Production of Mononitrotoluene

MATERIAL BALANCE

THE NITRATION PROCESS:

The reaction of toluene with nitric acid is normally out in the presence of sulphuric
acid in order to avoid the slowing down of the reaction by dilution of nitric acid as it is used
up and as water is liberated. The basic stoichiometric equation is: (Ref. –1)

C6H5CH3 + HNO3 = C6H4NO2CH3 + H2O

92 63 137 18

The toluene used in the process is assumed to contain 1 percent of paraffins in

accordance with a typical specification for nitration toluene. This will be unreacted and it is
known that a small amount of the toluene remains unreacted. For a working basis this is
assumed to amount to 1 percent and in addition a further 1 per cent is assumed to be
converted by the side reaction to nitrocresol.

C6H5CH3 + 3 HNO3 = C6H3OHCH3NO2 + 2 NO2 +2 H2O

92 189 153 92 36

Then 1 ton of toluene will yield a product containing 0.01 ton of paraffins, 0.01 ton of
153 137
unreacted toluene, 0.01 × = 0.016 ton of nitrocresol and, 0.97 × = 1.443 tons
92 92
of morionitrotoluenes.
The amount of nitric and sulphuric acids to carry out this conversion must now be
calculated. The stoichiometric equivalents of 100 per cent nitric acid, HNO3, are:
63
To mononitrotoluenes 0.97 × = 0.664
92
189
To nitrocresol 0.01 × = 0.020
92
Total = 0.684 ton

Allowing 1 per cent excess of nitric acid, 0.691 ton of 100 per cent HNO3 are required.

11
 Production of Mononitrotoluene

For nitration, the choice can be made between the two strengths of nitric acid
normally available. These are 60 per cent direct from the absorption tower of an ammonia
oxidation process or 96 per cent from a nitric acid concentration plant. The sulphuric acid
for making up the mixed acid for nitration can be obtained at 96 per cent strength from a
plant carrying out the concentration of dilute sulphuric acid. The substitution of one
nitro-group toluene can be carried out at reasonable rates, and with almost complete
consumption of the nitric acid used, if the final acid strength is not allowed to fall below 70
percent. For calculating this process, it will be assumed that the final acid strength does not
fall below 75 percent at which corrosion of cast iron and mild steel equipment in the cold is
not serious.
This concentration allows 60 per cent nitric acid to be used without requiring an
excessive quantity of sulphuric acid as will be calculated. The total water in the final acid is
made up of that brought in with the nitric and sulphuric acids plus that formed in the reaction.
If r is the quantity of 96 per cent sulphuric acid required, the total water from various sources
is
From 96 per cent sulphuric acid = 0.04 γ
0.4
From 60 per cent nitric acid × 0.691 = 0.460
0.6
18
From mononitrotoluene reaction 0.691 × = 0.190
92
36
From nitrocresol reaction 0.01 × = 0.004
92

Since the final ratio of sulphuric acid to water is 75:25 we have:

0.96 × γ 75
=
0.04γ + 0.460 + 0.190 + 0004 25
from which γ equals 2.338 tons.

12
 Production of Mononitrotoluene

The quantities involved in the reactions can now be tabulated:

Table 4.1
Reactants Products
Toluene 0.97 Mononitrotoluenes 1.443
0.01 Toluene 0.01
0.01 0.990 Nitrocresol 0.016
Paraffins 0.010 Paraffines 0.010
60% Nitric Acid HNO3 0.007
HNO3 0.691 NO2 0.010
H2O 0.460 1.151
96% Sulphuric Acid H2SO4 2.241
H2SO4 2.241 H2O 0.751
H2O 0.097 2.338
4.488 4.488

Separation of Mononitrotoluenes:

The reaction products form a two-phase mixture, which can. be separated by gravity
owing to the difference in densities between the crude nitration product and the spent acid.
These are respectively 1.167 and 1.670 at 18° C. The separation is not perfect and the
Technical Records of Explosives Supply give a sulphuric acid concentration of 0.8 per cent
in the nitration products and a mononitroluene content of 0.2 per cent in the acid.

