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Патент USA US2410071

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Patented Oct. 29, 1946
2,410,070
UNITED STATES PATENT ‘OFFICE
CATALYTIC ALKYLATI'ON PROCESS
Aaron W. Horton, Detroit, Mich., assigno'r to
Socony-Vacuum Oil Company, Incorporated,
a corporation of New York
No Drawing. Application December 8, 1943,
Serial No. 513,461
16 Claims. (Cl. 260—‘683.4)
This invention relates to the alkylation of par
af?nic hydrocarbons with ole?nic hydrocarbons
and is more particularly concerned with the pro
duction of high octane motor fuel by the catalytic
alkylation of parai?nic hydrocarbons with ole
?nic hydrocarbons.
2
and over 4000 pounds per square inch gauge,
respectively, or may be conducted in the presence
of alkylation catalysts, at lower temperatures and
pressures,v thereby assuring a high yield of desired.
,alkylate by avoiding extensive degradation of the
reactants, the occurrence of side and secondary
It is well known in the art to polymerize ole
reactants, and appreciable polymerization of the
?nic hydrocarbon gases to produce motor fuels
ole?nic reactant. The two methods are known
having constituents of an unsaturated character.
as thermal alkylation and as catalytic alkylation,
Various commercial processes have been proposed 10 respectively.
'
I
for ultimately eifecting the desired polymeriza
Several methods are known for the catalytic
tion of the ole?nic hydrocarbons. These proc
alkylation of isopara?‘lnic hydrocarbons with ole
esses have been predicated upon the dictates of
?nic hydrocarbons. For instance, it is known to
the chemical nature of the stocks available as
alkylate isopara?inic hydrocarbons with ole?nic
well as engineering considerations such as initial 15 hydrocarbons in the presence of sulfuric acid,
and operation costs; their essential feature being
phosphoric acid, metal phosphates, metal halides,
that in the course of treating the materials, the
aCtivatedclays and the like, as catalysts. In
ole?nic hydrocarbons produced in the earlier
these catalytic alkylation processes, the hydro
stages of the process, are eventually polymerized
carbon reactants forin with the alkylation cata
to gasoline. Accordingly, hydrocarbon gases may 20 lysts, ‘a heterogeneous system, during the alkyla
be passed along with cracking stock or naphtha
tion operation. Hence these alkylation catalysts
through a‘ cracking still to crack and polymerize
may be termed heterogeneous alkylation cata
such gases to gasoline simultaneously with the
lysts. Since under alkylation conditions, the cat
cracking or reforming, or para?inic hydrocarbon
alytic activity of the alkylation catalysts appears
gases maybe separately cracked to ole?nic hydro 25 to be predicated upon contact between the cata
carbon gases and these gases» aresubsequently
lysts and the vgaseous hydrocarbon reactants at
passed with naphtha through a polymerizing vand
the interfaces therebetween, in these processes,
reforming still. In some'instances, the processes
involve the use of catalysts for facilitating the
cracking and/or polymerization operations. ~ ‘
> It is‘ also well known in the artgto combine
paraf?nic hydrocarbons directly with ole?nic‘ hy
drocarbons by processes broadly called alkylatio'n
processes, to produce motor fuels'havingcons‘tit
uents of saturated character. ‘In alkylation‘proc
esses, a charge comprising almiigtur'e of aparaf?'nic
the catalysts are usedrin amounts varying be
tween 10% and 200% by weight, on the charge,
30 depending on ‘the catalyst used.
‘Due to these
comparatively high amounts, where possible, re
covery and regeneration of the catalysts have
been proposed. This, of course, involves high
initial‘ and operation‘ costs. Further, it is also
known that certain substances called promoters,
promote the catalytic action of these alkylation
hydrocarbon, called the para?inic- reactant, and
catalysts- Accordingly, several processes have
an ole?nic hydrocarbon, called-the ole?nicire
been’ proposed wherein small amounts of these
actant, is subjected to high temperature and
promoters, on theorder of about 1% to 3% by
pressure to produce a saturated alkylate product. 40 weight_of"thejcharge,‘are added‘ to the catalysts
‘Since conditions of alkylation also cause poly
to promote .theirialkylation catalytic activity.
