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Патент USA US2405516

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Patented Aug. 6, 1946
Herman Pines, Riverside, 111., assignor to Uni
versal Oil Products Company, Chicago, 111., a
corporation of Delaware
No Drawing. Application September 30, 1943,
Serial No. 504,459
7 Claims.
(Cl. 260—683.5)
This invention relates to the catalytic isomeri
zation of isomerizable saturated hydrocarbons
ditions in the presence of a minor amount of a
mono-cyclic aromatic hydrocarbon having more
than 8 carbon atoms.
I have discovered that the addition of these
and is more speci?cally concerned with an im
proved process wherein these hydrocarbons are
isomerized under carefully selected conditions of
aromatic hydrocarbons selectively suppresses the
decomposition reaction and permits the isomeri
zation of the saturated hydrocarbons to a degree
operation in the presence of a mono-cyclic aroma
tic containing more than 8 carbon atoms.
The isomerization of saturated hydrocarbons
has assumed considerable importance at the
previously considered unattainable. The exact
mechanism as to how the presence of these
present time, particularly in the isomerization of
aromatic compounds suppresses decomposition
para?inic hydrocarbons boiling within the gaso
reaction is not known but it is probable that it in
line range such as pentane, hexane, heptanes, etc.,
volves the alkylation of the aromatic with a
which upon isomerization produce compounds
small amount of the initial decomposition prod
which have very desirable antiknock properties
ucts, said alkylation producing hydrogen in situ
when included in aviation gasoline blends. 15 which prevents further decomposition of the
Further, these isomerized products may be
saturated hydrocarbon,
alkylated with an alklating agent such as an
One class of aromatic compounds having more
ole?n, alcohol, etc., to produce alkylated deriva
than 8 carbon atoms which is effective in the
tives which have very desirable antiknock' quali
process of the present invention is ell-substituted
ties and which may be included in aviation gaso 20 aromatics such as para-cymene, di-ethyl benzene,
line blends.
para-methyl secbutyl benzene and similar com
It is well known that saturated hydrocarbon
may be isomerized using catalysts of the Friedel
Another class of mono-cyclic aromatic hydro
Crafts type such as aluminum halides, zinc
carbons are mono-substituted aromatics in which
halides, zirconium halides or mixtures thereof in 25 a branched chain alkyl group is attached to the
the presence of a hydrogen halide. The primary
aromatic nucleus such as isopropyl benzene,
difficulty which arises in these isomerization op
secondary butyl benzene and tertiary butyl
erations is the excessive catalyst consumption due
to the formation of hydrocarbon-metallic halide
These aromatics may be derived from any
complexes from the products of decomposition re
source such as, for example, by the precise frac
actions Which occur simultaneously with the
tionation of gasoline fractions or by alkylation of
isomerization reaction.
benzene with various ole?ns to produce the
Various methods have been employed to pre
alkylated aromatic derivative. A particular suit
vent the decomposition of the saturated hydro
able charging stock for the operation is a care
carbon thereby preventing the excessive catalyst 35 fully separated gasoline fraction which contains
consumption. For example, it has been proposed
the desired amounts of the aromatic and saturated
hydrocarbons. The aromatic concentration de- '
to introduce hydrogen in the reaction zone to
suppress decomposition and to hydrogenate frag
sired is of the order of about 0.1 to about 10 per
mental hydrocarbons formed by decomposition to
cent by volume and more preferably about 0.2 to
avoid the formation of the hydrocarbon-metallic 40 about 3 per cent.
halide complex. The use of hydrogen as a de
I have found that some aromatic fractions,
composition suppressor has been found to be very
particularly those obtained by precise fractiona
expensive and entails the use of a considerable
tion of gasoline boiling range mixtures at times
amount of auxiliary equipment such as compres
contain impurities which prevent or decrease the
sors, separators, etc., to provide a means for re 45
effect of the mono-cyclic alkyl aromatic as a
cycling the hydrogen to the reaction zone.
decomposition suppressor. However, these aro
It is an object of the present invention to proe
matics may be subjected to a preliminary treat
vide a method for suppressing the decomposition
ment with alkali-acting materials such as mag
of the isomerizable hydrocarbons which is eco_
nomical and practical and which obviates the 50 nesia, alumina, calcium oxide or aqueous solu-'
tions of sodium hydroxide or other alkali agents,
di?iculties which are inherent in the use of hydro
7 sulfur dioxide, sulfuric acid or other well-known
treating agents to remove the impurities. The
products obtained from this preliminary treat
In one broad embodiment, the present invention
comp-rises a process for isomerizing a saturated
hydrocarbon by contacting said hydrocarbon with
an isomerizing catalyst under isomerization con
ment have been found to be entirely satisfactory’
in the process of this invention.
The following examples illustrate in a gen
eral way the e?ectiveness of the mono-cyclic
alkyl aromatics disclosed herein in suppressing
decomposition reactions during the isomeriza~
tion operation. 'It is‘ not intended that these
The operating conditions such as temperature
and pressure will vary somewhat depending upon
the alkylated aromatic and catalyst employed.
