close

Вход

Забыли?

вход по аккаунту

?

код для вставки
2,409,124
` Patented Oct. 8, 1946
UNITED STATES PATENT OFFICE
2.409.124
rar-:rana'rxon or AcaYLoNrrarLa
nalpn v. nemer. Glenbrook. conn.. assignm- zo
American Cyanamid Company, New York, N. Y.,
a corporation o! Maine
Application October 19. 1940, Serial No. 381,986
is claims. (Cl. 26m-464)
1
produce the above compolmd by reacting acet
the extent of approximately ily/2%. 'I'he other
halides. notably the iiuoride, are even less sol
uble. However. it has been found that their
water solubility may be increased if solution is
ylene and HCN in the presence of a catalyst in
cluding a cuprous halide.
effected in the presence of ammonium and alkali
metal halides, such as ammonium. sodium or po
The present invention relates to a process for
preparing acrylonltrile.
The principal object of the invention is to
The production of acrylonitrile from acetylene
and HCN may be represented as follows:
tassium chlorides. Acidiiication with inorganic
acids such as hydrochloric is also eiîective in in
creasing the catalyst solubility. Under such con
10 ditions, the amount oi cuprous halide dissolved
is amply suihcient to effectively carry out the
reaction using water as the reaction medium.
It has been proposed to carry out the above
inasmuch as it has been found that the copper
reaction using activated charcoal as a carrier for
halide is effective as a catalyst only in the cu
such alkaline catalysts as alkali metal or alka
line earth metal cyanides. Such a procedure is 15 prous state, it may be desirable under such cir
cumstances. to add a certain amount of metal
extremely diflicult due to the fact that it must
llc copper to insure the absence oi' any material
be conducted in gas phase, which means that
cupric salt.
large space volumes oi reactants must be han
Due to the fact that acetylene is only slightly
died, involving expensive equipment. Even un
der the most favorable conditions, poor yields 20 soluble in water. it may be desirable under some
circumstances, to use a reacting medium in
are obtainable and due to the high temperatures
which both reactants are more nearly soluble.
necessary for carrying out the reaction, there
For instance, both HCN and acetylene are known
are considerable side reactions taking place to
to have good solubillties in mono and polyhydric
gether with decomposition. As a consequence,
a very impure product is obtainable in very low 25 alcohols. By first dissolving the cuprous chlo
yields.
It is one oi the main objects o! the present in
vention to produce acrylonitrile by the above re
action by a method involving simple and inex
ride in water or in water containing a small
amount of ammonium chloride, this catalyst so
lution may then be completely disseminated
throughout the alcoholic medium inasmuch as
pensive apparatus. using a cheap catalyst which 30 the alcohol and water are completely misclble in
all proportions.
will produce yield eiliciencies higher than that
heretofore thought possible.
To this end, the invention contemplates in
one of its aspects. the use of a cuprous halide,
preferably cuprous chloride, as the catalyst.
While the reaction may, according to the present
invention, be carried out either in strictly gas
phase or using a liquid reaction medium. yet the
latter is preferred by reason of the simplicity of
Starting then with a. solution of the cuprous
catalyst, HCN and acetylene may be added there
to by bubbling the mixture through the reaction
carrier. Where the reaction takes place below
the boiling point of HCN, this reactant may be
added in liquid form. In any event, agitation
is desirable in order to insure intimate and com
plete eontact not only between the reactants but
the apparatus required and the more favorable 40 also with the catalyst.
While a relatively high temperature such as
contact obtainable between the reactants. An
75° C. is a desirable one for carrying out the re
other important consideration based on the lat
action due to the fact that under these circum
ter procedure is that under those circumstances.
stances, the acrylonitrile may be distilled from
the cuprous halide may be in solution. which fa
cilitates lts complete dissemination through the 45 the reaction mixture as fast as formed, yet this
reaction medium and insures a more intimate
is not at all necessary. Lower temperatures may
be used although it will be understood that tem
contact with the reactants.
peratures as low as 20° C. or below have a tend
The invention further contemplates the novel
ency to slow up the reaction. As a matter oi tact,
steps of the method and conditions under which
the reaction is carried out as more fully herein 50 the reaction being an exothermic one. it may be
desirable to install means for removing this re
after described and shown in the iiow sheet which
action heat from the reaction vessel.
diagrammatically illustrates a suitable arrange
Where a reaction carrier having a compara
ment oi apparatus for carrying out the invention.
tively low boiling point is used. it will be iound
The cuprous halides are substantially insoluble
desirable to equip the reaction vessel with a re
in water. cuprous chloride being soluble only to
3
9,409,124
ñux condenser in order to avoid abnormal losses.
