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2,411,992
Patented Dec. 3, 1946
UNITED STATES PATENT orrlca
2,411,992
/
" ALkYLA'rIoN or rmarm
‘ I
HYDROCARBONS
> Arlstid v. Grosse, Bronxvllle, N. Y., and Carl B.‘
Linn, Chicago, Ill., asslgnors to Universal Oil
Products Company, Chicago, 111., a corporation
of Delaware
No Drawing. _ Application May 18, 1942,
‘
Serial No. $3,490
6 Claims.
1
.
.,
I
'
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2
-
.
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or hydrogen bromide have the'usual disadvan
tages'inherent to the use of solid granular cat
was in ,that the‘ efficiency‘ of the reaction is to '
' ing application Seral No. 299,108, ?led October 12,
l
"
,
employed in the presence 01 hydrogen chloride
This is a continuation-in-part of our co-pend
1939.
,
(onto-cam)
r
This invention is concerned with the inter
action of isopara?‘lnic hydrocarbons with ethylene 5 some extent dependent upon/the ?neness of the
subdivision of the catalyst, the emciency of stir
in the presence of catalysts. It is more specifi
ring
or mixing of the reaction mixture, etc. The
cally concerned, with a simple and easilyreg
recovery of aluminum chloride .or other metal
ulated process involving the use of mixtures of
halides from the reaction products in suitable
normally liquid and normally gaseous compounds
'
of ?uorine which catalyze the desired conversion 10 form for recycling is difficult and expensive where
as the present catalyst mixture of boron ?uoride
with a high degree of e?lciency'and undergo sub
and hydrogen ?uoride is readily separable in a
stantially no alteration in the course of the re
form which can be recycled to further use in the -
actions.
.
alkylation reaction.
Processes for the formation of higher molecular
weight isopara?lnic hydrocarbons from isobu
15
tane, isopentane, and other alkylatable para?lnic '
hydrocarbons, .all herein included by the term
“isopara?lns,” are important from the standpoint
»
,
Thus considerable di?lculties have been en
countered previously in attempting to alkylate
isoparaillnic hydrocarbons with ethylene in the
presencev of such catalysts ‘as’sulfuric acid or hy
drogen ?uoride of about ,90 to [about 100% con-,
creasing quantities of isopara?lns boiling in the 20 centration, but we ?nd that the reaction be
tween ethylene and an lsoparafiln such as iso
range of gasoline motor'fuel.
'
‘
In one speci?c embodiment the'preserit inven- \ butane, isopentane, lsohexane, etc., or between
ethylene and <isopara?ln-normal para?ln mix- “_
‘tion comprises a process for synthesizing paraf?nc
> tures may be carried out readily in the presence‘
hydrocarbons by reacting an lsopara?lnic hy
drocarbon with ethylene under alkylating condi-‘ 25 of a mixture of boron‘ ?uoride and hydrogen ?uo
ride to give a relatively high yield of substantially
‘ _tlons in the presence of, hydrogen ?uoride
saturated hydrocarbons comprising essentially
boron ?uoride.
branched chain hexanes, heptanes, octanes, and
Considerable quantities of butanes and lighter
of the motor fuel industry which demands in
gases containing ethylene are available as by
v
higher boiling isoparaf?ns. The catalyst utilized ‘
products-from the cracking of petroleum _frac-‘ 30 in the»present invention is formed by mixing
boron ?uoride with hydrogen ?uoride. The
tions to produce relatively high primary yields
former is a gas at normal temperatures and boils
of gasoline, and ‘by segregation of butanes and
ethylene by‘ relatively simple iractional'distilla- ‘ at -'101° C. under atmospheric pressure 'while
1 tion methods. cuts are available-for recombinaJ
' substantially anhydrous hydrogen ?uoride is-a
tion to produce substantial yields of isomeric 35 liquid ‘boiling at about 20°- c. under an absolute
hexanes and higher boiling ‘isopara?lns of good _ pressure of 1 atmosphere.- vA mixture of boron
?uoride and hydrogen ?uoride can be used as
octane number. 'Isopara?ins boiling higher thano
hexanes may be formed by alkylation of isomeric
hexanes by further quantities of ethylene in the ‘
presence of the alkylation catalyst.
'
Catalysts previously utilized in the alkylation
of isoparaf?nic hydrocarbons with ole?nic hy
drocarbons include sulfuric acid, phosphoric acid,
and aluminum chloride, all of which have dis
alkylating' catalyst in apparatus which has‘ been -
cooled to maintain a temperature slightly below
40 the boiling point of hydrogen ?uoride and low '
enough to keep in liquid state a substantial ‘pro
portion of- theJcat'alyst, or the catalyst mixture
can be used at higher temperatures if su?lcient
pressure 'is' kept upon the'appa‘ratus. By main;
5- taining an excess of isopara?lns to ole?ns at all
times, polymerization reactions and the forma
vcome by the use of the mixed boron ?uoride-bye '
tion of ethyl ?uoride are kept relatively low so
drogen ?uoride catalyst of the present inven
that the products consist principally of alkylated
tion. Sulfuric acid, for example, has a tendency
derivatives of the original isopara?ln hydrocar- .
to oxidize hydrocarbons with the formation of
sulfur dioxide. Phosphoric acid can be utilized 50 bon.
