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Патент USA US2404444

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2,404,444
Patented July 23, 1946
UNITED STATE s2,404,444PATENT‘ OFFICE,1
rsoiunrnzArron PROCESS USING METAL
HALIDE COMPLEXES
'1
Charles A. Kraus, Providence, n. 1., and John 1).
v(Jalfee, West?eld, N. J., assignors to Standard
Oil Development 00mpany, va‘ corporation. ‘of’
Delaware '
No Drawing. Application November 1-6, 1943,
" 12 Claims.
Serial' No.
(c1.510,490
zoo-683.5)
_ _
'
1
their activity for the promotion of hydrocarbon
The present invention relates to the prepara
tion of metal halide complexes which have been
found to be suitable for aiding in the e?ecting of
visomerizations and condensations.
A principal object of ‘the invention is to isomer
ize normal para?ins of at least four carbonlatoms
per molecule to the correspondingbranched'chain
paraf?ns under isomerization reaction conditions
organic reactions such as, for example, the isom
erization of normal para?ins to isoparai?ns, the
alkylation of isoparaf?ns with monoole?ns, the
polymerization of monoole?ns, the cracking of re
in the presence of these novel catalyst complexes.
Other objects of the invention will become appar
duced petroleum crude oils, and the nuclear a1kyl~
ent upon a fuller understanding ofthe invention
ation of aromatic hydrocarbons with alkyl halides,
10 to be hereinafter moreffully described. ,
alcohols and/or monoole?ns.
The catalyst masses described herein remain
Metal halides of the Friedel-Crafts type have
active for catalyzing organic reactions for a
been used in the past to induce a number of re
greater length of time than‘has heretofore been
actions among which are those mentioned above,
found possibleusing the ordinary Friedel-C'rafts
but particularly in the case of the aluminum hal- _
ides such as aluminum chloride no completely sat 16 type metalhalide catalyst. A simple and con
venientmethod for the preparation of metal hal
isfactory catalyst mass has as yet been devised.
idegFriedel-Crafts
type catalyst complexes suit-'
Continued usage of aluminum chloride catalysts
able
for
catalyzing
the above mentioned organic
for effecting the isomerization of normal par
a?ins, the polymerization of ole?ns, the alkyla
tion of isopara?ins with ole?ns, and the like, re
reactions are also described. The catalyst mass
20
sults in a decomposition of the aluminum chloride
to form liquid, highly carbonaceoussubstances
comprises aluminum halide’ complexes which are
economicalvto produce and have excellent cat
alyst life when used to catalyze the abovejmen
tioned reactions.v , 'The, aluminum halide-lower
which are less ef?cacious for catalyzing these re
actions than the solid fresh aluminum chloride.
By the liquefying and degradation of aluminum
chloride or aluminum bromide in carrying out
such reactions, commercial'units oftentimes are
required to be shut down ‘and the reactors andcat
alkoxy metal halide reaction products. are of
porous structure and-adapted for use in catalyz
ing organic reactions. These complexes are rel
atively stable and maintain catalytic activity over
long periods of time. ,
I,
_ The novel catalyst complexes of the presentin
alyst beds cleaned and recharged with fresh cata- ' 30 vention are prepared in a number of ways. ' One
lyst before proceeding with the reaction. This is
often expensive and troublesome because of the
character of the sludges formed with the alumi
num chloride. In addition, of course, the catalyst
life is materially reduced due to this sludge for
mation and too frequently the catalyst must be
replaced with fresh aluminum chloride or alumi
num bromide catalyst compositions, thereby re
sulting in an uneconomical operation.
