Example 8 - 7 Production of Acetic Anhydride

Jeffreys
1
, 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 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 8000 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 two cases:

1. The reactor is operated adiabatically.
2. The reactor is surrounded by a heat exchanger where the heat-transfer coefficient is
110 J/m
2
AsAK and the ambient temperature is 1150 K.

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.

Solution

Let A = CH3COCH3, B = CH2CO, and C = CH4. Rewriting the reaction in symbols gives us
1. Mole Balance:

2. Rate law:



1
G. V. Jeffreys, "A Problem in Chemical Engineering Design: The Manufacture of Acetic
Anhydride", 2
nd
ed. (London: Institution of Chemical Engineers, 1964).
4 2 3 3
CH CO CH COCH CH +


T
k
222 , 34
34 . 34 ) ( ln



C B A +

A
R
A
r
dV
F d

A A
kC r

3. Stoichiometry:
4. Combining yields:

RT
P
F F F F
F
k
dV
F d
A Co Bo Ao
A
R
A
+ +

2


5. Energy Balance:

CASE I. Adiabatic Operation

For no work done on the system,
0

s W
, and adiabatic operation,
0

Q
(i.e., U = 0),
the energy balance becomes

( )

i
p
r
R
i
C F
r T at H
dV
T d


6. Calculation of mole balance parameters:

s mol h kmol
mol g
h kg
F
Ao
/ 3 . 38 / 9 . 137
/ 58
/ 8000



( )
( )
T
A
A
A T A A
A Co Bo Ao C B A T
A Ao Co C
A Ao Bo B
F
F
y
RT
P
y C y C
F F F F F F F F
F F F F
F F F F

+ + + +
+
+
2



7. Calculation of energy balance parameters:

( ) ( )
( )
( )
( )
( )( )
( )( )
( )( )
( ) ( ) ( )
3 3 6 2 2 3
3 3 6 6 6
2 2
298 2 6
2 6
2 6
298
298 10 267 . 1 298 10 75 . 5 298 8 . 6 / 80770
298 10 71 . 18 10 95 . 30 10 86 . 45
3
1
298 077 . 0 0945 . 0 183 . 0 5 . 0
298 39 . 13 04 . 20 63 . 26 / 77 . 80
10 71 . 18 077 . 0 39 . 13 1
10 95 . 30 0945 . 0 04 . 20 1
10 86 . 45 183 . 0 63 . 26 1
/ 77 . 80
298
+
+ +
+ +
+ + + +
1
1
1
]
1

+ +
+ +
+
+
+

T T T mol J
T
T
T mol kJ
dT
T T
T T
T T
mol kJ
dT C K at H T at H
T
K
i
T
K
p i r r
i

( )
( ) ( )( )
( ) ( )( )
( )
( )
2 6
2 6
2 6
2 6
2 6
10 8 . 3 0115 . 0 8 . 6
10 66 . 49 1715 . 0 43 . 33
10 71 . 18 077 . 0 39 . 13
10 95 . 30 0945 . 0 04 . 20
10 86 . 45 183 . 0 63 . 26
T T F
T T F
T T F F F
T T F F F
T T F
C F C F C F C F
A
Ao
A Ao Co
A Ao Bo
A
p
C
p
B
p
A
i
p i
C B A
i

+
+ +
+ + +
+ +
+ +

Substituting the values calculated above into the two balance equations we may solve the
material and energy balance equations simultaneously using the following MathCAD
program.

Example 8-7 Adiabatic Operation
First define all of the variables either as constants or functions
P 162 10
3
:
k T ( ) exp 34.34
34222
T

,
:
C
T
T ( )
P
8.31 T
:


F
Ao
38.3 :
DHr T ( ) 80770 6.8 T 298 ( ) + 5.75 10
3
T
2
298
2

( )
1.267 10
6
T
3
298
3

( )
:
FICPI F
A
T , ( ) F
Ao
33.43 0.1715 T + 49.66 10
6
T
2

( )
F
A
6.8 0.0115 T 3.8 10
6
T
2

( )
:
y
A
F
A
( )
F
A
2 F
Ao
F
A

:
Now give the initial conditions for the integrator
y
F
Ao
1035

,
:
and define the matrix that contains the two balance equations
D V y , ( )
k y
1
( ) y
A
y
0
( ) C
T
y
1
( )
DHr y
1
( ) k y
1
( ) y
A
y
0
( ) C
T
y
1
( )
FICPI y
0
y
1
, ( )

