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Патент USA US2404340

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July 16, 1946~
G. B. ZIMMERMAN
PRDDUGTION OF HIGH ANTIKNOGK FUEL
Filed July 19, 1945
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2,404,340
2,404,340
Patented July 16, 1946
UNITED STATES PATENT OFFICE
2,404,340
PRODUCTION 0F HIGH ANTIKNOCK FUEL
Gordon B. Zimmerman, Western Springs, Ill., as
signor to Universal 0i! Products Company, Chi
calo. lll., a corporation o! Delaware
Application July 19, 1945, Serial No. 605,994
7 Cillml. (Ul S60-_871)
l
This invention relates to a combination of
processes in which gasoline boiling range hydro
carbons are produced from hydrocarbons of nor
mally gaseous character. More specifically, the
invention relates to a novel combination o! cat
alytic processes for polymerizlng propylene, isom
erlzing the polymers thus produced, and alkylat
ing the isomerized product to yieldy a high anti
knock motor fuel suitable in itself for aviation
scale; the isomerized propylene polymer, there
forel also comprises a convenient source of hy
drocarbon oleflns employed in the alkylation step
of the present process.
A factor of further significance which may be
especially taken advantage oi when the source of
propylene ls considerably detached from the site
of utilization is the fact that when propylene is
polymerized into liquid polymers the said liquids
use or for motor fuel use when blended with 10 may be transported more economically and with
greater ease than propylene monomer which is
other hydrocarbons.
ordinarily gaseous. Thus, liquid propylene poly
It has previously been proposed to polymerize
mer may be transported in large quantities in
propylene under certain operating conditions and
tank car lots, whereas propylene itself is pref
in the presence of suitable catalysts to produce
normally liquid polymers. These polymers usu 15 erably liquefied under high pressures and sent
to its destination in this condition.
ally comprise hydrocarbons of varying chain
The alkylation product formed by the con
lengths containing at least one double bond per
densation of isomerized propylene polymers and
molecule, depending upon the conditions em
alkylatable hydrocarbons according to the proo
ployed in the polymerization reaction.
ess oi' the present invention is characterized by
It has, also, previously been proposed in the
art relating to conversion of hydrocarbons to
treat clarin-containing hydrocarbon liquids in the
presence of suitable olefin lsomerization catalysts
under appropriate conditions to effect isomeriza
its high octane number and other desirable prop
erties which render it suitable for motor fuel
use. I have found that especially preferred prod
ucts can be obtained from isomerized propylene
tion of the oletlns while maintaining a minimum 25 polymers whereas the non-isomerized propylene
polymers yield alkylation products of substan
production of normally gaseous products. In an
tially >poorer quality, especially in regard to lower
isomerlzation reaction of the type obtained in the
octane number. The present invention concerns
present process under the operating conditions
particularly the feature of isomerizing the prop
hereinafter specified, the oleiinic polymer not
only undergoes an alteration in structure, such 30 ylene polymers before alkylation. It is, there
fore, one object of my invention to provide a
as the formation of a highly branched carbon to
process for the production of high anti-knock
carbon skeleton, but also a shift in the pomtion
motor fuels, utilizing isomerlzed propylene poly
of the double bond within the molecule. More
mers as the charging stock to the alkylation step
over, the present process may be operated to ac
35
oi the process.
complish either type of isomerizatlon alone or
It is another object of this invention to poly
a combination of each in one step.
merize propylene, subject certain fractions of the
In the polymerization of oleñnic hydrocarbons,
propylene polymer to isomerization and utilize at
particularly propylene, followed by lsomerization
least a portion of said isomerised propylene poly
oi the polymer, highly branched chain products
mer to alkylate hydrocarbons alkylatable there
are obtained, the majority of which range in
with to produce a motor fuel having high anti
molecular weight from Cn to Cn hydrocarbons,
depending upon the conditions of polymerization
knock properties.