13
 Production of Mononitrotoluene

The nitration balance can then be split up:

Table 4.2
Component Acid layer Nitration product
Mononitrotoluenes 0.003 1.440
Toluene - 0.010
Nitrocresol - 0.016
Paraffins - 0.010
HN03 0.007 -
H2SO4 2.223 0.018
H2O 0.747 0.004
2.980 1.498
The NO2 is assumed to pass from the system as fume.

Addition of Cycle Acid:

These are balance sheets for the nitration process and show the quantities
theoretically necessary to meet the conditions so far laid down. These result in the nitrating
acid having a composition:

HNO3 0.691 19.81%

H2S04 2.241 64.22%
H2O 0.557 15.97%
3.489 100.00%

It has been found by experience that a concentration of nitric acid as high as this
causes a rapid nitration reaction and in batch nitrations could lead to a loss of control. To
avoid this the concentration should be kept down to about 5 per cent as a precautionary
measure. This is done by recirculating a large quantity of the spent acid separated after the
nitration reaction.
Since the fresh mixed acid has 19-81 per cent of nitric acid in a total of 3.489 tons,
about three times this quantity of cycle acid needs to be added to bring the final concentration
of nitric acid down to 5 per cent.

14
 Production of Mononitrotoluene

This is an approximation and an exact balance needs to take in the nitric acid content
of the cycle acid. If X is the weight of cycle acid added
0.007
0.691 + X
2.980 = 0.05
3.489 + X
and X equals 10.82 tons. The weight of cycle acid added and a balance for mixing fresh with
cycle acid can be drawn up.
Table 4.3
60 % Nitric Acid Mixed Nitrating Acid
HNO3 0.691 HNO3 5.0%
H2O 0.460 H2SO4 72.1%
1.151 H2O 22.7%
NO2C10H4CH3 0.2%
96% Sulphuric Acid 100.0%
H2SO4 2.241
H2O 0.097
2.338
Cycle Acid
HNO3 0.025
H2SO4 8.080
H2O 2.690
NO2C6H4CH3 0.025
10.820
14.309

MATERIAL BALANCE FOR THE NITRATION REACTION:

To obtain the final materials balance for the process in which one of toluene is
reacted with nitric acid, the quantity of cycle acid must be added to the balance already made.
The actual quantities involved in tons day are given in the table below.

15
 Production of Mononitrotoluene

Table 4.4
Input Output
Mixed Acid Nitration product
Item Weight Per cent Item Weight Per cent
HNO3 0.716 5.0 NO2C6H4CH3 1.436 96.4
H2SO4 10.321 72.1 NO2CH3C6H3OH 0.016 1.1
H2O 3.247 22.7 C7H8 0.010 0.7
NO2C6H4CH3 0.025 0.2 Paraffins 0.010 0.7
14.309 100.0 H2SO4 0.012 0.8
H2O 0.004 0.3
1.488 100.0

Toluene Acid layer

C7H8 0.99 99.0 NO2C6H4CH3 0.032 0.2
Paraffins 0.01 1.0 HNO3 0.032 0.2
1.00 100.0 H2SO4 10.318 74.8
H2O 3.429 24.8
13.811 100.0

Fumes
NO2 0.010
Total 15.309 Total 15.309

Washing the Nitration Products:

The process of purifying the crude nitration product after its separation from the used
acid begins with a washing process. The treatment of the acid to recover the sulphuric acid
in a concentration suitable for use again is not considered as part of the main material balance
being drawn up on the toluene. The washing process is carried out in three stages: the first,

16
 Production of Mononitrotoluene

a water wash to take out the sulphuric acid, the second an alkali wash to neutralize the
nitrocresol and any other acidic bodies, followed by a further water wash to remove excess
alkali and dissolved salts.

First Wash:
The amount of water to be used in the first wash should be kept as small as possible,
consistent with good washing, because of the loss of nitration product in solution.
Experiments have shown that the water layer will contain about 0.7 percent by weight of
rnononitrotoluene and that the use of about one part by weight of water to three parts of
nitration product gives satisfactory results in mixing with the removal of all the sulphuric
acid. The material balance over this stage is then:

Table
4.5

Alkali Wash:
In order to remove acidic bodies, particularly nitrocresol, the crude mononitrotoluenes
are next washed with a dilute solution of sodium carbonate. As in the previous stage,

