1

Nonisothermal Reactor Design

2
Example 8-1
Calculate the reactor volume necessary for 70% conversion

The reaction is exothermic and the reactor is operated adiabatically. As a result, the temperature
will increase with conversion down the length of the reactor.
B A
Solution
1. Mole Balance (design equation)
0 A
A
F
r
dV
dX
=
2. Rate Law
A
1
1 A A
C
T
1
T
1
R
E
exp k kC r
(

|
|
.
|

\
|
= =
3. Stoichiometry (liquid phase)
) X 1 ( C C
v C F
v C F
v v
0 A A
0 0 A 0 A
0 A A
0
=
=
=
=
3
4. Combining
A
1
1 A
C
T
1
T
1
R
E
exp k r
(

|
|
.
|

\
|
=
) X 1 ( C C
0 A A
=
) X 1 ( C
T
1
T
1
R
E
exp k r
0 A
1
1 A

(

|
|
.
|

\
|
=
0 A
A
F
r
dV
dX
=
0 A
0 A
0
C
F
v =
0 1
1
v
X 1
T
1
T
1
R
E
exp k
dV
dX
(

|
|
.
|

\
|
=
5. Energy Balance
another relationship relating
X and T or T and V is needed
X
C
H
T T
A
P
Rx
0
A
+ =
4
Energy Balance
First Law of Thermodynamics
For a closed system, in which no mass crosses the system boundaries, the change in
total energy of the system, dE, is equal to the heat flow to the flow system, oQ, minus
the work done by the system on the surroundings, oW.
W Q dE o o =
oQ and oW are not exact differentials of a state function.
(
(
(
(
(
(

(
(
(
(
(
(

+
(
(
(
(
(
(

(
(
(
(
(
(

=
(
(
(
(
(
(

em thesyst
of flowout
mass systemby
ving energylea
Rateof
system
othe int flow
mass systemby
addedto
ergy Rateofen
ng surroundi
onthe
m thesyste
doneby
rk Rateofwo
ng surroundi
fromthe
m thesyste
o ofheatt
ow Rateoffl
system
e withinth
ofenergy
on accumulati
Rateof
For an open system
5
out out in in
sys
E F E F W Q
dt
E

d
+ =

For one species,
For an open well-mixed
system that has n species
out
n
1 i
i i
in
n
1 i
i i
sys
E F E F W Q
dt
E

d

= =
+ =

F
i
molar flow rate
E
i
respective energy
Flow work is work that is necessary to get the
mass into and out of the system. For example,
when shear stresses are absent, we write
is separated into flow work and other work,
W

S
W

shaft work could be produced

from such things as a stirrer in a
CSTR or a turbine in a PFR.
s
out
n
1 i
i i
in
n
1 i
i i
W V
~
P F V
~
P F W

+ + =

= =
rate of flow work
Watts
s
Joules
s
1
) m Newton (
mol
m
m
Newton
s
mol
] [ V
~
P F
3
2
i i
= = = =
P is the pressure
is the specific molar volume of species i
i
V
~
6
out
n
1 i
i i
in
n
1 i
i i
sys
E F E F W Q
dt
E

d

= =
+ =

s
out
n
1 i
i i
in
n
1 i
i i
W V
~
P F V
~
P F W

+ + =

= =
out
n
1 i
i i i
in
n
1 i
i i i s
sys
) V
~
P E ( F ) V
~
P E ( F W Q
dt
E

d

= =
+ + + =

other gz
2
u
U E
i
2
i
i i
+ + + =
i i
U E =
In almost all chemical reactor situations,
the kinetic, potential, and other energy
terms are negligible in comparison with the
enthalpy, heat transfer, and work terms
out
n
1 i
i i
in
n
1 i
i i s
sys
H F H F W Q
dt
E

d

= =
+ =

i i i
V
~
P U H + =
U
i
is internal energy
H
i
is enthalpy
The energy of the system at any instant in time, is the sum
of the products of the number of moles of each species in the
system multiplied by their respective energies.
sys
E