Ordinarily temperatures within the range of
about 50*to 350°_ F. and more preferably between
the approximate 'range of about 120 to 250° F.
and pressures varying from substantially at
examples unduly limit the generally broad scope
of this invention to the numerical values indi
cated since the invention is broadly applicable
to the ranges hereinbefore speci?ed.
In the following experiments, 85 grams of nor
mal pentane was placed in an electrically heat
ed autoclave equipped with a stirrer. Weighed
mospheric to about 500 pounds or more are de-j '
Any of the well-known Friedel-Crafts type
isomerization catalysts may be employed. vIt is
desirable that hydrogen halides-such as hydro
gen chloride and hydrogen bromide be used in
conjunction with these catalytic materials. The
ordinary concentration of these. hydrogen halides
is within the range of about 1 to 49 mol per cent
of the charge and preferably 5 to 20 mol per
cent. These catalysts comprise the chlorides and
bromides of aluminum, zinc, zirconium, iron,
amounts of aromatics, substantially anhydrous
"aluminum chloride and HCl were added to the
pentane. The autoclave was sealed and main
tained at 167° F. for a period of 6 hours. A blank
run without aromatic addition was also made.
The results of these experiments are shown in
the table below.
Charge, grams:
N_ Pontmm
Di-ethyl benzene _______ _.
Iso- ropyl benzene ______________________________ __
utylbenzene ______________________ _; ...... __
Tertiary butyl benzene _________________________________________________________________ __
prod., mol per con
54 . 1
1a.. _______ _; ............................... __
. ____
n CsHu . _ _ . . . _ _ _ _ _ . _ . . . _ _
Higher boiling ......... _.
1. 4
.... __
1'1 {1.9 in {0.5
1.6 PM“
.... __ 65.6
_ _ . _ _-
.... ..
2. 9
3. 8
0. 9
2. 8
2. 7
I claim as my invention:
~ >
either alone orjin admixture with one another.
These compounds may be employed in the solid 40 l. A process for isomerizing an isomerizable
saturated hydrocarbon which comprises subject
granular state or upon inert supporting} mate
ing said hydrocarbon to contact with an isom
rials such as alumina, silica, thoria, crushed ?re
erizing catalyst of the Friedel-Crafts type in the
brick, quartz, activated clays and activated chars.
It is also within the scope of this invention to
employ mixtures of these compounds and in par
presence of a minoramount of a mono-cyclic
aromatic hydrocarbon having more than 8 car
bon atoms.
' .‘
ticular theraluminum halides with the halides of
antimony, bismuth, arsenic, to form low-melting
2. A' process for isomerizing an isomerizable
compound»; which are molten under the condi
saturated hydrocarbon which comprises subject
tions of operation.
ing said hydrocarbon to contact with an isomer
The isomerization operation may be conduct
izing catalyst of the Friedel-Crafts type in the
ed in various ways; for example, the heated hy
presence of a branched chain alkyl mono-cyclic
drocarbon mixture either in the liquid, vapor or
mixed phase may be passed through a reaction
3. A process for isomerizing an isomerizable
zone containing a bed of solid granular cata
saturated hydrocarbon which comprises subject
lysts either supported or unsupported, and the 55 ing said hydrocarbon to contact with an isomer
reaction product being separated into the desired
iZing catalyst of the Friedel-Crafts type in the
isomers and unconverted material which can be
presence of a di-sub-stituted mono-cyclic, aromatic
recycled to the reaction zone.
hydrocarbon having more than 8 carbon atoms.
Another method of operation consists of em
4. A process for isoinerizing an isomerizable
ploying a catalyst supply chamber containing a 60 saturated hydrocarbon which comprises subject
bed of granular catalyst through which a stream
ing said hydrocarbon to contact with. an isomer
of the hydrocarbon mixture in liquid phase is
introduced to dissolve the required amount of
catalyst. This catalyst-containing stream is in
troduced into a reaction zone along with a reg
izing catalyst of the Friedel-Crafts type in the
presence of a minor amount of a straight chain
alkyl mono-cyclic aromatic having more than 8
carbon atoms.
ulated amount of the hydrogen halide and a
substantial portion of the hydrocarbons isom
5. The process of claim 1 further charactere
ized in that said isomerizablesaturated hydro
erized therein.
carbon comprises a paraffin hydrocarbon.
This reaction zone may com
prise a large vessel which. will provide suf?cient
with a retaining material such as molten ‘salts,
metallic halide-hydrocarbon complexes or solid
packing materials such as bauxite, Raschig
6. The process of claim 2 further character
ized in that said branched chain mono-cyclic al
kyl aromatic comprises tertiary butyl benzene. '7. The process of claim 3 further character
ized in that said di-substituted mono-cyclic aro
rings, berl saddles, granulated quartz and other
matic hydrocarbon comprises para-cymene.
time for the reaction to occur or may be ?lled
materials well known to those skilled in the art.
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