Example 8-4 Production of Propylene Glycol in an Adiabatic CSTR

Propylene glycol is produced by the hydrolysis of propylene oxide:

C B A
O H C O H O H C
+
+
2 8 3 2 6 3


Over 800 million pounds of propylene glycol was produced in 1997 and the selling price was
approximately $0.67 per pound. Propylene glycol makes up about 25% of the major derivatives
of propylene oxide. The reaction takes place readily at room temperature when catalyzed by
sulfuric acid.
You are the engineer in charge of an adiabatic CSTR producing propylene glycol by this
method. Unfortunately, the reactor is beginning to leak, and you must replace it. (You told your
boss several times that sulfuric acid was corrosive and that mild steel was a poor material for
construction.) There is a nice overflow CSTR of 300-gal capacity sitting idle; it is glass-lined and
you would like to use it.
You are feeding 2500 lb/hr (43.04 lb mol/hr) of propylene oxide (PO) to the reactor. The
feed stream consists of (1) an equivolumetric mixture of propylene oxide (46.62 ft
3
/hr) and
methanol (46.62 ft
3
/hr), and (2) water containing 0.1 wt% H2SO4. The volumetric flow rate of
water is 233.1 ft
3
/hr, which is 2.5 times the methanol-PO flow rate. The corresponding molar
flow rates of methanol and water are 71.87 and 802.8 lb mol/hr, respectively. The water-
propylene oxide-methanol mixture undergoes a slight decrease in volume upon mixing
(approximately 3%), but you neglect this in your calculations. The temperature of both
feedstreams is 58

F prior to mixing, but there is an immediate 17

F temperature rise upon mixing of

the two feedstreams caused by the heat of mixing. The entering temperature of all feedstreams is
thus taken to be 75

F (see Figure E8-4.1).

Furusawa et al.
1
state that under conditions similar to those at which you are operating,
the reaction is first order in propylene oxide concentration and apparent zero order in water due to
the excess of water with the specific reaction rate

( )
1 / 32400 12 /
10 96 . 16

h e e A k
RT RT E


The units of E are BTU/lb mol.
There is an important constraint on your operation. Propylene oxide is a rather low boiling
substance (b.p. at 1 atm, 93.7

F). With the mixture you are using, you feel that you cannot exceed
an operating temperature of 125

F, or you will lose too much by vaporization through the vent

system.
Can you use the idle CSTR as a replacement for the leaking one if it will be operated
adiabatically? If so, what will be the conversion of oxide to the glycol?


1
T. Furusawa, H. Nishimura, and T. Miyauchi, J. Chem. Eng. Jpn., 2, 95 (1969).

SOLUTION

(All data used in this problem were obtained from the Handbook of Chemistry and Physics
unless otherwise noted.) Let the reaction be represented by

C B A +


in which

A is propylene oxide (MW=58.08; ?=0.859 g/cm
3
; Cp=35 BTU/lb mol-

F
2
)
B is water (MW=18.02; ?=0.9941 g/cm
3
; Cp=18 BTU/lb mol-F)
C is propylene glycol (MW=76.11; ?=1.036 g/cm
3
; Cp=46 BTU/lb mol-F
2
)
M is methanol (MW=32.04; ?=0.7914 g/cm
3
; Cp=19.5 BTU/lb mol-F)

In this problem neither the exit conversion nor the temperature of the adiabatic reactor is
given. By application of the material and energy balances we can solve two equations with two
unknowns (FA and T). Solving these coupled equations, we determine the exit flow rates
(conversion) and temperature for the glass-lined reactor to see if it can be used to replace the
present reactor.

1. Mole balance equation:

0 + V r F F
A A Ao

2. Rate law:

A A
C k r


3. Stoichiometry (liquid phase,

v v v out in
):

( )
( )

+

v
F
C
F F F F
F F F F
i
i
A Ao Co C
A Ao Bo B


4. Combining the results and solving for FA recalling that

v
V

gives


2
Estimated from the observation that the great majority of low-molecular-weight oxygen-
containing organic liquids have a mass heat capacity of 0.6 cal/g@
E
C" 15%.
( )
( ) ( )
RT E
Ao Ao
A
Ao Ao
A
A Ao
A A Ao
e A
F
k
F
F
F k F
V
v
F
k F F
V C k F F
/
1 1
1
0
0

This equation relates the temperature and molar flow rate of A.

5. The energy balance for this adiabatic reactor in which there is negligible energy input
provided by the stirrer is

( )
( )
( ) ( )
Ao A
A
T
T
out r p
inlet
i
A
A
T
T
out r p
inlet
i
T
T
out r p
inlet
i
F F T H dT C F
V
r
T H dT C F
V r T H dT C F Q
outlet
inlet
i
outlet
inlet
i
outlet
inlet
i

+
+

1
0


Since the heat capacities are all constants the integral shown on the left hand side of this
equation can be computed to give

T C F T C F T C F T C F dT C F
M C B A
outlet
inlet
i
p Mo p Co p Bo p Ao
T
T
p
inlet
i
+ + +

This equation can be substituted into the energy balance and, along with the fact that,
1
A

the energy balance can be solved to also give FA as a function of T

( ) ( )
( )
out r
Ao out r p Mo p Co p Bo p Ao
A
T H
F T H T C F C F C F C F
F
M C B A

+ + + +

We also need to have an expression for the heat of reaction at out
T
.

( ) ( )
( ) ( ) ( ) [ ]
( ) R T
dT
dT C T H T H
out
T
T
i
T
T
p i ref r out r
out
ref
out
ref
i
o
528 7 400 , 36
46 1 18 1 35 1 400 , 36

+ + + +
+

6. Solution:
We have two simultaneous equations in FA and T which must be solved simultaneously.
The following MathCAD program does this both graphically and numerically.

