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Патент USA US2135458

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Patented Nov. 1,‘ 1-938
' 2,135,458
* UNITED STATES PATENT- oFncE
sarm'rron or cons'rrruan'rs mom
oacmc comaxns
Raymond F. Schultz, Wilmington, Del., assignor
to E. I. du Pont de Nemours a Company, Wil
mington, Del., a corporation of Delaware t
No Drawing.‘ -
Application December 13, 1935,
Serial No. 54,851
. 12 Claims.
(Cl. 260-478)
the resulting mixture by distillation, extraction,
This invention relates to a process for the sep
aration 'of complexes into their constituents and
absorption; or other means. ‘After the removal
of the organic compound there remains the metal
more particularly to arprocess for the recovery
halide-inorganic compound complex. If, the
from complexes, formed between organic com
metal halide employed is an alkaline earth metal Ol
halide or calcium oxide and the inorganic com
ponent of the complex originally treated is vola
tile, as is boron ?uoride, such complexes can be
broken up‘by heating thereby driving off the
pounds and boron halogen containing compounds,
the boron-halogen-containing? and organic con
stituents.
-
'An object of the present invention is to provide
a process for the separation of constituents from
10 complexes containing the same.
‘volatile inorganic component. '
Another object
of the invention is to provide a process whereby
complexes containing an organic constituent and
a‘ boron-halogen-containing constituent can'be
separated into the organic constituent and the‘
boron-halogen-containing constituent. A fur
ther object of the invention is to provide a proc
ess whereby a .complex containing an organic
constituent and a boron-halide-constituent can
' be freed ofv the organic compound by the addition
20 of a metal halide. A more speci?c object of the
~ invention is t'o'provide a process wherein com
plexes containing boron ?uoride and an organic
acid, ester, or ether may be so treated that the
. organic acid, ester, or ether is freed from the com
plex and recovered, the ‘boron ?uoride likewise
being recovered 101'1'81158. Other objects and ad
vantages of the invention will hereinafter appear.
I have found that if a complex, such as those
containing an organic and an. inorganic constit
is, 0 uent, is treated with a metal halide the organic
constituent will beset freeand leave a complex
formed between the metal halide and the inor
ganic constituent, (should the inorganic portion
of the'complex be a metal halide the added metal
$2 Ll halide should be
a different metal ' halide).
Moreover, if alkaline earth metal halides are em
ployed, to decompose complexes containing a,
boron halide, the alkaline earth metal halide
boron halide complex formed will, upon heating,
40 give up the boron halide it contains leaving the
alkaline earth halide asa residue. Accordingly,
when employing alkaline vearth metal halides it
is possible to recover, from complexes containing
an organic and a boron-halogen-containing con
p. U! stituent the organic constituent and the boron
halogen-containing constituent.
I '
_
' Generally, the separation is effected, in the
10
The metal halides which have been found par
ticularly well adapted for replacing organic com
pounds from complexwompounds containing the
organic compound‘and a boron-halogen-contain
ing compound include, for example, calcium ?uo
ride, zinc chloride, aluminum ?uoride, aluminum
chloride, cuprous chloride, lead chloride, iron
chloride, tin chloride, calcium ch1oride,,barium
chloride, and analogous metal'?uorides, chlorides,
bromides'and iodides. While metal halides will
replace the organic constituent of , a ' complex
compound containing an organic constituent and
an inorganic constituent, such as boron tri?uo
ride, I have further found that the alkaline earth
halides and more especially the alkaline earth
?uorides form a complex with the boron ?uoride
from which the boron ?uoride or other analogous
‘easily volatilized halogen-containing compounds
may be recovered by heating. Together with the
alkaline earth halides such, for example, as the
?uorides, chlorides, and bromides of _ calcium,
barium or strontium,—-calcium oxide likewise has
the ability to not only displace the organic com
ponent of a complex containing boron ?uoride
giving a second complex containing boron ?uo 35
ridev and-'caiciumoxide but to permit the recov
ery of the-boron ?uoride from
complex.“ -‘
The advantages resulting from my process arev
readily appreciated when it is realized that when
using, for example, boron ?uoride in condensa
tion reactions, generally, it has been necessary
heretofore to destroy the boron ?uoride complex _
by passing it into water or a water-ice mixture’
.prior to recovery of the reaction products. Nat
urally the vboron ?uoride is hydrated by such 45
treatment and must be again dehydrated prior
to reuse and the ‘product is greatly diluted.~ In‘
accord with my‘ process, on the other hand, boron
?uoride and the product are recovered in a sub
following manner; ametal halide is added to they
complex containing both an organic and inor
50 ganic constituent and apparently due to the fact
that the inorganic portion thereof reacts more
readily with the metal halide than does the or
‘stantially anhydrous condition and the expensive
ganic portionpthe former forms preferentially a
metal halide-inorganic complex freeing the or
85 ganic constituent which may be removedtfrom
methods of separating various organic complexes
into their constituents but it will be distinctly 55
dehydration and concentration steps heretofore
required are entirely eliminated.
