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2,407,585‘
Patented - Sept. 10, 1946
UNlTED ‘STATES PATENT OFFlCE
, 2,401,585
ALKYLATION rnooass
William A. Stover, Woodbury, N. 5., assignor to
Socony-Vacuum Oil Company, Incorporated,
a corporation of New York
No Drawing. Application September ll, 1945,
Serial No. 615,695
12 Claims. (Cl.
'
260-683d)
1
‘
2
.
with the production of high-octane motor fuels
rI'he temperatures and to a certain extent, the
pressures employed in alkylation operations, de
pend upon whether the alkylation is effected in
the absence or presence of alkylation catalysts.
by the catalytic alkylation of paraf?nic hydro-_
The two methods are generally referred to as
This invention relates generally, to the aikyla
I tion of para?inic hydrocarbons with ole?nic hy
drocarbons, and is more particularly concerned
carbons with ole?nic hydrocarbons. ,
thermal and catalytic alkylation, respectively. As
It is well known in the art to polymerize ole
?nic hydrocarbon gases to produce motor fuels
having constituents of an unsaturated character.
Various commercial processes have been proposed 10
is well known in the art, thermal alkylation ordi
narily involves the use of temperatures of at least
about 950° F. and pressures of the order of 4000
pounds per square inch or higher. At these tem
for ultimately e?ecting the desired polymeriza
tion of the ole?nic hydrocarbons. These processes
have been predicated upon the dictates of the
chemical nature of the stocks available, as well as
peratures, the degradation of the hydrocarbon
reactants in the charge, and the occurrence of
side reactions, including polymerization of the
ole?nic reactant, is somewhat marked. On'the
other hand, catalytic alkylation involves the use‘
of appreciably lower temperatures, thereby as
suring a high yield of desired alkylate by avoiding
engineering considerations such as initial and op
eration costs; their essential feature being that
in the course of treating the materials, the ole
?nic hydrocarbons produced in the earlier stages
extensive degradation of the reactants, the oc
currence of secondary reactions, and appreciable
hydrocarbons boiling within the gasoline boiling 20 polymerization of the oleiinic reactant.
Several methods are known for the catalytic
range, Accordingly, hydrocarbon gases may be
alkylation of isopara?nic hydrocarbons with ole
passed along with cracking stock or naphtha
?nic hydrocarbons. For instance, it is known to
through a cracking still to crack and polymerize
alkylate isopara??nic hydrocarbons with ole?nic‘
such gases to gasoline simultaneously with the
of the process, are eventually polymerized into
cracking or reforming, or para?nic hydrocarbon 25 hydrocarbons in the presence of sulfuric acid,
phosphoric acid,_meta1 phosphates, metal halides,
gases may be separately cracked into ole?nic hy
activated claysrand the like, as catalysts. In
drocarbon gases and these gases are subsequently
these catalytic alkylation processes, the hydro
passed with naphtha through a polymerizing and
carbon reactants form with the alkylation cata
reforming still. In some instances, the processes
involve the use of catalysts for facilitating the 30. lysts, a heterogeneous system during the alkyla
tion operation. Hence, these alkylation catalysts
cracking and/or polymerization operations.
may be termed heterogeneous alkylation catalysts.
It is also well known in the art to combine
Since'under alkylation conditions, the catalytic
para?lnic hydrocarbons directly with ole?nic hy
activity ofthe alkylation catalysts appears to be
drocarbons by processes broadly called alkylation
processes, to produce motor fuels having constit 35 predicated upon contact between the catalysts
and the gaseous hydrocarbon reactants at the
uents of saturated character. In alkylation proc
interfaces therebetween, in these processes, the
catalysts are used in amounts varying between 10
per cent and 200 per cent by weight, on the
?nic reactant, and an ole?nic hydrocarbon, called
the ole?nic reactant or alkylating agent, is sub 40 charge, depending on the catalyst used. Due to
these comparatively high amounts, where possi
jected to high temperature and pressure to pro
ble, recovery and regeneration of the catalysts
duce a saturated alkylate product. Since condi
' have been proposed. This, of course, involves high
tions of alkylation also cause polymerization‘of
initial and operation costs. Further, it is also
the ole?nic reactant, it is necessary to maintain .a
relatively low concentration of the ole?nic react 45 known that certain substances called promoters,
esses, a charge comprising a mixture of an alkyl
atable paraf?nic hydrocarbon, called the paraf
promote the catalytic activity of these alkylation
catalysts. Accordingly, several processes have
ant in the charge. The only limit to the pressure
used appears to be the feasibility of maintaining
been proposed wherein small amounts of these
high pressures. On- the other hand, the tempera
promoters, on the order of about 1 per cent to
ture used is limited by degradation of the hydro
carbon “reactants in the charge to low molecular 50 3 per cent by weight on the charge, are added to
the catalystsv to promote their alkylation catalytic
weight hydrocarbons, and the occurrence of side,
reactions, including polymerization of the ole?nic
reactant, under high temperature conditions, that
activity.
substantially reduce the Purity of the product ob
tained.