Example Problem 8-4, Fogler
First define all of the constant values
F
Ao
43.03
lb mole
hr
: C
pA
35
BTU
lb mole R
:
F
Bo
802.8
lb mole
hr
: C
pB
18
BTU
lb mole R
:
F
Co
0.0
lb mole
hr
: C
pC
46
BTU
lb mole R
:
F
M
71.87
lb mole
hr
: C
pM
19.5
BTU
lb mole R
:
V 300 gal :
vdot 46.62
ft
3
hr
46.62
ft
3
hr
+ 233.1
ft
3
hr
+ :
vdot 40.687
gal
min

V
vdot
:
0.123hr
Sum F
Ao
C
pA
F
Bo
C
pB
+ F
Co
C
pC
+ F
M
C
pM
+ :


X 0.857
X
F
Ao
F
A

F
Ao
:
T 613.621R
F
A
6.146
lb mole
hr

F
A
T

,
find x y , ( ) :
x
Sum y 535 R ( ) DelHr y ( ) F
Ao
+
DelHr y ( )
0
lb mole
hr

x
F
Ao
1 k y ( ) +
Given
To start the solver we first type the key word "Given" then write the expressions we want solved
making sure to use the Boolean equal sign
y 600 R :
x 20
lb mole
hr
:
To invoke the solver routine in MathCAD we'll first need to provide initial guesses for both F
A
and T.
If we assume about 50% conversion then F
A
will be about 20. The initial temperature is 528R so
let's guess 600R since the reaction is exothermic.
k T ( ) 16.96 10
12
hr
1
exp
32400
BTU
lb mole

1.987
BTU
lb mole R
T

1
1
1
1
]
:
DelHr T ( ) 36400
BTU
lb mole
7
BTU
lb mole R
T 528 R ( ) :
F
C
F
A
( ) F
Co
F
Ao
F
A
( ) + :
F
B
F
A
( ) F
Bo
F
Ao
F
A
( ) :
Since there are two unknowns (F
A
and T) express all other variable in terms of these two.


We can also put together a plot like Fogler does in his example. To do this let's first define two
functions. One will be F
A
as determined by the material balance and the other will be F
A
as
determined by the energy balance.
F
Amb
T ( )
F
Ao
1 k T ( ) +
:
F
Aeb
T ( )
Sum T 535 R ( ) DelHr T ( ) F
Ao
+
DelHr T ( )
:
Now define a range of values for T
T
range
535 635 .. :
And now plot the results
520 540 560 580 600 620 640
0
0.002
0.004
0.006
FAmb
FAeb
Adiabatic CSTR Example
Temperature (R)
M
o
l
a
r

F
l
o
w

R
a
t
e

o
f

A

(
k
g
m
o
l
e
/
s
e
c
)
The common point for these two functions, i.e., the solution, is at about 613 R and F
A
=8x10
-4

kgmole/sec = 6.3 lbmole/hr
Example 8-5 CSTR with a Cooling Coil

A cooling coil has been located for use in the hydration of propylene oxide discussed in Example
8-4. The cooling coil has 40 ft
2
of cooling surface and the cooling water flow rate inside the coil is
sufficiently large that a constant coolant temperature of 85

F is maintained. A typical overall heat

transfer coefficient for such a coil is 100 BTU/h-ft
2
-R. Will the reactor satisfy the previous
constraint of 125

F maximum temperature if the cooling coil is used?

SOLUTION

Nothing changes from the previous solution except for the energy balance which now
becomes

( ) ( )
( ) ( )
Ao A
A
T
T
out r p
inlet
i
T
T
out r p
inlet
i hx
F F T H dT C F
V r T H dT C F T T UA Q
outlet
inlet
i
outlet
inlet
i
+
+

1


Solving this equation for FA gives the following result

( ) ( )
( )
out r
hx p Mo p Co p Bo p Ao
Ao A
T H
T T UA T C F C F C F C F
F F
M C B A

+ + + +
+


Again we have two simultaneous equations in FA and T which can be solved using the
following MathCAD program. As in the example in the text we obtain an outlet molar
flow rate for the propylene oxide of 27.4 lb mol/hr (36.3% conversion) and an exit stream
temperature of 563.7

R (103.7

F).

This portion of the MathCAD program is a continuation of the adiabatic case. Thus all of the
constants and functions of Fa and T have already been defined. We need to add only the values for
the heat transfer coefficient, the cooling coil area and the coolant temperature and then solve the
resulting simultaneous equations
U 100
BTU
hr ft
2
R
:
A 40 ft
2
:
T
hx
545 R :


Now invoke the solver as before
x 20
lb mole
hr
:
y 600 R :
Given
x
F
Ao
1 k y ( ) +
x F
Ao

U A T
hx
y ( ) Sum y 535 R ( )
DelHr y ( )
+ 0
lb mole
hr

F
A
T

,
find x y , ( ) :
F
A
27.422
lb mole
hr

T 563.655R
We may also construct the plot of each balance independently as we did in the adiabatic case
F
Amb
T ( )
F
Ao
1 k T ( ) +
:
F
Aeb
T ( ) F
Ao
Sum T 535 R ( ) UA T
hx
T ( )
DelHr T ( )
+ :
520 540 560 580 600 620 640
0
0.0013
0.0025
0.0038
0.005
0.0063
FAmb
FAeb
CSTR with Heat Exchange Example
Temperature (R)
M
o
l
a
r

F
l
o
w

R
a
t
e

o
f

A

(
k
g
m
o
l
e
/
s
e
c
)