Advanced Chemical Reaction Engineering-CHE5123 Sundar Madihally, PhD

Page 4.1

Chapter 4. Multiple Reactors and Reactions
4.1. The Stoichiometric Table in Conversion:
- (Also referred as mole balance table) allows to derive expressions for each species
conversion in terms of overall reaction progression.
- can be used for only one reaction, or when there are multiple reactions in series. When
reactions are in parallel, things may get a little harder.
- Procedure to write the Stoichiometric table:
(1) Choose one species to be the basis for conversion (e.g. X
A
)
(2) List all species present (including solvents, by-products, inerts etc.)
(3) List initial amount of each species.
(4) List change of each species, in terms of X
A
.
(5) List remaining amount of each species.

4.2. Expressing Rate of Reaction in Conversion.
1. Write concentration terms in molar flow rate or molar quantities and volumetric flow rates
or volume of the reactor.
2. Substitute conversion expressions from the stoichiometric table for each molar quantity.
3. For constant volume scenario (liquid phase and constant volume batch reactor), there is no
change in volume expressions
4. For change in volume, one has to develop expressions relating conversion to volume
change (will be dealt with later in the course)

4.3. Variable Volume of Streams:
- For gas-phase reactions, the volume changes with mole change.
- For gas-phase flow systems (e.g. CSTR, PFR), pressure is generally dictated by pressure
drop or isobaric operating conditions.
- In closed systems (e.g. Batch), V
R
could change to maintain constant P (i.e. moving piston)
- V
R
or v appear in rate law. (i.e. C
A
= F
A
/v or N
A
/V
R
),
- F
A
or N
A
from stoichiometric table but v or V
R
from where? We need an Equation of State
to relate Volume as a function of Temperature, Pressure and change in number of moles.
Equation of state (assume Z=1):
0 0 0 0
RT F
RT F
v P
Pv
T
T
=
Rearranging
P
P
T
T
F
F
v v
T
T 0
0 0
0
= (For a batch system
P
P
T
T
N
N
V V
T
T
R R
0
0 0
0
= )
Substitute this v expression into the rate law as well as the design equation and then solve.

Example 4.1. The following elementary gas phase reaction occurs in a CSTR.
A + 3B C + 2D with k= 0.5 L
3
mol
-3
min
-1

Feed containing 10 moles of A, 30 moles of B, 8 mole of inerts and 2 moles of D enters the
reactor at 50 moles/min. The volumetric flow rate is 40 L/min. What size reactor is required to
obtain 50% conversion?

Example 4.2. The manufacture of sulphuric acid required sulphur trioxide. In this process,
sulphur is first burned with air to produce sulphur dioxide. The sulphur dioxide is then oxidized
in a catalytic reactor to produce sulphur trioxide. The gas from a sulphur burner consists of 8
Advanced Chemical Reaction Engineering-CHE5123 Sundar Madihally, PhD

Page 4.2

SO
2
%, 11% O
2
, and 81% N
2
(all mol %). This gaseous mixture is passed to a catalytic reactor
where SO
2
is oxidized to SO
3
. The reactor exit temperature is 500C and the pressure is 1 bar.
The equilibrium constant at 500C is 85 and the fugacity coefficients are one. The reaction is
2 2 3
1

2
SO O SO +
Calculate the reactor exit conversion if equilibrium is established. If the reaction is carried out in
a PFR, what is the minimum volume required to achieve equilibrium conversion. If only 80% of
equilibrium conversion is required, how much volume is minimized?

Example 4.3. The vapor phase dehydration of ethanol over an ion exchange resin has been
studied. The rate of ethanol dehydration to diethyl ether at temperatures of 110 to 135C is
given by the following rate function
( )
( )
2 5 2 5 2 2 5
2
2 5 2 5 2 2
2 2
1
2
1
mol

s. g cat
1
s C H OH C H OH H O C H OH
A
C H OH C H OH H O H O
k K P P P
K
r
K P K P
| |

|
\ .
=
+ +

The constants are
8
12424 mol
1.5 10 exp
s. g cat
s
k
T
| |
=
|
\ .

2 5
7 -1
4741
2.0 10 exp kPa
C H OH
K
T

| |
=
|
\ .

1
1842
0.25exp K
T
| |
=
|
\ .