merization of the ole?nic reactant,‘it is necessary
A copendingiapplic‘ation',1Serial'Number'502?l8,
to maintain a relatively low concentration of the
?led‘ September 11, ‘194.3,ié directed to the process
ole?nic reactant in the charge. The only limit
of alkylatingL normal parai?hic and isopara?'inic
to- the pressure used appears'to- ‘be the feasibility
hydrocarbons with ole?nic hydrocarbons, which
of maintaining ‘high pressures. On the other‘
comprises'c'ontacting a' normal paraf?nic or iso
hand, the temperature used is liznited‘by degrada
tion of the hydrocarbon reactants in the charge
vto low molecular weight“ hydrocarbons, and the
occurrence of side reactions, including polymer
. par'a?‘inic hydrocarbon and an ole?nic hydrocar
bon in a reaction zone under alkylating condi
tions, with small or promoter amounts of what
has been‘ termed therein, a homogeneous gaseous
izatio-nof the ole?nic reactant, under high tem-'
perature conditions, that substantiallyreduce the
phase alkylation catalyst consisting essentially of
a'rmater'ial‘that forms with the'hy'dro'carbon re
purity of the product obtained.
actants, a, single homogeneous gaseous phase
under the.alkylationconditionsv of the reaction
~
'
Alk-ylation maybe conducted at high tempera
:tures and pressures, of the order of over 900°
v55 zone.
The alkylation conditions of the ‘process
£2,410,070
3
4
isobutane with propylene in the presence of hoe‘
mogeneous gaseous phase alkylation catalysts un—
of this copending application, comprise a broad
temperature range of about 590° F. to about
850° F., preferably, about 650° F. to about 825° F.,
and pressures of at least 500 pounds per square
inch gauge, preferably, pressures of at least 1500
pounds per square inch.
der alkylation conditions that favor the produc~
tion of triptane is manifest. It was also found
that in actual practice, it was impossible to ob
tain triptane exclusively, appreciable amounts of
2,2-dimethylpentane and Z-methylhexane being
Another copending application, Serial Number
always formed.
The speci?c classes of homogeneous gaseous
phase catalysts claimed in the above-noted co
10
directed to the process of alkylating isobutane
pending applications are organic halides, and,
with propylene, which comprises contacting iso
more particularly, organic chlorides and organic
butane with propylene in a reaction zone under
bromides.
,
closely controlled alkylating conditions, with pro
In still another copending application, Serial
moter or small amounts of the homogeneous gase
Number 502,812, ?led September 17, 1943, in
ous phase catalysts broadly disclosed in the co
which the inventor of the present application is
502,813, ?led September 17, 1943, in which the in
ventor of the present application is coinventor, is
pending application referred to hereinbefore, the
also coinventor, it was found that elemental hal
ogens, particularly chlorine and bromine, are
closely controlled alkylating conditions including '
a temperature range of about ‘750° F. to about 850°,
suitable homogeneous gaseous phase alkylatlon
F., preferably, about 775° F. to about 825° 11, and
catalysts and that isoparaflinic and normal par
20
pressures of at least 2500 pounds per square inch
a?inic hydrocarbons may be efficiently alkylated
gauge. In the alkylation of isobutane with pro;
pylene in the presence of homogeneous gaseous
with ole?nic hydrocarbons to produce high yields
of high octane gasoline by using small or pro
phase alkylation catalysts, it was found that the
alkylate obtained included constituents that are 7
moter amounts of elemental halogens to form
25
entirely different from the constituents of the hy
drocarbon alkylate obtained in the alkylation of
with the hydrocarbon reactants, a single ho
mogeneous gaseous phase during the alkylation
operation.
isobutane with propylene in the presence of known
.
I have now found that the alkylation catalytic
heterogeneous alkylation catalysts, i. e., A1013,
activity of homogeneous gaseous phase alkylation
Thus,
when
heterogeneous
H2804, and the like.
such as elemental halogens and organic
alkylation catalysts are used, 2,3-dimethylpen 30 catalysts
halides, may be promoted through the use of gas
.tane and ZA-dimethylpentane are important con
eous oxidizing agents during the gaseous phase
stituents of the hydrocarbon alkylate obtained.
catalytic allzylation operation.
On the other hand, when homogeneous gaseous
It is an object of the present invention to vpro
phase alkylation catalysts are employed, triptane,
vide an improved process for alkylating isoparaf
or 2,2,3-trimethylbutane, 2,2-dimethylpentane,
?nic or normal para?inic hydrocarbons with ole
and Z-methylhexane may be the predominant
?nic hydrocarbons in the presence of elemental
constituents of the hydrocarbon alkylate. In this
halogens or organic halides as homogeneous
.copending application, the formation of these
gaseous phase alkylation catalysts. Another ob
three compounds was postulated as follows:
40 ject of the present invention is to provide an
1.
improved process for alkylating isopara?inic hy
Isobutane
Propylene
drocarbons with ole?nic hydrocarbons in the
(‘3H3
if
(‘311:
presence of elemental halogens or organic halides
.as homogeneous gaseous phase alkylation cata
lysts, to produce high yields of high octane gaso
line. A more specific object is to provide a
HaC-CH + H2O=C—CH3 -—-—> H3C—-C-—CH2-—CH2——CH3
CH3
CH9,
2,2-dimethylpcntane
CH3
2.