Where commercial conditions dictate that it
is more convenient to operate under gas phase
conditions, the cuprous halide catalyst may be
incorporated with such carriers as granular
pumlce. silica gel. porous calcined bauxite, char
coal or the like.
4
I claim:
1. The process oi' preparing acrylonitrile which
comprises reacting acetylene and hydrocyanic
acid in an aqueous solution of a cuprous halide
as a catalyst at a temperature within the range
oi' 60° to 110° C.
`
2. The process oi preparing acrylonitrile which
Example I
comprises reacting acetylene andhydrocyanic acid
inan aqueoussolutionoicuprouschlorideasa
A solution oi' cuprous chloride may be made by 10 catalyst at a temperature within the range ot
dissolving the same in water containing a small
60° to 110° C.
amount of ammonium chloride acidiiied with hy
drochloric acid. A solution containing from 2
to 5% oi cuprous chloride is amply suincient ior
3.l The process oi preparing acrylcnitrile which
comprises reacting acetylene and hydrocyanic
be bubbled through the reaction carrier contain
ing the catalyst until an analysis oi thc out
4. The process of preparing acryionitrile which
comprises reacting acetylene and hydrocyanic
acid in an aqueous solution ot cuprous bromide
the purpose.
15 as a catalyst at a temperature within the range
A mixture oi HCN gas and acetylene may then
of 60° to 110° C.
going gases indicates that there is no further re
acid in an aqueous solution omtaining from 1.5
action. Acrylonitrile may then be recovered from 20 toi5% oiacuproushalideasacatalystanda
the reaction vessel by aseotropic distillation or
compound oi the class consisting of ammonium
solvent extraction methods.
and thealkalimetalhalidesasasolubiliaenthe
Example II
reaction being elected at a temperature within
53.5 liters of acetylene were bubbled through
liquid HON for 2.3 hours and the eiiluent gaseous
5. The process oi preparing acrylonitrile which
comprises reacting acetylene and hydxocyanic
the range ot 50' to 110’ C.
acid in an aqueous solution containing from 1.5
mixture bubbled through an aqueous solution oi
to45% oicuprouschlorldeasacataiystanda
cuprous chloride as above prepared. The reac
compound of the class consisting oi' ammonium
tion was
ed out at from 83 to 85° C. with
constant
during which time a distillate 80 and the alkali metal chlorides as a solubiiiser.
the reaction being eii'ected at a temperature with
containing acrylonitrile was recovered and puri
in the range of 60’ to 110’ C.
iled by fractional distillation.
6. The process of preparing acrylonitrile which
Example III
comprises reacting acetylene and hydrocyanic
35 acid in an aqueous solution containing from 1.5
52.5 liters of acetylene were bubbled through
to 45% of cuprous bromide as a catalyst and a
liquid BCN for 2.25 hours and the eilluent gas
compound of the class
of ammonium
mixture led into and below the surface of an aque
and the alkali metal bromides as a solubiliser.
ous solution of cuprous chloride prepared as above.
the reaction being enected at a temperature with
The contents of the reaction vessel were heated 40 in the range oi' 60° to 110° C.
to speed up the reaction. which proceeded more
7. The process oi preparing acrylonitrile which
or less quietly over a range of between Bl and
comprises reacting acetylene and hydrocyanic
83" C. during which time the mixture was con
acid in the presence ot a catalytic solution of a
stantly stirred. The product oi' this reaction.
cuprous halide.
while containing considerable quantities of ac-. 45
8. The process of preparing acrylonitrile which
rylonitrile, did not give as good a yield as the
comprises
reacting acetylene and hydrocyanic
previous examples.
acid in the presence oi an aqueous catalytic so
lution oi a cuprous halide.
Example IV
9. The process oi preparing acrylonltrile which
A solution oi cuprous bromide was prepared 50 comprises reacting acetylene and hydrocyanic
approximately like the catalyst or Example I by
acid in the presence ot an acidic catalytic solu
dissolving 394 g. oi' cuprous bromide in 260 g.
tion oi' a cuprous halide.
oi' water containing 296 g. of ammonium bromide
l0. The process of preparing acrylonitrile
acidined with 3 cc. oi hydrobromic acid. This
which comprises reacting acetylene and hydro
gave a solution containing 45% by weight ot 55 cyanic acid in the presence ct an acidic catalytic
cuprous bromide.
solution oi cuprous chloride.
A mixture of HCN gas and acetylene was bub
11. The process oi' preparing acrylonitrile
bled through the aqueous solution oi the above
which comprises reacting acetylene and hydro
cuprous bromide catalyst in a reaction vessel.
cyanic acid in the presence of an acidic catalytic
Heating the reaction mixture to 85' C. with con 60 solution oi cuprous bromide.
stant stirring Cave a distillate from which acry
12. The process oi preparing acrylonitrile
lonitrile was recovered by fractional distillation.
which comprises reacting acetylene and hydro
Although in the above examples cuprous chlo
cyanicacidinthepresenceoianacidieaqueous
ride is seemingly the most enective catalyst and
solution comprising 1.5 to 45% of a cuprous halide
hence is recommended, however the various other 65 as a catalyst and an ammonium salt as a solu