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

d

7
Overview of Energy Balances
8
9
10
Understanding the derivation of these equations will greatly facilitate their
proper application and evaluation to various reactors and reactions.
11
Examples on How to Use Table 8-1
) X 1 ( C
T
1
T
1
R
E
exp k r
0 A
1
1 A

(

|
|
.
|

\
|
=
X
C
H
T T
A
P
Rx
0
A
+ =
A
0 A
A
r
F
calculate r calculate
k calculate T calculate chooseX

A
0 A
r
F

X
V=?
0 1
1
v
X 1
T
1
T
1
R
E
exp k
dV
dX
(

|
|
.
|

\
|
=
A
P 0 A
Rx A a
C F
) T ( H r ) T T ( Ua
dV
dT A +
=
For a PFR with cooling
For a CSTR with cooling
) X 1 ( C
T
1
T
1
R
E
exp k
X F
V
0 A
1
1
0 A

|
|
.
|

\
|

=
A
P 0 A
0
A
P 0 A a Rx 0 A
C F UA
T C F UAT ) H ( X F
T
+
+ + A
=
12
Dissecting the Steady-State Molar Flow Rates
to Obtain the Heat of Reaction

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

d

1. The molar flow rates, F
i
and F
i0
2. The molar enthalpies, H
i
, H
i0

[H
i
=H
i
(T) and H
i0
=H
i
(T
0
)]
0 H F H F W Q
n
1 i
i i
n
1 i
0 i 0 i s
= +

= =

steady state
D
a
d
C
a
c
B
a
b
A + +
0 A
0 i
i 1 i 0 A i
F
F
) X ( F F = O v + O =
0 A i I
D 0 A D
C 0 A C
B 0 A B
0 A A
F F
X
a
d
F F
X
a
c
F F
X
a
b
F F
) X 1 ( F F
O =
|
.
|

\
|
+ O =
|
.
|

\
|
+ O =
|
.
|

\
|
O =
=
X F H H
a
b
H
a
c
H
a
d
] ) H H ( ) H H ( ) H H (
) H H ( ) H H [( F H F H F
0 A A B C D
I I 0 I D D 0 D C C 0 C
B B 0 B A 0 A 0 A
n
1 i
i i
n
1 i
0 i 0 i
|
.
|

\
|
+
O + O + O +
O + =

= =
Rx
H A
13
) T ( H ) T ( H
a
b
) T ( H
a
c
) T ( H
a
d
) T ( H
A B C D Rx
+ = A
All of enthalpies (e.g., H
A
, H
B
) are evaluated at the temperature at the outlet of the
system volume, and, consequently, [AH
Rx(
T)] is the heat of reaction at the specific
temperature T.
The heat of reaction is always given per mole of the species that is the basis of
calculation [i.e., species A (joules per mole of A reacted)].
X F ) T ( H ) H H ( F H F H F
0 A Rx i 0 i
n
1 i
i 0 A
n
1 i
i i
n
1 i
0 i 0 i
A O =

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

= =

0 X F ) T ( H ) H H ( F W Q
0 A Rx i 0 i
n
1 i
i 0 A s
= A O +

=

If a phase change takes place during the course of a reaction, this form of energy
balance must be used.
14
Dissecting the Enthalpies
Qi R
o
i i
) T ( H H AH + =
We are neglecting any enthalpy changes resulting from mixing so that
the partial molal enthalpies are equal to the molal enthalpies of the pure
components.
The molal enthalpy of species i at a particular temperature and pressure,
H
i
, is usually expressed in terms of an enthalpy of formation of species i
at some reference temperature T
R
, H
i
o
(T
R
), plus the change in enthalpy
AH
Qi
, that results when the temperature is raised from the reference
temperature, T
R
, to some temperature T.
(

