SULFONATION OF ANILINE
b b b The production of sulfanilic acid by a
partial-pressure evaporation system is shown to be
feasible on a laboratory scale. The difficulties of
local overheating and complete conversion of the
aniline sulfate to sulfanilic acid are overcome so
that a yield of over 95 per cent sulfanilic acid is
produced when stoichoimetric amounts of aniline
and sulfuric acid are used. The small loss of diluent
(7 per cent) can easily be lowered with a more
efficient condenser and better sealing of the joints
than is possible in the experimental work. Larger
scale operation will tend to minimize the loss of
diluent.
These results suggest the possibility of producing
sulfanilic acid b y the partial-pressure evaporation
system continuously on a larger scale. However,
the problem of the sulfanilic acid caking in larger
scale operation must be met. By the use of proper
agitating equipment, it may be possible to prevent
this caking and thereby make possible a continuous
process for the sulfanilic acid production.
0
NE of the important intermediates in the production of
azo dyes is the organic acid p-aminosulfonic, generally
termed “sulfanilic”, acid. These dyes are prepared by
coupling diazotized amines with other amines and with
sulfonic acids. The United States produces’about 1.5 million
pounds of sulfanilic acid annually.
I n making sulfanilic acid, water formed by the reaction
between aniline and sulfuric acid must be removed. One
commercial process does this by baking the aniline sulfate
(the initial reaction product) in vacuum oven; another proc-
ess uses 50 per cent excess concentrated sulfuric acid to with-
draw the water.
The over-all yield of pure sulfanilic acid on the basis of
aniline charged from the “bake” process is over 80 per cent.
The yields by the sulfonation process (1) are equivalent to
92 and 93 per cent on the basis of aniline charged.
Although the commercial methods do result in high yields
of sulfanilic acid, both of them have drawbacks. Both proc-
esses are batch operations; the bake process requires con-
siderable handling before the final product is obtained; and
the sulfonation process uses a large excess of sulfuric acid
which cannot be recovered.
The formation of sulfanilic acid by the reaction of sulfuric
acid and aniline may be considered to t,ake place in two
steps ( I ) :
The sulfuric acid and aniline first react to produce the salt of
the dibasic acid:
321
Application of
Partial- Pressure Distillation
Joseph Jr., Donald F. Othmer,
1. Jacobs,
and Allan Hokanson
POLYTECHNIC INSTITUTE, BROOKLYN, N. Y.
In the dehydration stage the sulfonic acid group shifts to the
para position, and water is removed to form sulfanilic acid:
HNH~ HNH~
o
s4
’‘
It was felt that the partial-pressure method might facilitate
removal of the water of reaction as it has in previously re-
ported cases (8, 8). Accordingly, the feasibility of carrying
out the reaction was investigated, using an acid-treated hy-
drocarbon fraction in the kerosene range as an entrainer.
Sulfanilic A c i d Production
Kerosene fractions of different boiling ranges were used.
They were always pretreated by boiling under reflux while
agitating with concentrated sulfuric acid for several hours.
A heavy scum of carbonaceous matter was removed, the two
layers were separated, and the kerosene layer was washed with
sodium carbonate solution and water, and finally distilled.
The apparatus consisted of a one-liter three-neck flask
fitted with a moisture determination tube, a condenser, and a
thermometer. (See Figure 1of the paper by Othmer, Jacobs,
and Buschmann, page 326). In the flask were placed the
sulfuric acid (commercial 93 per cent) and the diluent. The
aniline was poured in slowly over a period of 2 minutes. I n all
runs 40 grams (39 cc.) were used. Immediately the aniline and
the sulfuric acid reacted to form a pinkish-white precipitate,
aniline sulfate, with the evolution of heat. The mass was
agitated violently and heated gently. Vapors of diluent and
water bubbled through the molten mass of aniline sulfate and
passed up to the condenser where both the diluent and the
water condensed. The water collected a t the bottom of the
moisture determination tube, and the diluent refluxed back
into the flask.
Effect of Variables on A c i d
Yield
Several variables affect the pro-
duction of sulfanilic acid by the
partial pressure method; they were
investigated individually in so far
as it was possible to maintain the
other variables constant.
322 INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 35, No. 3