CH:
CH; CH3
‘process for promoting the, alkylation catalytic
activity of organic halides or of elemental halo—
H3C-— H+ CH -—-> H;C—C———C-—CH3
CH3
CH3
gens, during the gaseous phase catalytic alkylation
CH3 H
2,2,3-trimethylbu
of _ isobutane with propylene to produce high
'50 ,yields
of high octane gasoline. A very important
tone or triptane
3.‘
H
I
HaC-(‘]—CH3+H2C=Cl}-CH3 -—> HaC-FH—CHz—CHz-CH2—CH;
CH3
'
H
.
CH3
'
'
'
2~methylhexane
From a motor fuel standpoint, the 2,2-dimethyl
pentane produced by the ?rst reaction, has an
' octane number of about 80 CFR motor method;
the triptane produced by the second reaction has
an octane number of well over 100, and the 2
methylhexane obtained in the third reaction has
an octane numb-er of about 45. - In view of the
foregoing, in the manufacture of high octane mo
tor fuel by the alkylation of isobutane with
object of the present invention is ‘to afford a
.process capable of carrying out the above objects
by using small amounts of gaseous oxidizing
agents that form with the hydrocarbon reactants
and in the organic halides or elemental halogens,
a single, homogeneous’ gaseous phase during the
.alkylation operation. Other objects and advan
tages of the present invention will become appa
60 rent to those skilled in the art from the follow
ing description.
~
Broadly stated, my invention provides a process
for alkylating normal parafhnic or isoparainnic
>hydrocarbons, particularly isobutane, with ole
propylene, alkylation conditions that favor the 65 ?nic hydrocarbons, particularly ethylene, propyl
ene, and butylene, which comprises contacting
production of triptane obviously are preferable.
the paraf?nic and ole?nic hydrocarbons in gase
Further, since neoheXane which may be produced
ous phase and in a reaction Zone under alkylating
by the alkylation of isobutane with ethylene, has
conditions, with small amounts of an alkylation
an otcane number of 93.4, and since 2,3-dimethy1
pentane and- 2,4-dimethylpentane which are the 70 catalyst consisting essentially of elemental halo
gens, particularly chlorine and bromine, or of or
predominant constituents of the alkylate ob
ganic halides, particularly organic chlorides and
tained in the alkylation of isobutane with propyl
.bromides, that form with the hydrocarbon re
ene in the presence of heterogeneous alkylation
‘ actants', a single, homogeneous gaseous phase
catalysts, have octane numbers vor" 84 and 82, ‘re
75 under the alkylation conditions of the reaction
spectively, the importance of the alkylation of
32,410,070
5
6
"zone, in the presence of small amountsof avi'gase
ticularly. organic‘ chlorides ‘and organic bromides
and chlorine andbromine. "In 'the'alkylation of
visobutane with propylene, organic bromides and
I'brom'ine‘are the" preferred catalysts. 'It’wasifound
the known catalytic alkylation processes of the CI! that when bromineor an ‘organic bromide is used
, prior art which are only ‘capable of alkylating
‘as the ‘homogeneous gaseous phase alkylation
isopara?inic hydrocarbons, our process is capable
catalyst in the alkylation 1of isobutane‘with pro
of alkylating either normal paralhnic or iso
pylene, ‘the alkylate contains an appreciably
paraf?nic hydrocarbons with substantially equal
‘larger proportion of vthe triptane_ and 2,2-di
ease.
10 'méthy-lpentane-containing fraction, than the al
Another important feature of the process ‘of
lkylate obtained when ‘other organic halides or
the presentginvention is the relatively low-tem
other "halogens-‘are employed, However when an
ous oxidizing agent.