2
9 -1
7060
1.0 10 exp kPa
H O
K
T

| |
=
|
\ .

with T in K and P in kPa. The overall reaction for ethanol dehydration to diethyl ether is
( )
2 5 2 2 5
2
2 + C H OH H O C H OH
a) Convert the above rate expression to concentration units, i.e., replace
2 5 2
, ,
C H OH H O
P P and
( )
2 5
2
C H OH
P with respective concentrations. Use mol/m
3
for concentration units.
b) Calculate the equilibrium conversion of ethanol if pure ethanol is fed to a reactor at a total
pressure of 300 kPa and 130C.
c). The ethanol dehydration is to be carried out with a packed bed reactor (PBR) similar to that
available in Unit Operations Laboratory (3.5 diameter and 15 tall). For the packed bed,
literature suggests a void fraction of 0.34 and the density of the resin is 3 g/cm
3
. Pure ethanol
vapor is fed to the PBR at a rate of 1 mol/h. The reactor is operated at 300 kPa and 130C.
Calculate the steady state conversion of ethanol at the exit of the reactor.

4.4. Levenspiel Plot
It is easier to see how reactor volume relates to conversion and reaction rate by plotting
A
AO
r
F

vs X
A
without solving the differential equations. These are referred as Levenspiel plots.
For the PFR, the volume is equal to the area underneath the curve. For CSTR, it is the
rectangular area. You should prove to yourself that, whatever values you have for of v, C
AO
and
k, the curve will always have the same shape. For the isothermal reaction A B, the PFR is
always better than CSTR. However, one has to determine what the most efficient reactor design
would be for more complicated Levenspiel curves.


Advanced Chemical Reaction Engineering-CHE5123 Sundar Madihally, PhD

Page 4.3

4.5. Reactors in Series
Consider the simplest reaction, the liquid-phase irreversible reaction A B. By plotting
A
AO
r
F

vs
X
A
, you obtain

different profiles which can be used to estimate the volume of the reactor either
for a PFR or CSTR. For this purpose, you utilize the design equation in the graphical format.
For example when you have TWO CSTRs in SERIES:

TWO PFRs in SERIES:

Stacking PFRs in series gives no advantage in reducing the reactor volume and associated costs.
However, stacking multiple CSTRs in series does.

N TANKS IN SERIES:
As the number of tanks reach infinity, calculating total reactor volume from the Levenspiel plot
is equivalent to integrating the curve, i.e., as n infinity, approach the limit of one PFR volume.
Another interesting analysis is that a much more advanced reactor model that can describe
complex mixing.
The N-Tanks in Series Reactor Model: The Simplest Mixing Model for Reactor Design.
When you would ever build 5 or 10 (or even three) CSTRs in series? Well, a single poorly
mixed reactor can be modeled as two or more well-mixed volumes in series. There are three
ways we can model non-ideal mixing in CSTRs and Batch reactors, or equivalently to model
ideal mixing in a PFR:
X
A

F
AO
/-r
A

V
1

V
1
V
2

X
1

X
2

X
1
X
2

V
2

Total volume of two PFRs in series
is equal to the volume of one PFR.
}

=
1
0
1
X
A
A
AO
dX
r
F
V
}

=
2
1
2
X
X
A
A
AO
dX
r
F
V
X
A

F
AO
/-r
A

( ) 0
1 1

|
|
.
|

\
|

= X
r
F
V
A
AO

( )
1 2 1
X X
r
F
V
A
AO

|
|
.
|

\
|

=

V
1

V
1

V
2

X
1

X
2

X
1
X
2

V
2

The total volume of the two
CSTRs is less than if we just had
one huge CSTR.
Advanced Chemical Reaction Engineering-CHE5123 Sundar Madihally, PhD

Page 4.4

- N-Tanks in Series, as weve already discussed. EASIEST.
- PFR with Recycle, which results in some challenging model equations. HARDER.
- Axial Dispersion Model, which introduces second-order terms. HARDEST.
If mixing cannot be described by these models, then you have to solve the microscopic mass,
momentum and energy balances in multi-dimensional space.
Reactors in Parellel.
Advantage of assembling reactors is to split the total volume. Parallel configuration is used in
scenarios where small reactors are already purchased than what you need. Calculations are
similar to single reactors.
Example 4.4. 100 L/h of radioactive fluid having a half-life of 20 hours is to be treated by
passing through two ideal stirred tanks in series, V = 40,000 L each. In passing through this
system, how much will the activity decrease?