'
>
A copending application, Serial No. 502,018,
?led September 11, 1943‘, is directed to the process
55
of alkylating'normal para?inic or isoparaf?nic
2,407,685
3
4
‘
-
‘motor fuels by the alkylation of isobutane with
hydrocarbons with ole?nic hydrocarbons, which
propylene, alkylation conditions that favor the
comprises contacting a normal para?lnic or iso
para?inic hydrocarbon and an ole?nic hydrocar
bon in a reaction zone under alkylating condi
, production’ of triptane obviously are preferable.
It was also found that in actual practice, it was .
impossible to obtain triptane exclusively, appre
tions, with small or promoter amounts of what
ciable amounts of 2,2-dimethylpentane and 2
has been termed therein, a homogeneous gaseous
methylhexane being always formed.
phase alkylation'catalyst, which consists essen
The speci?c classes of homogeneous gaseous‘
tially of a material that forms-with the hydro
phase catalysts disclosed in these copending ap
carbon reactants, a single, homogeneous, gaseous
phase under the alkylation conditions of the re 10 plications are organic halogen compounds, and,
action zone. The alkylation conditions of the - more particularly, chlorine and bromine deriva
-tives of acyclic hydrocarbons. Chloroform, chlo
.process of this copending application, comprise a
rinated naphtha, chlorinated butane, carbon
broad temperature range of about 590° F.- to about
850° F., preferably, about 650° F. to about 825°
tetrachloride, ethylene .dibromide, propylene -di_
F., and pressures of at least 500 pounds per square 1.5 bromide, dibromisobutane, ethyl bromide, propyl
ene tribromide, and tertiary monobromobutane
inch gauge, preferably, pressures of at least 1500”
are among the speci?c chlorine and bromine de- '
pounds per square inch.
rivatives of acyclic hydrocarbons mentioned as
Another copending‘ application, vSerial No.
suitable homogeneous, gaseous phase alkylation
502,813, ?led September 17, 1943, is directed to
the process of alkylating isobutane with propyl 20 catalysts for the alkylation processes disclosed in
these copending applications.
'
ene, which comprises contacting isobutane and
The present invention is predicated on the use
of‘mixtures of carbon dioxide and water as homo
' propylene in a reaction zone under closely con
trolled alkylating‘ conditions, with'promoter or
geneous gaseous phase alkylation catalysts, in
catalysts broadly disclosed-in the copending-ap 25 the alkylation of para?inic hydrocarbons with
ole?nic hydrocarbons, under conditions of alkyl
plication referred to hereinbefore, the closely
small amounts of the homogeneous gaseous phase
controlled alkylating conditions including a tem
perature range of about 750° F. to about 850°.F.,
ation.
Accordingly, it is an object of the present-in
preferably, about 775° F. to about 825° ,F., and
vention to provide an eflicient process for alkyl- '
pressures of at least 2500 pounds per square inch 30 ating alkylatable isopara?inic or alkylatable nor“
mal paraffinic hydrocarbons with ole?nic hydro
gauge. In the alkylation of isobutane with
carbons. Another .object is. to provide an im
propylene in the presence of homogeneous gas
proved process for catalytically alkylating either
eous phase alkylation catalysts, it was found that
alkylatable normal para?lnic hydrocarbons or
the alkylate obtained included constituents that
are entirely different from the constituents of 35 alkylatable isopara?inic hydrocarbons with ole
?nic hydrocarbons. A more speci?c object is to
the hydrocarbon alkylate obtained in the alkyl
provide a process for catalytically alkylating al
ation of isobutane with propylene in the presence
kylatable normally gaseous isoparaf?nic hydro- of known heterogeneous alkylation catalysts, i. e.,
AlCla, H2804, and the like. Thus, when het
erogeneous alkylation catalysts are used, 2,3-di
methylpentane and 2,4-dimethylpentane are im
portant constituents of thevhydrocarbon alkyl
ate obtained. On the, other hand, when homog
40
carbons with normally gaseous ole?nic hydrocar
bons, to produce high yields of high-octane gaso
line. A very important object is to afford a proc
ess for alkylating isobutane with propylene, to
produce high yields of high-octane gasoline. A
further object is ‘to provide a process capable of
eneous gaseous phase alkylation'catalysts are em
ployed, triptane or 2,2,3-trimethylbutane, 2,2-di 45 carrying out the above objects by using mix
tures of carbon dioxide and water as homoge
methylpentane, and 2-methylhexane are the pre—
neous gaseous phase alkylation catalysts. Other
dominant constituents of the hydrocarbon alkyl
' objects and advantages of the present invention
ate. In this copending application, the forma
will become apparent to those skilled in th: art
tion of these three compounds was postulated as
follows:
~
.50
'
on,
H
\
'
2.
