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Патент USA US2411802

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Patented Nov. 26, 1946
,7 , c, . 4 ,
ions. F. Olin,
Grosse Ile, Mich., assignor to
, Sharnles, Chemicals Ina,v Bhiladelphia, Pa, a
_ corporation of-Delaware
No Drawing. ApplicationiMay 5, 1944,
Serial No. 534,353
G-Claims, (01. 260-585)
The present invention. pertainstothe puri?ca- '
tion ofv crude reaction mixtures resulting from
ammonationereduction of, aliphatic aldehydes. or
ketones by reaction thereof with ammonia or
amines, and hydrogen in the presence of a hy
drogenation catalyst. Amination reactions of
this general type are well-known in thear-t, and
thereafter removed by distillation from the re
sulting mixture, the operations of separating the
respective amines from each other and from im
purities is. greatly facilitated. While I do not
wish to belimited by any theoretical reasoning
concerning- results attained by the. practice'iof
the.‘ invention, itis believed that the treatment
ofuthe, crude reaction mixture by an inorganic
have been performed both in the liquid and in
the vapor phase, as illustrated?‘respectively by
base results ire-reactions by which certain-con‘
stituents of the amine-containing reaction'mlx-:
volume 172, page 223, and the copendingiappli
their conversion into=non-volatile, water-soluble;
the article by- Mignonac in. “Comptes Rendus,” 10 ture undergoa chemical change which'resultsi in
cation of John F. Olin- & James F. >McKenna,
salts, and that the removal of‘ these constituents
in the form of‘ an aqueous solution permits the
- .While the selective. production of mono-, di
remaining constituents of the reaction mixture
andtri-alkyl aminesmay, ‘to’ a large’ extent, be 15 to .be separated'from each other with greater
Serial Number 428,548,‘_?led~January 28, 1942.
controlled by appropriate control of the“ pro
portions of reactants employed, it ‘is inevitable
that,‘ in a process of this kind; a mixtureof the _
facility. » The basic treatment ‘also’ serves to
- liberate
the desired. amines from chemical com-'
bination in other constituents of the mixture,
three amines will .be“ obtained'in' use of ammonia
suchas carbamates and imines and thus to im
as the aminating-agentyor a mixture of‘ di-_
prove the yield‘ while facilitating ei?cient dis
and, tri-alkyl amines obtained in‘ cases in which
tillation. When ‘reaction ~mixtures containing
a mono-aliphaticfamine is used 'as the aminat- _
carbamates have been distilled, this has resulted
ing agent. In the majority'of cases of use of
in plugging distillation equipment and‘ also in
these amines, the user wishes to employ one of
inefficient separation of the amines from each
the three amines resulting from the reaction to 25 other. By the preliminary treatment of the
the virtual exclusion of ‘the other two. It isv also‘
present invention, .both of ‘these di?iculties. are
necessary that-the amines or mixture of: amines
obtained from the reaction be separated'from
The process of the present invention may be ac
, other contaminating;impurities,’ such as nitriles,
complished either by batch or continuous opera
carbamates, imines, ‘carbon dioxide, ammonia, 30 tion. ~ If it is accomplished by batch operation,
aldehydes or ketones, alcohols, etc. The removal
the crude amine-containing reaction mixture
of certain of these impurities presents a problem,
(after removal of ?xed gases, if desired) may be
not only because of the fact that the impuri
mixed with an aqueous basic solution for a suffi
ties are undesirable in the ?nished products, but
cient" length of time to effect solution in’ the
also because of the fact that the presence of- the 35 aqueous phase of reaction'products of'the'base
impurities in the reaction mixture renders, the
upon constituents of the reaction mixture. This
problem of separation'of the amines from each
may be accomplished at ‘atmospheric or superother more di?icult. Whilethe invention may be
atmospheric pressure, but I prefer to operate at
applied in puri?cation of reaction mixtures ob
super-atmospheric pressure, since, by so operat
tained by ammonation-reduction of either alde
ing, the reaction mixture may be maintained in
hydes or ketones regardless of carbon content, it
liquid phase at elevated temperatures, and the
is.‘ especially, recommended’ for treatment of such
use of elevated temperatures facilitates the rapid
mixtures obtained from aldehydes. Problemsen
completion of the reaction by which impurities
countered, in puri?cation of amine-containingre
which react with the base are converted into
action mixtures from ammonation-reduction of 45 non-volatile water-soluble salts. In' some cases,
aldehydes containing from two to six carbon
' the amine-containing reaction mixture will con
atoms can be solved with particular advantageby
practice of the invention. Ketones of from three
to six carbon atoms are also within the. preferred
range of the invention.