,
:
We now can start the integrator. We will integrate (as does Fogler) to a reactor volume of 5 m
3
.
Z Rkadapt y 0 , 5 , 100 , D , ( ) :
Change the molar flow rates for A (in the second column of Z) into conversion, then plot the results.
i 0 100 .. :

i 0 100 .. :
X
i
F
Ao
Z
i 1 , ( )

F
Ao
:
0 0.5 1 1.5 2 2.5 3 3.5 4
0
0.1
0.2
0.3
Conversion Profile
Reactor volume (m**3)
C
o
n
v
e
r
s
i
o
n

o
f

A


0 1 2 3 4
900
950
1000
1050
Temperature Profile
Reactor Volume (m**3)
T
e
m
p
e
r
a
t
u
r
e

(
K
)


As was observed by Fogler, the reaction essentially stops due to the lowering of the temperature
in the adiabatic reactor. Lets go on to the case with heat transfer.

CASE II. Operation of a PFR with Heat Exchange

We can use the material balance portion from the prior case without change. The changes in this
part of the problem come only in the energy balance portion. Thus,

5. Energy Balance

( ) ( )

i
p
hx r
R
i
C F
T T UA r T at H
dV
T d


6. Parameter Evaluation

The one thing we will have to change is the fact that the reactor is composed of 1000
individual tubes. Since the heat transfer area depends on the tube size we will need to
do our analysis on one tube, then multiply by 1000 to get the total. Thus the initial
molar flow rate of A into a single tube is (38.3 mol/s)/1000 or
s mol F
Ao
/ 0383 . 0


The surface area per volume in a cylindrical tube is 4/D so

1
150
0266 . 0
4 4

m
m D
A


All of the other parameters remain as for the adiabatic case. We now can solve the
material and energy balance equations simultaneously using the MathCAD program
below

Example 8-7 Operation with heat exchange
First define all of the variables either as constants or functions
P 162 10
3
:
U 110 :
A 150 :
T
hx
1150 :
k T ( ) exp 34.34
34222
T

,
:
C
T
T ( )
P
8.31 T
:
F
Ao
38.3 :
DHr T ( ) 80770 6.8 T 298 ( ) + 5.75 10
3
T
2
298
2

( )
1.267 10
6
T
3
298
3

( )
:
FICPI F
A
T , ( ) F
Ao
33.43 0.1715 T + 49.66 10
6
T
2

( )
F
A
6.8 0.0115 T 3.8 10
6
T
2

( )
:
y
A
F
A
( )
F
A
2 F
Ao
F
A

:
Now give the initial conditions for the integrator
y
F
Ao
1035

,
:
and define the matrix that contains the two balance equations
D V y , ( )
k y
1
( ) y
A
y
0
( ) C
T
y
1
( )
DHr y
1
( ) k y
1
( ) y
A
y
0
( ) C
T
y
1
( ) ( ) U A T
hx
y
1
( ) +
FICPI y
0
y
1
, ( )

1
1
1
1
]
:


We now can start the integrator. We will integrate (as does Fogler) to a reactor volume of 1 m
3
.
Z Rkadapt y 0 , 1 , 100 , D , ( ) :
Change the molar flow rates for A (in the second column of Z, into conversion, then plot the results.
i 0 100 .. :
X
i
F
Ao
Z
i 1 , ( )

F
Ao
:
0 0.2 0.4 0.6 0.8 1
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
Conversion Profile
Reactor Volume (m**3)
C
o
n
v
e
r
s
i
o
n

o
f

A
0 0.2 0.4 0.6 0.8 1
1010
1015
1020
1025
1030
1035
1040
1045
1050
Temperature Profile
Reactor Volume (m**3)
T
e
m
p
e
r
a
t
u
r
e

(
K
)