STEADY STATE

NONISOTHERMAL REACTOR
DESIGN
Chapter 8
Objectives
Describe the algorithm for CSTRs, PFRs, and PBRs
that are not operated isothermally.
Size adiabatic and nonadiabatic CSTRs, PFRs, and
PBRs.
Use reactor staging to obtain high conversions for
highly exothermic reversible reactions.
Carry out an analysis to determine the Multiple
Steady States (MSS) in a CSTR along with the
ignition and extinction temperatures.
Rationale and Overview
Calculate the volume necessary to achieve a
conversion, X, in a PFR for a first-order, exothermic
reaction carried out adiabatically. For an adiabatic,
exothermic reaction the temperature profile might look
something like this:

The combined mole balance, rate law, and stoichiometry yield:
Need another relationship relating X and T or T and V.
For an adiabatic reaction, the energy balance can be written in the
form


Algorithm Step Equation
Mole Balance


Rate Law


Stoichiometry

Combine


A A
C
T T R
E
k r
(

|
|
.
|

\
|
=
1 1
exp
1
1
) 1 ( X C C
AO A
=
O AO
o A
X
T T R
E
k
F
X C
T T R
E
k
dV
dX
v
) 1 (
1 1
exp ) 1 (
1 1
exp
1
1
1
1

(

|
|
.
|

\
|

|
|
.
|

\
|

=
Set X
Calculate T
Calculate k
Calculate -r
A
Calculate F
AO
/-r
A
Increment X &
repeat
Plot graph
Energy Balance
Energy Balance
Typical units for
each term are
J/s; i.e. Watts
dt
E d
F E F E W Q
sys
n
i
i i io
n
i
io
= +

= =
- -
1 1
Energy Balance In Terms Of
Enthalpy
Steady State Operation,
dE
system
/dt=0
For generalized reaction


In general



Assume no phase change,
Energy Balance In Terms Of
Conversion
) ( ) ( ) ( ) ( ) ( T H T H
a
b
T H
a
c
T H
a
d
T H
A B C D Rx
+ = A
0 ) ( ) (
1
= A O +

=
- -
X F T H H H F W Q
AO Rx
n
i
i io i AO
Energy Balance in terms of
Mean Heat Capacity
) (
) ( ) (
) (
io i Pi
Ti
Tio
Pi
Ti
T
P R
o
i
Tio
T
P R
o
i
i i io
T T C dT C
dT C T H dT C T H
T H H H
R R
= =
(
(

+
(
(

+ =
A =
}
} }
0 ) ( ) (
1
= A O

=
- -
X F T H T T C F W Q
AO Rx
n
i
io i Pi i AO
0 ) ( ) (
1
= A O +

=
- -
X F T H H H F W Q
AO Rx
n
i
i io i AO
) (
) ( ) ( ) ( ) (
) (
0 0 0 0
R PA PB PC PD
R A R B R C R D
Rx
T T C C
a
b
C
a
c
C
a
d
T H T H
a
b
T H
a
c
T H
a
d
T H

+ +
(

+
= A
) ( ) ( ) (
R P R
o
Rx
T T C T H T H
Rx
A + A = A
Energy Balance in terms of
Mean Heat Capacity
0 ) ( ) (
1
= A O

=
- -
X F T H T T C F W Q
AO Rx
n
i
io i Pi i AO
| | 0 ) ( ) (
) (
1
= A + A
O

=
- -
R P R
o
AO
n
i
io Pi i AO
T T C T H X F
T T C F W Q
Rx
User friendly
Energy Balance Equations
Refer to EBE
PFR with heat exchange

In terms of conversion, X

In terms of molar flow rates, Fi
) (
) ( ) (
X C C F
T H r T T Ua
dV
dT
P Pi i AO
Rx A a
A + O
A +
=
Pi i
Rx A a
C F
T H r T T Ua
dV
dT

A +
=
) ( ) (
Energy balance derivation for
PFR with heat exchange (W=0)
Heat exchange for a PFR:
a = heat exchange area per unit volume of reactor; for a tubular reactor, a = 4/D
) ( T T V Ua Q
a
A = A

General energy balance equation
0
1 1
= +

= =
- -
n
i
i i io
n
i
io
F E F E W Q
0 ) ( ) ( = A

dV
dT
C F r H T T Ua
pi i A Rx
a
0 ) ( ) ( =

dV
dT
C F r H T Ta Ua
pi i A i i
v
Rx i i
H H A =

v
Combine
both equation
Knows that
Rearrange
this equation

A
=
pi i
a A Rx
C F
T T Ua r H
dV
dT ) ( ) (
PFR energy
balance
equation
( )

A + O = X C C F C F
P Pi i Ao pi i
Energy balance derivation for
PFR with heat exchange (W=0)
Adiabatic Reactions
in PFR/PBR
Adiabatic Operation, Q=0
Q=0, W=0
| | ) ( ) (
) (
1
R P R
o
n
i
io Pi i
T T C T H
T T C
X
Rx
A + A
O
=

=
| |

=
=
A + O
A + O + A
=
n
i
P Pi i
R P
n
i
o Pi i R
o
C X C
T C X T C T H X
T
Rx
1
1
) (
Adiabatic Operation, Q=0
Adiabatic Energy Balance for variable heat
capacities
Reversible Reaction
(Adiabatic PFR/PBR)

