640 Unsteady-State Nonisothermal Reactor Design Chapter 13

13.2.2 Case History of a Batch Reactor with Interrupted Isothermal

Operation Causing a Runaway Reaction

In Chapters 5 and 6 we discussed the design of reactors operating isothermally.

This operation can be achieved by efficient control of a heat exchanger. The fol-
lowing example shows what can happen when the heat exchanger suddenly fails.

Example 13–2 Safety in Chemical Plants with Exothermic Runaway Reactions 2

A serious accident occurred at the Monsanto plant in Sauget, Illinois, on August 8

at 12:18 A.M. (see Figure E13-2.1). (Sauget (pop. 200) is the home of the 1988
Mon-Clar League Softball Champions.) The blast was heard as far as 10 miles away
in Belleville, Illinois, where people were awakened from their sleep. The explosion
occurred in a batch reactor that was used to produce nitroaniline from ammonia and
o-nitrochlorobenzene (ONCB):
NO2 NO2

Cl NH2

# 2 NH3 # NH4Cl

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 is 25!C. By adjust-
ing the coolant rate, the reactor temperature could be maintained at 175!C. At the
maximum coolant rate, the ambient temperature is 25!C throughout the heat
exchanger.
Let me tell you something about the operation of this reactor. Over the years,
the heat exchanger would fail from time to time, but the technicians would be
“Johnny on the Spot” and run out and get it up and running within 10 minutes or so,
and there was never any problem. It is believed that one day someone in manage-
ment looked at the reactor and said, “It looks as if your reactor is only a third full
A decision was and you still have room to add more reactants and to make more product and more
made to triple money. How about filling it up to the top so we could triple production?” They did,
production. and started the reactor up at 9:45 p.m. Around midnight the reactor exploded and
the aftermath is shown in Figure E13-2.1.

Figure E13-2.1 Aftermath of the explosion. (St. Louis Globe/Democrat photo by

Roy Cook. Courtesy of St. Louis Mercantile Library.)

2 Adapted from the problem by Ronald Willey, Seminar on a Nitroaniline Reactor Rupture.
Prepared for SAChE, Center for Chemical Process Safety, American Institute of Chemi-
cal Engineers, New York (1994). Also see Process Safety Progress, vol. 20, no. 2 (2001),
pp. 123–129. The values of "HRx and UA were estimated from the plant data of the
temperature–time trajectory in the article by G. C. Vincent, Loss Prevention, 5, 46–52.
Section 13.2 Energy Balance on Batch Reactors (BRs) 641

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 NH3 , and
103.7 kmol of H2O. Normally, the reactor is charged with 3.17 kmol of
ONCB, 103.6 kmol of H2O, and 43 kmol of NH3 .
2. The reaction is normally carried out isothermally at 175°C over a 24-h period.
However, approximately 45 min after the reaction was started, cooling to the
reactor failed, but only for 10 min, and cooling was again up and running at
the 55-minute mark. Cooling may have been halted for 10 min or so on pre-
vious occasions when the normal charge of 3.17 kmol of ONCB was used and
no ill effects occurred.
The reactor had a rupture disk designed to burst when the pressure exceeded
approximately 700 psi. If the disk would have ruptured, the pressure in the reactor
would have dropped, causing the water to vaporize, and the reaction would have
been cooled (quenched) by the latent heat of vaporization.
(a) Plot and analyze the temperature–time trajectory up to a period of 120
min after the reactants were mixed and brought up to 175!C (448K).
(b) Show that all of the following three conditions had to have been present for
the explosion to occur: (1) increased ONCB charge, (2) cooling stopped for
10 min at a time early in the reaction, and (3) relief-system failure.

Additional information:

Rate law: %rONCB $ kC ONCBCNH3

m3
with k $ 0.00017 ------------------------- at 188!C (461K) and E = 11,273 cal/mol
kmol & min
The reaction volume for the new charge of 9.0448 kmol of ONCB
V $ 3.265 m3 ONCB/NH3 # 1.854 m3 H2O $ 5.119 m3

Case History The reaction volume for the previous charge of 3.17 kmol of ONCB:

V $ 3.26 m3
"HRx $ %5.9 ' 105 kcal ( kmol
CPONCB $ CPA $ 40 cal ( mol & K
CPH O $ CPW $ 18 cal ( mol & K CPNH $ CPB $ 8.38 cal ( mol & K
2 3

Assume that "CP ! 0

35.85 kcal
UA $ ------------------------- with T a $ 298 K
min !C

Solution

A # 2B → C # D

Mole Balance:

dX V
------- $ %rA --------- (E13-2.1)
dt N A0

Rate Law:
%rA $ kC ACB (E13-2.2)
642 Unsteady-State Nonisothermal Reactor Design Chapter 13

