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Патент USA US2112847

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Patented \Aprr5, v1938
1,113,847 ,.
Vladimir Ipatie? and Herman‘l’lnca. Chicago,
Universal Oil Products Com
pany, Chicago, 111., a corporation of Delaware
No Drawing. Application May 1, 1937,
Serial No. 149,164
6 Claims. (CL 260-169)
polymerization of the ole?n involved. In other
. This invention relates particularly to the treat
ment of para?in hydrocarbons which are gaseous ' words,vat the selected low temperatures employed '
at ordinary temperatures and pressures, and par .the rate of the polymerization reactions is re
ticularly isobutane.
duced while apparently the rate of the alkylation
In, a more speci?c sense, the invention is con . reactions is not reduced to the same extent so 5
cerned with a novel process 'for-ealkylating iso-. , that alkylation takw place in preference to poly-I
butane with ole?ns which are normally gaseous to merization.
produce saturated hydrocarbons of higher molec
The total reactions occurring when isobutane is
ular weight which can be utilized ‘as constituents alkylated with an ole?n such as propylene within
10 of motor fuel for automobile and aeroplane en
the preferred range of conditions will necessarily 10
involve to some extent not only‘ simple alkylation
The cracking process which is operated princi
pally with the object of producing gasoline from
heavier and less valuable petroleum fractions
15 incidentally produces considerable yields of ?xed
gases comprising hydrogen, methane, ethane,
propane, and butanes as well asethylene, pro
pylene, and butylenes in varying quantities and'
corresponding to the addition of one or more
molecules of the ole?n to the isopara?ln but also
. some reaction of polymerization and some reac-
tions of decomposition, so that the net result is 15_
the production of a mixture of hydrocarbons hav-'
ing a considerable
proportion bolling‘range
of mono- and
but containing
In most instances, these gases are ' products as will be shown in a later example.
20 considered to have merely a fuel value though at
tempts are made from time to time to utilize the
The actual operation of the process admits of 20
some modi?cation depending upon the normal
ole?nic constituents for the manufacture of hy
phase of the reacting constituents and whether
drocarbon derivatives on a commercial basis.
batch or continuous operations arev employed. In
a simple type of batch operation involving sub
stantially only the pure compounds isobutane and 25
propylene the isobutane is cooled to a tempera
In one application of the present process the
25 isobutane and propylene present in cracked gas
mixtures are utilized as a source of additional
yields of motor fuel fractions to augment those. ture of 0° C. or below in the presence of a minor
primarily produced by the‘cracking operation.
percentage of anhydrous aluminum chloride and
While the process is particularly applicable to 'alkylation is eifected by the gradual introduction
30 the utilization of the hydrocarbons in cracked gas . of. propylene under the surfacev of the liquid 30
mixtures, and particularly selected fractions pro
which may be mechanically stirred to prevent
duced therefrom in the stabilizers of cracking. subsidence‘ of the solid aluminum chloride par- ,
plants, it is also applicable to the treatment of. ticles. A small percentage of hydrogen chloride is ._ ‘
isobutane and propylene produced from anyother preferably admitted along with the stream of ole
35 source.
?n vapor, and for eifecting more rapid and com- 35
In one speci?c embodiment the present inven
plete alkylation it is best practice to add also a‘
tion comprises the alkylation of isobutane with small percentage of a more reactive ole?n’ such
propylene at temperatures of 0° C. or below with as, for example, isobutylene or normal butylenes._
catalysts comprising aluminum chloride and hy After a treatment is completed the aluminum
40 drogen chloride.
_' 'I
chloride layer is allowed to settle, and the upper 40
In a preferred embodiment of the invention the hydrocarbon layer is removed by 'decantation and
desired allwlation reactions are activated or so
subjected to'fractionation for the removal of un- , -'
celerated by the presence of small quantities of combined hydrocarbons as a light overhead and
ole?ns more reactive than propylene which may the recovery of an intermediate motor fuel frac--.