The present invention restslupon the discovery
that, when reaction mixtures such as those dis-_
thoroughly .mixed with an
above are
tain, a sui?cient amount of water to dissolve the
added base, and in such case the base may be‘
added in solid form.
After the desired_ contact between the crude
reaction mixture and the basic solution is accom
plished, the constituents-of the reaction mixture
which are notconverted into non-volatile com
aqueousisolution of an inorganic base, and the
pounds; bit tteatmentwith. the. base. are. removed
amines ‘contained in the reaction mixture, are 5,5
from the aqueous phase by distillation. This
may be accomplished by fractional distillation
from the aqueous phase; 1. e., by distilling and
‘separately condensing and collecting the sepa
drogen through a heated reaction tube was ?rst
vented, through a column carrying an ammonia
re?ux, to remove hydrogen and most of the am
monia of the reaction mixture. 120 grams of
?ake sodium hydroxide were added to 938.5 grams
of the residual crude reaction mixture, contain
rate constituents of the reaction mixture; or it
may be accomplished by distilling overhead all
of the constituents of the mixture resulting from
ing the three ethyl amines and various impurities.
the treatment with the basic solution which are
The resulting mixture was shaken vigorously,
more volatile than the basic solution itself, and
thereafter subjecting the mixture of organic con 10 causing the added sodium hydroxide to dissolve
in the water contained in the crude reaction mix
stituents so obtained in the distillate to a sep
ture. The resulting mixture was then fraction
arate fractionation by distillation.
ally distilled, with the result that 359 grams of
The present invention may be very effectively
monoethyl amine, 139-grams of diethyl amine and
practiced in a continuous manner by mixing the
230 grams of wet triethyl amine (consisting of an
crude amine reaction mixture with the aqueous
basic solution during continuous flow of the crude :- azeotropic mixture of triethyl amine and water)
were obtained.v
reaction mixture, and subjecting the resulting
mixture formed by addition of the base to distil
lation in the same apparatus in which the mix-‘
ing operation takes
fractions. When an attempt was made to sep
arate an equivalent reaction mixture without the
place, or in separate appara- -
tus. If such an operation is performed, it may
involve concurrent flow of the amine mixture
and basic solution to the zone of separation, or
counter-current ?ow of the basic solution with
respect to the amine-containing mixture with
separation being accomplished immediately fol
lowing the counter-current treatment. 'Thus,
for example, the amine-containing mixture may
This distillation was accom
plished Without any di?iculty, and the respective
amines were obtained as very sharply de?ned
preliminary sodium hydroxide treatment, diffi
culty was encountered both in connection with
the purity of ‘the respective amine fractions, and
because of plugging of the distillation equipment.
' Example II
A crude reaction mixture formed by the reac-'
of acetaldehyde with ammonia and hydrogen
be introduced into a fractionating column under
by continuous vapor phase amination, was cooled
pressure and temperature conditions ‘at which it
to liquefy the ethyl amines and the higher boil
is maintained in vapor phase, and the basic solu 30 ing
products and also part of the ammonia. Hy
tionmay be introduced into an upper part of the
hydrocarbon and some ammonia were
same column in liquid phase. Such an operation
separated from the reaction mixture, and the re
results 'in intimate contactv between the basic
maining liquid products were passed into the cen
solution and the amine-containing mixture, with 35 tral
portion of a scrubbing column maintained at
prompt reaction to form non-volatile salts, which
a temperature of about 100° C. An aqueous so
are dissolved in the aqueous phase, as discussed
dium hydroxide solution of 10% concentration
above, the aqueous phase passing downwardly
was run into the column at a temperature of 125°
_C., and a pressure of about -75 pounds per square
through the column at the same time that the
remaining amine-containing reaction mixture is
removed overhead as a distillate.
In case of practice of the invention on a re
40 inch, was maintained on the system during per
formance of the ‘scrubbing operation by flow of
_ the reaction mixture in ‘counter-current direc
action mixture obtained by a continuous am
tion to the ascending stream of gases to perform
monation-reduction (amination) reaction, the
the scrubbing operation. The liquid leaving the
bottom of the scrubber‘consisted ‘essentially of
water, sodium carbonate and. ‘sodium acetate,
operation of treatment of the reaction mixture
with a base is also preferably performed continu
ously, and is preferably accomplished by intro
while the volatile organic substances and‘ am
duction of the amination reaction mixture con
tinuously into the lower part of a column while
introducing an aqueous basic solution into the
upper part of this same column.
monia passed overhead. Upon subsequent frac
tionation of the overhead fraction, sharp separa
In case of this 50 tions between the respective amines were ob
type of operation, the basic solution is prefer
ably relatively dilute, caustic soda solutions of be
' tween 5 and 15%
Part or all of the ?xed gases of the reaction
Example III
concentration being preferred,
although a considerably wider range is permis~
sible. - By using relativelyv dilute basic solutions
in practice of the process continuously, the di?i
culty of precipitation of reaction products in the
extraction column is avoided.