Still another object of my invention comprises
isomerized polymers of propylene constitute a
alkylating organic compounds with isomerized
45
valuable source of supply of hydrocarbons utiliz
propylene polymers, or select fractions thereof, to
able in the synthesis of high anti-knock fuels,
form highly branched chain derivatives of the
since it has been shown in the art that branched `
said organic compound.
chain hydrocarbons tend to reduce the knocking
In one speciilc embodiment the present inven
tendency oi. motor fuels in which the said hydro
tion comprises catalytlcally polymerizing prop
50
carbons are present. Moreover, propylene is
ylene in the presence of a suitable polymerization
readily available in large amounts at a low cost,
catalyst and under polymerlzing conditions, cat
and as such comprises a particularly `desirable
alytically isomerlzing the propylene polymers thus
charge stock to be polymerlzed. Likewise, prop
produced, and alkylating an alkylatable hydro
ylene polymer, as well as its isomerization prod
uct may be produced economically on a large 55 carbon with at least a portion of said isomerized
‘ and isomerization.
The highly branched chain
3
AMB»
propylene polymer in the presence oi' an alkyla
tion catalyst and under alkylating conditions.
The improved results oi' the present invention
are not obtained, for example. when butylene
polymers are subjected to isomerization prior to
alkylation thereof.
In the alwlation step of the present invention,
4
aluminum chloride. (preferably in coniunction
_ with hydrogen chloride), and boron triñuoride.
The exact conditions of operation‘to be employed
in this step will depend upon the purity oi' the
charge stock and upon the particular degree of
polymerization desired, but in general. when a
product containing a high proportion oi' propyl
the aforementioned isomerized polymers o! prop
ene trimer is desired, the polymerization is con
ylene or select fractions thereof are alkylated
ducted in the presence of a phosphoric acid, and
with any suitable alkylatable hydrocarbon to pro 10 particularly with a precalcined mixture ot phos
duce the subsequent high octane number product
of the present process. Such alkylatable hydro
carbons. in general, are well known in the art
dealing with the alkylation of hydrocarbons.
Briefly, the group comprises the saturated paraf
flnic hydrocarbons such as normal butane, iso
phoric acid and kieselguhr, known generally in
the art as a “solid phosphoric acid catalyst.” 'I‘he
process temperature utilized in the polymerization
will range from about 180° to about 300° C., the
pressure will preferably be superatmospherlc and
will range from about 200 to about 1500 pounds,
or thereabouts, per square inch. Any suitable
type of apparatus may be employed and the par
ticular one chosen for this purpose will depend
matic hydrocarbons, as for example benzene, 20 upon the characteristics of the particular catalyst
toluene, etc., and the homologs and alkyl deriva
utilized. These are well known in the art at the
tives of the above classes. A particularly pre
present time and no novelty for the polymeriza
ferred charging stock in the alkylation step of
tion process or apparatus per se is claimed in this
the present process comprises isobutane which
invention.
yields an isomerized propylene polymer alkylate 25
The products from polymerization zone I are
possessing especially desirable characteristics as
directed through line 3 to separation zone l, which
a gasoline component from the standpoint of
may comprise- one or a, plurality oi suitable frac
octane number, volatility, etc. The choice of
tionating or distilling zones where the products
allqrlatable hydrocarbon to be utilized in the pres
will be separated into fractions containing the
ent process will depend upon the particular al 30 desired polymers. Unconverted propylene which
kylate desired. In order to produce an alkylate
leaves separation zone 4 through line 5 connect
having the desired volatilityl aromatic hydrocar
ing with line i is recycled into polymerization
bons will generally be alkylated with the lower
zone 2. A polymer fraction boiling below or sub
molecular weight oleilnic isomerized propylene
stantially within the range oi' gasoline, but pref
polymers, such as the dimer, for example. On 35 erably containing from about 6 to about 9 carbon
the other hand, low molecular weight paramns
atoms per molecule depending on the oleiln de
such as propane, butane, isobutane, the pen
sired in the subsequent alkylation step is sepa
tanes, etc., will yield alkylates having the desired
rated in zone 4 and removed through line B. A
butane, normal pentane, isopentane, the cyclo
paraiiinic (naphthenic) hydrocarbons, such as
cyclobutane, cyclopentane. cyclohexane, the aro
properties of a motor fuel or an aviation gasoline
relatively small proportion of higher boiling frac
from the isomerized propylene trimers, tetram 40 tions formed in the polymerization reaction may
ers. pentamers, and even higher molecular weight
be discharged from the process through line 1 for
propylene polymers. ‘Thusl it is obvious that the
other uses not related to the present invention.