45 be added continuously during a run or used to
treat the catalyst prior to its use in the alkylation
reactions with propylene. This point will be de
veloped in greater detail in a later portion of the
An essential feature of the present invention is
, the utilization of sui?ciently' low temperatures of
treatment so that the ordinarily vigorous action
' In continuous operation'liquid isobutane con
taining suspended therelnthe requisite amount of
aluminum chlorldeand cooled to a suitably low
temperature mayv be. pumped through a tubular
treater at the entrance to which it receives the 50
necessary addition of propylene and hydrogen
chloride, the desired allrylation taking place dur-i ,_ ‘
of aluminum chloride in catalyzing condensation, ing pasage through the treater and the frac- ‘
reactions among hydrocarbons is moderated and tionaticn of the products being accomplished in
.55 reactions of alkylation occur rather than simple ., va submlent ‘fractions-for. The details of con-1“
tinuous process ofthis general character are more pm chloride.
or less familiarlto those skilled in oil refinery
operations and any necessary addition to or modi- '
However, by maintaining the
proper excess of the paraffin hydrocarbon the
course of the reactions may be kept principally
,?cations of the above general procedures will be 'in the direction of production of‘ alkylated prod-_
more 'or less obvious, and ‘can be made without j pots of a saturatedrather thanfan ole?nicfcharéf
departing from the general scope, of the invention. acter; In‘order to balance up ‘any disproportion"
The preliminary activation of the" alkylation on the side of either the ole?n or the para?ln, to‘
I‘ reaction may be effected by treating the granular produce products of the desired degree‘of alkyla
tion either may be added from outside sources to
aluminum chloride intended for use in the reac
produce a mixture of proper proportions. It will 10
tions with either normal or isobutylenes by pass
beshown in subsequent examples that there is
ing a limited amount of these compounds in liq
uid-phase in contact with the granular material some production of isodecanes as well as isohep
during vigorous agitation. The pronounced'ef
tanes, the former compounds corresponding to
alkylation of isobutane by two isopropyl groups.
fect of this activation upon the speed of subse
quent alkylation ‘reactions with propylene is
The process may be utilized for the direct im
somewhat diilicult to explain on a theoretical
provement of low antiknock value gasolines by
basis though it may be suggested that intermedi
suspending aluminum chloride therein at the re
ate addition compounds are formed which are
the real catalysts of the reaction in the presence
quired low temperatures and passing a. propor
tioned mixture of isobutane and propylene into
of the'hydrogen chloride which is continuously
the suspension along with a trace of hydrogen
added. It is further possible that a certain
amountof morereactive olefinv which is com
vent and a reaction medium and the alkylation
chloride. . The gasoline functions both as a sol
products are formedand blended with the gaso
line at the same time to increase its antiknock
of reaction which has the e?ect of energizing the value to an extent depending upon’ the amount of
bined with the aluminum chloride tends to alkyl
ate the isobutane and evolve considerable energy
less reactive - propylene.
It has been observed
alkylated'products formed.
that the activating effect is gradually lost so-that
in a strict sense it is notrentirely catalytic. ‘This
feature of the present process is important from
30 a practical standpoint since, when using pure
. The following examples are given as illustrative
of the type of results normally obtainable by the
use of the present process, although it is not given
with the intention of limiting the scopev of the 30
propylene or at least propylene free from other .invention in exact conformity with the data pre
ole?ns, the. speed of the alkylation reactions is
sometimes below a practical level at the tempera
‘tures necessary to prevent polymerization. The
Example I
Granular anhydrous aluminum chloride was 35
35 preliminary treatment of granular aluminum
"placed in a reaction vessel which was cooled to
a'temperature of —'30° C. To activate this ma
chloride with relatively highly reactive ole?ns,
such as isolmtylene or normal‘ butylenes, has been
terial a total of two parts by weight of an equal
mixture of isobutane and isobutyiene was con-‘
tacted with the material. Leaving the activating 40
observed to have a still further effect of‘practical
signi?cance, in‘ that there is a greatly decreased
40 tendency for the chloride particles to become very
hydrocarbon mixture in place the liquid mixture
?nely divided under vigorous agitation but rather
to maintain their original size, which prevents
of isobutane and propylene was contacted in such
a way that the charge entered below the surface
the carrying o? of the catalyst in colloidal sus- - of the hydrocarbon liquid containing the sus
pension in continuous processes.
aluminum chloride while reaction prod 45
The reacting hydrocarbons required for 'the pended
ucts were siphoned from the reaction vessel at
present process may be obtained from any con
a su?iciently high level to avoid removal‘ of the
venient source. As a rule the best sources are the
cracked gas mixtures produced in the pyrolysis of
heavy oils ‘with the primary object of producing .