I
,
An important feature of the process of the
present invention is the fact that, contrary to
perature that may be used. As a result, degrada
organic‘brom‘ide' or "bromine is used, the concen
tion of the hydrocarbon reactants in the charge
ltrationlof the ltriptanein the triptane- and 2,2
to low molecular weight hydrocarbons and the 15 d'imethylpentane-containing fraction is always
pronounced occurrence of side reactions-includ
lower than that obtained when other organic
ing polymerization of the ole?nic hydrocarbons
halides or other halogens are employed. The
are substantially avoided. Consequently, in my
process, I obtain high yields of a high grade
higher yield of 2,2-dimethylpentane thus ob
tainedfis accompanied ‘by a decrease ‘in the
product that is almost entirely paraihnic in 20 2-methylhexane_ Therefore, since it thus- ap
nature and is substantially free from impurities.
pears that organic bromides and bromine favor
A very important feature‘ of the presentinven
the ?rst and second alkylation reactions referred
tion is the fact that, contrary to known catalytic _ to hereinbefore; while organic chlorides .and
alkylation processes of the prior art in which the
chlorine favor the ?rst and third alkylation‘reac
hydrocarbon reactants being processed form with
tions referred to; and since the ?rst and second
the alkylation catalysts, .a heterogeneous system
alkylation reactions referred to, produce prod
during the alkylation operation, the alkylation
ucts that have the highest and higher octane
process of my invention employs alkylation cata
numbers,~respectively, the advantages of employ
lysts consisting essentially of materials that
ing an organic bromide or bromine as the homo
form with the hydrocarbon reactantsbeing proc- geneous gaseous phase alkylation catalyst for the
essed, a single, homogeneous gaseous phase under
manufacture of high octane motor fuel by my
alkylating conditions. The alkylation catalysts of
process are manifest. By way of illustrative vex
the present invention are called, therefore and
as noted hereinbefore, homogeneous gaseous
phase alkylation catalysts, in contradistinction
to the alkylation catalysts of the prior art which
are referred to as heterogeneous alkylation cata
lysts. Accordingly, as a result of the catalysts
being in the same phase or state as the hydro
ample, it is possible to obtain a fraction contain
ing 10 parts of triptane, 85 parts of 2,2-dimethyl
pentane and only 5 parts of Z-methylhexane.
This fraction is considerably larger per pass
when an organic bromide orbromine is used as
the catalyst, than when chlorine or an organic
chloride is employed. The overall per pass yield
carbon reactants being processed, fouling of the 40 of 2,2-climethylpentane is increased appreciably.
catalyst is substantially eliminated and agitation
Therefore, even though the yield of triptane is
and/or mixing problems are non-extant. Fur
only slightly increased, it still seems favorable to
ther, since the catalytic activity of alkylation
produce 80 octane 2,2-dimethylpentane at the
catalysts appears to be predicated somewhat upon _
contact between the catalysts and the hydrocar
bon reactants at the interfaces therebetween, it
expense of 45 octane Z-methylhexane.
The amount of organic halide or of elemental
halogen used in my process varies between about
follows that the catalytic'e?iciency of a given
0.5% and about 3%, and preferably ‘between
catalyst increases with the increase in area of
about 1% and about 1.25%, with respect to the
interfacial contact, other variables remaining con
stant. Hence, since the homogeneous gaseous 50 total charge of hydrocarbon reactants, It must
be noted, however, that ‘larger amounts of or
phase alkylation catalysts of my process inher
ganic halide or of elemental halogen maybe em
ently furnish the greatest possible “interfacial
ployed if desired, although no additional advan
contact” between the catalyst and the hydrocar
tages result therefrom,
7
bon reactants under the conditions of alkylation,
As disclosed in application Serial Number
efficient catalytic activity with a concomitant
high vyield of high grade alkyla-te is achieved using
relatively small amounts of homogeneous gaseous
phase alkylation catalyst.
In View of the foregoing, an operation feature
of the process of the present invention that ‘is of
considerable practical importance is that small or
promoter amounts of organic halides or of ele
mental‘halogens are used as alkylation catalysts.
‘These amounts are so small that they may be dis
carded feasibly, thereby obviating recovery’and
regeneration v‘problems and eliminating high ini
tial and operation costs.
As disclosed in application Serial ‘Number
‘502,813, "?led'September 17, 1943, ‘and in applica
tion ‘Serial Number 502,812, ?led September 17,
1943, a most important feature of homogeneous
gaseous phase alkylation is that high yields of
high octane motor fuel are obtained by alkylatl
ing isobutane withwpropylene ‘in the presence of
organic halides or of elemental halogens, par 75
502,018, ?led September 11, 1943, the organic
halides that are used as homogeneous gaseous
phase alkylation catalysts, may be solids, liquids
or gases under normal conditions. ‘However, it
is likewise essential for the purposes of my ,proc
ess, that the organic halides and the elemental
halogens form with the hydrocarbon reactants
beingprocessed, a single, homogeneous gaseous
phase under the alkylation conditions of the
process. The organic halide catalysts comprise
halogen derivatives of hydrocarbons, wherein
halogens have been substituted for'part or all
the hydrogen of an organic compound.