polymerization step of the present process will
'I'he desirable propylene polymer fraction which
be so directed to yield the specific charge stocks
may contain from Cs to Cu or higher molecular
desired in the alkylatlon step of the process, de
weight oleñnic hydrocarbons or select portions
pending upon the particular alkylatable hydro
thereof removed from separation zone I are with
carbon utilized.
drawn through line 6 and directed to isomeriza
It may be desirable under some circumstances
tion zone 8. In this zone the polymers are con
to prepare highly branched chain hydrocarbons
tacted with suitable catalysts under conditions
which may be utilized for purposes other than
to effect isomerization thereof into more highly
for motor fuel use.` The operating conditions
branched chain oleñnic hydrocarbons while at
employed in any particular instance may then be
the same time producing only a minor amount of
modiiled for this purpose, the conditions used de
normally gaseous products. Any suitable catalyst
pending upon the speciñc charging stocks em
having oleñn isomerization properties may be em
ployed. In a particularly noteworthy application
ployed in this step, among which may be men
of the present invention, aromatic hydrocarbons
tioned: (l) composites of silica with alumina,
may be alkylated with relatively high molecular
zirconia. and/or thoria, either alone or in com
weight isomerlzed propylene polymers. such as
bination with an inert refractory material such
the pentamer or hexamer, to produce valuable
as kaolin, ilreclay, diatomaceous earth, pumioe,
intermediates for various synthetic products un
etc., (2) naturally occurring clays which prefer
obtainable from natural or other sources.
ably are acid or otherwise chemically treated, (3)
The invention will be further illustrated in con
aluminiferous materials, including aluminum
nection with the following description and the
oxide, (4) aluminum sulphate-containing cat
' attached ilow diagram, the drawing illustrating
nlysts, (5) phosphates of certain metals such as
one specific operation oi the process, which, how
alumina, magnesio., etc., (6) ñuorides of certain
ever, should not be construed as unduly limiting
metals such as aluminum, magnesium, etc., and
the invention in accordance thereto.
('î) phosphoric acid-containing catalysts. It is
'I'he charge stock, comprising predominantly
understood that these are alternative catalysts
propylene. is introduced through line' I and di
and are not exactly equivalent in their action.
rected into propylene polymerization zone 2
The conditions utilized in the isomerization step
wherein the propylene is polymerized under the 70 o1' the process will depend upon the particular cat
proper conditions in the presence of a suitable cat
alyst employed and the particular oleñnic poly
alyst. These catalysts are wen known in the art
and include, among others a phosphoric acid,
mer treated. In general, with catalysts contain
ing silica composited with alumina. zirconia
(preferably pyrophosphoric acid). sulfuric acid. '1,5 and/or thoria. temperatures of about 400° to
2,404,340
6
alkylating catalyst, among which may be men
tioned the following: (1) sulfuric acid of 80 to
100% or over concentration (preferably of 00 to
and space velocities of about 5 to about 25 vol
100% acid strength), (2) substantially anhydrous
umes of liquid charging stock per hour per unit
volume of catalyst may be used. In general, with 5 hydrogen fluoride which. however, may contain
up to 15% water, (3) anhydrous aluminum
the phosphate and fluoride types of catalysts. sim
chloride, preferably in the presence of hydrogen
ilar pressure and temperature conditions may be
chloride, (4) boron triñuoride, with or without
employed, but the space velocity may be extended
added hydrogen iluoride. (5) alkyl iluorides or
to from about 3 to about 100 volumes of liquid
metallic iluoride salts, (6) suli'onic acids of usually
charging stock per hour per unit volume of cat
alkyl or aromatic derivation. (7) phosphoric acids.
alyst. The type oi’ apparatus to be employed is
generally deposited on various supporting mate
conventional and will likewise depend upon the
rials such as alumina, or a siliceous material such
characteristics of the particular catalyst em
as kieselguhr, and (8) hydrogen chloride, usually
ployed.
