542 Unsteady-State Nonisothermal Reactor Design Chap.

Example 9-2 Safety in Chemical Plants with Exothermic Reactions

A serious accident occurred at Monsanto plant in Sauget, Illinois, on August 8 at
A. M. (see Figure E9-2.1). The blast was heard as far as miles away in
Belleville, Illinois, where people were awakened from their sleep. The explosion
occurred in a batch reactor that was used to produce from ammonia and
o-nitrochlorobenzene (ONCB):

Was a Potential Figure E9-2.1 Aftermath of the explosion. Louis Globe Democrat photo by
Problem Analysis
carried out? Roy Cook of Mercantile Library.)

This reaction is normally carried out isothermally at 175°C and about 500 psi. The
ambient temperature of the cooling water in the heat exchanger 25°C. By adjusting
the coolant rate the reactor temperature could be maintained at 175°C. At the maxi-
mum coolant rate the ambient temperature 25°C throughout the heat exchange.
On the day of the accident, two changes in normal operation occurred.
1. The reactor was charged with 9.044 kmol of ONCB, 33.0 kmol of and
103.7 kmol of Normally, the reactor charged with kmol of
ONCB, 103.6 kmol of and 43 of

Adapted from the problem by Ronald Seminar on a Reactor

Prepared for Center for Chemical Process Safety, American Insti-
tute of Chemical Engineers, New York (1994). The values of and UA were esti-
mated in the plant data of the temperature-time trajectory in the article by G. C.
Vincent, Loss Prevention, Vol. 5. p. 46-52, AIChE, New York NY.
 9.2 Unsteady Operation of CSTRs and Semibatch Reactors 543

A management 2. The reaction is normally carried out isothermally at 175°C over a 24-h period.
decision was made Approximately 45 after the reaction was started, cooling to the reactor
to triple production was halted, but only for 10 min. Cooling may have been halted for 10 min or
so on previous occasions when the normal charge of 3.17 kmol of ONCB was
used and no ill effects occurred.
The reactor had a safety relief valve whose disk would rupture when the pres-
sure exceeded approximately 700 psi. Once the disk ruptures, the water would
vaporize, and reaction would be cooled (quenched) by the release of the latent
heat of vaporization.
Plot the temperature-time trajectory up to a period of 120 min after the reac-
tants were mixed and brought up to 175°C. Show that the following three conditions
had to have been present for the explosion to occur: (1) increased ONCB charge,
(2) reactor stopped for 10 min, and (3) relief system failure.

Additional Information: The rate law is

with k = 0.00017 at 188°C

kmol min
The reaction volume for the charge of 9.044 kmol of ONCB:

3.265 + 1.854 5.119

The reaction volume for the charge of 3.17 kmol of ONCB:

V = 3.26
AH,, = -5.9 mol
E = 11,273
= = 40 K
= = 18 = = 8.38

Assume that :

Solution

C+D

balance:

Rate law:
= (E9-2.2)
Stoichiometry (liquid phase):
544 Unsteady-State Nonisothermal Reactor Design Chap. 9

with

Combine:
(E9-2.5)

= -

Energy Balance:

(E9-2.6)

For 0,

Let be the heat generated = and let be the

removed Q, = -

(E9-2.7)

Then (E9-2.8)

Parameter evaluation for day of explosion:

+ +

A. Isothermal Operation Up to 45 Minutes

We will first out the reaction isothermally at 175°C up to the time the cooling
was turned of fat 45 min. Combining and canceling yields

(E9-2.9)

33

At 175°C = 448 K, = Integrating Equation

gives us

(E9-2.10)
 Unsteady Operation of CSTRs and Semibatch Reactors 545

Substituting the parameter values

5.119 3.64 -
min 1 - X)
0.0001 167

Solving for we find that at = 45 min, then X = 0.033.

