Steady State Nonisothermal

Steady State Nonisothermal

Reactor Design
Reactor Design
Dicky Dermawan
Dicky Dermawan
www.dickydermawan.net78.net www.dickydermawan.net78.net
dickydermawan@gmail.com dickydermawan@gmail.com
ITK-330 Chemical Reaction Engineering
ITK-330 Chemical Reaction Engineering
Rationale
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
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?
Why Energy Balance?
Imagine that we are designing a nonisothermal PFR for a Imagine that we are designing a nonisothermal PFR for a
first order liquid phase exothermic reaction: first order liquid phase exothermic reaction:
Performance Performance
equation: equation:
0 A
A
F
r
dV
dX

Kinetics: Kinetics:

A
r
k A
C
The temperature
will increase with
conversion down
the length of
reactor
1
]
1

,
_

T
1
T
1
R
E
exp k k
1
a
1
Stoichiometry: Stoichiometry:
0

A 0 A
C F
0 A 0 0 A
C F ) X 1 ( C C
0 A A

Combine: Combine:
0
X 1

1
]
1

,
_

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
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

+
+


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
( ) ( ) ( )
( ) ( )
1
]
1

+ +
+ +

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 ( )

n
1 i
i 0 i i 0 A
H H F
) T ( H X F
Rx 0 A

Energy Balance (cont)
Energy Balance (cont)



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

n
1 i
0 i i i 0 A
H H F
) T ( H X F
Rx 0 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 +
R
T
T
pi
pi
T T
dT C
C

) 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
+
pA pB
a
b
pC
a
c
pD
a
d
p
C C C C C +

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



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

n
1 i
0 i i i 0 A
H H F
) T ( H X F
Rx 0 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
+
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
+

So what?
Energy Balance (cont)
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
+

( ) [ ]
R p R
o
Rx
n
1 i
0 i pi i
T T C

) T ( H
) T T ( C
~
X
+

This is the X=X(T) weve been looking for!

Application to Adiabatic CSTR Design
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
1
]
1

,
_

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
+

Calculate k
Calculate V using combining equation
Application to Adiabatic CSTR Design
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
1
]
1

,
_

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
+

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
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
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
1
]
1

,
_

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

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

) T ( H
) T T ( C
~
X
+

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

K cal/mol 30 15 15 C C C
~
pB B pA
n
1 i
pi i
+ +

cal/mol 6000 - kcal/mol 6 15 20 41 H H H ) 273 ( H

o
B
0
A
o
C
o
Rx
+ +
0 15 15 30 C C C C

pB pA pC p

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

1
]
1

,
_

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

Application to Adiabatic CSTR Design

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
+

Case B (Rating): V specified, calculate X (and T)

Performance equation:
Kinetics:
Stoichiometry:
Mole balance:
A
0 A
r
X F
V

1
]
1

,
_

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

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

1
]
1

,
_

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
Application to Adiabatic PFR/PBR Design
T
T
P
P
X 1
X 1
C C
0
0
0 A A

+

( ) [ ]


T T C

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

Example for First Order Reaction

Performance equation:
Kinetics:
Stoichiometry:
Pressure drop:
1
]
1

,
_

T
1
T
1
R
E
exp k k
1
a
1
Energy balance:

A
r
k A
C
for PFR/small P:
P/P
0
= 1
) X 1 (
P / P
P
T
T
2 dW
dP
0
0
0
+

) 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
+
+ +

+ + +
+

) 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
Sample
Problem
Problem
for
for
Adiabatic
Adiabatic
PFR
PFR
Design
Design
P8-6A
Sample Problem for Adiabatic PBR
Sample Problem for Adiabatic PBR
Design
Design
NINA = Diabatic Reactor Design
NINA = Diabatic Reactor Design
Heat Transfer Rate to the Reactor
Heat Transfer Rate to the Reactor
( )0 TTC) T(HX F)TT( C~F W R p RoRx0 A n1i 0i pii0A s + 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

NINA = Diabatic Reactor Design

NINA = Diabatic Reactor Design
Heat Transfer Rate to the Reactor (cont)
Heat Transfer Rate to the Reactor (cont)
( )0 TTC) T(HX F)TT( C~F W R p RoRx0 A n1i 0i pii0A s + 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

( ) T T A U
1 a

The energy balance becomes:
Sample
Sample
Problem for
Problem for
Diabatic
Diabatic
CSTR
CSTR
Design
Design
P8-4B
P8-4B
Sample Problem for Diabatic CSTR Design
Sample Problem for Diabatic CSTR Design
Application of Energy Balance to Diabatic
Application of Energy Balance to Diabatic
Tubular Reactor Design
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

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

Application of Energy Balance to Diabatic
Tubular Reactor Design
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