‘
I shall now illustrate by way of examples
2
,
.
9,185,458
-
,
understood that the invention shall not be lim
-cium ?uoride. It will be appreciated that when
ited speci?cally thereto.
‘
_
employing boron ?uoride as a condensing agent
Example 1-188 grams of (CHsCOOHhBFs (1 in organic acid reactions the use of’calcium
‘ mol) ‘was treated with 45 grams Call‘: (.58 mol) ?uoride is particularlyuseful for the reason that
in a ?ask attached to a shortx‘fractionation col
the condensing agent can be entirely recovered 5’
umn. The mixture was heated in an oil bath to and used over and over- again the sole loss in
. not more than 250°-C., during which the acetic
acid distilled out. Y About 117 grams glacial acetic
catalyst occurring from
operating
causes rather than from loss due to by-pro'ductv
acid was obtained, which is 97.5% of that‘ the
formation.
_
.
~
I‘
This distillation can be ei-' - Whilemy, invention has been described with 1o
fected at atmospheric or reduced pressures.
- particular reference to complex compounds which ,
Subsequent heating of the solid residue, which contain a boron halide it may likewise be em
10 oretically possible.
consists mainly of ' Ca(BI"4)s, to temperatures
ployed to free the organic constituent from its
between 300° 0., and 500° 6.,‘ resulted in-the evo
complex with other halides such, for example, as
lution of boron ?uoride according to the equa
the valuminum halides, tin . halides, titanium 15 .
halides, silicon halides, sulfur halides and
analogous halides which form complexes. For
Approximately 58.5 grams boron ?uoride “was re
'20 covered, which is 86.5% of theoretical. ‘Temper;
use'in the second step of my process via, the
Empte 2.—94 grams of (CHsOOOHlsBl'E (.5
absorption methods are used for recovering one
7 mol) was treated with 25 mm! (.6 mol)’ in a
or
' From
the other
a consideration
constituent. ofI the above specifics?
separation into its constituents of the wholly in- " '
atures below and above those given may be usedv organic complex,-one of the halide‘ should be 20
more volatile than the other, unless extraction or_ .
but the range‘ given is preferred.
_
?ask attached to ashort fractionation column.
tlon it will be appreciated that many changes
may bemade in the process herein described with
out. departing from the scope of the invention or
sacri?cing any of the ‘advantages that may be
'I'hemixturewasheatedinanoilbathtonot
more than 250° 0., during which time glacial
acetic acid distilled over. About 43 grams of»
acetic acid was recovered, which is 78% of that
30 theoretically possible. The distillation can be
done at atmospheric or reduced pressures. The
gBlls can be recovered by heating the solid, which
derived therefrom.
I claim:
‘
‘
v
-
v
.
'
1
.,
1. In a process of separating an organic com
pound from its complex with a boron halide the
consists mainly of NaBFs, to higher temperatures.
trample 3.—About 94 grams (CHsCOOH)s.B1"s
steps which comprise adding an alkaline’ earth
metal halide thereto whereupon the organic con- '
as in la ?ask attached to a short fractionating . stituent is freed from the boron halide andlan
column. The mixture was heated in an oil bath alkaline earth metal halide-boron halide "is _
to not more than 250° 0., and about 40 grams of formed, separating the organic constituent,.and
‘essentially glacial acetic acid distilled over. ‘1111s subsequently separating the boron halide from
the alkaline earth halide-boron halide complex.
40 was about 67% of theoretical. The distillation
2. In a process of.separating methyl acetate
can be carried out at atmospheric or reduced
(.5 mol) was treated with 60 grams NaCl (1 mol)
Pressures.
from its complex with boron ?uoride the steps
which comprise adding calcium ?uoride to the
complex, separating methyl acetate from the re
sulting mixture by distillation, heating the residue
containing the ‘calcium ?uoride-boron ‘?uoride
‘
The boron ?uoride can be separated from the
solid residue (Nam-B15) lay-further heating to
45 from 300-500’ C.
.
,' My process is particularly well adapted for use
in the separation of addition compounds contain-' complex and collecting the boron- ?uoride driven
in; an organic constituent and an inorganic con
stituentv and pore. particularly such addition
50 compounds in which the inorganic constituent is
o?.