Bi-molecular Langmuir Hinshelwood Kinetics CO + O
2
CO
2
,
B B A A
B A
A
C K C K
C kC
r
+ +
=
1


Example 4.5. The exothermic reaction AB+C was carried out adiabatically using 300
mol/min molar flow rate of A and the following data recorded.
X
A
0 0.2 0.4 0.6 0.8 0.9
-r
A
(mol/dm3.min) 1.0 1.67 5.0 5.0 1.25 0.91
1/(-r
A
) 1 0.6 0.2 0.2 0.8 1.1
a) What are the PFR and CSTR volumes necessary to achieve 40% conversion?
b) Over what range of conversion would the CSTR and PFR reactor volumes be identical?
c) What is the maximum conversion that can be obtained in a 10.5-dm
3
CSTR?
X
A

F
AO
/-r
A

V
1

X
1

X
1

}

=
1
0
1
X
A
A
AO
dX
r
F
V
( )
1 2 2
X X
r
F
V
A
AO

|
|
.
|

\
|

=


V
2

X
2

X
2

X
A

F
AO
/-r
A

V
2

X
2

X
1

( ) 0
1 1

|
|
.
|

\
|

= X
r
F
V
A
AO

}

=
2
1
2
X
X
A
A
AO
dX
r
F
V

V
1

X
1

X
2

V
1

X
1

Advanced Chemical Reaction Engineering-CHE5123 Sundar Madihally, PhD

Page 4.5

d) What conversion can be obtained if a 72 dm
3
PFR is followed in series by a 24 dm
3
CSTR?
e) What conversion can be obtained if a 24 dm
3
CSTR is followed in series by a 72 dm
3
PFR?

Example 4.6. A radioactive disposal company initially planned to lower the activity of a gas
stream containing Xe-138 (14 min half-life) using two holdup tanks in series. Both tanks were
well mixed and the size of each tank had a mean residence time of 15 days in each tank. You are
suggesting that using a long tube (assume PFR) is better to save space and safety. If so, what
must be the size of this tube compared to the two stirred tanks? State all your assumptions.

4.6. Multiple Reactions
Generally, the syntheses of chemical products do not involve a single reaction but rather multiple
reactions. The goal is to maximize the production of the desirable product and minimize the
production of unwanted byproducts. In general there are four cases of multiple reaction systems:
1) Parallel reactions AB and AC. Two reactions compete for the same reactant A.
Usually, one of these products is much more valuable than the other. Eg. Oxidation of Ethylene
to Ethylene Oxide
2) Reactions in Series: ABC. Typically, product B is much more valuable than product C.
3) Independent Reactions: Neither products or reactants react themselves or each other.
4) Complex Networks: Some species behave in series, and some species react in parallel. For
example, ethylene is produced by the dehydrogenation of ethane:
C
2
H
6
C
2
H
4
+ H
2

C
2
H
6
+ H
2
2CH
4

C
2
H
4
+ C
2
H
6
C
3
H
6
+ CH
4

The last two reactions produce undesirable products.

Example 4.7. The following liquid phase reactions are carried out isothermally in a semi- batch
reactor.
A +2B C + D r
D1
= k
D1
C
A
C
B
2
k
D1
=0.25 L
2
/mol
2
.min
3A + 2D C + E r
E2
= k
E2
C
A
C
D
2
k
E2
= 0.1 L/mol.min
B +2C D + F r
F3
= k
E3
C
B
C
C
2
k
F3
= 5 L
2
/mol
2
.min
CA0 = 1.5 mol/L; CB0 = 2.0 mol/L; vo= 10 L/min. Initially the reactor contains 40 L liquid. .
Plot the species concentrations and conversion of A as a function of time for two cases 1) A is
fed to B and 2) B is fed to A. What differences do you observe for these two cases? Solve if
carried out in a PFR, CSTR.

Example 4.8. The following liquid phase reactions are carried out isothermally in a PFR.
A +2B C + 2D r
C1
= k
C1
C
A
C
B
2
k
C1
=0.2 L
2
/mol
2
.min
3A + 2C D + 2E r
D2
= k
D2
C
A
3
C
C
2
k
D2
= 0.002 L
4
/mol
4
.min
B +3D E + 2F r
E3
= k
E3
C
B
C
D
3
k
E3
= 0.08 dm
3
/mol
3
.min
a) If the desired product is D, what is the optimum reactor volume? At the optimum D values, if
F is the undesirable product, what is the selectivity? F
A0
=20 mole/min, F
B0
=30 mole/min, vo= 10
L/min. b) Instead of using the optimal PFR, if the same volume of CSTR is used, then what is
the amount of D formed. Is it a good idea to have a CSTR?