The isomerization products are directed 15 in the anhydrous state. Generally, the preferred
catalysts of my invention comprise sulfuric acid
through line 9 into separation zone l0 which may
of approximately 95% concentration and hydro
comprise one or a plurality of fractionating, dis
gen nuoride of 90 to about 05% concentration,
tilling, absorbing. and stripping zones, whereby
although it is to be understood that under suit
normally gaseous products may be separated from
able conditions the catalyst may be selected from
normally liquid products. The normally gaseous
another member of the above group. In utilizing
products produced in the above named isomeriza
hydrogen fluoride catalyst, the molal ratio of
tion step, which usually contain a large propor
alkylatable hydrocarbon to olefin is generally
tion of propylene, may be removed from separa
maintained within the range of about 2:1 to about
tion zone l0 through line Il which connects with
line B feeding into line i and polymerization zone 25 10:1, or higher, with space-time values ranging
from about 5 to about 80 minutes. The tempera
2. Thus, the propylene if produced as a by
ture may range from about _30° to about 100° C.
product from the isomerization reaction, 4may be
(preferably from about 0° to about 50° C.) .
recycled through the process to further increase
Superatmospheric pressures are preferred, but
the yields of products therefrom. Other by
usually, pressures in excess of 200 atmospheres
products of isomer-ization, such as hydrogen
are unnecessary, since the catalyst and hydro
and/or lower or higher boiling hydrocarbons than
carbons in the reactor may be maintained in sub
propylene, but unsuitable for further processing,
stantiaily liquid phase at or below this pressure.
may be removed from separation zone i0 through
The process conditions vary with the particular
line i2 and thereby discharged from the process.
A portion of the products from isomerizing zone 35 charge stocks employed, but the broad range o!
conditions named above will usually satisfactorily
I may comprise incompletely isomerized hydro
apply to most hydrocarbon charge stocks and to
carbons and these may be withdrawn from sepa
the catalysts specified above.
ration zone l0 through line lß'and returned to
In alkylation reactions involving sulfuric acid
isomerizing zone 8 as recycle stock. The fraction
as the catalyst, the reactants are maintained at
vaporizing at the boiling point of the desired
a temperature usually below about 100° C., but
propylene polymer may be fractionated further by
not substantially below 0° C. Superatrnospheric
means not shown on the accompanying diagram
pressures are preferred as in the case of hydrogen
to separate nonyienes and/or lower or higher
iluoride catalyzed reactions and the catalyst to
molecular weight olefins therefrom which are utl
lized in the subsequent alkylation step. Prefer 45 hydrocarbon ratio may range between about
0.5: l to about 10:1, the particular ratio depending
ably, however, the fraction is separated to con
primarily upon the reaction conditions. In the
centrate Ca-Ce hydrocarbons therein, if the said
attached drawing the catalyst is introduced
fraction comprises the preferred charge stock to
about 600° C., pressures of atmospheric to mildly
superatmospheric, up to about 100 atmospheres,
through line il into alkylation zone It and com
the alkylation zone as in the case of alkylating
isobutane. As an alternative method of operation, 50 mingled in the said zone with the mixture of
isomerized propylene polymer and alkylatable
it is within the scope of the present invention to
hydrocarbon introduced into the alkyiation zone
supply the total products from isomerizlng zone 8
through line il. Mixing may be accomplished by
to the subsequent alkylation zone without inter
suitable agitating devices such as single or mul
vening fractionation. Whatever the charge
stock to the alkylation zone, whether the total 65, tiple stirring paddles, oriilce mixers, and/or by
product from isomerizing zone I or a select frac
means of inert gases introduced under high pres
tion thereof , it is withdrawn from separation mne
» sures and at high velocities into the mixture o!
i0 through line Il into alkylation zone. i5 in ad
mixture with an alkylatable hydrocarbon intro
hydrocarbon and catalyst.