cuprous halides may likewise be used. particu
biliaer tor the cuprous salt.
larly where ammonium or alkali metal halides
13. The process oi' preparing acrylonitrlle
are used to facilitate their solution in an acldliled
which comprises reacting acetylene and hydro
reaction medium.
cyanic acid in the presence of an acidic aqueous
While the invention has been shown and de 70 solution comprising 1.5 to 45% oa' a cuprous halide
scribed with particular rei'erence to speciilc em
as a catalyst and an ammonium halide as a solu
bodlments. it is to be understood that it is not to
biliaer for the cuprous salt.
be limited thereto but is to be construed broadly
14. The process ci’ preparing acrylonitrile
and restricted solely by the scope of the appended
claims.
which comprises reacting acetylene and hydro
cyanic acid in the presence oi anacidic aque
9,400,1:4
5
.
ous solution comprising 1.5 to 45% of cuprous
chloride as a catalyst and ammonium chloride
as a solubilizer i’or the cuprous chloride.
cyenic acid in the presence oi' an aqueous cata
lytic solution at a temperature of 60° to 11a’ C.
and comprising 1.5 to 45% by weisht of a cuprous
15. The process of preparing acrylonitrile
which comprises reacting acetylene and hydro
halide as a catalyst and an ammonium salt as
cyanic acid in the presence of an acidic aqueous
containing copper powder suspended therein to
maintain the copper in the cuprous state.
18. Process for the manufacture of acrylonitrile
which comprises bringing acetylene together with
solution comprising 1.5 to 45% ot cuprous chlo
ride as a catalyst and ammonium chloride as a
solubilizer i’or the cuprous chloride. said solution
- containing copper powder suspended therein.
16. The process of preparing acrylonitrile
a solubilizer for »the cuprous salt, said solution
10 hydrocyanio acid into contact with an aqueous
acid reacting solution oi cuprous chloride, said
which comprises reacting acetylene and hydro
solution containing also a salt of the class con
cyanic acid in the presence of an aqueous so
sisting oi ammonium and alkali metal salts.
19. The process oi’ preparing acrylonitrile
iution containing 1.5 to 45% by weight oi’ cuprous
chloride as a catalyst and ammonium chloride 15 which comprises reacting acetylene and hydro
cyanio acid in an acidic aqueous solution com
as a solubilizer for the cuprous chloride. said so
lution containing copper powder suspended there
prising cuprous chloride and ammonium chloride
in to maintain the copper in the cuprous state.
as a solubilizer for the cuprous chloride.
17. The process of preparing acrylonitrile
which comprises reacting acetylene and hydro
RALPH V. HEUSER.
Disclaimer
2,409,124.--Ralph V. Heuser, Glenbrook, Conn.
PREPARATION 0F ACRYLONITRILE.
Patent. dated Oct. 8 1946. Disclaimer filed Mar. 30, 1949, by the assignee,
American Oyanam'id’ Company.
Hereby enters this disclaimer to claims 1, 2, 4, 5, 7, 8, 9, 10, 12, 13, 14, 15, 16,
17, 18, and 19 of said patent.
[Oficial Gazette April 26, 1.949.]
9,400,1:4
5
.
ous solution comprising 1.5 to 45% of cuprous
chloride as a catalyst and ammonium chloride
as a solubilizer i’or the cuprous chloride.
cyenic acid in the presence oi' an aqueous cata
lytic solution at a temperature of 60° to 11a’ C.
and comprising 1.5 to 45% by weisht of a cuprous
15. The process of preparing acrylonitrile
which comprises reacting acetylene and hydro
halide as a catalyst and an ammonium salt as
cyanic acid in the presence of an acidic aqueous
containing copper powder suspended therein to
maintain the copper in the cuprous state.
18. Process for the manufacture of acrylonitrile
which comprises bringing acetylene together with
solution comprising 1.5 to 45% ot cuprous chlo
ride as a catalyst and ammonium chloride as a
solubilizer i’or the cuprous chloride. said solution
- containing copper powder suspended therein.
16. The process of preparing acrylonitrile
a solubilizer for »the cuprous salt, said solution
10 hydrocyanio acid into contact with an aqueous
acid reacting solution oi cuprous chloride, said
which comprises reacting acetylene and hydro
solution containing also a salt of the class con
cyanic acid in the presence of an aqueous so
sisting oi ammonium and alkali metal salts.
19. The process oi’ preparing acrylonitrile
iution containing 1.5 to 45% by weight oi’ cuprous
chloride as a catalyst and ammonium chloride 15 which comprises reacting acetylene and hydro
cyanio acid in an acidic aqueous solution com
as a solubilizer for the cuprous chloride. said so
lution containing copper powder suspended there
prising cuprous chloride and ammonium chloride
in to maintain the copper in the cuprous state.
as a solubilizer for the cuprous chloride.
17. The process of preparing acrylonitrile
which comprises reacting acetylene and hydro
RALPH V. HEUSER.
Disclaimer
2,409,124.--Ralph V. Heuser, Glenbrook, Conn.
PREPARATION 0F ACRYLONITRILE.
Patent. dated Oct. 8 1946. Disclaimer filed Mar. 30, 1949, by the assignee,
American Oyanam'id’ Company.
Hereby enters this disclaimer to claims 1, 2, 4, 5, 7, 8, 9, 10, 12, 13, 14, 15, 16,
17, 18, and 19 of said patent.
[Oficial Gazette April 26, 1.949.]
Документ
Категория
Без категории
Просмотров
0
Размер файла
437 Кб
Теги
1/--страниц
Пожаловаться на содержимое документа