A
+
(
(
(

+
(

A
+
(
(
(

+
(

A
+
(
(
(
(
(
(

=
(
(
(
(

toT gasfromT
g inheatin H
atT
vaporation
Heatof
toT mT liquidfro
g inheatin H

atT
melting
Heatof
toT T solidfrom
g inheatin H
T phaseat
olid iinthes
s ofspecie
n formatio
f Enthalpyo
atT
as iintheg
species
f Enthalpyo
b
Q
b
b R
Q
m
m R
Q
R
} } }
+ AH + + AH + + =
T
T
i
Pg b vi
T
T
i
Pl m mi
T
T
i
Ps R
o
i i
b
b
m
m
R
dT C ) T ( dT C ) T ( dT C ) T ( H ) T ( H
15
dT C ) T ( H H
T
T
Pi R
o
i i
R
}
+ =
single-phase chemical reactions
C
Pi
is heat capacity of species i
2
i i i Pi
T T C + | + o =
] T T [ C dT C
dT C ) T ( H dT C ) T ( H H H
0 i Pi
T
T
Pi
T
T
Pi R
o
i
T
T
Pi R
o
i 0 i i
0 i
0 i
R R
= =
(

+
(

+ =
}
} }
without phase change
constant heat capacities
0 X F ) T ( H ) H H ( F W Q
0 A Rx i 0 i
n
1 i
i 0 A s
= A O +

=

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

=

16
) T ( H ) T ( H
a
b
) T ( H
a
c
) T ( H
a
d
) T ( H
A B C D Rx
+ = A
) T T ( C ) T ( H dT C ) T ( H H
R Pi R
o
i
T
T
Pi R
o
i i
R
+ = + =
}
) 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
R
A
P
B
P
C
P
D
P
R
o
A R
o
B R
o
C R
o
D Rx

+ =
(

+ = A
) T ( H ) T ( H
a
b
) T ( H
a
c
) T ( H
a
d
) T ( H
R
o
A R
o
B R
o
C R
o
D R
o
Rx
+ = A
The heat of reaction at temperature T is given in terms of the enthalpy
of each species at temperature T
The heat of reaction at the reference temperature T
R
) T T ( C ) T ( H ) T ( H
R P R
o
Rx Rx
A + A = A
A
P
B
P
C
P
D
P P
C C
a
b
C
a
c
C
a
d
C + = A
overall change in the heart capacity
per mole of A reacted
T
R
=25C
pressure
17
Example 8-2
Calculate the heat of reaction for the synthesis of ammonia from hydrogen and nitrogen
at 150 C in kcal/mol of N
2
reacted and also in kJ/mol of H
2
reacted.
Solution
3 2 2
NH 2 H 3 N +
) T ( H ) T ( H 3 ) T ( H 2 ) T ( H
R
o
N R
o
H R
o
NH R
o
Rx
2 2 3
= A
Calculate the heat of reaction at the reference temperature using the heat of formation of the
reacting species obtained from Perrys Handbook or the Handbook of Chemistry of Physics.
reacted molN / cal 22040
molN
cal
) 11020 ( 2
H 2 0 ) 0 ( 3 ) T ( H 2 ) T ( H
2
2
o
NH R
o
NH R
o
Rx
3 3
= =
= = A
reacted molN / kJ 22 . 92 reacted molN / kcal 04 . 22 ) K 298 ( H
2 2
o
Rx
= = A
The minus sign indicates the reaction is exothermic
18
K molNH / cal 92 . 8 C
K molN / cal 984 . 6 C
K molH / cal 992 . 6 C
3
NH
P
2
N
P
2
H
P
3
2
2
=
=
=
K reacted molN / cal 12 . 10
984 . 6 ) 992 . 6 ( 3 ) 92 . 8 ( 2
C C 3 C 2 C
2
N
P
H
P
NH
P P
2 2 3
=
=
= A
) T T ( C ) T ( H ) T ( H
R P R
o
Rx Rx
A + A = A
2 2
2 2
Rx
molN / kJ 5 . 97 kcal / kJ 184 . 4 molN / kcal 3 . 23
molN / kcal 31 . 23 molN / cal 23310
) 298 423 )( 12 . 10 ( 22040 ) K 423 ( H
= =
= =
+ = A
2 2 2
2
Rx
molH
kJ
15 . 32
molN
kJ
5 . 97
molH 3
molN 1
) K 423 ( H =
|
|
.
|

\
|
= A
The heat of reaction based on the moles of H
2
reacted is
19
0 X F ) T ( H ) T T ( C F W Q
0 A Rx 0 i i
n
1 i
Pi i 0 A s
= A O