Chlorin- ,
ated naphtha, chloroform, carbon tetrachloride,
1,2,3-trichloropropane, benzyl chloride, propylene
tribromide, propylene dibromide, ethyl bromide
may be mentioned byway of non-limiting exam
"ples of organic halides suitable for use as homo
geneous gaseous phase alkylation catalysts. It
is understood, of course, that'hydrogen halides,
2,410,070
7
reacting with hydrocarbons, can be used to form
the organic halide catalysts in situ;
8
temperature conditions, side reactions occur that
substantially reduce the purity of the product ob
‘
tained. In the alkylation of isobutane with pro
pylene in accordance with the process of the
present invention, it must be noted that even
within the preferred temperature range, side re
In accordance with the present invention, the
promoters for the homogeneous gaseous phase
alkylation catalysts, organic halides and elemen
tal halogens, are oxidizing agents which may be
solids, liquids or gases under norma1 conditions.
actions occur that account for substantial por- '
tions of the total alkylate, but a fraction boiling
However, it is also essential for the purposes of
at 79° C. to 82° C. and consisting of 15 parts of
my process, that these oxidizing agents form with
triptane to 85 parts of 2,2-dimethylpentane may
the hydrocarbon reactants being processed, and 10
with the organic halides or elemental halogens, a
single, homogeneous gaseous phase under the al
kylation conditions of the process. Oxygen or
be obtained.
effective promoters of this type.
kylation of isobutane with propylene, the most
The pressure to be used in my process may vary ‘
from about 500 pounds per square inch to about
6000 pounds per square inch or more, and pref
oxygen-containing gases, sulfur oxides, nitrogen
erably from about 2500 pounds per square inch
15
oxides, and so forth, have been found to be very
to about 6000 pounds per square inch for the al
The amount of promoter used in my process
suitable pressure being more or less dependent
varies between about 0.1% and about 2.0%, and
upon the particular temperature involved. In
preferably between about 0.5% and about 1.25%,
general, the higher the pressure, the higher the
with respect to the total charge of hydrocarbon 20 yield of alkylate. Accordingly, the criterion for
reactants. It must noted, however, that larger
establishing an upper limit to the pressure range
amounts of oxidizing agents may be employed if
used is primarily the feasibility of maintaining
desired, although no additional advantages re
sult therefrom.
'
The paraf?nic and ole?nic hydrocarbons to be
such pressure.
25
used in my process may be derived from any suit
able source, as is well known in the art, and
may be used either in the pure state or in ad
'
-
In my process it is desirable, as in known iso
para?in-ole?n alkylation processes, to keep the
concentration of the ole?nic hydrocarbons rela
tively low during the alkylation reaction, in or
der to eliminate as much ole?n polymerization
as possible. Accordingly, it is advisable to main
The paraf?nic and ole?nic hydrocarbons usually 30 tain the ole?n concentration in the charge be
employed in the preferred operation of manu
low about 25% by volume, and preferably be
facturing motor fuels, will be the normally gas
tween about 7% and about 12% by volume.
eous paraflinic hydrocarbons, except methane
The alkylate product that I obtain distills over
and ethane, and the normally gaseous ole?nic hy
a fairly large boiling range, but a greater part of
drocarbons, as is well understood in the art.
the alkylate, usually from about 85% to about
Here again this process has a distinct advantage
90%, distills in the boiling range of aviation gas
over many of the prior art processes, in that the
olines. The iodine number or the aviation dis
ole?n ethylene may be used for alkylating the
tillate is low, on the order of about 5 to 10. As
paraffinic hydrocarbons. It is well known that
mentioned hereinabove, the alkylate product con
40
ethylene cannot be used in many catalytic proc
sists predominantly of branched para?inic hydro
esses, including the sulfuric acid process, where
carbons.
by the supply of available ole?nic hydrocarbons
Numerous experimental data could be adduced
is restricted. Therefore, an important aspect of
to indicate the results obtainable by employing
the present invention is the fact that butane, for
45 the promoters of the present invention in the
instance, may be alkylated with ethylene.
homogeneous gaseous phase alkylation in the
A conventional and preferred source of paraf
presence of organic halides or of elemental halo
?nic and ole?nic hydrocarbons is the ?xed gases
gens, but the following examples are suf?ciently
obtained around petroleum re?neries. These
characteristic:
?xed gases may furnish substantially all the de
sired paral?nic and ole?nic hydrocarbons, or it 50
Run 1 Run 2 Run 3 Run 4
mixture with other constituents not undesirable.
may be necessary or desirable to obtain addi
tional supplies, as is well understood. Additional
ole?nic hydrocarbons, if required, may be formed
from a portion of the para?inic hydrocarbons.