Propylene
on,
on,
0H,
C Ha
Ha
'
3'
2, 2-dliggthylpentane
on; em
in gaseous phase and in a reaction zone under
alkylating conditions, with mixtures of carbon
C H; H
2, 2, S-trimcthylbutan
60
or triptane
.
.
H
v
isopara?ilnic hydrocarbons, particularly isobu-'
tane, with ole?nic hydrocarbons, particularly
65 propylene and ethylene, which comprises con
tacting the‘ para?inic and ole?nic hydrocarbons
HaC—-(:3H + gH -———> HaC—C,—C—CHa
Isobutane Propylene
-
Broadly stated, my invention provides a process
for alkylating alkylatable normal para?lnic or
HSC-éH +-H2c=d-cHr --'» HiC-éf-CHr-GHg-CH:
lsobutalgé
from the following description.
dioxide and water.
An important feature is the relatively low tem
perature that may be used.- As a result, degrada
tion of the hydrocarbon reactants in the charge
to low molecular weight hydrocarbons and the
CH:
pronounced occurrence of side reactions, includ
65 ing polymerization of the ole?nic hydrocarbons,
IsobutHahe
Propylene
Z-methylhexnne
_
are substantially completely avoided.
Conse
quently, in my process, I obtain high yields of a
From‘ a motor fuel standpoint, the 2,2'-dimethyl
high grade ‘product that is almost entirely‘ paraf
pentane .produced by the'?rst reaction has] an ' ?nic in nature and is substantially free from .
octane number of about 93_CFR motor method; 70 impurities.
the Lriptane produced by the second reaction has
A very important feature of the present inven
an octane number of well overv 100; and the
tion is ‘the fact that, contrary to known catalytic
2-methylhexane- obtained in 'the third reaction Y‘ . ,alkylation processes ofithe prior art in which
has an octane number of about 45.’ 'In View. of
the hydrocarbon reactants being processed form‘
the foregoing, in the manufactureof high-octane 75 with the alkylation catalysts, a heterogeneous
2,407,685
system during the alkylation operation, the al
kylation process of my invention, employs
alkylation catalysts consisting essentially of ma
terials that form with the hydrocarbon re
isobutane, for instance, may be aiky‘lated with
ethylene.
I
‘
A conventional and preferred source of paraf
finic and ole?nic hydrocarbons is the iixed gases -
actants being processed, a single, homogeneous 5 obtained around petroleum re?neries. These
gaseous phase under alkylating conditions. The
?xed gases may furnish substantially all the de
'alkylation catalysts of the present invention
sired para?lnic and ole?nic hydrocarbons, or it
are called, therefore and as noted hereinbefore,
' may be necessary or desirable to obtain addi
homogeneous , gaseous phase alkylation cata
tional supplies, as is well understood.‘ Addi
lysts, in contradistinction to the alkylation cat 10 tional ole?nic hydrocarbons, if required, may be
alysts of the prior art which are referred to
formed from a portion of the para?nic hydro
‘ as heterogeneous alkylation catalysts. Accord
carbons. On the other hand, additional paraf- ‘
ingly, as a result of the catalyst’s being in
?nic hydrocarbons may be admixed to increase
the same phase or state as the hydrocarbon re
the concentration of para?inic hydrocarbons to
actants being processed, fouling of the catalyst 15 a desired magnitude.