After the reaction period speciiled above, the
duced through line i6 and connecting with line Il 60 products of alkylation zone I5 are directed
through line il into separation zone il, which
from sources not indicated on the attached draw
ing, but hereinafter more fully described.
The present invention here illustrated indicates
likewise may comprise one or a plurality ot suit
able i'ractlonating. distilling. absorbing, and/or
decanting zones, whereby the catalyst phase and
duced into alkylation zone I5 are alkyiated in 85 the hydrocarbon phase, which are usually im
xnlscible, may be separated from each other, The
commingled state with an alkylatable hydrocar
catahst phase may be withdrawn through line
bon supplied through line I0. The characteris
that the isomerized propylene polymers intro
20 to a catalyst recovery or reconcentration plant,
tics of these hydrocarbons have heretofore been
not indicated on the drawing or a portion or all
described, but in general, the hydrocarbons may
be derived from petroleum distillates or fractions 70 thereof may be withdrawn through line Il and
line Il which connects with catalyst suppl! line
thereof, or they may be produced by various
line Il, feeding into alkylation zone Il, thereby
processes involving hydrocarbon conversion proc
providing for the recycling of all or a portion of
esses not related to the present invention.
the catalyst. The hydrocarbon layer separated
The hydrocarbons supplied to zone Il are al
inflated therein in the presence of any suitable 76 in separation zone Il may comprise unalkylated
7
.
hydrocarbons which may be withdrawn from the
said separation sone through line 22 and red into
line i8 to be recycled into alkvlation sone Il.
'l'he desirable alhlated products removed from
79.
8
The leaded octane number for the same
äièaction (3 cc. oi' tetraethyl lead per gallon) is
The results indicated by the above comparison
separation zone Il are withdrawn through line
show conclusively the advantages obtained by
Il into storage or these may be further treated
isomerising the propylene polymer prior to al
kyiation.
to remove albi ñuorides or other ioreign prod
ucts formed in alkylation zone I l. The means
I claim as my invention:
for treating the alkylation products are not
1. The process which comprises pciymerizing
shown on the accompanying diagram but may 10 propylene. subjecting at least a portion of the
comprise auxiliary processes auch as dcliuorina-y
resultant polymers to the action o! an oleiin
` tion towers containing aluminia or other suitable
isomerizing catalyst at isomerizing conditions,
treating agents well known in the art. No novel
and alkylating an alkvlatable hydrocarbon with
ty for such treating processes or apparatus per se
is claimed in the present invention.
at least a portion oi' said isomerized propylene
polymer.
The following example is introduced for the
purpose ot further illustrating the novelty and
utility of the present invention, but should not
2. The process ot claim 1 further character
terized in that thepropylene polymer is isom
erized in the presence ol a silica-containing cat
be construed as limiting the same in any of its
alyßt.
aspects in accordance thereto.
3. A process for producing branched chain
hydrocarbons which
Example
Propylene may be passed over a solid phos
phoric acid catalyst at a temperature of 180° C.
and at a pressure oi' 180 pounds per square inch
to yield a liquid product comprising primarily
propylene trimer having a boiling range ci from
about 93° C. to about 171° C. and having an oc
tane number of '17.
A Cs to C» Iractionseparated from the prod
ucts oi' the above polymerization step may be
isomerised by passing the hydrocarbons over a
sllica-alumina-sirconia catalyst at a temperature
o! 510° C.. at atmospheric pressure, and at a
space velocity or 15 volumes of liquid charging
stock per hour. The resulting isomerized poly
comprises
polymerizlng
propylene, subiecting at least a portion oi' the re
sultant polymers to the action of an olenn isom
erizing catalyst at isomerizing conditions, and
alkylating an alkylatable hydrocarbon with at
least a >portion of said isomerized propylene
polymer.
4. A process for producing branched chain
aromatic hydrocarbons which comprises poly
i merizing propylene. subjecting at least a portion
ci’ the resultant polymers to the action of an
isomerizing catalyst at isomeriaing conditions.
and aykylating an aromatic hydrocarbon with
at least a portion ci said isomerised propylene
polymer.