On the other hand, additional para?inic hydro
carbons may be admixed to increase the concen
tration of para?inic hydrocarbon-s to a desired
magnitude.
In carrying out my process, I use temperatures
varying between about 590° F. and about 850° F.,
and preferably temperatures varying between
about 650° F. and about 825° F. In the alkyla
tion of isobutane with propylene, however, it was
found, as disclosed in copending application
Serial Number 502,813, ?led September 17, 1943,
that the best yields of desired alkylate are ob
lsobutane . _ _ _ . _ _ _
_ _ . . ..grams
Propylene“
625
__do ..
55
625
l
10
er ...... _.
(2)
Wt. of promoter.__.. ._
Temperature, ° F.___
~
Pressure, lbs/sq. in _____________ ..
,
625
75
l
lift. of catalyst
Prom
625
( >75
> v _ _ __
75
1
( )lO
( > 20
(2)
(a)
0.5
2. 3
775
3, 800
775
3,800
2. 3
775
3, 800
126
170
168
Yield of alkylate based on pro
pylenemnl ........ "percent ..
100
1 1,2,‘i-trinhloro-propanc.
1 Air.
The alkylate produced by my process is con
taminated by various halogen compounds which
are present in small concentration. These com
pounds cause a negative susceptibility to tetra
ethyl lead, and therefore should be removed. Re
tained when the alkylation is conducted at tem
moval of the halogen compounds is possible in a
peratures falling within about 750° F. to about
variety of ways, as set forth in copending appli
850° F., and preferably, about 775° F. to about
70 cations Serial Number 477,450, filed February 27,
825° F.
1943; Serial Number 502,504, ?led September 15, ~
The alkylate produced under these conditions
1943; and Serial Number 504,436, ?led Septem
‘contains no more than 5% of ole?nic hydrocar
ber 30, 1943.
lbon's and no aromatics so that the predominance
The present invention may be embodied in
of alkylation obtained thereby is a distinct fea
ture of the process. Under appreciably higher 75 other speci?c forms without departing from the
2,410,070
spirit or‘ essential attributes thereof; and it is
therefore ,desired'that the present embodiments
, rivatives of; hydrocarbons, chlorine’ andrbromine,
in, the presence of oxygen, and maintaining said
isobutane in excess'over said propylene in said re
action zone so that alkylation is the principal re
be considered in’ all respects as illustrative‘ and
not restrictive, reference being‘hadto‘ the ap
pended claims rather than'to the foregoing de
scription to indicate the scope of the invention.
.71 claim:
.
;
-
action.
-
6. A process for manufacturing triptane which
comprises‘ contacting. isobutane and‘ propylene in
'
. -1. A process for manufacturing triptane which
gaseous'yphaseand in a reaction zone under'gal
comprises contacting isobutane and propylene in
kylating conditions including temperatures vary
gaseous phase and in areactionzone underal
ing between about '775°-F. and-about 825° Fpand
kylating conditions including: temperatures vary
. pressures in excess of-2500-pounds'per square
ing between" about 775° F: and about 825° F. and
pressures in, excess of- 2500 pounds per square
inch, with a homogeneous gaseous phase alkyla
tion catalyst consisting-essentially of a chlorine
inch, with a homogeneous gaseous phase alk/ylae
tion‘catalyst ‘consisting essentially of- a: bromine 1
derivative of a light aliphatic hydrocarbon-in the
presence of oxygen, and. maintaining saidi-so
derivative , of alight aliphatic hydrocarbon,‘ in the
butane in excess over said propylene insaid-re
action zone so that alkyla-tionis the princip'alre
action.
>
.
presence of oxygen; and maintaining‘ said iso
butane in excess over said propylene injsaiol‘re
action zone so that alkylation'r is the principal
reaction.
,
,
'7. In a process of manufacturing high octane
gasoline‘ by alkyiating a normally gaseous paraf
.
2. In a processor" manufacturing high. octane
gasoline by alkyla-ti'ng' a normally gaseous par
?nic hydrocarbon with a‘ normally gaseous ole‘
a?inic hydrocarbon with‘anormally gaseous ole
?nic hydrocarbon in a reaction Zone ‘under al
kylating conditions and in the presence of cat
finic hydrocarbon in, a- reaction zonev under‘ al
kylating'oonditionsand inthe pres'enceof cat,- .
