I. CHEM. E. SYMPOSIUM SERIES NO.

68

HAZARDS OF THE DISTILLATION OF MONO NITROTOLUMES

G.F.P.Harris, N.Harrison, P.E.MacDermott*

Experimental techniques have been developed to define

conditions for the safe distillation of mixtures of
mono nitrotoluenes. A combination of small scale
temperature programmed thermal stability tests and
induction time measurements have been used to
establish that mono nitrotoluene mixtures can be
distilled safely provided that the maximum batch
temperature does not exceed 190°C.

INTRODUCTION

The mononitration of toluene produces a mixture of 2,3 and 4

nitrotoluenes, all of which are valuable intermediates for the manufacture
of a wide range of dyestuffs and allied products.

Considerable quantities of the major isomers, 2 and 4 nitro-

toluenes can be separated from the nitration product by a series of
distillations and sweatings to leave a residue, which is enriched in
3 nitrotoluene and contains approximately equal amounts of the three
mono nitrotoluenes together with about 0.5% each of dinitrotoluene
and unchanged toluene. This residue is available in quantity and has
considerable commercial value, particularly as a source of the minor
isomer, 3-nitrotoluene.

The only satisfactory method of separating the mono-nitro-

toluenes is distillation. Due to the relatively high boiling points
and the narrow boiling range (220-238°C under atmospheric pressure) of
the three isomers this distillation is difficult and requires the use
of an efficient fractionating column with the nitrobodies held at high
temperatures for long periods of time.

A number of incidents have occurred during the distillation of

mono nitrotoluenes. These incidents have usually been due to explosions
in stills where nitrotoluenes have been heated to excessively high
temperatures or held at more moderate temperatures for long periods of
time. This paper deals with both the inherent thermal instability of
nitrobodies and the so called "induction time" effect, where thermal
instability develops after a period of time at high temperature. The
experimental techniques developed are also applicable to the distillation
of other types of compound.

*Research Department, I.C.I. Organics Division, Blackley, Manchester.

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EXPERIMENTAL

Two basic types of experiment were carried out in this work.

(a) Programmed Thermal Stability Tests

These tests has the objectives of determining the ultimate

decomposition temperature of the material under test and enabling the
stabilities of various samples of nitrotoluenes to be compared quickly.
The samples were heated at an arbitrary rate of 2°C/min until decomposition
occurred.

(b) Induction Time Tests

In these tests a measure of the effect of slow decomposition

during long periods at elevated temperatures was obtained. The samples
used in these experiments were held at a fixed temperature until
decomposition occurred.

(1) Programmed Thermal Stability Tests

About 10 gms of the sample under test were placed in a

glass tube fitted with a 20 mm long thermocouple pocket, which reached
to the centre of the sample. To assess the effect on stability of
materials of still body construction approximately 0.5 gms of the still
body material, usually mild steel, were added to the test material in some
experiments. The tube was then sealed and placed in an electrically heated
air bath. The bath temperature was raised at 2°C/min and the temperature
at the centre of the sample recorded continuously to monitor onset of
heat development (see Fig.1).

The materials used in the experiments were:-

(a) two separate samples of undistilled nitrotoluenes containing

approximately equal amounts of the 3 isomers,

(b) the residues (99% 4-nitrotoluene) from the distillation of

one mixed nitrotoluene sample,

(c) samples prepared by the addition of known amounts of

dinitrotoluenes to the mono nitro toluene mixture.

These samples all behaved similarly. An exotherm commenced

at a temperature in excess of 250°C, accelerated as the batch temperature
was raised and eventually exceeded bath temperature and the tube burst.
The results of these experiments are shown in Table (1).

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TABLE 1 - Thermal Stabilities of Nitrotoluenes

Expt. Exotherm Exotherm Tube Burst

No. Sample Detected (°C) Accelerated (°C) (°C)

Sample Bath Sample Bath Sample Bath

1 Mixed Nitrotoluenes
Sample A:-
31% 2-NT
37% 3-NT 280 296 319 326 340 330
31% 4-NT
2 Mixed Nitrotoluenes
Sample A 283 300 320 323 337 327
+ Mild Steel
3 Mixed Nitrotoluenes
Sample B:-
33% 2-NT
33% 3-NT 275 301 320 330 359 333
33% 4-NT
+ Mild Steel
4 Sample A
+10% Dinitro-
280 297 310 318 347 323
toluenes
+ Mild Steel
5 Sample A
+ 50% Dinitro-
263 283 295 304 342 309
toluenes
+ Mild Steel
6 Residues from
distillation of
Sample B 250 273 290 305 335 320
+ Mild Steel

(2) Induction Time Tests

The programmed thermal stability tests were carried out under

conditions where the bath temperature continued to rise at. 2°C/min even
when an exotherm was detected. This is likely to increase the velocity
of the decomposition process. To investigate the effects of holding
nitrotoluene mixtures for prolonged periods at high temperatues and'
to define more closely the safe temperature for the distillation a
second series of experiments was carried out.

