Patented Get. 13, 1925.

STATE

Qt

ATET

ANTHONY GEORGE, 0F NIAGARA FALLS, NEW YORK, ASSIGNOR TO THE MATHINON

ALKALI WORKS, INC., OF NEW YORK, N. Y., A CORPORATION OF VIRGINIA.
MANUFACTURE OF BENZOIC ACID FROM BENZQTRIGHLORIDE.
N0 Drawing.

Application, ?led July 22, 1924. Serial No. 727,412.

To all whom it may concern:

that it will react as fast as it is added, the

Be it known that I, ANTHONY Gnoncn, formation of benzoic acid with the evolution
a citizen of Greece (who has declared his of hydrochloric acid as*can be brought

intention of becoming a citizen of the about at temperatures in the neighborhood

United States), residing at Niagara Falls,

in the county of Niagara, State of

10

New York, have invented certain new and

useful Improvements in the Manufacture of
Benzoic Acid from Benzotrichloride; and
I do hereby declare the following to be a

full, clear, and exact description of the in

of 100 to 110 o.

60

It is important, in carrying out the pres

ent process, that the rate of addition of
water or steam should not be in excess of
the rate at which it reacts. If excess water

accumulates in the reaction vessel, it will

dissolve the catalyst and thereby retard or

65

vention, such as Will enable others skilled inhibit the reaction. In order that the re
in the art to which it appertains to make action may proceed properly, the catalyst
and use the same.
should remain in suspension as an army
This invention relates to an improved drous solid or as solid particles with some 70
method for the manufacture of benzoic acid adsorbed water; at no time should sufficient

from benzotrichloride, and includes im water be present to dissolve the catalyst

provements in the puri?cation of the ben~ as such aqueous solutions are not e?'ective
zoic acid as well as in the method of its in promoting the reaction.
20 production.

It is also im- '

portant that the agitation be sufficient to 75

The usual method. of converting benzo disperse the water and to maintain the catas
trichloride to benzoic acid is to treat the lyst in suspension, so that intimate contact
chloride with an aqueous alkaline solution will be brought about between the water,
'

either in the presence or in the absence of the catalyst and the benzotrichloride.
25

some catalyst such as iron powder. The

30

alkali reacts with the benzotrichloride form

ing a water solution of alkali chloride and
benzoate. This solution must then be
treated with acid in order to precipitate the
benzoic acid and so render possible a sepa
ration from the chloride by ?ltration. '

The production of benzoic acid from ben

zotrichloride according to the usual method
thus referred to requires a large amount of
labor for the operation and maintenance of
the plant and is otherwise an objectionable
method.
The present invention'relates to an im

40

tions are obviated, and according to which

the hydrolysis of the benzotrichloride with
water is effected in the absence of such aque
ous alkaline solution.

80

the catalyst is to impregnate some light in

ert material such as pumice, charcoal, or

asbestos, etc., with the zinc chloride. By

the use of such an inert material as a carrier

for the zinc chloride, the zinc chloride is

readily brought to the surface of the hen
zotrichloride with a minimum of agitation,

86

so that it comes in contact with the water

as soon as the water enters the reactor.

The accumulation of water, with the con

90

sequent retardation of the reaction is there

by prevented. When zinc chloride is used

without such an inert carrier, the agitation

proved method for the manufacture of hen should be increased in order to bring about
zoic acid from benzotrichloride according a sufficiently intimate contact between the
to which the use of aqueous alkaline solu

45

'

An advantageous method of- providing

95

zinc chloride, the added water or steam, and

the benzotrichloride.

At the end of the reaction, the fused ben

zoic acid layer can advantageously be
washed with hot water before itis drawn Nil

The direct hydrolysis of benzotrichloride o?t. A product is thus obtainable practically

with water alone, to produce benzoic acid free from chloride and sufficiently pure for
and hydrochloric acid, can be effected at conversion into sodium benzoate by the usu
50

high temperatures. under pressure, e. g., at al procedure of dissolving in caustic soda,

temperatures around 140 to 190 C.
with further puri?cation, if desired, in any
We have found, however, that if a small suitable manner.
amount of a catalyst, such as, for example,
In carrying out the process of the present

105

anhydrous zinc chloride, be suspended in invention, other catalysts than zinc chloride

ti

the benzotrichloride, and water or steam can be used, althou h I consider zinc chlo

slowly added with agitation at such a rate ride particularly a vantageous.

