Patented May 14, 1935

2001,284
UNITED STATES PATENT office 2,001284
MANUFACTURE OF ANTLINEFROMCELORO
BENZENE AND AMMONA ... . .
Walter Prahl and Wilhelm Mathes, Ludwig
shafen-on-the-Rhine, Germany, assignors to
Dr. F. Raschig G. Tan. b. B., Ludwigshafen-one
the-Rhine,
many
Bavaria, Germany, a firm of Ger
No Drawing. Application October 14, 1931,
Serial No. 568,866. In Germany October 23,
1930.
14 Claims. (CI. 260-1305)
It is known that remarkable quantities of ani sentative of the second class of substances be
line besides other products are formed by treat sides copper or its compounds. Among the pos
ing liquid chlorobenzene with ammonia at ele sible combinations it has been found especially
wated temperatures and pressures. It has been useful to introduce phosphoric acid together with
repeatedly tried to substitute an operation in the substances capable of forming heat resistant
vapor phase for the operation in the liquid phase complex compounds with phosphoric acid. The
which is delicate and comparatively dangerous most important compounds of this character are
especially in consequence of the high pressures molybdic and tungstic acid.
used. Chlorobenzene and ammonia, have been The sequence and the shape in which these
passed at different temperatures over several constituents are combined to form a catalyst or O
catalysts consisting for instance of nickel, so are applied to their carrier have no substantial
dium Carbonate, lime and the like and it has been influence on their action or their efficiency.
tried to facilitate the reaction by adding other When these catalysts are used the reaction be
gases. However, the result of all these experi tween chlorobenzene and ammonia begins at
ments was that the formation of aniline was ab about 250° C. The temperature most favorable 15
solutely unsatisfactory and that by using the with respect to the degree of reaction and to the
Catalysts hitherto proposed the formation of by yield is from about 300 to 450° C., depending
products in proportion to the quantity of aniline upon the nature of the catalyst used. Below 300
formed at the same time was rather increased C. the degree of reaction is in most cases too
than decreased. Small for allowing industrial application; above 20
Under the circumstances it was not probable 450° C. the yield decreases materially in conse
that it WOuld be possible to find a process Suit quence of secondary reactions. At higher tem
able for industrial production of aniline by pass peratures, an upper limit is soon reached insofar
ing chlorobenzene in the vapor phase together as commercial interest in the reaction is con
with ammonia over catalysts. cerned, for, as already stated, the reaction then
However, we have found that very high yields becomes quite unfavorable. This is due princi
approximating 100% of aniline can be obtained pally to the reduction in amount of the output of
gby passing chlorobenzene vapor and ammonia at the aniline obtained and the increased propor
an elevated temperature Over catalysts compris tion of undesirable by-products produced. As be
ing at the same time at least one representative ing a matter of perhaps academic interest, it
of each of two classes of substances which are de may be further stated that at yet higher tem
fined as follows. The first class comprises the peratures than definitely given herein, it is
metals copper, cobalt, nickel, iron and their com nevertheless still possible to obtain a small out
pounds, while the second class comprises those put of aniline, although the by-products and
35 elements of groups 5 and 6 of the periodic sys unfavorable features render the reaction too ex 35
tem which are solid at room temperature and of pensive and impractical to use.
which the salts are not precipitated as hydroxides, It is advisable to allow the reaction to proceed st
by adding ammonium sulfide to their aqueous in the presence of an essential excess of am
solution and the compounds of such elements.
Preferably the catalysts complying with these monia, say for instance at least 15 of the the
oretical quantity and to transform during one 40
requirements are distributed in known manner passage over the catalyst not more than about
on carriers having a large surface area such as 20% of the quantity of chlorobenzene present,
silica gel, bleaching earth, pumice stone, metal as otherwise substantial quantities of diphenyl-.
oxides and the like. amine are formed instead of aniline.