Stoichiometry (liquid phase):

CA $ CA0 ( 1 % X ) (E13-2.3)

with CB $ CA0 ( )B % 2X ) (E13-2.4)

N B0
)B $ --------
-
N A0
Combine:
2
%rA $ kC A0 ( 1 % X )( )B % 2X ) (E13-2.5)

Substituting our parameter values into Equation (3-21)

E  1 1 
k = k (T0 ) exp   −   (3-21)
 R  T0 T1  
We obtain

11273  1 1
3
m
k $ 0.00017 exp ---------------  --------- % ---  -------------------------
1.987  461 T  kmol & min

Energy Balance:
dT UA ( T a % T ) # ( rAV )( "HRx )
------ $ -------------------------------------------------------------------- (E13-2.6)
dt ∑ N i C Pi

For "CP $ 0 ,
∑ N i CPi $ NC P $ N A0CPA # N B0CPB # N WCPW

Parameter evaluation for day of explosion:

NCP $ (9.0448)(40) # (103.7)(18) # (33)(8.38)

NCP $ 2504 kcal/K

Again, let Qg be the heat generated, i.e., Qg $ ( rAV )( "HRx ), and let Qr be the heat
removed, i.e., Qr $ UA ( T % T a ) .
%Qr Qg














dT UA ( T a % T ) # ( rAV )( "HRx )
------ $ -----------------------------------------------------------------------------
- (E13-2.7)
dt N A0CPA # N B0CPB # N WCPW

Qg $ ( rA V ) ( "HRx )
dT Qg % Qr
Qr $ UA ( T % T a ) Then ------ $ -----------------
- (E13-2.8)
dt NC P

A. Isothermal Operation Up to 45 Minutes

We will first carry out the reaction isothermally at 175!C (448 K) up to the time the
cooling was turned off at 45 min. Combining and canceling yields
dX
------- $ kC A0 ( 1 % X )( )B % 2X ) (E13-2.9)
dt
33
)B $ ---------- $ 3.64
9.04
Section 13.2 Energy Balance on Batch Reactors (BRs) 643

Integrating Equation (E13-2.9) gives us

V  1  )B % 2X
t $ ------------  ----------------  ln -------------------------
- (E13-2.10)
kN A0  B
) % 2  )B ( 1 % X )

At 175!C $ 448 K, k $ 0.0001167m3 ( kmol & min .

Substituting for k and the other parameter values

5.119 m3  1  3.64 % 2X
45 min $ ----------------------------------------------------------------------------------------------- '  ---------- ln ----------------------------
-
0.0001167 m ( kmol & min ( 9.044 kmol )
3
 1.64 3.64( 1 % X )
The calculation
and results can also Solving for X, we find that at t $ 45 min, then X $ 0.033.
be obtained from the
Polymath output We will calculate the rate of generation, Qg, at this temperature and conversion and
compare it with the maximum rate of heat removal, Qr, that is available for a con-
stant coolant temperature of Ta = 298 K. The rate of generation, Qg, is

N A0 ( 1 % X )N A0 [ ( N B0 ( N A0 ) % 2X ] V ( %"HRx )
Qg $ rAV "HRx $ k ---------------------------------------------------------------------------------------------------------------
- (E13-2.11)
V2

At this time (i.e., t $ 45 min, X $ 0.033, T $ 175!C), we calculate k, then Qr and

Qg . At 175!C, k $ 0.0001167 m3 /min&kmol.

( 9.0448 )2 ( 1 % 0.033 ) 33
Qg $ ( 0.0001167 ) --------------------------------------------------- -------------------- % 2( 0.033 ) 5.9 ' 105
5.119 ( 9.0448 )

Qg $ 3830 kcal ( min

The corresponding maximum cooling rate is

Qr $ UA (T % 298 )
$ 35.85( 448 % 298 ) (E13-2.12)
Qr $ 5378 kcal ( min

Therefore

Everything is OK. Qr * Qg (E13-2.13)

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

B. Adiabatic Operation for 10 Minutes

Unexpectedly, the cooling failed from 45 to 55 min after the reaction was started.
We will now use the conditions at the end of the period of isothermal operation as
our initial conditions for the adiabatic operation period between 45 and 55 min
t $ 45 min X $ 0.033 T $ 448 K
Interruptions in the Between t $ 45 and t $ 55 min, Qr $ 0. The Polymath program was modified to
cooling system have account for the time of adiabatic operation by using an “if statement” for Qr in the
happened before program, i.e., Qr $ if (t > 45 and t < 55) then (0) else (UA(T % 298)). A similar “if
with no ill effects.
statement” is used for isothermal operation, i.e., (dT/dt) = 0.
644 Unsteady-State Nonisothermal Reactor Design Chapter 13