' method of preparing these catalysts resides inithe
‘use of lower alkoxy metal halides or lower tri
alkoxy metal halidesv being contacted and ‘ad
mixed with a Friedel-Crafts' type catalyst of the
metal halide type, followed by heat fusing of the
resultant admixture to a temperature su?iciently
’
Attempts have been made in the past to im
prove aluminum chloride catalysts for use in or
ganic reactions, particularly hydrocarbon reac
Z40
high to completely fuse the mass; Following
fusion, the mass is kept at an elevated tempera
ture of between about 80° C. and about 200° C. un
til the liquid is converted into a dry solid material
and evolution of alkyl halide is essentially com
plete. , A catalyst so prepared has been found to
tions,»by resorting to drastic‘ reaction conditions
have the desired catalytic activities. A preferred
and short contact times in order to minimize this
method of preparing the-catalyst mass, however.
sludge formation, but these expedients have not 45 involves not only the heat fusing of the resultant
been particularly successful since appreciable
admixture but a further heating, to a slightly
cracking of the reactants occurred rather than a
minimizing of the sludging tendency. Further
more, under certain reaction conditions which are
higher temperature for a length of time to allow
for the removal by vaporization of any uncom
bined or free metal halide contained in the cata
particularly conducive to catalyzing some organic 50 lyst mass. The removal of the free halide may
he accelerated by conducting'the sublimation un—
reactions, such as the isomerization of the higher
molecular weight straight chain para?ins, alumi
.‘er. reduced ‘pressure. This method resulted in a
num chloride has been found to be impractical
catalyst complex which had even better catalytic
activity than the ?rst method of. preparation.
even under the best conditions known, because
the cracking tendency of the aluminum chloride 55 Still a third method of preparing the catalyst
appears to be superior to the isomerization tend
mass resides in the preparation of the metal hal~
ide alcohol addition complex in the presence of
ency and hence aluminum chloride is not particu
larly suitable for this type of reaction. Further
excess amounts of a Friedel-Crafts type metal
more, aluminum chloride and aluminum bromide
halide, followed by heat fusion, formation of the
have been found to be relatively short lived in .00 alkoxy halide by splitting out hydrogen chloride,
2,404,444
3
4.
.
subsequent formation of active catalyst through
vThey are non-volatile under the 1 elevated tem
peratures customarily employed. If! desired, the
elimination of the alkyl halide, and the removal
catalyst complexes may be prepared on a carrier
heatj Such a method, for example, would involve 'Y such as activated alumina, partially dehydrated
the reaction of methyl alcohol in the amount of 11
bauxite, activated carbon, silica gel, alumina gel
of excess. Friedel-Crafts typemetal halide
mol With more than 1 mol of aluminum chloride.
and the like.
The preparation of» aluminum methoxy halides ~
may be carried out in an anhydrous carbon disule,
?de medium by adding alcohol to a re?uxing InlX~
ture of carbon disul?de and the metal halide. The 10
pregnation of the carrier mass with vapors of ,
Such a process involves the im
aluminum chloride or aluminum bromide or other
suitable ,Friedel-Crafts type catalyst, followed by
contacting ill the impregnated mass with methyl
resultant aluminum methoxy compound may then
or ethyl alcohol vapors or some other suitable
be separated from the solvent and heated at a
temperature of 80° C.-200° C. in the presence'of
lower alkyl monohydric alcohol into the carrier
“ mass so impregnated.
' excess aluminum chloride to form a compound ,
This mass is then gradu
ally heated to a temperature between about 40° C.
15 and 200° C., thereby forming the novel catalyst
having an empirical formula of
complexes within the carrier selected. A stream
slcuoomimool
of superheated inert vapor such as hydrogen, ni
trosen, carbon dioxide and the like, may . be
Methoxy aluminum chloridemay be mixed with
passed through the carrier mass maintained at
aluminum bromide and the active catalyst termed
by fusing the mixture and then maintaining it 20 the desired temperature so that the mass is-thel'e
‘by freed of any free or uncombined metal'halide
at a .su?'iciently elevated temperature to cause
contained therein.