‘
is substantially eliminated and agitation and/or
In carrying out my process, I use temperatures
mixing ‘problems are non-extant. Further,
varying between about 590° F. and about 850° F.,
since the catalytic activity of alkylatlon catalysts
and preferably temperatures varying between
appears to be predicated somewhat upon contact
about 650'‘ Hand about 825° F. ‘In the allcyla
between the catalysts and the hydrocarbon re 20 tion of isobutane with propylene, however, it, was
actants at the interfaces therebetween, it follows
found, as disclosed in copending application Se
that the catalytic efficiency of a given catalyst
rial No. 502,813, filed September 17, 1943, that
increases with the increase in area of interfacial
the best yields of desired alkylate are obtained
contact, other variables remaining constant.
when the alkylatlon is conducted at temperatures
Hence, since the homogeneous gaseous phase al 25 falling within about 750° F. to about 850° F., and
kylation catalysts of my process inherently fur
preferably within about 775° F. to about 825° F‘. ,
nish the greatest possible “interracial contact"
The alkylate produced under these conditions
between the catalyst and the hydrocarbon react
contains no more than 5 per cent of oleiinic hy
ants under the conditions of allrylation, e?cient
drocarbons and no aromatics so that the pre
catalytic activity with a concomitant high yield
dominance of alkylation obtained thereby is a
of high grade alkylate is possible although using 30 distinct feature of the process. Under appre
relatively small amounts of homogeneous gaseous
ciable higher temperature conditions, secondary '
phase alkylation catalyst.
,
reactions _ occur that substantially reduce the
In view of the foregoing, an operation feature
purity of the product obtained. In the alkyla
of the process of the present invention that is of 35 tion of lsobutane with propylene in accordance
considerable practical importance, is that rela
with the process of the present invention, it must
tively small amounts of carbon dioxide and water
may be .used as allrylaticn catalysts. These
be noted that even within the preferred temper-,
ature range, side reactions occur that account for
amounts are so small and the materials are so
substantial portions of the total allrylate.
cheap that they may be discarded feasibly, there 40 The pressure to be used in my process may
by obviating recovery and regeneration problems
vary from about 500 pounds per square inch to
and eliminating high initial and operation costs.
about 6000 pounds per square inch or more, and
‘ The amounts of carbon dioxide and water used
preferably from about 2500 pounds per square
in my process may vary between about 3 per cent
inch to about 6000 pounds per square‘inch, the
by weight and 50 per cent by weight, and be 45 mostv suitable pressure being more or less depend
tween about 3 per cent by weight and 50 per cent
ent upon the particular temperature involved.
by weight, respectively, and preferably, between
In general, the higher the pressure, the higher
about 5 per cent by weight and 20 per cent by
the yield of alkylate. Accordingly, the criterion
weight, and about 5 per cent by weight and about I for establishing an upper limit to the pressure
20 per cent by weight, respectively, with respect 59 range used is primarily the feasibility of main
taining such pressure.
to total charge of hydrocarbon reactants. It
must be noted, however, that larger amounts of
‘ The process may be carried out as a batch,
each may be employed if desired, although no
continuous or semi-continuous type of operation.
additional advantages seem tovresult therefrom.
Particularly when the process is carried out on a
The paramnlc and ole?nic hydrocarbons to be 55 commercial scale, economic considerations make
used in my process may be derived from any suit
it preferable to operate in a continuous manner.
able source, as is well known in the art, and may
For emcient operation, whether the process is»
be used either in the pure state or in admixture
carried out on a batch or continuous ‘basis, it is
essential that the hydrocarbon reactants be inti
with other constituents not undesirable. The
paramnic and ole?nic hydrocarbons usually em m mately contacted with the homogeneous gaseous
phase catalysts of my invention. This may be
ployed in the preferred operation of manufactur
e?ected in several ways, as is Well known in the
ing motor fuels, will be the normally gaseous-pan
art.
ammo hydrocarbons, except methane and eth
In my process it is desirable, as in known iso
ane, and the normally gaseous ole?nic hydrocar
65
paraffin-ole?n
alkylation processes, to keep the
bons, as is well understood in the art. Here
concentration of the olefinlc hydrocarbons rela
again this process has a distinct advantage over
tively low during the alkylation reaction, in order
many of the prior art processes, in that the ole
to eliminate as much ole?n polymerization as ‘
?n ethylene may be used for alkylating the alkyl
Accordingly, it is advisable to main
'atable para?inlc hydrocarbons. It is well known 70 possible.
tain the ole?n concentration inthe charge below
that ethylene cannot be used in many catalytic
about 25 per cent by volume, and preferably be
processes, including the sulfuric acid process,
tween about 5 per cent and about 12 per cent by
whereby the supply of available ole?nic hydro
volume. In continuous operation, this is effected
carbons is restricted. Therefore, an important
by introducing the oleflnic reactant at a number
aspect of the present invention is the fact that 75 of points in the reaction zone or by adding the
2,407,585
ole?nic reactant to a recirculating mass of ex
other speci?c forms without departing from the
cess parail‘lnic hydrocarbon reactant, reaction
product, and catalyst.