Integrate mole balance



Rate law


dX
r
F
V
X
A
Ao
}

=
3
0
(

|
|
.
|

\
|
=
T T R
E
k k
1 1
exp
1
1
(

|
|
.
|

\
|

A
=
T T R
H
T K K
Rx
C C
1 1
exp ) (
1
1
|
.
|

\
|
=
Kc
C C
C C k r
D C
B A A
Stoichiometry
Gas phase, P=P
o



Combine


Relate
energy balance


| |

=
=
A + O
A + O + A
=
n
i
P Pi i
R P
n
i
o Pi i R
o
C X C
T C X T C T H X
T
Rx
1
1
) (
T
T
X
X
C C
o
i
i
Ao i
) 1 (
) (
c
v
+
+ O
=
2
0
2
2
2
2
2
) 1 (( ) 1 (
) 1 (
|
.
|

\
|
|
|
.
|

\
|
+

=
T
T
Kc X
X
X
X
kC r
Ao A
c c
Solution for reversible reaction
(Adiabatic PFR/PBR)
Integrate mole balance
Set X=0
Calculate T
Calculate k
Calculate K
c
Calculate T/T
o
Calculate r
A
Calculate F
Ao
/-r
A
Prepare table of X vs. (F
Ao
/-r
A
)
Use numerical integration formula (App. A) or ODE
(Polymath)
Use the techniques
developed in Chapter 2 to
size reactors and reactors in
series.


PFR Shaded area is the volume
40% conversion 70% conversion
CSTR Shaded area is the volume
40% conversion 70% conversion
CSTR+PFR
OR
Which one probably the best?
Looks like the best arrangement is a CSTR with a 40% conversion followed by a PFR
up to 70% conversion.
PFR/PBR with
Heat Effects
Solve for Design
Non-Isothermal PFR with Heat Effect
Energy balance
equation
( ) X C C F
T T Ua r H
dV
dT
P Pi i Ao
a A Rx
A + O
A
=

) ( ) (
Mole balance
equation
Ao
A
F
r
dV
dX
=
If coolant temperature
varies down the reactor,
coolant balance
Pc c
a a
C m
T T Ua
dV
dT

) (
=
PFR/ PBR Algorithm for Heat
Effect
Refers to Table 8.3 (Fogler, 4
th
Edition)
T and X Profile with heat effect
CSTR with Heat Effect
| | 0 ) ( ) ( ) ( = A + A O

X F T T C T H T T C F W Q Ao
R P R
o
io
i
P i AO s
Rx

Energy balance equation
Assuming the temperature inside the
CSTR, T, is spatially uniform:
At high coolant flow rates
Since the coolant flow rate is high, T
a1
= T
a2
= T
a
:
For conversion, X for
non-adiabatic operation
(W=0; AC
p
=0)
| | ) (
) ( ) (
R
o
Rx
o Pi i a
Ao
T H
T T C T T
F
UA
X
A
O +
=

For temperature, T for
non-adiabatic operation
| |

O +
O + + A
=
i P i
A
i P i A a R
o
A
C F UA
C T F UAT T H X F
T
Rx
0
0 0 0
) (
Adiabatic CSTR & CSTR
with Heat Exchange
Algorithm CSTR design
(b) Given X
Find T and V


Solution: linear progression of calc T cal k calc K
C
calc -r
A
calc V
(a) Given T
Find X and V


Solution: linear progression: calc X calc k cal K
C
calc -r
A
calc V


Refers to Table 8.4
(c) Given V
Find X at T
Solution: plot X
EB
vs. T and X
MB
vs. T on the same graph:

Equilibrium conversion
and
Adiabatic Temperature
Equilibrium conversion decrease as temperature increase
c
c
e
K
K
X
+
=
1
Equilibrium conversion
for 1
st
Order reaction
Energy balance equation
for adiabatic reaction
) (
) (
T H
T T C
X
Rx
o Pi i
EB
A
O
=

X
EB

T
Q=0,
W=0
Adiabatic exothermic reaction
X
e

T
Q=0,
W=0
Equiblibrium conversion exothermic reaction
Exothermic Reaction
Maximum conversion for 1
st
order adiabatic
exothermic reaction
X
e

T
Q=0,
W=0
Equilibrium
Energy balance
T
o
T
01
, Adiabatic
temperature
Interstage cooling used for exothermic
reaction to increase the conversion
Endothermic Reaction





X
e

T
Q=0,
W=0 Xe
Interstage heating to
increase the conversion
Equilibrium conversion
increase as temperature
increase

X
e

T
Q=0,
W=0
Xe
X
EB

Multiple Steady State
CSTR
Energy balance equation
Po Ao
C F
UA
= k
k
k
+
+
=
1
o a
c
T T
T
Let
0 ) ( ) ( ) ( = A O

X T H T T C T T
F
UA
R
o
o Pi i a
Ao
Rx
Therefore

= O
Po Pi i
C C
) )( 1 ( ) (
c Po R
o
T T C T H X
Rx
+ = A k
MSS: More than one intersection between of the
energy and mole balance curves.
Replace X with r
A
V/F
Ao
) )( 1 ( ) )( / (
c Po
o
Ao A
T T C H F V r
Rx
+ = A k
G(T)
(Heat- generated term)
= R(T)
(Heat-removed term)
X F V r
Ao A
=
Mole balance equation
Heat Removed Term
R(T)
T
Increase T
o
Vary entering
temperature
R(T)
T
Increase
Vary Non-
Adiabatic
parameter,
k
k
Heat Generated Term
1
st
Order reaction
RT E
RT E
Ae
Ae H
T G
Rx
/
/ 0
1
) (

+
A
=
t
t
High E
Low E
G(T)
T
G(T)
T
Increasing
Find X. Combine the mole balance, rate law, Arrhenius Equation, and
stoichiometry.
Plot R(T) and G(T) on the same graph
Multiple steady state
with T
o
varied
Temperature ignition-
extinction curve
The End