7
7
essentially .‘f?lll'e?iths of the methyl groups to be
An excellent method for preparing the catalyst
evolved as the methyl halide.- ‘* The empirical
on a suitable support consists of mixing the alu
composition of the catalyst following removal
of» all free
halide is AlX20CIrI3-Al0X 2.5 minum methoxide with the aluminum halide,
fusing, and before evolution of the alkyl halide
where
may be chlorine or bromine, or both
commences, soaking the inert carrier in the melt.
chlorine and bromine in the same molecule- .A
iur-ther vexample of a particular catalyst prea
pared
aoeordanoe with the process described
herein involved the reaotionof AlGhOCI-Ia with 30
SbGls to give the thermal decomposition product.
of
vn1ethoxy chloride chemically commood in part, at least, with an antimony halide,
the antimony/content vfalling between 01% by‘
weight .01.’ the aluminum compound and that re '
quired for the compound AlQlzOC‘I-IsASbQCl, de
pending upon the experimental conditions, It
is believed, based on- experimental determiner-l
3 tions, that the empirical iormula,
AlClzOGHaAAlOCl
‘ represents a close approximation of the true
The carrier may then be removed and the decom
position to form the catalyst conducted at the
proper temperature.
'
The catalysts so formed vhave been 'foundto
be particularly effective in catalyzing the isomer
ization of normal para?ins to isopara?lns as will
be more fully "hereinafter described. Although,
as ‘has been stated heretofore, it is preferred to
use the novel catalyst complexes substantially
free of uncombined F'riedelaCrafts type metal
halide, and, as has previously ‘been stated, some
free and. uncombined FriedeleCrafts type metal
halide catalyst may remain in admixture \with
the v?I-ial catalyst complex, it is within :the con
templation of the present invention to add fur-v
composition of the type of compounds produced , ther amounts of FriedeleCrafts type‘ catalyst to
the resultant catalyst mass and to employ such
‘3 but the invention should be understood as not
i being-limited thereto but as being'dil'ected to 45 admixtures as catalysts where the activity'of the
?nal catalyst composition demands that-a "more
the compounds ‘Produced by the reaction of .
active catalyst be employed. In: general, the
. v.F‘riedeleGrafts tyne metal halides with lower alkyl
novel catalyst.oomplexes'herein described may
monohydric alcohols or with the lower alkoxv
be prepared by admixing a compoundha-vlng the
l derivatives of metal halides
accordance with
‘ the‘ methods herein outlined. .In general, the 60
formula
>
1 tioned are heated at least to the fusion point and
1 preierably they are heated to a temperature be
1 tween about 80° C. and about 20.0” G. for .a period
of time suf?oient to insure completion of the re
.
~
(ROM/M992
admixtures of the reactants heretofore ‘men.
with from one to six'mols of a metal halide "hav
ing the formula
.
55
action giving rise to theevolution of the alkyl
halide. The unreaoted metal halide is removed
‘ by sublimation upon continued heating, prefer
‘ ably under reduced pressure. he will be seen ‘
.from the data hereinafter-set forth, active cata
1 lysts are produced by the .deoompositionof the
metallic alkoxy halide in the presence of tree
metallic halide and that it is preferable to .re
move any free or unoombined li‘riedel-Craits type
Friedelegrafts
metal halide that
type
may
metal
be contained'therein,
halide may be employed
'
' ‘
~M'vXn
'
V
wherein R represents a lower alkyl group, pref
erably methyl or ethyl, M and M’in at least one
of the compounds represents a metal whose halide
is a Friedel-Crafts type catalyst (M and M’ may
be the same or a different metal), X represents
a halogen such as, for example, chlorine or bro
mine, y is an integer, 1, 2 or 3, while 2 represents
'3-.-y, and 'n. represents an integer of 6 or less.
Speci?c compounds contemplated as the ‘initial
reactant in preparing the novel catalyst ‘com
plexes are as follows:
'
. in .asubstantial molar/excess of the amount of '
. lower alkyl monohydric-alcohol or lower alhoxy
metal halide used, but in such a case it is pref
AICIBI'OCHS
AMDCzHsla '
erable to remove the excess or unoombined metal 170
AICI (OCHs) 2
SbClZQCI‘Ia
halide from the ?nal catalyst complex prior to
.using the samefor patalyzin‘g the heretpjoree '
mentioned organic reactions.