Among the combinations of Substances suitable aniline formed during the passage over 4
as catalysts according to this invention those theThe
catalyst can be separated from the gas mix
catalysts are especially efficient which contain. ture in known manner. Preferably the hot gas
copper or its compounds as the representatives eous mixture issuing from the contact oven is
of the first class, the second class being repre cooled down to normal temperature after sep
sented by substances having a decidedly acid aration of the ammonia chloride formed. The 5)
character, such as for instance phosphoric acid, remaining, ammonda gas is returned to the cycle
vanadic acid, molybdic acid or tungstic acid. of operations and andline is separated by frac
The qualities of these catalysts may be im tional distillation from the liquified mixture of
proved especially in respect of resistance and chlorobenzene and aniline. The chlorobenzene
efficiency by introducing more than one repre may also be returned into the cycle of opera 55
 2 2,001,284
tions. It is also possible to separate aniline with
a little chlorobenzene by fractional condensa the salts are not precipitated by ammonium sul
tion of the mixture and to return the remaining fide as hydroxides from their aqueous solutions.
mixture of chlorobenzene and ammonia into the 3. The process of manufacturing aniline by
5 cycle and to pass it again over the contact, the passing a mixture of chlorobenzene vapor and
quantities spent in the reaction being replaced ammonia at a temperature of about 250° C. to
by new material, if desired. - about 450 C., over a catalyst which consists
"mainly of at least one of the compounds phos
Eacample 1 phoric acid, vanadic acid, molybdic acid and
0 tungstic acid and at least one of the metals
1000 ccm. of silica gel are impregnated with copper, cobalt, nickel and iron, the catalyst being 10
a solution of 50 g. of ammonium phosphate, 50
g. of ammonium tungstate and 20 g. Of cupric precipitated on a suitable carrier.
chloride in 300 ccm. of water. The mass is dried passing a mixtureofof manufacturing
on the water bath and above this catalyst there ammonia
4. The process aniline by
chlorobenzene vapor and
is passed at 400° C. a current of chlorobenzene cor about 450;atC.,a temperature of about 250° C. to
over a catalyst which consists
responding to a vaporized quantity of 300 g. per mainly of phosphoric
hour and mixed with 50 litres of gaseous am at least one compoundacid in combination with
capable of forming com
monia per hour. The hot gases issuing from the plex phosphoric acid compounds, of one of those
20 oven are cooled and the aniline is separated in . elements of groups 5 and 6 of the periodic Sys
known manner from the chlorobenzene. After tem which are solid at room temperature and of
separation the yield is 45 g. of aniline per hour. which the salts are not precipitated by ammonium 20
Eacample 2 sulfide as hydroxides from their aqueous solu
25 100 g. of ammonium molybdate and 10 g. of cobalt, tions and at least one of the metals copper,
cupric chloride are dissolved in 300 ccm. of water tated onnickel and iron, the catalyst being precipi
and poured on 1000 ccm. of Florida earth. The 5. The a process suitable carrier. . . . . .
of manufacturing aniline by
dry mixture is used as the catalyst over which passing a mixture of chlorobenzene vapor and
there are passed at 350° C. the vapors of 250 g. ammonia at a temperature of about 250 C. to
30 of vaporized chlorobenzene and 50 litres of am about 450° C., over a catalyst which mainly
monia per hour. By separation in the usual way consists of phosphoric acid in combination with 30
25; g. of aniline are obtained per hour. a tungsten compound capable of forming com
Eacample 3 plex phosphoric acid compounds and at least one
of the metals copper, cobalt, nickel and iron, the
35 60 g. of ammonium vanadate, 80 g. of am catalyst being precipitated on a suitable carrier.
monium phosphate and 20 g. of nickel chloride 6. The process of manufacturing aniline by
(NiCl2) are dissolved in 600 ccm...of water and passing a mixture of , chlorobenzene vapor and
poured on 1200 ccm. of aluminium hydroxide. ammonia, at a temperature of from about 250 to
The mass is dried and over this catalyst there about 450° C., over a catalyst, which consists
40 are passed at 450° C. the vapors of 400 g. of mainly of phosphoric acid in combination with
chlorobenzene and 60 litres of ammonia, per a molybdenum compound capable of forming 40
hour. The yield is 30 g. of aniline per hour. complex phosphoric acid compounds and at least
Eacample 4 one of the metals copper, cobalt, nickel and iron,
the catalyst being precipitated on a suitable
45 50 g. of ammonium molybdate are dissolved carrier. . . . . . . . . . . .';
in hot water and mixed with 75 g. of phosphoric 7. The process of manufacturing aniline by
acid. With this solution 1000 ccm, of silica gel passing a mixture of the vapors of 300 g. of 45
are impregnated and the mass is dried some chlorobenzene and 50 litres of gaseous ammonia
hours on the water bath. A Solution of 25 g. of per hour at 400° C. over a catalyst consisting of
50 manganese chloride and 20 g. of cupric chloride 1000 ccm. of silica gel impregnated with a solu
in water is poured on the mass which is then tion of 50 g. of ammonium phosphate, 50 g. of
again dried. By passing over this catalyst at ammonium tungstate and 20 g. of cupric chloride, 50
400° C. the vapors of 300 g. of chlorobenzene and cooling the hot gases issuing from the oven and
25 litres of gaseous ammonia per hour 30 g. of separating the aniline from the chlorobenzene.