17
 Production of Mononitrotoluene

sufficient water is used to keep the proportion of the wash liquor up to about one-third that of
the mononitrotoluenes. The nitrocresol reacts with sodium carbonate according to the
equation:

C6H3OH.NO2CH3 + Na2CO3 = C6H3ONaNO2CH3 +NaHCO3

153 106 175 84
0.016 0.011 0.019 0.008

Allowing for a slight excess of sodium carbonate 0.012 is added and total of 0.028 sodium
salts is formed. Waste wash liquor will again contain 0.7 percent of mononitrotoluenes
and the material balance for the stage is:
Table 4.6
Materials in Materials out
Crude nitration Washed nitration product Neutral washings
product
Mnononitrotoluene 1.432 1.428 98.1% 0.004
Nitrocresol 0.016 Trace (Na salts)
C7H8 0.010 0.010 0.7%
Paraffins 0.010 0.010 0.7%
H2O 0.007 0.007
1.475 1.455 100.0%

Wash liquor
H2O 0.513 0.513
Na2CO3 0.012 Na salts 0.028
0.525 0.545
2.00 Total: 2.00

18
 Production of Mononitrotoluene

Final Water Wash:

A final wash with water is given to remove traces of excess alkali and sodium salts in
solution, which might be concentrated in subsequent processing to the point where they
became explosive.
The materials balance is:
Table 4.6
Materials in Materials out
Crude nitration Washed nitration product Waste water
product
Mnononitrotoluene 1.428 1.424 98.1% 0.004
Nitrocresol trace
C7H8 0.010 0.010 0.7%
Paraffins 0.010 0.010 0.7%
H2O 0.007 0.007 0.5%
1.455 1.451 100.0%

Wash water
H2O 0.513 0.513
Na salts trace
0.517
1.968 Total: 1.968

Purification of the Crude Mononitrototoluenes:

The washed nitration products shown in 'the material balance above is contaminated
with paraffins, unreacted toluene and water. There may, in addition, be traces of polynitro
compounds or other side reaction products. These must be separated before the mixed
mononitrotoluenes can be obtained in a suitable state for the subsequent processing—
separation of the isomers. The separation can be conveniently effected by batch distillation.
The method of doing this is to charge one day's output to a batch still, take off water,
paraffins and toluene as forerunnings, an intermediate fraction and about four-fifths of the

19
 Production of Mononitrotoluene

mononitrotoluenes as a heart-cut. The next day's output is charged on top of the residue)
together with the intermediates) and the process repeated. This is repeated until the residue
of about one-fifth of the still charge represents about 4 percent of the mononitrotoluenes
distilled and it is then discarded. The material balance of each distillation is different, but it
is not necessary to work through each in detail to obtain the overall result corresponding with
one day's operation. From the composition of the nitration product in the balance for the last
washing process, the overall balance is:

Table 4.7
Materials in Materials out
Washed nitration product 1.451 Forerunnings 0.027
Pure mononitrotoluenes 1.367
Residue 0.057
1.451 1.451

lt was calculated that feed of 18.105 tons of toluene per 24 h, with which are associated
0.183 tons of paraffins, 17.739 tons react with 12.143 tons of nitric acid to produce 26.20
tons of mixed mononitrotoluenes, leading in full scale production after allowing for losses to
an output of 25 tons a day, while 0.183 tons react with 0.366 tons of nitric acid to form
nitrocresol, and 0.183 tons remain unconverted. The nitric acid requirement is therefore
12.509 tons/24 h, and, allowing an excess of 1 per cent, 12.637 tons are used in the form of
22.906 tons of 60 per cent nitric acid. The reaction also requires 96 per cent sulphuric acid,
and the two acids are mixed in a jet with cycle acid from the separator. Table below is a
materials balance sheet over the nitrators. It shows the mixed nitric acid, sulphuric acid, and
cycle

20
 Production of Mononitrotoluene

Table 4.8 Material Balance Sheet over Nitrators

Basis: 24 hrs.
Materials Tons Tons Materials out
in
H2O 59.381 26.262 MNT
H2SO4 188.75 0.293 Nitrocresol
HNO3 13.094 0.183 C7H8
MNT 0.457 0.183 Paraffin
261.682 Mixed 0.919 H2SO4
Acids 0.073 H2O
C7H8 18.105 Nitrobody 27.213
Paraffins 0.183 NITRATORS Layer
0.585 MNT
18.288 Toluene 0.585 HNO3
188.696 H2SO4
62.710 H2O