1
1
]
1

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

1
1
]
1

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
Sample Problem for Diabatic Tubular Reactor
Design
Design
Design for Reversible Reactions
Design for Reversible Reactions
Endotermik: Endotermik: K naik dengan kenaikan T X X
eq eq
naik naik reaksikan pada T
max
yang diperkenankan
K ln T R G
2
Rx
T R
H
dT
K) (ln d

Eksotermik: Eksotermik: K turun dengan kenaikan T X X
eq eq
turun 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
Design for Reversible Highly-Exothermic
Reactions
Reactions
-r -r
A A
= -r = -r
A A
(X,T) (X,T)
Generally: Generally: Higher X Higher X slower reaction rate slower reaction rate
Higher T Higher T faster rate faster rate
At X = X At X = X
eq eq
: : -r -r
A A
= 0 = 0
Design for Equilibrium Highly-Exothermic
Design for Equilibrium Highly-Exothermic
Reactions
Reactions
#1 #1 Starting with R-free solution, between 0 dan 100 Starting with R-free solution, between 0 dan 100
o o
C determine the C determine the
equilibrium conversion of A for the elementary aqueous reaction: equilibrium conversion of A for the elementary aqueous reaction:
A A R R
cal/mol 18000 H
cal/mol 3375 G
0
298
0
298

The reported data is based on the following standard states of The reported data is based on the following standard states of
reactants and products: reactants and products:

1mol/L C C
0
A
0
R

Assume ideal solution, in which case: 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 In addition, assume specific heats of all solutions are equal
to that of water to that of water
C cal/g. 1 C
0
p

Design for Equilibrium Highly-Exothermic
Design for Equilibrium Highly-Exothermic
Reactions:
Reactions:
Reaction Rate in X T Diagram
Reaction Rate in X T Diagram
k T ( ) 0.0918exp 5859
1
T
1
298

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

,
:
Reaction Rate in The X T Diagram
Reaction Rate in The X T Diagram
at C
at C
A0 A0
= 1 mol/L
= 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
Design for Equilibrium Highly-Exothermic Reactions
:
:

Optimum Temperature Progression
Optimum Temperature Progression
in Tubular Reactor
in Tubular Reactor
#3 #3
a. a. Calculate the space time needed for 80% conversion of a feed starting with initial Calculate the space time needed for 80% conversion of a feed starting with initial
concentration of A of 1 mol/L concentration of A of 1 mol/L
b. b. Plot the temperature and conversion profile along the length of the reactor Plot the temperature and conversion profile along the length of the reactor
Let the maximum operating allowable temperature be 95 Let the maximum operating allowable temperature be 95
o o
C C

Design for Reversible Reactions: Heat
Design for Reversible Reactions: Heat
Effect
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

Design for Equilibrium Highly-Exothermic
Reactions
Reactions
:
:
CSTR Performance
CSTR Performance
Design for Equilibrium Highly-Exothermic
Design for Equilibrium Highly-Exothermic
Reactions
Reactions
:
:
CSTR Performance
CSTR Performance
#4 #4 A concentrated aqueous A-solution of the previous A concentrated aqueous A-solution of the previous
examples, C examples, C
A0 A0
= 4 mol/L, F = 4 mol/L, F
A0 A0
= 1000 mol/min, is to be 80% = 1000 mol/min, is to be 80%
converted in a mixed reactor. converted in a mixed reactor.
a. a. If feed enters at 25 If feed enters at 25
o o
C, what size of reactor is needed? C, what size of reactor is needed?
b. b. What is the optimum operating temperature for this What is the optimum operating temperature for this
purpose? purpose?
c. c. What size of reactor is needed if feed enters at optimum What size of reactor is needed if feed enters at optimum
temperature? temperature?
d. d. What is the heat duty if feed enters at 25 What is the heat duty if feed enters at 25
o o
C to keep the C to keep the
reactor operation at its the optimum temperature? reactor operation at its the optimum temperature?
Interstage Cooling
Interstage Cooling
Review on Energy Balance in CSTR Operation
Review on Energy Balance in CSTR Operation
Bila term kerja diabaikan dan H
Rx
konstan:

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

X F
0 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
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
:
( ) +

,
_

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

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
+
+

+
+

+
+

Multiple Steady
Multiple Steady
State & Stability of
State & Stability of
CSTR Operation
CSTR Operation
1
T T
T
a 0
c
+
+

) T T (
a 0
+
( ) +

,
_

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

) 1 ( T
c
+
+ ) 1 ( T [ C
0 p
) T T ( ) 1 ( C
c 0 p
+
+ T T [ C
0 p
]
]
( )
0
Rx
H X
) T T ( ) 1 ( C
c 0 p
+

) 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
+

Review on Energy Balance in CSTR Operation

Review on Energy Balance in CSTR Operation
Multiple Steady
Multiple Steady
State: Stability of CSTR
State: Stability of CSTR
Operation
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
Sample Problem on Multiple Steady State in
CSTR Operation
CSTR Operation
P8-17B
P8-17B