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In these experiments a sample of nitrotoluene weighing 12-15 gms

was heated to a pre-selected temperature and held there for a prolonged
period or until decomposition occurred. The test mixtures (+ 0.5 gms
mild steel turnings) were again sealed in 20 mm diameter glass tubes fitted
with thermocouple pockets. An electric heating wire was wound round the
tube and it was inserted into a close fitting (250 ml) Dewar flask closed
with a cork to limit heat losses. The samples and Dewar flask were placed
in an oven at the test temperature and the sample temperature raised
rapidly to oven temperature by means of the heating wire. The heater
was then switched off and the temperature at the centre of the sample
recorded continuously throughout the test (see Fig.2).

This procedure enabled the nitrotoluene mixtures to be tested

under conditions of near zero heat loss. If a slow exotherm commenced
due to thermal decomposition of the sample the heat losses through the
walls of the Dewar are small and are considered, on the basis of previous
(unpublished) experimental work, to give a reasonable approximation to the
heat losses through the walls of a large plant vessel such as the still
body during a distillation.

The results of these induction time experiments are shown in

Table (2). The two samples, A and B, of mixed nitrotoluenes from
different sources used in the thermal stability experiments (Table 1)
were tested. The residues (99% 4-nitrotoluene) from the full scale
distillation of Sample B to remove the lower boiling 2 and 3 isomers
were also examined.

In practice, in the experiments where decomposition occurred,

either a slow exotherm was observed and violent decomposition with bursting
of the tube occurred later (experiments 3, 6, 7, 8 and 9) or no exotherm
was observed and the tube burst suddenly (experiments 2 and 4).

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TABLE 2 - Induction Time Experiments

Expt. Sample Test Exotherm Tube Burst After

No. Temp Commenced (Hrs.)
(°C) After (Hrs.)

1 Mixed Nitrotoluenes 190 − Did not burst after

Sample A 1005 hrs. when test
discontinued.
2 Mixed Nitrotoluenes 230 − 87.5
Sample A
3 Mixed Nitrotoluenes 250 14.0 18.6
Sample A
4 Mixed Nitrotoluenes 220 − 165.3
Sample B
5 Residues from 190 − Did not burst after
Distillation of 640 hrs. when test
Sample B discontinued.
6 Residues from 230 27 39.75
Distillation of
Sample B
7 Residues from 255 1.6 4.16
Distillation of
Sample B
8 Residues from 235 22.5 30.0
Distillation of
Sample B
9 Residues from 250 4.0 7.75
Distillation of
Sample B

DISCUSSION OF RESULTS

1) Programmed Thermal Stability Tests

The results of the temperature programmed thermal stability

tests (Table 1), indicate that decomposition of mixed nitrotoluenes
commences at 275-283°C and becomes violent at about 320°C on the small
(1C gm) scale. Addition of materials of plant construction (mild steel)
had no effect on sample stability (compare experiments 1 and 2).

It is possible that distillation of the mono nitrotoluene

mixture could cause an increase in the concentration of the small
amount (approx 0.5%) of dinitrotoluenes present initially in the
mixture. Experiments 4 and 5, where 10% and 50% by weight respectively
of dinitrotoluenes (2:4 and 2:6 dinitrotoluene) were added to the
mono nitrotoluene mixture, were carried out to investigate the effect
of this concentration effect on thermal stability. Only a gross increase
in dinitrotoluene concentration (experiment 5) produced a significant
decrease in stability.

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The least stable sample tested was the residues (experiment 6)

from a full scale distillation lasting about 2 weeks. This sample
contained about 99% of the least volatile isomer, 4-nitrotoluene. It
was tarry in appearance and also contained some decomposition products
produced by holding the nitrobodies at high temperature for a prolonged
period. This decrease in stability with time was investigated more
fully in the induction time experiments, but some estimate is necessary
of the effect on decomposition temperature of scale up from the 10 gm
samples to full scale distillation.

1.1. Scale Up Effects on Decomposition Temperature

Self heat development leading to violent decomposition occurs

when the rate of heat generation by decomposition reactions exceeds
the rate of heat loss, thermal equilibrium being established when both
rates are equal. For a spherical reaction mass thermal equilibrium is
established when

where kT = reaction rate constant

= density of reaction mass

= radius of spherical mass

∆H = heat of reaction

h = heat transfer coefficient

T = equilibrium temperature

Ta = ambient temperature

From (l) the radii of spherical reacting masses under thermal

equilibrium at different temperatures is given by

Reactions with activation energies in the normal range of

20-30 kcals/mol give a 2-3 fold increase in the reaction rate for a 10°C
rise in temperature. Since density changes are small (<1%) over a 10°C
temperature range they can be ignored, and it is possible to calculate
from equation (2) the volume (mass) ratio of spherical reaction masses
that achieve thermal equilibrium i.e. temperature stability at temperatures
differing by 10°C. The results of such calculations are shown in Table (3),
where it is assumed that ambient temperature is 20°C.