Acid 252.576
Layer
Fumes 0.183 NO2

TOTAL 279.970 279.972 TOTAL

acid containing some mononitrotoluene entering the nitrators, into which is also fed the
toluene, which contains paraffins as impurity. A stream of liquid leaves the nitrators,
consisting of nitrobody layer and acid layer, and some fumes are evolved. The composition
of each stream is shown, with the totals for each, and the -inlet and outlet balance.
The acid layer is separated from the nitrobody in a gravity separator, and the nitrobody is
then treated in three Holley-Mott washers in series, for which operation Table below is a
materials balance sheet. This sheet sets out the composition of the feed to the first washer,
and the washing agent for each washer, and shows the composition of the three washings
and of the washed nitrobody, together with an overall materials balance.
The process then changes from continuous operation to batch distillation. The plant
works continuously for 5 days, or 120 hr week, except for the distillation of the washed
nitrobody in 4 batches a week. Table 4.10 is a materials balance sheet for one of these batch
distillations. The residue of 0.512 tons from each batch is collected for the 4 batches, and
then the 26.05 tons are distilled to give a further 20.8 tons of mononitrotoluene and 5.2 tons
of final residues; this second distillation is not shown on a material balance sheet.

21
 Production of Mononitrotoluene

Table 4.9. Materials Balance Sheet over Washer:

Basis: 24 hrs.
Materials Tons Tons Materials out
in
MNT 26.261
Nitrocresol 0.293
C7H8 0.183
Paraffin 0.183 9.327 H2O
H2SO4 0.219 0.219 H2SO4
H2O 0.073 0.073 MNT
27.212 Nitrobody 9.619
ACID Washings
Water 9.382 Water WASHER

H2O 9.382 9.382 H2O

Na2CO3 0.219 0.510 N-creso salts
0.073 MNT
9.601 ALKALI 9.965
WASH 9.382 HO2
0.004 Na2CO3
0.073 MNT
Water 9.382 ALKALI 9.459
WASH
26.042 MNT
0.183 Paraffin
0.128 H2O
0.183 C7H8
26.596

TOTAL 279.970 279.972 TOTAL

The operation then becomes continuous again. The 20.05 tons of first distillate per batch,
equivalent to 104.2 tons per 120 h, plus the 20.8 of second distillate, give a feed of 25 tons of
mixed mononitrotoluens per 24 h to the continuous still, for which Table 4.11 is a materials
balance sheet.

22
 Production of Mononitrotoluene

Table 4.10. Materials Balance Sheet For first Batch Distillation

Basis: One batch
4 batches in 120 hours.
Materials Tons Tons Materials out
in
MNT 32.562 0.229 C7H8
C7H8 0.229 0.229 Paraffins
Paraffins 0.229 0.16 H2O
H2O 0.160 Forerunnings 0.160
33.180 Washed BATCH
Nitrobody STILL Distillate 20.05 MNT

6.512 MNT

TOTAL 33.180 33.180 TOTAL

Table 4.11. Materials Balance Sheet For Continuous Still

Basis: 24 hours
Materials Tons Tons Materials out
in
Ortho 15.000 14.700 Ortho
Meta 1.000 0.150 Meta
Para 9.000 0.150 Para
25.000 MNT Tops 15.000
CONTINUOUS 0.300 Ortho
STILL 0.850 Meta
8.850 Para
10.000
Bottom

TOTAL 25.000 25.000 TOTAL

This shows substantial removal of the ortho-compound in the fraction from the top of the
still, while the para-compound with some meta-isomer and small amounts of the ortho-
isomer is obtained from the bottom of the Table 4.12 is a material balance sheet for the
centrifuge.

23
 Production of Mononitrotoluene

Table 4.12. Materials Balance Sheet over Centrifuge

Basis: 24 hours
Materials Tons Tons Materials out
in
Ortho 0.300
Meta 0.850
Para 8.850
10.000 Slurry CONTINUOUS Crystals 7.500 Para
STILL 0.300 Ortho
0.850 Meta
1.350 Para
Mother liquor 2.500

TOTAL 10.000 10.000 TOTAL

24