alyic material; the improvement which comprises
contacting said normally gaseous paraffmic hy
valytic material; the improvement which com
drocarbon and said: normally gaseous ole?nic hy
prises contacting said. normally.~ gaseous pa'r'a'?in- - ‘ drocarbon in gaseous? phase and in a reaction
vic hydrocarbon and said normally gaseous ole?nic
zone ‘under alkylating conditions including tem
hydrocarbon in gaseous phase and in. areaction
peratures varying between. about 590°- F. and
zone under alkylating conditions‘ including tem
about 850° F. and pressures in excessof 500
peratures. varying between about 590°’ F; and
pounds persquare inchgwitha homogeneous gase
about 856?» F. ‘and pressures. in- excess of 500. ’
pounds-per squareincli, with a homogeneous
ous p-hasealkylation catalyst consisting essentially
of a bromine derivativeof a light aliphatic hydro
gaseous. phase alkylation catalyst consisting" es
carbon, inthe presence or oxygen, and maintain
sentiallyof'chlorine, in the presence. of oxygen, . ‘,ing said normally gaseous paraf?nic’ hydrocarbon
and maintaining said normally gaseous‘ppara?inic
.inexcess over said normally gaseous ole?nic hy
drocarbon in said reaction zone so‘ that alkylation
hydrocarbon in excess over said'normally-gaseous
ole?nic hydrocarbon in said reaction zone so that
alkylation is the principalreaction.
.,
is the principal reaction.
3. A‘ process for manufacturing. high octane
.
I
,
8; A process of vmanufacturing:tript'ane which
V
40
comprises contacting isobutane and propylene in
gasoline, which comprises contacting isobutane
gaseous phase and in a reaction‘ zone under. al
and. propylene in gaseousphase and ina reac
kylating conditions including. temperaturesvarye
tion zone under alkylating conditions, including
temperatures varying between about. 750° Fl and
ing between about 775°‘ F. and. about 825° F. and
pressures‘ in excess of'2500 pounds'per square
about 85031“. and pressures in‘ excess of. 2500
pounds per square inch, with a homogeneous
gaseous phase alkyiation oatalystconsisting- es
.415
in the presence of oxygen, and maintaining said
isobutane in excess over said propylene in said
sentially of chlorine, in the presence ofi‘oxygen,
and maintaining said isobutane in excess over
reaction zone so'that a'lkylation is the principal
said propylene in said reaction zone so that- al-l 50
kylation is the principal reaction. 1
,
4. In a process of alkylating: a paraf?nichydro
carbon with an ole?nic hydrocarbon in a reaction
zone under alkylati'ng conditions and in the pres
inch; with homogeneous gaseous phase alkyla
tion catalyst consisting essentially of chlorine,
reaction._
.
9. vIna process; of .alkylatingi a’ paraf?nic' hy
drocarbon with an ole?nic hydrocarbon in a re
action. zone under allrylating.v conditions and in
the presence of catalytic material; theimprove
ence of catalytic material; the improvement 55 ment which comprises contacting said para?inic
which comprises contacting said para?inic hy
hydrocarbon and said ole?nic hydrocarbon in
drocarbon and said ole?nic hydrocarbon in
gaseous phase and in a reaction zone under al
gaseous phase and in a reaction zone under al
kylating conditions, with a homogeneous gaseous
kylating conditions including temperatures vary
ing between about 590° F. and about 850° F. and
phase alkylation catalyst consisting essentially of 60 pressures in excess of 500 pounds per square inch,
a bromine derivative of a light aliphatic hydro
with a homogeneous gaseous phase alkylation
carbon, in the presence of oxygen, and maintain
catalyst consisting essentially of a chlorine de
ing said para?inic hydrocarbon in excess over
rivative of a light, aliphatic hydrocarbon, in the
said ole?nic hydrocarbon in said reaction zone so
presence of oxygen, and maintaining said. par
that alkylation is the principal reaction.
5. A process for manufacturing triptane, which
comprises contacting isobutane and propylene in
gaseous phase and in a reaction zone under al
65 a?inic hydrocarbon in excess over said ole?nic
hydrocarbon in said reaction zone so that alkyla
tion is the principal reaction.
10. In a process of manufacturing high octane
gasoline by alkylating a normally gaseous par
kylating conditions including temperatures vary
ing between about 775° F. and aboutv 825° F. and 70 af?nic hydrocarbon with a normally gaseous ole
pressures in excess of 2500 pounds per square
?nic hydrocarbon in a reaction zone under al
inch, with a homogeneous gaseous phase al
kylating conditons and in the presence of cat
alytic material; the improvement which com
kylation catalyst consistingressentially of mate
rial selected from the group consisting of chlo
rine derivatives of hydrocarbons, bromine de
prises contacting said normally gaseous paramnic
75 hydrocarbon and said normally gaseous ole?nic
v2,410,070
hydrocarbon in gaseous phase and‘ in a reaction
zone under alkylating conditions including tem
peratures varying between about 650° F. and
about 825° F. and pressures in excess of 1500'
pounds per square inch, with a homogeneous gas
eous phase alkylation catalyst consisting essen
tially of a chlorine derivative of a light aliphatic
hydrocarbon, in the presence of oxygen, and
12
gaseous phase alkylation catalyst consisting es
sentially of a chlorine derivative of a light ali
phatic hydrocarbon, in the presence of oxygen,
and maintaining said isobutane in excess over
said propylene in said reaction zone so that al
kylation is the principal reaction.