A crude reaction mixture resulting from pas
sage of butyraldehyde together with a molecular
excess of hydrogen and ammonia over a catalyst
consisting of pelleted nickel on kieselguhr at a
temperature of approximately 155°C. was mixed
with 10% of its weight of 50% NaOH solution
and fractionally distilled with no appearance of
interfering solid precipitated material in the col
umn or condenser. Monobutyl amine of high
mixture may be removed before the treatment
with the base and subsequent distillation, and
when the invention is practiced by accomplishing
titre was obtained directly in this’fractionation.
‘the basic treatment in batch, this sequence is or
Dibutyl amine and tributyl amine ‘were distilled
dinarily used. In case of batch operation, much
overhead as azeotropic mixtures with Water and
more concentrated solutions may be-used than 65 separated from the water by decantation. The
in case of continuous operation, and the inven
water was returned continuously to the pot of
tion may even by practiced by introducing the
the distillation column. until all of the >di-' and
base as a solid in the case of batch operation,
since the reaction mixture will ordinarily con
tri-butyl amines had been removed. The mix
ture of di- and tri-butyl amines obtained in this
tain suiiicient water to dissolve the added base, 70 way was dried by treatment with a‘ 50% 'NaOH
solution. The amine layer containingthe dry
Example I
di- ‘and tri-butyl amines was then fractionated
as pointed out above.
toY-separate these amines from each other, and
A crude reaction mixture obtained by passage
respective amines
were obtained in a'hlgh
of acetaldehyde together with ammonia and hy— 75 these
degree of purity.
‘ '
2,41 1,802
'sequently separating the amine bases from the
resulting aqueous solution and distilling said
amines to separate them from each other.
4. In the puri?cation of amine-containing re
action mixtures resulting from reaction of ali
phatic aldehydes containing from 2 to 6 carbon
atoms with aminating agents and hydrogen, the
process comprising mixing the crude reaction
While the invention has been especially useful
in treatment of reaction mixtures containing
amines of from 2 to 6 carbon atoms in their alkyl
also be prac
radicals as discusscd'above, it can
ticed in treatment of crude methyl amine reac
tion mixtures obtained by ammonation-reduc
tion of formaldehyde, and by treatment of reac
tion mixtures containing amines of more than
mixture containing the amine bases with an
six carbon atoms in their alkyl radicals.
10 aqueous solution of an inorganic base and sub
Various modi?cations are possiblewithin the
sequently separating the amine bases from the
scope of the invention, and I do not therefore
resulting aqueous solution by distillation.
wish to be limited except by the scope of the fol
5. In the puri?cation of ethyl amine-contain
ing reaction mixtures resulting from reaction of
lowing claims.
I claim:
1. In the puri?cation of amine-containing re
action mixtures resulting from reaction of ali
phatic aldehydes with aminating agents and hy
acetaldehyde with aminating agents and hydro
gen, the process comprising passing the crude
reaction mixture upwardly in vapor phase
through a distillation column in counter-cur
drogen, the process comprising mixing the crude
reaction mixture containing the amine bases with
rent relationship to an aqueous solution of an
from the resulting aqueous solution by distilla
umn 'while the amine-containing mixture is
passed upwardly in vapor phase through said col
inorganic base passed downwardly through said
an aqueous solution of an alkali metal hydroxide 20 column and removing the resulting aqueous solu
and subsequently separating the amine bases
tiondownwardly from a lower portion of the col
' 'tion.
2. In the puri?cation of amine-containing re
action mixtures resulting from reaction of ali
25 umn.
6-. In the puri?cation of amineécontaining re
phatic aldehydes with aminating agents and hy
' action mixtures resulting from reaction of a car
drogen, the process comprising mixing the crude
reaction mixture containing the amine bases with
bonyl compound chosen from the class consist
ing of aliphatic aldehydes and ketones, with
an aqueous solution of an inorganic base and sub
aminating agents and hydrogen, the process com
sequently separating the amine bases from the 30 prising mixing the crude reaction mixture con
resulting aqueous solution by distillation.
taining the amine bases with an aqueous solu
3. In the puri?cation of amine-containing re
tion of an inorganic base and subsequently sep
'action mixtures resultingy
from reaction of ali
arating the amine bases from the resulting aque
aldehydes with aminating' agents and hy 35 ms solution by distillation.
drogen, the process comprising mixing the crude
reaction mixture containing the amine bases with
an aqueous solution of an inorganic base and sub
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