'
,
1 v
3. In a process of separating acetic acid from
its complex with boron ?uoride the steps which
comprise adding calcium ?uoride to. the complex,
, a-relatively highly volatile halide such, for ex-v separating
acetic acid from the resulting mixture
ample, as the ?uorides,‘ chlorides, bromides, and .by distillation,- heating‘the residue containing the
calcium ?uoride-boron/?uori'de complex and col
iodides of.boron, but it is likewise particularly
useful in the separation of organic containing
55 complexes generally, in which the metal halides
preferentially replace the organic compound from
its complex with the inorganic halide, among
lecting the boron ?uoride driven off.
.
4. In a process of "separating propionic acid
from its complex withv boron ?uoride the steps
comprise adding calcium ?uoride ‘to the
.suchcompounds are-included. for example, the, 'which
complex, separating propionic acid friompthe re
aliphatic acid-boron ?uoride complexes, e, g.. ‘sulting ,mixture by, distillation, heating the ‘resi
~
(encompass. (cmcmcoomim.
-
omwrmscoomnrs
_ due containing the calcium ?uoride-boron ?uo-.
ride complex and collecting the boron ?uoride
driven off.
aliphatic ether-boron ?uoride complexes, e. g.. Y '
(CHDIOsBFJ, <czmlsosnrs -etc., (.1: indicates
‘any integer or,fra_ction), aliphatic ester-boron
'
'
_
I
~'
5. A process for the-separation of acetic acid
from its'association with boron ?uoride which
comprises treating approximately 1 mol of a com- I
?uoride complexes, aliphatic alcohol-boron ?uo-r plex, containing approximately two male of
ride complexes'and more speci?cally the com-a ' Y acetic acid and one moi of boron ?uoride, with
approximately .58‘mol of calcium ?uoride, dis
- plexes formed between boron ?uoride and metha
nol, ‘ethanol, propanol, butanol,'l.-isobutanol and
higher alcohols. Calcium ?uoride is particularly
‘ tilling the vresulting mixture to drive oi! the acetic '
acid, and subsequen’tLv heating ‘the residue be
well adapted to separate not only the organic ' tween a temperature of@300° 0., .to 500°_ c., to
_acid-boron ?uoride complex into the organic acid
. and a complex containing calcium ?uoride and
boron tri?/uoride, but ‘to separate alsov the latter
I“. ' complex upon heating into boron ?uoride andcal
i
evolve the boron ?uoride. .
'
I 6. In'a process of separating an aliphatic-or
ganic acid from its complexv with; aboron-?uo- ~
the compound the steps which'comprise adding?"
'
3
_
.
-
arouse
calcium ?uoride to the complex. heating the
mixture to separate the aliphatic organic acid,
and heating ‘the resulting residue more strongly
to separate the boron ?uorine compound.
' 7.111 a process of separating an aliphatic or
ganic acid from its complex with a boron halide
the steps which comprise adding calcium ?uoride
to the complex, heating the mixture to separate
the aliphatic organic acid, and heating the re
10 suiting residue more strongly to separate the
boron halide.
'
'
8. In a process of separating an aliphatic or
ganic ester from its complex with a boron halide
10. In a process of separating an organic com
pound ,irom its complex with a boron ‘halide the
steps which comprise adding ‘an alkaline earth
metal halide which preferentially. with respect
to the organic compound, forms a complex with
the boron halide, separating the organic com;
pound from the resulting solution by distillation,
and subsequently separating the boron halide by
distillation at a higher temperature.
.
1.1. In a process oi separating an'organic com 10
pound irom its complex with a boron halide, the
steps which comprise adding thereto a metal
halide which forms a complex with the boron
the steps which comprise addingcalcium ?uoride ‘halide, and subsequently separating the organic
compound fromvthe metal halide-boron halide 15
16 to the complex, heating the mixture to separate“
the aliphatic organic ester, and heating the re
suiting residue more strongly to separate the
complex.
_
'
12. In a process oi'separating'an ‘organic comq
9. In a process of separating acetic acid from
itscassociatlon with boron ?uoride by means of
pound from its complex with boron ?uoride, the
steps which comprise adding thereto a metal
halide which forms a complex with the boron
calcium ?uoride the steps which comprise pre
paring a mixture of the acetic acid and boron
?uoride. and subsequently separating the organic
compound from the vmetal halide-boron ?uoride
?uoride with the callcium ?uoride, heating the
mixture to separate the acetic acid, and heating
the residue to separate the boron ?uoride.
complex.
boron halide.
'
'
.
F. SCHULTZ.
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