I I I I I I 80 I I I I
2

I I I I I
IO 20 30 40 50
EXCESS SULFURIC ACID - PER CENT

0" I I I I I

30

200
t I
250
1
300 350
I I
400
I
450
1
500
60

8 9 10 II
- 0
12
5
165 170 175 180 185
VOLUME OF DILUENT - Cc. WATER C O L L E C T E D - C C. TEMPERATURE
OF DILUENT - 'c.
Figure 1. Effect of Amount of Diluent on Yield of Sulfanilic Acid
Figure 2. Effect o f Amount o f Sulfuric Acid over That Required Stoichio-
metrically on Yield o f Sulfanilic Acid
Figure 3. Effect of Amount o f Water Removed on Yield o f Sulfanilic Acid
Figure 4. Effect o f Temperature o f Reaction on Yield o f Sulfanilic Acid

DILuENT \ r ~ ~ ~In ~some f ~ of . the initial experiments the

aniline sulfate first formed tended to cake and char. This Table 111. Effect of Amount of Water Removed
difficulty was overcome by adding larger volumes of hydro- Co. Water Tempera- % 7 Diluent
Removed ture, O c. Yield gecovered
carbon diluent (boiling range 155-190" C.). In order to test 7.3a
quantitatively the effect of larger amounts of diluent, a series 9.oa
10.0
of runs was made in which the volume of diluent was varied. 10.4
It might ordinarily be expected that the amount of hydro- 10.7
11.1
carbon preqent would have little effect upon yield. But in a These r u m were made
this case the caking of the aniline sulfate and the consequent lower recovery.
reduction in yield seems to be influenced by the quantity of
diluent. Table IV. Effect of Reaction Tem erature (Boiling Point of Diluent)
The effect of increasing the volume of diluent is shown in on g e l d
Table I and Figure 1. Tempera- Cc. Water CI % Diluent
ture, C. Removed Ydl: Recovered
EXCESS SULFURIC ACID. The use of the partial pressure 168 10.4 57.0 85.0
method is predicated upon the ability of the diluent to remove 169 10.7 67.2 84.0
169 9.8 64.3 63.2
the water of reaction as it is formed and hence maintain a high 170 10.4 58.4 86.0
concentration of sulfuric acid. If this concentration is main- 170 11.1 71.7 86 0
171 11.3 75.3 77.3
tained, the necessity for using excess sulfuric acid is eliminated 172 10.0 65.8 86.0
179 11.0 81.0 85.0
since its only function in ordinary sulfonations is to keep the 183 11.0 95.7 93.0
desired high acid concentration.
A series of runs was made in vihich the quantity of excess
sulfuric acid was varied while the temperature and amount prevent the sulfonation acid from falling below a limiting con-
of water removed were kept substantially constant. The centration.
results are shown in Table I1 and plotted in Figure 2; they WATERREMOVAL. Different amounts of water were with-
indicate that the sole function of excess acid in a sulfonation drawn from the reactants in order to observe the effect on
is t o remove chemically the water formed by the reaction and sulfanilic acid yield. The conditions mere kept constant for
these runs, including the optimum amount of kerosene
(500 cc.) and the theoretical amounts of sulfuric acid for the
Table I. Effect of Volume of Diluent fixed amount of aniline. The results are shown in Table I11
(Temperature, 169' C.: excess HaSOa, 1%: water removed, 9.0 cc.) and Figure 3; they indicate that the reaction yields are prac-
Volume Yield of Volume Yield of. tically proportional to the amount of water removed within
o f Diluent, Cc. Sulfanilic Acid, yo of Diluent, Cc. Sulfanilic Acid, the range studied in this series.
a00 34.4 400 61.3 REACTION TEMPERATURE.Higher boiling fractions of
250 40.3 450 54.3
300 50.5 500 64.3 kerosene were tried in order to find the effect of reaction tem-
350 51.9 perature on the yield of sulfanilic acid. I n previous runs a
simple single-blade agitator operating a t low speeds was
Table 11. Effect of Excess Sulfuric A c i d used. However, high-speed agitation served to produce a
yo Excess Temppa- Cc. Water more uniform reaction mass and, consequently, allowed the
Has04 ture, C. Removed Yzld sulfonation to proceed more smoothly. The runs shown in
0 Table IV were made with this improved procedure. Again
10
20
30
500 cc. of diluent were used with the stoichiometric amount
40 of sulfuric acid for the aniline. However, instead of feeding
aniline into the kerosene and sulfuric acid mixture as in pre-