Steady State Nonisothermal

Reactor Design
Dicky Dermawan
www.dickydermawan.net78.net
dickydermawan@gmail.com

ITK-330 Chemical Reaction Engineering
Rationale
All reactions always accompanied by heat effect:
exothermic reactions vs. endothermic reactions
Unless heat transfer system is carefully
designed, reaction mass temperature tend to
change
Design of heat transfer system itself requires the
understanding of this heat effect
Energy balance is also needed, together with
performance equations derived from mass
balance
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.
Analyze multiple reactions carried out in CSTRs, PFRs,
and PBRs which are not operated isothermally in order
to determine the concentrations and temperature as a
function of position (PFR/PBR) and operating variables
Why Energy Balance?
Imagine that we are designing a nonisothermal PFR for a
first order liquid phase exothermic reaction:
Performance
equation:
0 A
A
F
r
dV
dX
=
Kinetics: =
A
r
k A
C
The temperature
will increase with
conversion down
the length of
reactor
(

|
|
.
|

\
|
=
T
1
T
1
R
E
exp k k
1
a
1
Stoichiometry:
0
u = u
A 0 A
C F u =
0 A 0 0 A
C F u = ) X 1 ( C C
0 A A
=
Combine:
0
X 1
u

(
|
|
.
|

\
|
=
1
a
1
T
1
R
E
exp k
dV
dX
T
1
) V , T ( X X =
) V ( T T =
) X ( T T = ) V ( X X =
Energy Balance

=
+ + + + =
n
1 i
0 I 0 I 0 D 0 D 0 C 0 C 0 B 0 B 0 A 0 A 0 i 0 i
H F H F H F H F H F H F : In

=
+ + + + =
n
1 i
I I D D C C B B A A i i
H F H F H F H F H F H F Out
At steady state:
dt
E

d
H F H F W Q
sys
n
1 i
i i
n
1 i
0 i 0 i s
= +

= =

=
+
n
1 i
s
W Q

0 i
F
0 i
H

=

n
1 i
i
F
i
H
0 =
Consider
generalized
reaction:
D C B A
a
d
a
c
a
b
+ +
I 0 A I
a
d
D 0 A D
a
c
C 0 A C
a
b
B 0 A B
0 A A
F F
) X ( F F
) X ( F F
) X ( F F
) X 1 ( F F
O =
+ O =
+ O =
O =
=
Upon substitution:
( )
A B
a
b
C
a
c
D
a
d
A0
H H H H X F - +

= =

n
1 i
i i
n
1 i
0 i 0 i
H F H F
( ) ( ) ( )
( ) ( )
(

O + O +
O + O +
=
CI 0 I I D 0 D D
C 0 C C B 0 B B A 0 A
0 A
H H H H
H H H H H H
F

= =

n
1 i
i i
n
1 i
0 i 0 i
H F H F ( )

=
O =
n
1 i
i 0 i i 0 A
H H F
) T ( H X F
Rx 0 A
A
Energy Balance (cont)

= =

n
1 i
i i
n
1 i
0 i 0 i
H F H F ( )

=
O =
n
1 i
0 i i i 0 A
H H F
) T ( H X F
Rx 0 A
A
}
+ =
T
T
pi R
o
i i
R
dT C ) T ( H H
From thermodynamics, we know that:
}
+ =
0 i
R
T
T
pi R
o
i 0 i
dT C ) T ( H H
Thus:
) T T ( C
~
dT C H H
0 i pi
T
T
pi 0 i i
0 i
= =
}
0 i
T
T
pi
pi
T T
dT C
C
~
0 i

=
}
( )
R p R
o
Rx Rx
T T C

) T ( H ) T ( H A + A = A
R
T
T
pi
pi
T T
dT C
C

A
= A
}
) T ( H ) T ( H ) T ( H ) T ( H ) T ( H
R
o
D R
o
D
a
b
R
o
D
a
c
R
o
D
a
d
R
o
Rx
+ = A
pA pB
a
b
pC
a
c
pD
a
d
p
C C C C C + = A

=
O =
n
1 i
0 pi i 0 A
) T T ( C
~
F
Energy Balance (cont)

= =

n
1 i
i i
n
1 i
0 i 0 i
H F H F ( )

=
O =
n
1 i
0 i i i 0 A
H H F
) T ( H X F
Rx 0 A
A
Upon substitution:

= =

n
1 i
i i
n
1 i
0 i 0 i
H F H F
( )] T T C

) T ( H [ X F
R p R
o
Rx 0 A
A + A
Finally.
0 H F H F W Q
n
1 i
i i
n
1 i
0 i 0 i s
= +

= =

( ) 0 T T C

) T ( H X F ) T T ( C
~
F W Q
R p R
o
Rx 0 A
n
1 i
0 i pi i 0 A s
= A + A O

=

So what?
Energy Balance (cont)
For adiabatic reactions:
The energy balance at steady state becomes:
After rearrangement:
0 Q =

When work is negligible:

0 W
s
=

( ) | | 0 T T C

) T ( H X F ) T T ( C
~
F
R p R
o
Rx 0 A
n
1 i
0 i pi i 0 A
= A + A O

=
( ) | |
R p R
o
Rx
n
1 i
0 i pi i
T T C

) T ( H
) T T ( C
~
X
A + A
O
=

=
This is the X=X(T) weve been looking for!
Application to Adiabatic CSTR Design
) X 1 ( C C
0 A A
=
Case A: Sizing: X specified, calculate V (and T)
Performance equation:
Kinetics:
Stoichiometry:
Combine:
A
0 A
r
X F
V

=
=
A
r
k A
C
(

|
|
.
|

\
|
=
T
1
T
1
R
E
exp k k
1
a
1
) X 1 ( C k
X F
V
0 A
0 A


=
Solve the energy balance for T
( ) | |
R p R
o
Rx
n
1 i
0 i pi i
T T C

) T ( H
) T T ( C
~
X
A + A
O
=

=
Calculate k
Calculate V using combining equation
Application to Adiabatic CSTR Design
) X 1 ( C C
0 A A
=
Case B (Rating): V specified, calculate X (and T)
Performance equation:
Kinetics:
Stoichiometry:
Mole balance:
A
0 A
r
X F
V

=
=
A
r
k A
C
(

|
|
.
|

\
|
=
T
1
T
1
R
E
exp k k
1
a
1
) X 1 ( C k
X F
V
mb 0 A
mb 0 A


=
Energy balance:
( ) | |
R p R
o
Rx
n
1 i
0 i pi i
eb
T T C

) T ( H
) T T ( C
~
X
A + A
O
=

=
Find X & T that satisfy BOTH the material balance
and energy balance,
viz. plot X
mb
vs T and X
eb
vs T in the same graph: the
intersection is the solution
Application to Adiabatic CSTR Design
Example: P8-5A
The elementary irreversible organic liquid-phase reaction:
A + B C
is carried out adiabatically in a CSTR. An equal molar feed in A
and B enters at 27
o
C, and the volumetric flow rate is 2 L/s.

(a) Calculate the CSTR volume necessary to achieve 85%
conversion
(b) Calculate the conversion that can be achieved in one 500 L
CSTR and in two 250 L CSTRs in series
mol / kcal 41 ) K 273 ( H
mol / kcal 15 ) K 273 ( H
mol / kcal 20 ) K 273 ( H
o
C
o
B
o
A
=
=
=
cal/mol.K 30 C
cal/mol.K 15 C
cal/mol.K 15 C
pC
pB
pA
=
=
=
cal/mol 10000 E
K 300 at 01 . 0 k
a
s mol
L
=
=

mol/L 1 . 0 C
0 A
=
Application to Adiabatic CSTR Design
Case A: Sizing: X specified, calculate V (and T)
Performance equation:
Kinetics:
Stoichiometry:
Combine:
A
0 A
r
X F
V

=
=
A
r
k B A
C C
(

|
|
.
|

\
|
=
T
1
T
1
R
E
exp k k
1
a
1
2
0 A
0
2 2
0 A
0 A
) X 1 ( C k
X
) X 1 ( C k
X F
V

u
=


=
Energy balance:
( ) | |
R p R
o
Rx
n
1 i
0 i pi i
T T C

) T ( H
) T T ( C
~
X
A + A
O
=

=
Calculate k
Calculate V using combining equation
) X 1 ( C C
0 A A
=
) X 1 ( C ) X ( C C
0 A B B 0 A B
= v O =
K cal/mol 30 15 15 C C C
~
pB B pA
n
1 i
pi i
= + = O + = O