catalyst particles; - The charge consisted of ap
proximately 7'7 per cent of isobutane and 23 per- _
cent of ‘propylene, calculated on a gas basis; and 50
The technique of hydrocarbon frac
a steady feed of a small amount of hydrogen
tionation is su?icientiy developed at the present chloride
was maintained during the run. '
-_ _
time so that it is commercially feasible‘ to pro
3250 volumes of isobutane-propylene mixture
duce relatively pure propylene and isobutane.- A produced
650 volumes of liquids boiling within the
method which may be employed to obtain propyl . ordinary range
of commercial gasoline or up to 5'5 1
55 ene which is not contaminated with paraiiin hy
approximately 225° C. 90% of the'total liquid
drocarbons consists in the use of solvents which products boiled below.220° C. and the'octane
selectively abstract ole?ns from the gas mixtures,
number of this gasoline fraction was ‘81 when
which oieilns are then ' separately fractionated.
tested by the motor method. Careful fraction
In such a process the residual unabsorbed paraf
?n mixture may be employed as the source of the ation indicated that 42% of the total liquid prod
50 gasoline.
required isobutane. .Propylene may also ‘be pre- 7 " ucts- consisted of isoheptanes boiling between 88
pared by the selective catalytic dehydrogenation
of propane or propane fractions.
Over the preferred low temperature conditio
and 90° C. and another 20 percent of the liquid
_ products correspondedyto isodecanes boiling -be-'
‘tween 150 and‘154° C.
of operation and in the presence of an excessoi' _ '
isobutane, one molecule of propylene ‘tends to re
act with its molecular ‘equivalent of isobutane
while the excess-of isobutane remains unaffected.
when more propylene is used than corresponds to
Example II
' ;
A run was made at the upperlimit of tem-j
perature corresponding to the economical and
practical operation of the
The general
70 about one mole'of propylene to three moles of . procedure was the same as iriExampie I in‘
isobutane there is an increased tendency for poly--v to the relative proportions: the hydrocarbons
merirationgreactions‘to occur in preference to
alkylation reactions; " m is to be expected to
- some .extent on account of the readiness with
.78 which propylene aloneis polymerized by alumi
reacted in the‘ presence of
chloride. ,
In‘this case, however, 30001volurne‘s oi’ isobutane-y
propylene mixture produced .600 volumes of liq-v
uiids boiling up to 220° 0., 92% .0! which boiled
below 200° C. The octane numberof the 200° 0..
end point fraction was 83 by the motor method
3. A process for the production of alkyl deriva
tives of isobutane which comprises subjecting said
isobutane to the action of propylene and a minor
and it was noted that there was a somewhatv proportion of a more reactive ole?n in the pres
higher percentage of material boiling below the
50% point in the distillation test. In comparison
with the ?rst case, a careful fractionation showed
that 39% of the total liquid products consisted
of isoheptanes instead of 42% as in the first ex
ence of aluminum chloride and hydrogen chloride
at a temperature of 0° C. or below.
4. A process for the production of alkyl deriva
tives of isobutane which comprises subjecting said
isobutane to the action of propylene and a minor
proportion of 'a butylene in the presence of alumi
The foregoing speci?cation has disclosed the num chloride and hydrogen chloride at a tem
character and scope of the present invention and perature of 0° C. or below.
the examples have shown its practical aspects
5. A process for the production of alkyl deriva~
but neither section is to be considered as unduly , tlves of isobutane which comprises subjecting said
isobutane to the action of propylene and a minor
This application is a continuation-in-part of I proportion of a normal butylene in the presence
I our co-pending application Serial No. 103,389, of aluminum chloride and hydrogen chloride at a
?led September 30, 1936. ‘
We claim as our invention:
1. A processior the production of alkyl deriv
atives of isobutane which comprises subjecting
said isobutane to the action of propylene in the
presence of aluminum. chloride and hydrogen
temperature of 0° C. or below.
chloride at a-temperature of 0° C. or below.
perature of 0° C, or below.
2. A process for the production of alkyl derivaé .
25 tives of isobutane which comprises subjecting said
isobutane to the action of propylene in the pres
ence of aluminum chloride and hydrogen chloride
at temperatures within the range of 0° C.
—50° C.
6. A process for the production of alkyl deriva
tives of isobutane which comprises subjecting said
isobutane to the action of propylene and a minor
proportion of isobutylene in the presence of alu
minum chloride and hydrogen chloride at-a tem
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