=

) T T ( C ) T ( H ) T ( H
R P R
o
Rx Rx
A + A = A
0 X F )] T T ( C ) T ( H [ ) T T ( C F W Q
0 A R P R
o
Rx 0 i i
n
1 i
Pi i 0 A s
= A + A O

=

In most systems, the work term, can be neglected.
In almost all of the systems, the reactants will be entering the system at
the same temperature; therefore T
i0
=T
0
.
Unless the reaction is carried out adiabatically, the above equation is still
difficult to evaluate because in nonadiabatic reactors, the heat added to
or removal from the system varies along the length of the reactor.
s
W

0 X F )] T T ( C ) T ( H [ ) T T ( C F Q
0 A R P R
o
Rx 0 Pi i 0 A
= A + A O

20
Adiabatic Operation
0 X F )] T T ( C ) T ( H [ ) T T ( C F Q
0 A R P R
o
Rx 0 Pi i 0 A
= A + A O

)] T T ( C ) T ( H [
) T T ( C
X
R P R
o
Rx
0 Pi i
A + A
O
=

) T T ( C ) T ( H
R P R
o
Rx
A >> A
P Pi i
R P 0 Pi i R
o
Rx
C X C
T C X T C )] T ( H [ X
T
A + O
A + O + A
=

0 ) T ( H
R
o
Rx
< A
applying to CSTR, PFR, PBR and batch reactor
) T , X ( r
dV
dX
F
A 0 A
=
T=f(V)
X=f(V)
C=f(V)
T=f(X) k=f(X)
-r
A
=f(X)
V=?
21
P Pi i
R P 0 Pi i R
o
Rx
C X C
T C X T C )] T ( H [ X
T
A + O
A + O + A
=

0 C
P
~ A
pure A enters
PA
R
o
Rx
0
C
)] T ( H [ X
T T
A
+ =
22
T=f(X)
k=f(X)
-r
A
=f(X)
K
c
=f(X)
T
0
/T
F
A0
/-r
A

X vs. F
A0
/-r
A

23
Example 8-3
Normal butane, C
4
H
10
, is to be isomerized to isobutane in a plug-flow reactor. Isobutane is a
valuable product that is used in the manufacture of gasoline additives. For example, isobutane
can be further reacted to form iso-octane. The 2004 selling price of n-butane was 72 cents per
gallon, while the price of isobutane was 89 cents per gallon.
The reaction is to be carried out adiabatically in the liquid phase under high pressure using
essentially trace amounts of a liquid catalyst which gives a specific reaction rate of 31.1 h
-1
at 360
K. Calculate the PFR and CSTR volumes necessary to process 100000 gal/day (163 kmol/h) at
70% conversion of a mixture 90 mol % n-butane and 10 mol % i-pentane, which is considered an
inert. The feed enters at 330 K.
K mol / J 141 C
K mol / J 161 KC mol / J 141 C
e tan Pen i e tan Bu
m / kmol 3 . 9 dm / mol 3 . 9 C , C 60 at 03 . 3 K
mol / kJ 7 . 65 onenergy activati , e tan bu mol / J 6900 H
B i
P
P i
P
B n
P
3 3
0 A C
Rx
=
= =

= = =
= = A

24
Solution
B A
H C i H C n
10 4 10 4

Mole Balance
0 A
A
F
r
dV
dX
=
Rate Law
|
|
.
|

\
|
=
C
B
A A
K
C
C k r
Stoichiometry (liquid phase, v=v
0
)
(

|
|
.
|

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

|
|
.
|

\
|

A
=
T
1
T
1
R
H
exp ) T ( K K
2
Rx
2 C C
X C C
) X 1 ( C C
0 A B
0 A A
=
=
Combining
(
(

|
|
.
|

\
|
+ = X
K
1
1 1 kC r
C
0 A A
dX
r
F
V
X
0
A
0 A
}

=
25
Energy Balance
0 X F )] T T ( C ) T ( H [ ) T T ( C F W Q
0 A R P R
o
Rx 0 Pi i 0 A s
= A + A O