5. A process for producing high octane number
mer fraction has a clear A. S. T. M. octane num
ber of 81 and a leaded octane number (with 3 cc.
tetraethyl lead per gallon) of 83.
,
gasoline which comprises polymerizing propylene
The yield of gasoline boiling range fraction oi
the alkylation product is about 168%. based up
on the weight of polymer fraction charged into
into a i'raction containing hydrocarbons having
6 to 9 carbon atoms per molecule, isomerizing
said fraction, and alkylating isobutane with said
in the presence of a solid phosphoric acid cata
lyst, isomerizing at least a portion oi' the result
A mixture ot technical isobutane and the isom 40 ant polymer in the presence of a silica-contain
eriaed propylene polymer fraction produced as
ing catalyst, and alkylating isobutane with at ’
above containing a molar ration of isobutane to
least a portion of said isomerised polymer in the
oleñn of about 4:1 is charged with an equal vol
presence of a hydrogen~ iiuoride-containing cat
ume ci' hydrogen iluoride into an alkylaticn re
alyst to form said high octane number gasoline.
actor at a temperature of 10° C. and with a resi 45
B. The process of claim 5 further character
dence time in the reactor oi' about 15 minutes.
ized in that said propylene polymer is separated
the reaction. The alkylalte has a, clear A. S. 'I'. M.
octane number of 89 and a leaded octane num
ber (3 cc. tetraethyl lead per gallon) ci' 105.
In an alkylation experiment in which process
conditions similar to the above are maintained.
that is, similar temperatures, pressures, oleiln to
paramn ratios, and space time conditions, but
utilizing a non-isomerized propylene polymer
containing Ca-Cn polymers, an alkylate is ob
tained containing a gasoline boiling range irac
' isomerized fraction.
7. A process for producing a high octane num
ber gasoline which comprises polymerizing pro
pylene in the presence oi a solid phosphoric acid
catalyst, isomerizing atleast a portion of the re
sultant polymer in the presence of a silica-con
taining catalyst, and alkylating isobutane with
at least a portion of said isomerized polymer in
the presence oi' suli'uric acid catalyst.
'
' GORDON B. ZINMERMAN.
tion having a clear A.. S. T. M. octane number of 60
`
Disclaimer
`2,404:,340.---i'ílordou B. Zimmerman, Western Springs, Ill. PRODUCTION or HIGH
ANTIKNOCK FUEL. Patent dated July 16, 1946. Disclaimer filed Apr. 12,
‘
1948, by the assignee, Universal Oil Products Company.
Heroby enters this disclaimer to claims 1 and 3 of said patent.
[O_?ícùil Gazette May 11, 1948.]
7
.
hydrocarbons which may be withdrawn from the
said separation sone through line 22 and red into
line i8 to be recycled into alkvlation sone Il.
'l'he desirable alhlated products removed from
79.
8
The leaded octane number for the same
äièaction (3 cc. oi' tetraethyl lead per gallon) is
The results indicated by the above comparison
separation zone Il are withdrawn through line
show conclusively the advantages obtained by
Il into storage or these may be further treated
isomerising the propylene polymer prior to al
kyiation.
to remove albi ñuorides or other ioreign prod
ucts formed in alkylation zone I l. The means
I claim as my invention:
for treating the alkylation products are not
1. The process which comprises pciymerizing
shown on the accompanying diagram but may 10 propylene. subjecting at least a portion of the
comprise auxiliary processes auch as dcliuorina-y
resultant polymers to the action o! an oleiin
` tion towers containing aluminia or other suitable
isomerizing catalyst at isomerizing conditions,
treating agents well known in the art. No novel
and alkylating an alkvlatable hydrocarbon with
ty for such treating processes or apparatus per se
is claimed in the present invention.
at least a portion oi' said isomerized propylene
polymer.
The following example is introduced for the
purpose ot further illustrating the novelty and
utility of the present invention, but should not
2. The process ot claim 1 further character
terized in that thepropylene polymer is isom
erized in the presence ol a silica-containing cat
be construed as limiting the same in any of its
alyßt.
aspects in accordance thereto.