7
The resultant catalyst complexes appear as .a
AlClzOCgHs
and the like.
Sb (OC_H_3)_3 ,
'
‘Compounds representative of the class
‘ porous, brittle ‘mass, white to light yellow in color. 15 which. maybe employed in accordance with the‘
2,404,444
tillate was collected in a graduated receiver; The
process of the present invention are those custo
marily identi?ed as the Friedel-Crafts type metal
percentage of product boiling between 80° C. and
halides. These are, for example,
branched chain heptanes produced in the isomer
?gb
Alcfgr I
A1013”
-' she; I
3
93° C. was a measure of the amount of the
'
Tic,‘
Zrcl‘
5 ization reaction. The catalyst mixture in Run
No. 4,‘ although being heated at 150° 0., was
heated for a su?icient length of time to decom
UCI 4
4
pose the mass but not to remove from the mix
ture the free metal halide contained therein.
AS913
m The catalyst was prepared at 150° C. and then
cooled, immediately to room temperature.
and the like.‘
Table
isomerization of N-heptane at room temper
Gatalyst preparation
v
Reactants employedinpreparing
' atureinatmosphere ofdryHOl
Decompo-
Free
sition tem-
metal
perature,
° 0.
removed
catalyst, molar ratios
halide
Catalyst N-heptane,
grams
0. 0.
AlBr2OGH3+AlBr3n
_
.AlBr: ______________ __
160
Yes__-__
‘_._
AlOl2OGH3+AlBn _________________ ._
160. Yes.--"
CH|OH+ZAIBH ___________________ ..‘.'~
180
Yes-._._
Distillate
and reac-
80-930 0.,
tion contact
vol. per
cent
time, hours
10
8
6
5
10
_____
_._-_
Agitation
5
7.1
5
v5
29.0
22.0
29.0
20
17
2.5
2.5
7.5
30
20'
20
20
15
‘
18
11.5
5.5
5.5
7.0
14.0
7
8
19
21.0
22.5
31.0
2.5
34.5
22
18
2
7
30
18
35.0
6.8
30
18
41.5
10.0
lFused.
As previously pointed out, still a further modi 35 Having now fully described and illustrated the
character of the invention, what is desired to be
?cation involves the reaction of a lower alkyl
secured by Letters Patent is:
monohydric alcohol such as methyl alcohol, ethyl
alcohol, n-propyl alcohol, isopropyl alcohol, etc.,
1. A process of isomerizing normal para?ins
‘containing at least four carbon atoms per mole
mentioned Friedel-Crafts type metal halides. The 40 cule to form the corresponding branched chain
paraf?ns which comprises contacting said normal
resulting compounds are thought to have the fol
para?ins under isomerization reaction conditions,
lowing empirical formula, although there is no
in the presence of a halogen-containing promoter,
intention to limit the invention to this formula
with two or more mols of one of the herein
with a catalyst mass prepared by admixing a
since at best it constitutes merely an empirical
formula based upon analytical data. The for 45 metal halide of ‘the Friedel-Crafts type with an
alkoxy derivative of an aluminum halide, and
mula is believed to be as follows:
heating the resultant mass to remove alkyl halide.
2. A process as in claim 1 wherein the catalyst
mass is heated su?iciently to remove a major por
wherein the characters have the same designa
50 tion of the uncombined metal halide of the
tion as previously stated.
Friedel-Crafts type therefrom.
The following examples, the data of which are
3. A process as in claim 1 wherein the catalyst
presented in the accompanying table, are illus
mass is prepared from an aluminum halide and
trative of the character of the invention. It is
a methoxy derivative of an aluminum halide and
not intended, however, that the invention be
limited thereto.