0 141 141 C C C
0 W
0 Q
A
P
B
P P
s
= = = A
=
=

O
A
+ =
Pi i
o
Rx
0
C
X ) H (
T T
Parameter Evaluation
K mol / J 159 161
9 . 0
1 . 0
141 C C C
PI I PA Pi i
=
|
.
|

\
|
+ = O + = O

X 4 . 43 330 X
159
) 6900 (
330
C
X ) H (
T T
Pi i
o
Rx
0
+ =

+ =
O
A
+ =

1
1
1
h
T 360
360 T
7906 exp 3 . 31
T
1
360
1
314 . 8
65700
exp 3 . 31
T
1
T
1
R
E
exp ) T ( k k

(

|
.
|

\
|

=
(

|
.
|

\
|
=
(

|
|
.
|

\
|
=
(

|
.
|

\
|

=
(

|
.
|

\
|

=
(

|
|
.
|

\
|

A
=
T 333
333 T
3 . 830 exp 03 . 3
T
1
333
1
314 . 8
6900
exp 03 . 3
T
1
T
1
R
H
exp ) T ( K K
2
Rx
2 C C
26
Equilibrium Conversion
(
(

|
|
.
|

\
|
+ = X
K
1
1 1 kC r
C
0 A A
C
C
e
K 1
K
X
+
=
0 r
A
=
) T ( f K
C
=
) T ( f X
e
=
PFR Solution ~ hand calculation
3
3
A
0 A
3 3 1
A
e
C
1
m 78 . 2
h m / kmol 8 . 52
) h / l kmoltota 163 )( moltotal / e tan molbu 9 . 0 (
r
F
h m / kmol 8 . 52 ) 2 . 0 (
9 . 2
1
1 1 ) dm / mol 3 . 9 )( h 76 . 7 ( r
74 . 0
9 . 2 1
9 . 2
X
9 . 2
) 6 . 338 )( 333 (
333 6 . 338
3 . 830 exp 03 . 3 K
h 76 . 7
) 6 . 338 )( 360 (
360 6 . 338
7906 exp 1 . 31 k
K 6 . 338 ) 2 . 0 ( 4 . 43 330 T
2 . 0 X
=

=
(

|
.
|

\
|
+ =
=
+
=
=
(

|
|
.
|

\
|
=
=
(

|
|
.
|

\
|
=
= + =
=

27
3
6 . 0
0
7 . 0
6 . 0
A
0 A
A
0 A
7 . 0
0
A
0 A
m 60 . 2
] 29 . 23 99 . 5 4 88 . 3 [
2
1 . 0
3
1
] 88 . 3 50 . 2 3 78 . 2 3 74 . 3 [
3
6 . 0
8
3

dX
r
F
dX
r
F
dX
r
F
V
=
+ + + + + + =

=
} } }
PFR Solution ~ computer solution
B A X
K
1
1 1 kC r
C
0 A A
=
(
(

|
|
.
|

\
|
+ =
Near the entrance to the reactor, T
increases as does k, causing term A to
increase more rapidly than term B
decreases, and thus the rate increases.
Near the end of the reactor, term B is
decreasing more rapidly than term A
is increasing. As a result, owing to
theses two competing effects, we have
a maximum in the rate of reaction.
X=0.4
V=1.15 m
3
28
CSTR Solution
(
(

|
|
.
|

\
|
+ = X
K
1
1 1 kC r
C
0 A A
A
0 A
r
X F
V

=
(

|
|
.
|

\
|
+
=
X
K
1
1 1 kC
X F
V
C
0 A
0 A
3
3
m 0 . 1
h m / kmol 6 . 58
) 4 . 0 )( h / e tan kmolbu 7 . 146 (
V =

=
4 . 0 X=
CSTR volume (1 m
3
) to achieve 40%
conversion in this adiabatic reaction
is less than PFR volume (1.15 m
3
).
29
Steady-State Tubular Reactor with Heat Exchange
0 H F H F Q
V V
i i
V
i i
= + A
A +

Assume that there no radial gradients in

the reactor and that the heat flux through
the wall per unit volume of reactor is as
shown in Figure 8.3
) T T ( V Ua ) T T ( A U Q
a a
A = A = A