=
cal/mol 6000 - kcal/mol 6 15 20 41 H H H ) 273 ( H
o
B
0
A
o
C
o
Rx
= = + + = = A
0 15 15 30 C C C C

pB pA pC p
= = = A
K 470 200 85 . 0 300 T
200
300 T
) 6000 (
) 300 T ( 30
85 . 0 = + =

=


=
s mol
L
317 . 4
470
1
300
1
987 . 1
10000
exp 01 . 0 k

=
(

|
.
|

\
|
=
L 175
) 85 . 0 1 ( 1 . 0 317 . 4
85 . 0 2
V
2
=


=
Application to Adiabatic CSTR Design
) X 1 ( C C C
0 A B A
= =
( ) | |
R p R
o
Rx
n
1 i
0 i pi i
eb
T T C

) T ( H
) T T ( C
~
X
A + A
O
=

=
Case B (Rating): V specified, calculate X (and T)
Performance equation:
Kinetics:
Stoichiometry:
Mole balance:
A
0 A
r
X F
V

=
(

|
|
.
|

\
|
=
T
1
T
1
R
E
exp k k
1
a
1
2
mb 0 A
mb 0
) X 1 ( C k
X
V

u
=
Energy balance:
=
A
r
k B A
C C
2
mb
mb
) X 1 ( 1 . 0
T
1
300
1
987 . 1
10000
exp 01 . 0
X 2
500

(

|
.
|

\
|

=
200
300 T
) 6000 (
) 300 T ( 30
X
eb

=


=
0
0.2
0.4
0.6
0.8
1
300 350 400 450 500
Xmb
Xeb
T 300 310 320 330 340 350 360 370 380 390 400 410 420 430 440 450 460 470 480 482 484 485 490 500
Xmb 0.172 0.245 0.325 0.406 0.482 0.552 0.613 0.666 0.711 0.750 0.783 0.810 0.834 0.854 0.871 0.885 0.898 0.908 0.918 0.919 0.921 0.922 0.926 0.933
Xeb 0.000 0.050 0.100 0.150 0.200 0.250 0.300 0.350 0.400 0.450 0.500 0.550 0.600 0.650 0.700 0.750 0.800 0.850 0.900 0.910 0.920 0.925 0.950 1.000
Application to Adiabatic PFR/PBR Design
T
T
P
P
X 1
X 1
C C
0
0
0 A A

c +

=
( ) | |


T T C

) T ( H
) T T ( C
~
X
R p R
o
Rx
n
1 i
0 i pi i

A + A
O
=

=
Example for First Order Reaction
Performance equation:
Kinetics:
Stoichiometry:
Pressure drop:
(

|
|
.
|

\
|
=
T
1
T
1
R
E
exp k k
1
a
1
Energy balance:
=
A
r
k A
C
for PFR/small AP:
P/P
0
= 1
) X 1 (
P / P
P
T
T
2 dW
dP
0
0
0
c +
o
=
) X 1 ( C C
0 A A
=
Gas
liquid
0 A
A
F
r
dW
dX
=
| |
| |
| |
p
n
1 i
pi i
n
1 i
0 pi i R p
o
Rx
n
1 i
0 pi i R p
o
Rx p
n
1 i
pi i
n
1 i
n
1 i
0 pi i pi i R p p
o
Rx
C

X C
~
T C
~
T C

X H X
T
T C
~
T C

X H X T C

X T C
~

T C
~
T C
~
T C

X T C

X H X
A + O
O + A + A
=
O + A + A = A + O
O O = A + A A

=
=
= =
= =
) X ( T T =
Combine:
) X ( k
) X ( T T
) T ( k k
)
`

=
=
) P , X ( C C
) X ( T T
) P , T , X ( C C
A A
A A
=
)
`

=
=
) P , X ( r r
]) P , X [ C ], X [ k ( r r
A A
A A A
=
=
) P , X ( g ) P , T , X ( g
dW
dP
) P , X ( f ) r ( f
dW
dX
A
= =
= = Thus
The combination results in 2 simultaneous
differential equations
Sample
Problem
for
Adiabatic
PFR
Design
P8-6A
Sample Problem for Adiabatic PBR
Design
NINA = Diabatic Reactor Design
Heat Transfer Rate to the Reactor
( ) 0 T T C ) T ( H X F ) T T ( C~ F W R p R oRx 0 A n1 i 0 i pi i 0 A s = A + A O = Q

Rate of energy transferred between the reactor and the coolant:

The rate of heat transfer from the
exchanger to the reactor:
|
|
.
|

\
|

=
2 a
1 a
2 a 1 a
T T
T T
ln
T T
A U Q

Combining:

: :

0 H X F ) T T ( C
~
F W
Rx 0 A
n
1 i
0 i pi i 0 A s
= A O

=

NINA = Diabatic Reactor Design

Heat Transfer Rate to the Reactor (cont)
( ) 0 T T C ) T ( H X F ) T T ( C~ F W R p R oRx 0 A n1 i 0 i pi i 0 A s = A + A O = Q

At high coolant flow rates the exponential term
will be small,
so we can expand the exponential term as a
Taylor Series, where the terms of second
order or greater are neglected:
Then:
0 H X F ) T T ( C
~
F W
Rx 0 A
n
1 i
0 i pi i 0 A s
= A O

=

( ) T T A U
1 a

The energy balance becomes:
Sample
Problem for
Diabatic
CSTR
Design
P8-4B
Sample Problem for Diabatic CSTR Design
Application of Energy Balance to Diabatic
Tubular Reactor Design
Heat transfer in CSTR:
( ) T T A U Q
1 a
=

In PFR, T varies along the

reactor:
( ) ( ) dV T T
V
A
U dA T T U Q
V
a
A
a
= =
} }

( ) T T a U
dV
Q d
a
=

Thus:
D
4
L
L D
a
a
reaktor tabung volume
reaktor tabung selimut luas
V
A
4
D
2
=

t
=
= =
t
For PBR: dW
1
dV
W
V
V
W
b b
b

= =
Thus:
( ) T T
a U
dW
Q d
a
b

Application of Energy Balance to Diabatic Tubular

Reactor Design
The steady state energy balance, neglecting work term:
Differentiation with respect to the volume V:
( ) T T a U
dV
Q d
a
=

and recalling that

Or:
( ) 0 T T C

) T ( H X F ) T T ( C
~
F Q
R p R
o
Rx
0 A
n
1 i
0 i pi i 0 A
= +

=

0 dT C ) T ( H X F dT C F Q
T
T
p R
o
Rx
0 A
T
T
pi i 0 A
R o
=
(
(

+
} }

Inserting
0
dV
dX
dT C ) T ( H F
dV
dT
C X F
dV
dT
C F
dV
Q d
T
T
p R
o
Rx
0 A p 0 A pi i 0 A
R
=
(
(

+
}

dV
dX
F r
0 A A
=
( ) T T a U
a

( )
dV
dT
C X C F
p pi i 0 A
+

( ) )] T ( H [ r
Rx
A
+
0 =
( ) ( )
( )
p pi i 0 A
Rx
A a
C X C F
)] T ( H [ r T T a U
dV
dT


+
+
=

Coupled with
0 A
A
F
r
dV
dX
=
) T , X ( g =
) T , X ( f =
Form 2
differential with 2
dependent
variables X & T
Sample Problem for Diabatic Tubular Reactor
Design
Design for Reversible Reactions
Endotermik: K naik dengan kenaikan T X
eq
naik reaksikan
pada T
max
yang diperkenankan
K ln T R G =
2
Rx
T R
H
dT
K) (ln d

=

Eksotermik: K turun dengan kenaikan T X
eq
turun reaksikan
pada T rendah


Laju reaksi lambat pada T rendah!
Ada trade off antara aspek termodinamika dan kinetika
X
eq
= X
eq
(K)
= X
eq
(T)
Design for Reversible Highly-Exothermic
Reactions
-r
A
= -r
A
(X,T)
Generally: Higher X slower reaction rate
Higher T faster rate
At X = X
eq
: -r
A
= 0

Design for Equilibrium Highly-Exothermic
Reactions
#1 Starting with R-free solution, between 0 dan 100
o
C
determine the equilibrium conversion of A for the elementary
aqueous reaction:
A R
cal/mol 18000 H
cal/mol 3375 G
0
298
0
298
=
=

The reported data is based on the following standard states of

reactants and products:
1mol/L C C
0
A
0
R
= =
Assume ideal solution, in which case:
C
A
R
0
A
A
0
R
R
K
C
C
C / C
C / C
K = = =
In addition, assume specific heats of all solutions are equal
to that of water
C cal/g. 1 C
0
p
=
Design for Equilibrium Highly-Exothermic
Reactions:
Reaction Rate in X T Diagram
k T ( ) 0.0918 exp 5859
1
T
1
298

\
|
|
.