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TABLE 3 - Volume Ratios of Reacting Masses in Thermal Equilibrium

Temperature Coefficient Temperature Volume Ratio V2/V1 Average Value V2/V1

of Reaction rate Constant Range
Per 10°C T1/T2 °C

100/90 5.36
150/140 6.29 6.36
2 200/190 6.80
250/240 7.00

100/90 18.09 21.47

3 150/140 21.23
200/190 22.96
250/240 23.62

Using the average values of 6.36 and 21.47 for the temperature
coefficient of the equilibrium volumes per 10°C temperature change, it is
possible to calculate the effect of mass on the temperature at which a
reacting mass establishes a conditions of thermal equilibrium with
its surroundings. The results of such calculations for spherical masses,
again assuming an ambient temperature of 20°C, are given in Tables (4A) and
(4B).
TABLE 4 - Equilibrium Temperature - Mass Temperature Relationship

(A) Equilibrium Volume Temperature Coefficient = 6.36/10°C

Equilibrium Temperature (°C)

T T-10 T-20 T-30 T-40 T-50 T-60 T-70

Mass of material (kgs) 0.01 0.06 0.40 2.6 16.4 104 662 4210

(B) Equilibrium Volume Temperature Coefficient = 21.47/10°C

Equilibrium Temperature (°C)

T T-10 T-20 T-30 T-40 T-50 T-60 T-70

Mass of material 0.01 0.21 4.61 99.0 2124 45,620 979,000 -
(kgs)

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From the above tables and the results of the small scale (10 gm)
thermal stability tests the temperature at which self heat development will
occur for large scale reaction masses undergoing thermally induced
decomposition can be predicted.

As an approximate practical estimation, if an exotherm is

observed at T°C in the 10 gm sealed tube test this means that decomposition
will commence at (T-60)°C on the 660 kg scale and at (T-70)°C on the
4200 kg scale (Table 4A). This assumes that the decomposition reaction
giving rise to the exotherm has an activation energy at the low end of the
scale i.e. about 20 kcals/mol. If. the activation energy is at the high
end (30 kcals/mol) then the temperature factor to be subtracted from the
results of the small scale test will be less (see Table 4B) and the
60-70°C factor will err on the safe side.

In the case of the mixed nitro toluenes, the thermal stability

tests in Table (l) indicate that decomposition will commence on the
660-4200 kg scale at 205-215°C and become violent at about 250°C.
The still residues (experiment 6) will be less stable and decomposition
could commence on the large scale at 180-190°C. These figures are
obviously not precise, but they do give a good indication of the order
of thermal instability on the large scale. Considerable practical
experience on the scale up of this type of thermal stability data for
a large number of different systems has shown that this method is reliable
and, at least, does not underestimate the danger.

2) Induction Time Experiments

The significance of the result of the induction time experiments

given in Table (2) is best displayed by plotting log time (to decomposition)
against the reciprocal of test temperature. This is shown in Fig.3.

Examination of Fig.3 shows that the results of the experiments

on the undistilled mono nitrotoluenes and the residues from their
distillation lie on two straight lines and the time to violent decomposition
falls very rapidly with increase in test temperature. The small scale
programmed thermal stability testsindicated that decomposition will.commence
on the large scale (660-4200 kg) in the 205-215°C temperature range.
The data in Fig.3 show that if the nitrotoluene mixture or the distillation
residues are held in this temperature range, violent decomposition will
occur in 200-600 hours (8.3 - 25 days). Reducing the temperature to 200°C
will increase the time to violent decomposition to 890 hours (37 days),
while a further reduction of the maximum batch temperature to 190°C will
give a lifetime of 2000 hours (83 days).

CONCLUSIONS

Safe operating conditions for the large scale distillation of

nitrotoluenes can be defined by a combination of small scale programmed
thermal stability tests and induction time measurements.

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The temperature programmed tests indicate that decomposition

will commence on the large scale at 205-215°C. They also enable the
thermal stabilities of various samples of nitrobodies to be compared quickly.
The induction time measurements define how long the distillation batch
can be held at high temperature without violent decomposition. If the
maximum batch temperature does not exceed 190°C then decomposition will
not occur for at least 80 days, which should prove adequate for all
practical purposes.

Obviously attention must be paid to the maximum temperature

attainable by the still heating medium. If the distillation is carried out
on a batch basis, the still residues should also be discharged between
batches to prevent possible build-up of unstable impurities over a long
period of time.

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FIG (1):- TEMPERATURE PROGRAMMED THERMAL STABILITY TEST

FIG (2):- INDUCTION TIME TEST

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FIG (3): - RESULTS OF INDUCTION TIME EXPERIMENTS

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