For the 45- to 55-min period without cooling, the temperature rose from
448 K to 468 K, and the conversion increased from 0.033 to 0.0424. Using this tem-
perature and conversion in Equation (E13-2.11), we calculate the rate of generation
Qg at 55 min and see that it has increased to
Qg $ 6591 kcal ( min
The maximum rate of cooling at this reactor temperature is found from Equa-
tion (E13-2.12) to be
Qr $ 6093 kcal/min
Here, we see that at the end of the 10-minute down time, the heat exchange system
is now operating again, but now
The point of
no return Qg * Qr (E13-2.14)

and the temperature will continue to increase. We have a Runaway Reaction!! The
point of no return has been passed and the temperature will continue to increase,
as will the rate of reaction until the explosion occurs.

C. Batch Operation with Heat Exchange

Return of the cooling occurs at 55 min after startup. The values at the end of the
period of adiabatic operation (T $ 468 K, X $ 0.0423) become the initial condi-
tions for the period of restored operation with the heat exchange. The cooling is
turned on at its maximum capacity, Qr $ UA(T – 298), at 55 min. Table E13-2.1
gives the Polymath program to determine the temperature–time trajectory. (Note that
one can change NA0 and NB0 to 3.17 and 43 kmol in the program and show that, if
the cooling is shut off for 10 min, at the end of that 10 min, Qr will still be greater
than Qg and no explosion will occur.)
The complete temperature–time trajectory is shown in Figure E13-2.2. One
notes the long plateau after the cooling is turned back on. Using the values of Qg
and Qr at 55 min and substituting into Equation (E13-2.8), we find that

dT ( 6591 kcal ( min ) % ( 6093 kcal ( min )

------ $ ---------------------------------------------------------------------------------------
- $ 0.2!C ( min
dt 2504 kcal ( !C

TABLE E13-2.1 POLYMATH PROGRAM

Section 13.2 Energy Balance on Batch Reactors (BRs) 645

The explosion
occurred shortly
after midnight. Runaway

Figure E13-2.2 Temperature–time trajectory.

Consequently, even though dT/dt is positive, the temperature increases very slowly
at first, 0.2!C/min. By 11:45, the temperature has reached 240!C and both the “heat
generated” and the temperature begin to increase more rapidly. This rapid increase
is a result of the Arrhenius temperature dependence, which caused the temperature
to increase exponentially. The reaction is running away! One observes in Figure
E13-2.2 that 119 min after the batch was started, the temperature increases sharply
and the reactor explodes at approximately midnight. If the mass and heat capacity
of the stirrer and reaction vessel had been included, the NCp term would have
increased by about 5% and extended the time until the explosion occurred by 15 or so
minutes, which would predict the actual time the explosion occurred, at 12:18 A.M.
When the temperature reached 300!C, a secondary reaction, the decomposi-
tion of nitroaniline to noncondensable gases such as CO, N2 , and NO2 , occurred,
releasing even more energy. The total energy released was estimated to be 6.8 ' 109 J,
which is enough energy to lift the entire 2500-ton building 300 m (the length of
three football fields) straight up.

D. Safety Disk Rupture Failure

We note that the pressure-safety-relief disk should have ruptured when the tempera-
ture reached 265!C (ca. 700 psi) but did not and the temperature continued to rise.
If it had ruptured and all the water had vaporized, 106 kcal would have been drawn
from the reacting solution, thereby lowering its temperature and quenching the run-
Spring away reaction.
relief valve If the disk had ruptured at 265!C (700 psi), we know from fluid mechanics
Pressure
gauge
that the maximum mass flow rate, ṁ vap, out of the 2-in. orifice to the atmosphere
(1 atm) would have been 830 kg/min at the time of rupture. The corresponding heat
Rupture
disk removed would have been

Qr $ ṁ vap "Hvap # UA ( T % T a)
kg kcal kcal
$ 830 --------- ' 540 ---------- # 35.83 ----------------- ( 538 % 298 )K
min kg min & K
kcal kcal
$ 4.48 ' 105 ---------- # 8604 ----------
min min
kcal
$ 456, 604 ----------
min
This value of Qr is much greater than the “heat generated” Qg (Qg $ 27,460
kcal/min), so that the reaction could have been easily quenched.