’ 55 wherein the resultant catalyst mass is heated
sufficiently to remove a major portion of the un
Runs Nos. 1 and 10 are inserted in the table‘v
combined metal halide and methyl halide there
merely for comparative purposes. These cata
from.
lysts were CP grade of aluminum chloride and
4. A process of isomerizing normal para?lns
aluminum bromide, respectively. The decom
position temperature stated is that temperature 60 containing at least four carbon atoms per mole
cule to form the corresponding branched chain
to which the reaction mass was heated in order
para?ins which comprises contacting said normal
to eliminate the alkyl halide as formed in the
para?ins under isomerization reaction conditions
process of reaction. The resultant catalyst in
in the presence of a halogen-containing promoter
each instance, in the amount indicated in grams,
was contacted at room temperature, under an 65 and a catalyst mass prepared by admixing an
atmosphere of dry hydrogen chloride, with liquid
normal heptane in the amount indicated and the
admixture agitated for the speci?ed number of
hours. The liquid was then separated from the
solid catalyst complex and distilled in a distilla
tion column packed with a glass spiral wrapped
on‘a solid glass rod. The fractionating power of
the column used was considered to be equivalent
to about '7 theoretical plates. The distilland was
measured by volume and on fractionation the dis 75
aluminum halide taken from the group consisting
of aluminum chloride and aluminum bromide
with an alkoxy derivative of an aluminum halide
taken from the group consisting of aluminum
chloride and aluminum bromide and heating the
resultant mass to remove alkyl halide.
5. A process of isomerizing normal heptane to
form the corresponding branched chain heptanes
which comprises contacting said normal heptane
under isomerization reaction conditions in the
-
amen/1
7
‘erization reaction conditions in the presence of a
‘halogen-containing promoter and a catalyst mass
prepared by admixing a metal halide, of the
resultant mass to remove alkyl halide.
6. A process as in claim 5 wherein the catalyst
mass is heated between about 80° C. and about
200° C. sufficiently to remove a major portion of
mass to remove alkyl halide.
the uncombined metal halide and alkyl halide
therefrom.
>
'
' '7. A process as in vclaim'5 wherein the catalyst
mass is prepared from an aluminum halide and
a methoxy derivative of an aluminum halide and
wherein the catalyst mass is heated between
about 80° C. and about 200° C, su?ciently to re
move a‘ major portion of. the uncombined alumi
num halide and methyl halide therefrom.
_
8
presence of a halogen-containing promoter‘ and
a catalyst mass'prepared by admixing a metal
halide of the Friedel-Crafts type with an alkoxy
derivative of an aluminum halide and heating the
8. A process as in claim 5 wherein the »metal'
Friedel-Crafts type with an alkoxy derivative of
an aluminum halide and heating the resultant
10. A process as in claim 9 wherein the catalyst
mass is heated between about 80? C. and’ about
200° C. su?lciently to remove a major portion of
10 the uncombined metal halide and alkyl halide
therefrom.
v
11. A process as in claim 9 wherein the catalyst
mass is prepared from an aluminum halide and a
methoxy derivative of an aluminum halide and
15' wherein the catalyst mass is heated between about
80° C. and about 200° C. su?iciently to remove a
‘ major portion of the uncombined aluminum hal
- ide and methyl halide therefrom. t
halide ‘is taken from the group consisting of alu
12. A process as in claim 9 wherein the metal
minum chloride and‘ aluminum bromide and 20 halideis taken from the gro
consisting of alu
wherein the alkoxy derivative is of an aluminum
minum chloride and alum,‘ m bromide and
halide taken from the group consisting of alumi
wherein the alkoxy derivative'is of an alumi
num chloride and aluminum bromide, the re
num halide taken from the group consisting of
sultant catalyst mass being heated between about
aluminum chloride and aluminum bromide, the
80° C. and about 200° C. sufficiently to remove a
25' resultant catalyst mass being heated between
major portion of the uncombined aluminum
about 80° C. and about 200° C. su?‘iciently to re
halide and alkyl halide therefrom.
‘
‘
move a major portion of the uncombined alumi
9. A process of isomerizing normal butane to
num halide and alkyl halide therefrom.
form the corresponding isobutane which com-A
CHARLES A. KRAUS.
prises contacting said normal butane underisom
. JOHN D. CALFEE.
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