The process of- the present invention vmaybe as catalyst for the alkylation of isopara?lnic hy
carried
out utilizing either batch or continuous
drocarbons but the reaction is not accelerated
.typ'e operations. In batch type operation‘ the
to a practical degree'unless high temperatures
preferredprocedure is to agitate a mixture of hy
and pressures are employed. ‘Aluminum chloride
and similar metal halides which are generally 55 drogen ?uoride, boron ?uoride, and an isoparamn
advantages which are, in a large measure, over
2,411,992
3
which was operated while‘ ethylene‘ was intro
and to introduce gradually thereto ethylene, an
ethylene-ethane fraction, a mixture of ethylenev ‘ duced at 20° C. to a total pressure of 35 atmos
and an'isopara?ln, or a mixture of a normal
pheres. 'I'he stirring at 20° C. was continued for
paraffin, an isopara?in and-ethylene. After‘ a.
about 12 hours after which the reaction mixture
time of mixing su?icient to eii’ect substantially
was removed from the autoclave and separated
complete reaction of the ethylene with the iso
into unconverted isobutane, hydrogen ?uoride
para?in, the latter being present in excess of the ' boron ?uoride catalyst, and about 200 parts by
weight of an alkylation product consisting of sub
ole?n at all times, the agitation isv stopped and
the reaction mixture is separated into catalyst,
' stantially saturated hydrocarbons containing 90%
unconverted isopara?in, and alkylation product, 10 by volume of gasoline with an end boiling-point
after which the excess isoparailln and used cata_-‘
of 205° C. The gasoline fraction contained about
_ lyst may be utilized in a subsequent alkylation
55% by volume of branched chain hexanes.
treatment.
The foregoing speci?cationand example indi—
cate the character and practical value of ‘the pres
' The process may be made continuous by pro-.
viding a mixing zone through which the react-1 15 ent invention, although it is not intended that
ing hydrocarbons and catalyst are passed and in ' I‘ - either section should impose undue limitations
which su?icient time is given for the completion _. thereon.
of the desired alkylation. ‘The products from _
We claim as our invention:
such a reaction zone are then directed to a sep- ‘
1. A process for thelproduction of normally
'
arating zone in which the desired alkylation prod 20 liquid saturated hydrocarbons which comprises‘
ucts are separated from unconverted isopara?ln's‘
. reacting an isopara?in with an ole?n under alky
and catalyst components. The recovered un
lating conditions in the'presence of an alkylation
converted isopara?ins and catalyst are then re
catalyst consisting essentially of a major propor
cycled to ‘further contact with the isopara?lns and
tion of hydrogen ?uoride-and a minor propor
ethylene being charged to the process.
25 'tion of boron ?uoride.
The activity of a boron ?uoride-hydrogen ?uo
2_. A process for the production of normally
ride catalyst is dependent upon the relative pro
liquid saturated hydrocarbons which comprises
portions of these materials forming thecatalyst
reacting an isopara?in with ethylene under alky
mixture. The diiferent catalytic composites
lating conditions in the presence of an alkylation
which may-be utilized are not necessarily equiva 30 catalyst consisting essentially of a major propor
_
tion of hydrogen ?uoride and a minor proportion
of boron ?uoride.
' lent in their action particularly when diiferent
' isopara?ins are alkiated by ethylene.
While al
3. A process for synthesizing hydrocarbons
which_comprises reacting an isopara?in with an
ole?n under alkylation conditions in the presence
of a metal-free alkylating catalyst predominating
kylation reactions occur at temperatures of from
about —30° to'about 100° C., the use of a tem
perature of between about 0° and about 50° C. is.
preferred.
Pressures utilizable may vary from
substantially atmospheric to approximately 50 at- "
mospheres or more. In .order to obtain high :
in hydrogen ?uoride and containing a minor pro-v
a ‘portion of boron ?uoride.
‘
yields of alkylation product with substantially no
4. A process for synthesizing hydrocarbons’
formation of ole?n polymers, it is desirable to 40 which comprises reacting an isopara?ln with‘
maintain a molar excess of isopara?‘in to ole?n
ethylene under alkylation conditions in the pres
’
- , throughout the entire reaction.
euce of a metal-free alkylating catalyst predomi- .
Generally up to
about 25‘molarproportions of isopara?ins are,
nating in hydrogen ?uoride and containing a
present per molecular proportion of ole?n intro
minor proportion of boron ?uoride.
duced to alkylation.
The amount of ole?n poly- ‘ -
liquid saturated hydrocarbons which comprises
merization is thus not only kept low but the
formation of ethyl ?uoride is also kept low so that
the reaction product consists principally of al
kylated derivatives of the original isopara?in con
taining relatively small amounts of ethyl ?uoride.
The following example shows results obtained
when utilizing the present process for alkylating
an .is'opara‘?‘inic hydrocarbons wlth'..,ethylene al
though the example given should. 'not be con
. ,-
5.v A process for the production of normally ,
reacting an alkylatable para?ln with an ole?n
under alkylating conditions in the presence of an
alkylation' catalyst consisting essentially of a
and a
50 major proportion of hydrogen ?uoride
‘ minor proportion of boron ?uoride.
strued to impose undue limitations upon the gen
’erally broad scope of the invention.
100 parts by weight of. hydrogen'?uoride, 10'
parts by weight of boron ?uoride, ‘and 300 parts
6. A process for synthesizing hydrocarbons
which comprises meacting an alkylatable para?in
with an ole?n under alkylati'on conditions in the
presence of a metal-free alkylating catalyst pre
dominating in hydrogen ?uoride and containing
a minor proportion of boron ?uoride,
by weight of isobutane were charged to an auto-U
clave provided with a mechanically driven stirrer 60
_
. anrs'rm v. GROSSE.
CARL 13. mm.
I
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