 350-390C

Acrolein is desired product

Major by-products
9

Water
CO and CO
2

Acetadehyde

O H CO O H C
2 2 2 6 3
3 3 5 . 4 + +
O H CO O H C
2 2 6 3
3 3 3 + +
O H C O H C
4 2 2 6 3
6 3 4 +
C
3
H
6
+ O
2
C
2
H
4
O + H
2
O

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

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

( )
AF AF AI AI AH AH AC AC A B a
A B AI a
I
k n k n k n k n c c k
c c k k
r
+ + + +
=
2 / 1
2 / 1
3

( )
AF AF AI AI AH AH AC AC A B a
A B AF a
F
k n k n k n k n c c k
c c k k
r
+ + + +
=
2 / 1
2 / 1
4
Symbol Species
Chemical
Formula
A Propylene C
3
H
6

B Oxygen O
2

C Acrolein C
3
H
4
O
D Water H
2
O
E Carbon Oxides CO
x

F Acetaldehyde C
2
H
4
O
G Nitrogen N
2

H
Carbon
Dioxide
CO
2

I
Carbon
Monoxide
CO
All Design 3 assumptions 2830 kg/m
3
is catalyst particle
density
10

Tan et al. reaction kinetics representative
9


CO
2
reaction rate independent of temperature
Modified the reactor to include multiple reactions
Used approved reaction kinetics to calculate species flow rates

V

= 287.5 m
3
Temperature (K)
Acrolein Outlet
Flow (kmol/s)
Carbon Oxides and
Acetaldehyde Total
Outlet Flow (kmol/s)
Acrolein Selectivity
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

I H F
C
FHI C
F F F
F
S
+ +
=
/
~
*Selectivity of acrolein increases with temperature

All Design 4 assumptions

227 W/m
2
-K is heat transfer coefficient
6

Heat capacities are constant

Heats of reactions are constant

Coolant temperature is constant at 618.15 K
6


( ) ( ) | |
( ) | |
j
p j
m
j
Rxij ij
n
i
a
bulk
c F
H r T T
Ua
dW
dT
1
1
=
=
E
A E +
=

An energy balance across the reactor was introduced to further validate
the model as a suitable representation of the actual reactor
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 m
3
Gain measures the dynamic stability of the reactor

A Gain< 2 is desired
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
coolant
HS
T
T
Gain
A
A
=
The catalyst void fraction is 0.4
6


Catalyst bulk density is 1698 kg/m
3
for -Bi
2
Mo
3
O
12

10

The inlet pressure is 3 atm
6


The inlet temperature is 663.15 K
9


The coolant temperature is constant at 658.15 K
6


FEED
PRODUCT
B1
Specification Value
Feed
Conditions
Temperature 663.15 K
Pressure 3 atm
Propylene:Oxygen Ratio 1:11
Propylene Conversion 85%
Catalyst
Bed Voidage 40%
Particle Diameter 5 mm
Bulk Density 1698 kg/m
3

Bed Weight 185047.25 kg
Bed Volume 108.98 m
3

Reactor
Length 2.40 m
Overall Reactor Diameter 7.60 m
Tube Diameter 0.0259 m
Number of Tubes 86,304
Heat Transfer Coefficient 227 W/m
2
-K
Coolant Temperature 658.15 K
Pressure Drop 9.54%
660
662
664
666
668
670
672
674
676
0 0.4 0.8 1.2 1.6 2 2.4
T
e
m
p
e
r
a
t
u
r
e

(
K
)

Reactor Length (m)
Species Annual Production (Metric Tons)
Propylene, C
3
H
6
12,363
Oxygen, O
2
613,288
Nitrogen, N
2
2,269,470
Acrolein, C
3
H
4
O 75,008
Water, H
2
O 36,226
Acetaldehyde, C
2
H
4
O 6,783
Carbon Dioxide, CO
2
25,779
Carbon Monoxide, CO 2,421

1
John J. McKetta. Acrolein and Derivatives Encyclopedia of Chemical Processing and Design.

2
Toxicological Profile for Acrolein, U.S. Department of Health and Human Service, Agency for Toxic
Substance and Disease Registry (August 2007).

3
Acrylic Acid and Derivatives. Kirk-Othmer Encyclopedia of Chemical Technology. 4
th
Edition.

4
Chemical Database Property Constants. DIPPR Database [Online]. Available from Rowan Hall 3
rd
Floor
Computer Lab. (Accessed on 1/26/08).

5
L. D. Krenzke and G. W. Keulks, The Catalytic Oxidation of Propylene: VIII. An Investigation of the
Kinetics over Bi
2
Mo
3
O
12
,

Bi
2
MoO
6
, and Bi
3
FeMo
2
O
12
. The Journal of Catalysis Volume 64 (1980) p. 295-
302.

6
Dr. Concetta LaMarca

7
Reaction Technology. Kirk-Othmer Encyclopedia of Chemical Technology. 4
th
Edition.

8
Perry, Robert. Perry's Chemical Engineers' Handbook. 7th. New York: McGraw-Hill, 1997.

9
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.

10
Cerac Incorporated. MSDS Search 25 March 1994. Accessed: 8 April 2008.
<http://asp.cerac.com/CatalogNet/default.aspx?p=msdsFile&msds=m000443.htm>