We will calculate the rate of generation at this temperature and conversion and
compare it the maximum rate of heat removal The rate of generation is

At this time = 45 min, X = 0.033, T = 175°C) we calculate k, then and

Q,. At = 0.0001167

The: corresponding maximum cooling rate is

298)
= 5378

Everything is OK

The reaction can be controlled. There would have been no explosion had the cooling
not been turned off.

B. Adiabatic Operation for 10 Minutes

The cooling was turned off for 45 to 55 min. We now use the conditions at the
end of the period of isothermal operation as our initial conditions for adiabatic oper-
ation period between 45 and 55
t = 45 min X = 0.033 448
Between = 45 and 55 min UA = 0. The POLYMATH program adiabatic oper-
ation is the same as that in Table E9.2-I except that = - which
is same as setting UA = 0.
For the 45- to 55-min period without cooling, the temperature rose from
448 K to 468 K and the conversion from 0.033 to Using this temperature
and conversion in Equation we calculate the rate of generation at
55 rnin as
Q, 6591
The maximum rate of cooling at this reactor temperature is found from
tion (E9-2.12) to be
Q, = 6093
 546 Unsteady-State Nonisothermal Reactor Design Chap. 9

Here we see that

The point of no
(E9-2.14)

and the temperature will continue to increase. Therefore, the point of no return has
been passed and the temperature will continue to increase, as will the rate of reac-
tion until the explosion occurs.

C. Batch Operation with Heat Exchange

Return of the cooling occurs at min. The values at the end of the period of adia-
batic operation = 468 K, X = 0.04.23) become the initial conditions for the
period of operation with heat exchange. The cooling is turned on at its maximum
capacity, Q = - T ) , at min. Table E9-2.1 gives the POLYMATH pro-
gram to determine the temperature-time trajectory.

T ABLE POLYMATH P ROG RAM

Equations:
467.992
0.0423866

= 55, = 121

Interruptions in the Note that one can change and to 3.17 and 43 kmol in the program and show
cooling system have that if the cooling is shut off for 10 min, at the end of that min will still be
happened before greater than and no explosion will occur.
with no ill effects
The complete temperature-time trajectory is shown in Figure E9-2.2. One
notes the long plateau after the cooling is turned back on. Using the values of
and at 55 min and substituting into Equation we find that

(6591 - (6093
dt 2504

Consequently, even though is positive, the increases very slowly

at first, By the temperature has reached 240°C and is beginning
to increase more rapidly. One observes that 119 after the batch was started the
 9.2 Unsteady Operation of CSTRs and Semibatch Reactors 547

E
The explosion
after midnight
occurred shortly Isothermal Cooling Restored

175

PM 1218
t=O Midnight
Figure E9-2.2 Temperature-time trajection.

temperature increases sharply and the reactor explodes at midnight,

If the mass and heat capacity of the stirrer and reaction vessel had been included,
the term would have increased by about 5% and extended the time until the
explosion occurred by or S O minutes, which would predict the actual time the
explosion occurred, at A. M.
When the temperature reached a reaction, the
tion of nitroaniline to noncondensable gases such CO, and occurs, releas-
ing even more energy. The total energy released was estimated to be 6.8 X J,
which is enough energy to lift the entire 2500-ton building 300 m (the length of
three football fields) straight up.

D. Disk Rupture
We note that the. pressure relief disk should have ruptured when the temperature
reached 265°C (ca. 700 psi) but did not and the temperature continued to rise. If it
had ruptured and all the water had kcal would have been drawn
the reacting solution, thereby lowering its temperature and quenching it.
If the disk had ruptured at 265°C (700 psi), the mass flow rate, m ,
out of the 2-in. orifice to the atmosphere atm) would have been 830 at the
time of rupture.

830 540 kcal + 35.83 kcal

- (538
K
4.48 X 'kcal
- 8604 kcal
min mm
-
= 4.49 x 105 kcal
min

This value of Q, is much greater than 27,460 so that the

tion could easily be quenched.