3. A process for producing branched chain
hydrocarbons which
Example
Propylene may be passed over a solid phos
phoric acid catalyst at a temperature of 180° C.
and at a pressure oi' 180 pounds per square inch
to yield a liquid product comprising primarily
propylene trimer having a boiling range ci from
about 93° C. to about 171° C. and having an oc
tane number of '17.
A Cs to C» Iractionseparated from the prod
ucts oi' the above polymerization step may be
isomerised by passing the hydrocarbons over a
sllica-alumina-sirconia catalyst at a temperature
o! 510° C.. at atmospheric pressure, and at a
space velocity or 15 volumes of liquid charging
stock per hour. The resulting isomerized poly
comprises
polymerizlng
propylene, subiecting at least a portion oi' the re
sultant polymers to the action of an olenn isom
erizing catalyst at isomerizing conditions, and
alkylating an alkylatable hydrocarbon with at
least a >portion of said isomerized propylene
polymer.
4. A process for producing branched chain
aromatic hydrocarbons which comprises poly
i merizing propylene. subjecting at least a portion
ci’ the resultant polymers to the action of an
isomerizing catalyst at isomeriaing conditions.
and aykylating an aromatic hydrocarbon with
at least a portion ci said isomerised propylene
polymer.
5. A process for producing high octane number
mer fraction has a clear A. S. T. M. octane num
ber of 81 and a leaded octane number (with 3 cc.
tetraethyl lead per gallon) of 83.
,
gasoline which comprises polymerizing propylene
The yield of gasoline boiling range fraction oi
the alkylation product is about 168%. based up
on the weight of polymer fraction charged into
into a i'raction containing hydrocarbons having
6 to 9 carbon atoms per molecule, isomerizing
said fraction, and alkylating isobutane with said
in the presence of a solid phosphoric acid cata
lyst, isomerizing at least a portion oi' the result
A mixture ot technical isobutane and the isom 40 ant polymer in the presence of a silica-contain
eriaed propylene polymer fraction produced as
ing catalyst, and alkylating isobutane with at ’
above containing a molar ration of isobutane to
least a portion of said isomerised polymer in the
oleñn of about 4:1 is charged with an equal vol
presence of a hydrogen~ iiuoride-containing cat
ume ci' hydrogen iluoride into an alkylaticn re
alyst to form said high octane number gasoline.
actor at a temperature of 10° C. and with a resi 45
B. The process of claim 5 further character
dence time in the reactor oi' about 15 minutes.
ized in that said propylene polymer is separated
the reaction. The alkylalte has a, clear A. S. 'I'. M.
octane number of 89 and a leaded octane num
ber (3 cc. tetraethyl lead per gallon) ci' 105.
In an alkylation experiment in which process
conditions similar to the above are maintained.
that is, similar temperatures, pressures, oleiln to
paramn ratios, and space time conditions, but
utilizing a non-isomerized propylene polymer
containing Ca-Cn polymers, an alkylate is ob
tained containing a gasoline boiling range irac
' isomerized fraction.
7. A process for producing a high octane num
ber gasoline which comprises polymerizing pro
pylene in the presence oi a solid phosphoric acid
catalyst, isomerizing atleast a portion of the re
sultant polymer in the presence of a silica-con
taining catalyst, and alkylating isobutane with
at least a portion of said isomerized polymer in
the presence oi' suli'uric acid catalyst.
'
' GORDON B. ZINMERMAN.
tion having a clear A.. S. T. M. octane number of 60
`
Disclaimer
`2,404:,340.---i'ílordou B. Zimmerman, Western Springs, Ill. PRODUCTION or HIGH
ANTIKNOCK FUEL. Patent dated July 16, 1946. Disclaimer filed Apr. 12,
‘
1948, by the assignee, Universal Oil Products Company.
Heroby enters this disclaimer to claims 1 and 3 of said patent.
[O_?ícùil Gazette May 11, 1948.]
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