(
(

:=
rA X T , ( ) k T ( ) CA0 1 X
X
K T ( )

\
|
|
.
:=
Reaction Rate in The X T Diagram
at C
A0
= 1 mol/L
0 10 20 30 40 50 60 70 80 90 100
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
Suhu, C
K
o
n
v
e
r
s
i
r
A
0 01 ,
r
A
0 025 ,
r
A
0 05 ,
r
A
0 1 ,
r
A
0 25 ,
r
A
0 5 ,
r
A
1
r
A
2
r
A
4
Design for Equilibrium Highly-Exothermic Reactions:
Optimum Temperature Progression
in Tubular Reactor
#3
a. Calculate the space time needed for 80% conversion of a feed
starting with initial concentration of A of 1 mol/L
b. Plot the temperature and conversion profile along the length of
the reactor

Let the maximum operating allowable temperature be 95
o
C

Design for Reversible Reactions: Heat Effect
( ) | |
R p R
o
Rx
n
1 i
0 i pi i a
0 A
T T C

) T ( H
) T T ( C
~
) T T (
F
A U
X
+
+

=

=

Design for Equilibrium Highly-Exothermic

Reactions: CSTR Performance
Design for Equilibrium Highly-Exothermic
Reactions: CSTR Performance
#4 A concentrated aqueous A-solution of the previous
examples, C
A0
= 4 mol/L, F
A0
= 1000 mol/min, is to be 80%
converted in a mixed reactor.

a. If feed enters at 25
o
C, what size of reactor is needed?

b. What is the optimum operating temperature for this
purpose?

c. What size of reactor is needed if feed enters at optimum
temperature?

d. What is the heat duty if feed enters at 25
o
C to keep the
reactor operation at its the optimum temperature?
Interstage Cooling
Review on Energy Balance in CSTR Operation
Bila term kerja diabaikan dan AH
Rx
konstan:

=
O
n
1 i
0 pi i 0 A s
) T T ( C
~
F W

( ) T T A U
a

0 H X F
0
Rx 0 A
= A
X F
0 A
( ) ( )
|
|
.
|

\
|

+ O = A

=
a
0 A
n
1 i
0 pi i 0 A
0
Rx
T T
F
A U
) T T ( C
~
F H
Untuk CSTR:

A
0 A
r
X F
V

=
( ) V r
A
( ) ( )
|
|
.
|

\
|

+ = A
a
0 A
0 0 p 0 A
0
Rx
T T
F
A U
) T T ( C F H
Pembagian kedua ruas dengan F
A0
:

( ) + = A
|
|
.
|

\
|

0 p 0 0 p
0
Rx
0 A
A
C ) T T ( C H
F
V r
0 p 0 A
C F
A U

( )
a
T T
0 p 0 A
C F
A U

= k
1
T T
1
T T
C F A U
T A U T C F
T
a 0
C F
A U
a
C F
A U
0
0 p 0 A
a 0 0 p 0 A
c
0 p 0 A
0 p 0 A
+ k
k +
=
+
+
=
+
+
=

Multiple Steady
State & Stability of
CSTR Operation
1
T T
T
a 0
c
+ k
k +
=
k
) T T (
a 0
k +
( ) + = A
|
|
.
|

\
|

) T T [( C H
F
V r
0 0 p
0
Rx
0 A
A
( )] T T
a

) 1 ( T
c
+ k
+ k = ) 1 ( T [ C
0 p
) T T ( ) 1 ( C
c 0 p
+ k =
k + = T T [ C
0 p
]
]
( )
0
Rx
H X A
) T T ( ) 1 ( C
c 0 p
+ k
=
) T ( G ) T ( R =
A
0 A
r
X F
V

=
( ) | |

T T C

) T ( H
) T T ( C
~
X
dengan Bandingkan
R p R
o
Rx
n
1 i
0 pi i
A + A
O
=

=
Review on Energy Balance in CSTR Operation
Multiple Steady State: Stability of CSTR
Operation
Temperature Ignition Extinction Curve
Finding Multiple Steady State: Varying T
o
Upper steady state
Lower steady state
Ignition temperature
Extinction temperature
Runaway Reaction

Sample Problem on Multiple Steady State in
CSTR Operation
P8-17B