Thus, I

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1,557,153

have found that zinc oxide, hydroxide, oxy water is added, but this rate of addition is
chloride, benzoate and sulphate are effective nevertheless so regulated that it is not in
when in ,a dry state. These compounds are excess ofpthe rate at which it reacts. The
rapidly converted to the chloride when the hydrochloric acid evolved, which contains
reaction starts; Similar dry compounds of only traces of organic impurities, ma be

absorbed in water according to any 0 the

copper, tin, nickel, manganese, aluminum7 well-known
methods, and thus recovered as
and iron have been found to promote the re

hydrochloric acid.
action. Zinc chloride, however, possesses aqueous
In order to prevent solidi?cation as the
high catalytic activity and a minimum tend

15

ency to blacken the reaction mass, and it is reaction proceeds, the temperature is gradu 75
available in ample amounts and at a low ally raised until near the end of the reaction
it reaches 110-115 C. It should not exceed
cost.
about
1200 C. as a maximum, otherwise ex
The purity of the benzoic acid produced is
somewhat dependent upon the purity of the cessive decomposition or charring will occur. 80
benzotrichloride treated. Impurities in the When the reaction is completed, as indicated
benzotrichloride are largely condensed to by absence of hydrochloric acid evolution,
form dark-colored compounds or carbon. about 10 to 12 lbs. of water are added and
The amount of such condensation is greater the mixture is allowed to digest for about

with large amounts of catalyst and at higher 1/2 hour with stirring. The water lowers
temperatures. When the benzotrichloride the solidi?cation point so that the tempera

85

may be reduced for this digestion to

contains benzal chloride, low yields of ben ture
zaldehyde are obtained if the hydrolysls is about 95 to 100 C. The total water used
carried out at about 100 C. It is possible, up to this point will amount to about 125

After digestion is complete, about 15

however, when large amounts of benzal chlo lbs.
gallons of hot water are run in and the
ride are present, to carry out the hydrolysis

90

below 100 C., in which case higher yields of mass stirred for about 14; hour at about 90

benzaldehyde are obtained. Ring chlorin to 100 C. This washing serves to remove
ated benzotrichloride is probably hydro the zinc chloride and hydrochloric acid to
lyzed to from chlorbenzoic acid which will the water layer. The lower layer'is then

30

be present in the roduct. In order to ob

siphoned off to a receiver in which the

35

tain high yields 0 a good quality product, molten benzoic acid is allowed to solidify.
the benzotrichl'oride itself should be of_ high The water layer is run to a cooling tank,
quality. Such a high quality benzotrlchlo where the dissolved benzoic acid separates
ride can be produced by chlorination in light out and can be subsequently ?ltered off and
The solid portion containing
at 100 to 150 C. until the speci?c gravity washed.

40

obtained from the benzotrichloride, and the

organic chlorine compounds in the puri?ed lng off the pumice, and urifying the benzo

95

100

is 1.375 to 1.385 at 20 C. When toluene is water, pumice, and about 90% of the yield
chlorinated under these conditions, prac of benzoic acid can, if desired, be converted
tically theoretical yields of benzoic acid are to sodium benzoate of high uality simply

by dissolving in sodium hydroxide, ?lter

less than 0.2%.

The invention will be further illustrated

by the following speci?c .descriptiombut it

45

50

105

product are present only in traces, e. g., ate solution, if desire , in any suitable
manner.

The crude benzoic acid present in the re

actor at the end of the reaction may contain

is intended and will be understood that the around 1 to 3% of inorganic chlorine pres
invention is illustrated thereby, but is not ent as hydrochloric acid and zinc chloride.
This inorganic chlorine can, however, be re~
limited thereto:

750 lbs. of chlorinated toluene, roduced

for example as described above, 0 speci?c
gravity 1.38 at 20 C., are placed in a 100
gal. stoneware vessel provided with a stirrer
and capable of being heated as for instance
by placing it in an oil bath. A re?ux con

110

duced to as low as 0.2 to 0.3% or lower by

adding water to the product before remov

ing the product from the reactor, and by

agitating the product with the water, in the

115

manner above described. The lower layer

consisting of benzoic acid and some water

denser is not required. With the agitator in can then be drawn off and treated to convert

o ration the temperature of the benzotri the benzoic acid into sodium benzoate, as 120
c loride 1s brought to about 100 C. and above described. Some benzoic acid is dis

60

pumice impregnated with zinc chloride is solved in the water and is, separated with
added in such amounts that about 5 lbs. of the water layer. This can be recovered in
pure form by simply cooling the solution,
zinc chloride are introduced.
Water is then run in slowly, preferably ?ltering, and washing with cold water.
Other methods of puri?cation of the ben
through a glastube extending underneath

the surface of the liquor, and this water is zoic acid produced can be used. For ex
distributed by the agitation. Hydrochloric ample, the reaction mass may be withdrawn
acid gas is evolved immediately at a rate from the reactor at the end of the reaction,

05

directly controllable by the rate at which and puri?ed by crystallization from water,

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1,557,153
sublimation, or other suitable method of equal to that at which it reacts, and the re
puri?cation of benzoic acid. The method of action being carried out at a gradually in
puri?cation above described, however, is a creased temperature to prevent solidi?cation
particularly advantageous method and is in as the reaction proceeds.
cluded as a part of the invention.
5. The method of producing benzoic acid

The process of the above speci?c descrip

70

from benzotrichloride which comprises add

tion is believed to be the best method of ing water gradually to the benzotrichloride
carrying out the invention, but the speci?c at a temperature of about 100 to 120 C.,