T
a
is ambient temperature
T is reactor temperature
actor lumeofre erunitvo ngeareap heatexcha
D
4
4
L D
DL
V
A
a
2
= =
t
t
= =
0
dV
) H F ( d
) T T ( Ua
i i
a
=

0
dV
dH
F H
dV
dF
) T T ( Ua
i
i i
i
a
=

30
) r ( r
dV
dF
A i i
i
v = =
dV
dT
C
dV
dH
i
P
i
=
0
dV
dT
C F ) r ( H v ) T T ( Ua
i
P i A i i a
=

A
=
i
P i
a Rx A
C F
) T T ( Ua H r
dV
dT
heat generated
heat removed
) X ( F F
i i 0 A i
v + O =
) X C C ( F
H r ) T T ( Ua
dV
dT
P
i
P i 0 A
Rx A a
A + O
A +
=

A +

=
i
P i
Rx A a
b
C F
H ' r ) T T (
Ua
dW
dT
packed bed reactor
c
P c
a a
0 A
A
C m
) T T ( Ua
dV
dT
) T , X ( f
F
r
dV
dX
) T , X ( g
dV
dT

=
=

=
=
) V ( function X
) V ( function T
=
=
31
Example 8-4
When we checked the vapor pressure at the exit to the adiabatic reactor in Example 8-3 where
the temperature is 360 K, we found the vapor pressure to be about 1.5 MPa for isobutene, which
is greater than the rupture pressure of the glass vessel being used. Fortunately, there is a bank of
ten partially insolated (Ua=5000 kJ/hm
3
K) tubular reactors each 6 m
3
over in the storage shed
available for use. We are also going to lower the entering temperature to 310 K. The reactors are
cooled by natural convection where average ambient temperature in this tropical location is
assumed to be 37C. The temperature in any of the reactors cannot rise above 325 K. Plot X, X
e
,
T, and the reaction rate along the length of the reactor. Does the temperature rise above 325 K?
Solution
h / kmol 7 . 14
10
1
) h / kmol 163 )( 9 . 0 ( F
0 A
= =
(
(

|
|
.
|

\
|
+ = X
K
1
1 1 kC r
C
0 A A
Mole Balance
0 A
A
F
r
dV
dX
=
Rate Law and Stoichiometry
1
h
T 360
360 T
7906 exp 3 . 31 k

(

|
.
|

\
|

=
(

|
.
|

\
|

=
T 333
333 T
3 . 830 exp 03 . 3 K
C
32
C
C
e
K 1
K
X
+
=
At equilibrium
) X C C ( F
H r ) T T ( Ua
dV
dT
P
i
P i 0 A
Rx A a
A + O
A +
=

0 C
P
= A

O
A +
=
i
P i 0 A
Rx A a
C F
H r ) T T ( Ua
dV
dT
mol / kJ 6900 H
K 310 T
K h m / kJ 5000 Ua
K kmol / kJ 159 C
Rx
a
3
Pi i
= A
=
=
= O

Note that the temperature did not rise

above 325 K.
33
Balance on the Coolant Heat Transfer Fluid
~The heat transfer fluid will be a coolant for exothermic reactions and a heating
medium for endothermic reactions.
~If the flow rate of the heat transfer fluid is sufficiently high with respect to the
heat released (or adsorbed) by the reacting mixture, then the heat transfer
fluid temperature will be constant along the reactor.
~We develop the basic equations for a coolant to remove heat from exothermic
reactions, however these same equations apply to endothermic reactions where
a heating medium is used to supply heat.
We carry out the balance on the coolant in the annulus between R
1
and R
2
and
between V and V+AV. The mass flow rate of coolant is . We will consider
the case when the outer radius of the coolant channel R
2
is insulated.
em othesyst ataddedt isthehe Q

c
m

34
Case A Co-Current Flow
0 V ) T T ( Ua H m H m
0
erwall theinn
h ionthroug byconduct
eatadded Rateofh
V outatV
ergy Rateofen
inatV
ergy Rateofen
a
V V
c c
V
c c
= A +
=
(
(
(