aniline per hour are obtained which may be sep 8. The process of manufacturing aniline by
arated in the known manner. passing a mixture of the vapors of 250 g. Of 55
What we claim is: chlorobenzene and 50 litres of ammonia, per hour
1. The process of manufacturing aniline by at 350° C. over a catalyst consisting of 1000 ccm.
passing a mixture of chlorobenezne vapor and of Florida earth impregnated with 100 g. of
60 ammonia at a temperature of from about 250 to ammonium molybdate and 10g, of cupric chloride
about 450° C., over a catalyst which consists. and separating the aniline from the gases issuing 60
mainly of at least one of those elements of groups from the oven. '.
5 and 6 of the periodic system which are solid at 9. The process. of manufacturing aniline by
room temperature and form salts which are not passing the vapors of 400 g. of chlorobenzene and
65 precipitated by ammonium sulfide as hydroxides 60 litres of gaseous ammonia at 450° C. over a
from their aqueous solutions, and at least one of catalyst consisting of 1200 ccm. of aluminium hy 65
the metals copper, cobalt, nickel and iron. droxide impregnated with 60 g. of ammonium
2. The process of manufacturing aniline by vanadate, 80 g. of ammonium phosphate and 20
passing a mixture of chlorobenzene vapor and g. of nickel chloride and separating the aniline
ammonia at a temperature of about 250° C. to from the gases issuing from the oven. . . . .
about 450° C., over a catalyst which consists 10. The process of manufacturing aniline by 70
mainly of copper and at least one compound of passing a mixture of chlorobenzene vapor and a
decidedly acid character of one of those ele material excess of ammonia at a temperature of
75
ments of groups 5 and 6 of the periodic system about 250° C. to about 450° C. over a catalyst
which are solid at room temperature and of which which consists mainly of at least one of those ele
ments of groups 5 and 6 of the periodic system 75
 2,001,284 3
which are solid at room temperature and of which rating the aniline from the gases issuing from
the salts are not precipitated by ammonium Sul the oven and returning into the cycle the chloro
fide as hydroxides from their aqueous Solutions benzene and ammonia recovered after separation
and at least one of the metals copper, cobalt, of the aniline from the reaction mixture.
nickel and iron. 13. The process of manufacturing aniline by
11. The process of manufacturing aniline by passing a mixture of chlorobenzene vapor and
passing a mixture of chlorobenzene vapor and ammonia at a temperature of from about 250° C.,
ammonia at a temperature of about 250° C., to to about 450° C., Over a catalyst which consists
about 450° C., Over a catalyst which consist main mainly of a compound of at least one element of
0. ly of at least one of those elements of groups 5 those found in groups 5 and 6 of the periodic O
and 6 of the periodic system which are Solid at System which is solid at room temperature and
room temperature and of which the salts are not forms salts, which are not precipitated by am
precipitated by ammonium sulfide as hydroxides monium sulfide as hydroxides from their aqueous
from their aqueous solutions and at least one of Solutions, and at least one of the metals copper,
5 the metals copper, Cobalt, nickel and iron, the Cobalt, nickel and iron. 15
speed of flow of the mixture of vapors being so 14. The process of manufacturing aniline by
regulated that not more than about 20% of the passing a mixture of chlorobenzene vapor and
chlorobenzene present is transformed into aniline ammonia at a temperature ranging from about
during one paSSage. 250 C. upward to a temperature at which the
20 12. The process of manufacturing aniline by reaction becomes unfavorable over a catalyst con
passifhg a mixture of chlorobenzene vapor and sisting mainly of at least one element of those
ammonia at a temperature of about 250 C., to found in groups 5 and 6 of the periodic system
about 450° C., over a catalyst which consists main which is solid at room temperature and forms salts
ly of at least one of those elements of groups 5 which are not precipitated by ammonium sulfide
25 and 6 of the periodic system which are solid at as hydroxides from their aqueous solutions, and 25
room temperature and of which the Salts are not at least one of the metals copper, cobalt, nickel
precipitated by ammonium sulfide as hydroxides and iron.
from their aqueous Solutions and at least One of WILHELMI MATHES.
the metals copper, cobalt, nickel and iron, Sepa WAER, PRAHL,