10

15

20

proceduredescribed can be varied and the the benzotrichloride being agitated and con
invention is not limited to these particular taining in suspension therein a catalyst car

conditions. For example, the kind of cata ried by an inert carrier, the catalyst con
lyst used and the method of adding it to the sisting of an anhydrous metal compound.
reactor can be varied, as well as the method
6. The method of producing benzoic acid
of adding the water, whether as vapor or from benzotrichloride which comprises add
liquid, and the type of apparatus used. The ing water gradually to the benzotrichloride

temperatures, length of time of digestion, at a temperature of about 100 to 120 0.,

and method of puri?cationJ may also be va the benzotrichloride being agitated and con
ried without departing from the spirit or taining in suspension therein a catalyst sup
digressing'beyond the limits of the inven ported on an inertcarrier, the catalyst con

Cl

80

tion, except in so far as the speci?c puri?ca taining as an active agent only anhydrous
tion process of the invention is claimed in zinc chloride.

certain of the claims.

7. The method of producing benzoic acid

It will thus be seen that the invention

provides an improved method for the pro
25 duction of benzoic acid from benzotrichlo
ride without the use of aqueous alkaline solu
tion and with the direct combination of wa
ter with the benzotrichloride in the presence
of a catalyst such as zinc chloride, the water
30 being added in regulated amounts at such a
rate that it will react as fast as it is added,
thus avoiding excess of water or accumula
tion of excess water during the reaction.
I claim:

' 1. The method of producing benzoic acid

from benzotrichloride, which comprises hy

drolyzing the benzotrichloride directly with
water in the presence of a catalyst in a re
action vessel at a temperature of about 100
to 120 C. until hydrochloric acid gas is no

90

longer evolved, the water being added at

substantially the rate at which it reacts,
thereafter adding water to the reaction
product in the same reaction vessel and
maintaining the mixture at an elevated tem

perature, and subsequently separating the

aqueous solution from the product.
8. The method of producing benzoic acid

100

from benzotrichloride which comprises hy from'benzotrichloride, which comprises hy

drolyzing the benzotrichloride directly with drolyzing the benzotrichloride directly with

till

water in the presence of an anhydrous metal water in the presence of a catalyst at a tem
compound at a temperature of about 100 to perature of about 100 to 120 (1, the reaction

120 (3., the reaction mixture being agitated, mixture being agitated and the water being
and the water being added at substantially added at substantially the rate at Whichit
the rate at which it reacts.
reacts, and the reaction mixture being heated
2. The method of producing benzoic acid for a further period of time after the addi
from benzotrichloride which comprises hy tion of the water has been completed.
drolyzing the benzotrichloride directly with 9. The method of producing benzoic acid

105

110

water in the presence of anhydrous zinc from benzotrichloride which comprises hy

chloride at a temperature of about 100 to

50

55

60

drolyzing the benzotrichloride directly with

120 C., the reaction mixture being agitated, water in the presence of anh drous 'zinc
and the water being added at substantially chloride at a temperature of a out 100 to
the rate at which it reacts.
120 (1, the reaction mixture being agi
3. The method of producing benzoic acid tated, and the water being added at sub
from benzotrichloride which comprises sus

115

stantlally the rate at which it reacts, and

pending an anhydrous catalyst in the ben the heatin of the reaction mixture being
zotrichloride, heating the benzotrichloride to continued or a further period of time after
a temperature of about 100 C., and intro~
of the water has been completed. 120
ducing water slowly with agitation, the wa the10.addition
The method of producing benzoic acid
ter being introduced at a rate approximately from benzotrichloride which comprises add
equal to that at which it reacts.
'
ing water gradually to the benzotrichloride
4. The method of producing benzoic acid at a temperature of about 100 to 120 (1,
from benzotrichloride which comprises sus the benzotrichloride being agitated and con 125
pending an anhydrous catalyst in the hen taining in suspension therein anhydrous zinc '
zotrichloride, heating the benzotrichloride chloride supported on an inert carrier, and
to a temperature of about 100 (3., and intro the reaction mixture being heated for a fur
ducing water slowly with agitation, the wa ther period of time after the addition of the
ter being introduced at a rate approximately water has been completed.
-

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1,557,153
11. The method of producing benzoic vacid from benzotrichloride, which comprises hy

from benzotrichloride, which comprises hy drolyzing the benzotrichloride directly with

drolyzing the benzotrichloride directly with water in the presence of a catalyst contain
water in the presence of a catalyst contain ing as an active agent only an anhydrous
ing as an active agent only anhydrous zinc metal compound at a temperature of about
chloride at a temperature of about 100 to 100 to 120 0., the reaction mixture being

120 C., the reaction mixture being agitated, agitated, and the water. being added at sub

and the water being added at substantially stantially the rate at which it reacts.
In testimony whereof I a?ix my signature.
the rate at which it reacts.
'
ANTHONY GEORGE.
12. The method of producing benzoic acid

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