+
(

A +

A +

e innertub ureinthe atingmixt ofthere emperature Tisthet
erature olanttemp istheco T
a
The reactant and the coolant flow in the same direction.
0 ) T T ( Ua
dV
dH
m
a
c
c
= +
dV
dT
C
dV
dH
a
c
P
c
=
c
P c
a a
C m
) T T ( Ua
dV
dT

=
0 V A
35
Case B Counter-Current Flow
The reacting mixture and coolant flow in opposite direction.
0 V ) T T ( Ua H m H m
0
erwall theinn
h ionthroug byconduct
eatadded Rateofh
V inatV
ergy Rateofen
outatV
ergy Rateofen
V inatV
ergy Rateofen
a
V
c c
V V
c c
= A +
=
(
(
(

+
(

A +
+
(

A +
A +

0 ) T T ( Ua
dV
dH
m
a
c
c
= +
dV
dT
C
dV
dH
a
c
P
c
=
c
P c
a a
C m
) T T ( Ua
dV
dT

=
0 V A
0 a a f
2 a a
T T V V
T T 0 V
= =
= =
) V ( f T
a
=
36
Solution to the counter current flow problem to find the exit conversion and
temperature requires a trial-and-error procedure.
Consider an exothermic reaction where the coolant stream enters at the end of
the reactor (V=V
f
) at a temperature T
a0
, say 300 K. We have to carry out a
trail-and-error procedure to find the temperature of coolant exiting the reactor.
Assume a coolant temperature at the feed entrance (X=0, V=0) to the reactor to
be T
a2
= 340 K as shown in (a).
Use an ODE solver to calculate X, T, and T
a
as a function of V. We see from
Figure (a) that our guess of 340 K for T
a2
at the feed entrance (V=0 and X=0)
gives an entering temperature of the coolant of 310 K (V=V
f
), which does not
match the actual entering coolant temperature of 300 K.
Now guess a coolant temperature at V=0
and X=0 of 330 K. We see from Figure (b)
that an exit coolant temperature of T
a2
=
330 K will give a coolant temperature at
V
f
of 300 K, which matches the actual T
a0
.
37
38
39
40
41
Jeffreys, in a treatment of the design of an acetic anhydride manufacturing facility states
that one of the key steps is the vapor-phase cracking of acetone to ketene and methane:

He states further that this reaction is the first-order with respect to acetone and that the
specific reaction rate can be expressed by


where k is in reciprocal seconds and T is in kelvin. In this design it is desired to feed 7850
kg of acetone per hour to a tubular reactor. The reactor consists of a bank of 1000 1-inch
schedule 40 tubes. We will consider three case:
A.CASE 1 The reactor is operated adiabatically.
B.CASE 2 The reactor is surrounded by a heat exchanger where the heat-transfer
coefficient is 110 J/m
2
sK, and the temperature of the heating medium, T
a
, is
constant at 1150 K.
C.CASE 3 The heat exchange in Case 2 now has a variable heating medium temperature.
The inlet temperature and pressure are the same for both cases at 1035 K and 162 kPa
(1.6 atm), respectively. Plot the conversion and temperature along the length of the
reactor.
Example 8-5
4 2 3 3
CH CO CH COCH CH +
T
34222
34 . 34 k ln =
42
C B A
CH CO CH COCH CH
4 2 3 3
+
+
Solution
0 A
A
F
r
dV
dX
=
Mole Balance
Rate Law
A A
kC r =
Stoichiometry (gas-phase reaction with no pressure drop)
1 ) 1 1 1 ( 1 y
T ) X 1 (
T ) X 1 ( C
C
0 A
0 0 A
A
= + = o = c
c +

=
Combing
T
T
X 1
) X 1 ( kC
r
0 0 A
A
+

=
T
T
X 1
X 1
v
k
F
r
dV
dX
0
0 0 A
A
|
.
|

\
|
+

=
To solve this differential equation, it is
first necessary to use the energy balance
to determine T as a function of X.
43
CASE 1. ADIABATIC OPERATION
) X C C ( F
H r ) T T ( Ua
dV
dT
P
i
P i 0 A
Rx A a
A + O
A +
=