maintaining said normally gaseous parafiinic hy
14. In a process of alkylating a paramnic hy
drocarbon with an ole?nic hydrocarbon in a re
action zone under alkylating conditions and in
alkylation is the principal reaction.
hydrocarbon and said ole?nic hydrocarbon in
drocarbon in excess over said normally gaseous 10 the presence of catalytic material; the improve;
ment which'comprises contacting said para?inic
olefinic hydrocarbon in said reaction zone so that
gaseous phase and in a reaction zone under al
11. In a process of alkylating isobutane with
kylating conditions, with a homogeneous gaseous
propylene in a reaction zone under alkylating
conditions and in the presence of catalytic ma 15 phase alkylation catalyst consisting essentially of
material selected from the group consisting of
terial; the improvement which comprises con
chlorine derivatives of hydrocarbons, bromine
derivatives of hydrocarbons, chlorine and bro
mine, in the presence of oxygen, and maintaining
kylating conditions including temperatures vary
ing between about 750° F. and about 850° F. and 20 said paraffinic hydrocarbon in excess over said
tacting said isobutane and said propylene in
gaseous phase and in a reaction zone under al
pressures in excess of 2500ipounds per square
ole?nic hydrocarbon in said reaction zone so that
inch, with a homogeneous gaseous phase alkyla
alkylation is the principal reaction.
tion catalyst consisting essentially of a bromine
derivative of a light aliphatic hydrocarbon, in the
presence of oxygen, and maintaining said iso
15; 'In a process of alkylating isobutane with
propylene in a reaction zone under alkylating
25 conditions and in the presence of catalytic ma
butane in excess over said propylene in said re
terial; the improvement which comprises con
action zone so that alkylation is the principal
‘ tacting said isobutane and said propylene in
gaseous phase and in a reaction zone under al
reaction.
'
kylating conditions including temperatures vary
para?inic hydrocarbon with a normally gaseous 30 ing between about ‘750° F. and about 850° F. and
12. A process for alkylating a normally gaseous
ole?nic hydrocarbon, which comprises contacting
said normally gaseous para?inic hydrocarbon
pressures in excess of 2500 pounds ,per square
inch, with a homogeneous gaseous phase alkyla
tion catalyst consisting essentially of material
selected from the group consisting of chlorine de
in gaseous phase and in a reaction zone under
alkylating conditions including temperatures 35 rivatives of hydrocarbons, bromine derivatives of
hydrocarbons, chlorine and bromine, in the pres
varying between about 590°‘F; and about 850° F.
ence of oxygen, and maintaining said isobutane
and pressures in excess of 500 pounds per square
in excess over said propylene in said reaction
inch, with a homogeneous gaseous phase alkyla
tion catalyst consisting essentially of material
zone so that alkylation is the principal reaction.
16. In a process of alkylating a para?inic hy
selected from the group consisting of chlorine de 40
drocarbon with an ole?nic hydrocarbon in a re
rivatives of hydrocarbons, bromine derivatives of
action zone under alkylating conditions and in
hydrocarbons, chlorine and bromine, in the pres
ence of oxygen, and maintaining said normally
the presence of catalytic material; the improve
ment which comprises contacting said para?inic
gaseous para?inic hydrocarbon in excess over
said normally gaseous ole?nic hydrocarbon in 4.5 hydrocarbon and said ole?nic hydrocarbon in
and said normally gaseous olefinic hydrocarbon
said reaction zone so that alkylation is the prin
gaseous phase and in a reaction zone under al
cipal reaction.
~kylating conditions, with‘a homogeneous gaseous
phase alkylation catalyst consisting essentially of
,
13. A process for manufacturing high octane
gasoline which comprises contacting isobutane
chlorine, in the presence of oxygen, and main
and propylene in gaseous phase and in a reaction '~ 50 taining said para?inic hydrocarbon in excess over
said ole?nic hydrocarbon in said reaction zone so
zone under alkylating conditions including tem
peratures varying between about 750° F. and
about 850° F. and pressures in excess of 2500
pounds per square inch, with a homogeneous
that alkylation is the principal reaction.
AARON W. HORTON.
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