) X C C ( F
)]) T T ( C ) T ( H [ )( r (
dV
dT
P
i
P i 0 A
R P R
o
Rx A
A + O
A + A
=

) 0 U ., e . i ( 0 Q
0 W
s
= =
=

) X C C ( F
)]) T T ( C ) T ( H [ )( r (
dV
dT
P
A
P 0 A
R P R
o
Rx A
A +
A + A
=
A
P
i
P i
C C = O

3
3
3
0 A
0 A
0
3
3
0 A
0 A
0 A
dm 5
tubes 1000
m 5
sV / dm 037 . 2
C
F
v
dm / mol 8 . 18
) K 1035 (
K kmol
m kPa
31 . 8
kPa 162
RT
P
C
s / mol 0376 . 0
tubes 1000
1
mol / g 58
h / kg 7850
F
= = = =
=

= =
= =
44
mol / kJ 77 . 80
mol / kJ ) 67 . 216 ( ) 81 . 74 ( ) 09 . 61 (
) T ( H ) T ( H ) T ( H ) T ( H
mol / kJ 81 . 74 ) T ( H
mol / kJ 09 . 61 ) T ( H
mol / kJ 67 . 216 ) T ( H
R
o
A R
o
C R
o
B R
o
Rx
R
o
C
R
o
B
R
o
A
=
+ =
+ = A
=
=
=
K mol / J 9
K mol / J ) 163 71 83 (
C C C C
K mol / J 71 C
K mol / J 83 C
K mol / J 163 C
A
P
C
P
B
P P
C
P
B
P
A
P
=
+ =
+ = A
=
=
=
45
As temperature drops, so does k and hence the rate, -r
A
, drops to an insignificant value.
Note that for this adiabatic endothermic reaction, the reaction virtually dies out after 3.5 m
3
,
owing to the large drop in temperature, and very little conversion is achieved beyond this
point. One way to increase the conversion would be to add a diluent such as nitrogen, which
could supply the sensible heat for this endothermic reaction. However, if too much diluent is
added, the concentration and rate will be quite low. On the other hand, if too little diluent is
added, the temperature will drop and virtually extinguish the reaction.
A bank of 1000 1-in. schedule 40 tubes 1.79 m in length corresponds to 1.0 m
3
and gives 20%
conversion. Ketene is unstable and tends to explode, which is a good reason to keep the
conversion low. However, the pipe material and schedule size should be checked to learn if
they are suitable for these temperatures and pressures.
46
CASE 2. HEAT EXCHANGE WITH CONSTANT HEATING MEDIUM TEMPERATURE
1
s
T
1
1035
1
34222 58 . 3 ) T ( k

(

|
.
|

\
|
=
) X C C ( F
H r ) T T ( Ua

) X C C ( F
H r ) T T ( Ua
dV
dT
P
A
P 0 A
Rx A a
P
i
P i 0 A
Rx A a
A +
A +
=
A + O
A +
=

K s m / J 16500
m 150 K s m / J 110 Ua
m 150
m 0266 . 0
4

D
4
L ) 4 / D (
DL
a
3
1 2
1
2
=
=
= =
=
t
t
=

47
One notes that the reactor temperature goes through a minimum along the length of the
reactor. At the front of the reactor, the reaction takes place very rapidly, drawing energy
from the sensible heat of the gas causing the gas temperature to drop because the heat
exchange cannot supply energy at an equal or greater rate. This drop in temperature,
coupled with the consumption of reactants, slows the reaction rate as we move down the
reactor. Because of this slower reaction rate, the heat exchanger supplies energy at a rate
greater than reaction draws energy from the gases and as a result the temperature
increases.
48
CASE 3. HEAT EXCHANGE WITH VARIABLE HEATING MEDIUM TEMPERATURE
c
P c
a a
C m
) T T ( Ua
dV
dT

=
Air will also be used as a heating stream in a
co-current direction entering at a temperature
of 1250 K and at molar rate of (0.11 mol/s).
The heat capacity of the air is 34.5 J/molK.
K s / J 83 . 3
K mol
J
5 . 34
s
mol
11 . 0 C m
c
P c
=
|
.
|

\
|

|
.
|

\
|
=