The reaction period during which the reactants
spirit or essential attributes thereof, and it is
therefore desired that the present embodiments
be considered in all respects as illustrative and
not restrictive, reference being had to the ap
pended claims rather than to the foregoing de
scription to indicate the scope of the invention.
are present in the reaction zone, depends upon
the temperature, and to a certain extent, upon
the pressure. Ordinarily, a reaction period vary
ing between 1-2 minutes and 1-2 hours is satis
1 claim:
'
.
'
_
1. The process of alkylating alkylatable paraf
factory.
It must be understood, that the reaction vari-‘ 10 ?nic hydrocarbons with ole?nic hydrocarbons,
which comprises contacting an alkylatalble paraf
ables are more or less interdependent, hence.‘
?nic hydrocarbon with an ole?nic hydrocarbon,
when one is arbitrarily ?xed, the limits within
in gaseous phase and in a. reaction zone under
which the others may be varied, are somewhat
alkylating conditions, in the presence of a mix
restricted. In any particular instance, the most
desirable conditions can be readily ascertained 15 ture of carbon dioxide and water, and maintain.
by one skilled in the art, the preferred ranges of
ing said alkylatable para?inic hydrocarbon in
these variables having been indicated hereinbe
excess over said ole?nic hydrocarbon in said re
fore.
\
action zone, so that alkylation is the principal
The alkylate product that I obtain distills over
reaction.
7 a fairly large boiling range, but 'a greater part of 20
the alkylate, usually from about 85 per cent to
about 90 per cent, distills in the boiling range of
aviation gasolines. ‘The iodine number of the
'
-
-
_
-
2. The process of manufacturing a high-oc
tane motor fuel, which comprises contacting an
alkylatable normally gaseous para?lnic hydro
carbon with a normally gaseous olefinic hydro
aviation distillate is low, on the order of about
carbon, in gaseous phase and in a reaction zone
' 5 to 10. As mentioned hereinbefore, the alkyl 25 under alkylating conditions, in the presence of'
ate product consists predominantly of branched
a mixture‘ of carbon dioxide and water, and.
para?lnic hydrocarbons.
maintaining said alkylatable normally gaseous
Numerous experimental data could be adduced
para?inic hydrocarbon in excess over said nor
to indicate the results obtainable by employing
mally gaseous ole?nic hydrocarbon in said re
the homogeneous gaseous phase catalysts of the 30 action zone, so that alkylation is the principal
present invention, but the following examples are
sufficiently characteristic:
reaction.
TABLE I
Alkylation of isobutane with ethylene to produce
neohexane ~
7
3. The process of manufacturing a high-oc
tane motor fuel, which comprises contacting iso
butane with propylene, in gaseous phase and in
35 a reaction zone under alkylating conditions, in _
the presence of a mixture of carbon dioxide and
water, and maintaining said isobutane in excess
Continuous operation
over said propylene in said reaction zone, so
that alkylation is the principal reaction.
Run'No.
l
40
2
Temperature, ° F _______________________________ ._
855
Pressure, lbs. per sq. in ______ _.
2, 500.
. Contact time, minutes _______ ._
10.0
Carbon dioxide, per cent by weight of hydrocarbon
charge ________________________________ ___ _______ _.
0
4- 6
Water. per cent by weight of hydrocarbon charge. _
0
12.2
Ethylene, per cent by weight of liydrocarbon'chargen
Volume per cent of alkylate boiling between 44° C.
6. 4
5. 2
and 54° C.- ______________________ _: ____________ __
a reaction zone under alkylating conditions, in
the presence of a mixture of carbon dioxide and
45 water, and maintaining said isobutane in excess
over said ethylene in said reaction zone, so that
alkylation is the principal reaction.
'
5'. The process of alkylating alkylatable paraf
50. 6
?nic hydrocarbons with ole?nic hydrocarbons,
95+ 50 which comprises contacting an alkylatable par
a?inic hydrocarbon with an ole?nic hydrocarbon,
36. 5
Weight per cent of neohexane in 44-54“ 0. cut of
alkylate _____ _, ________________________________ __
4. The process of manufacturing a high-oc
tane motor fuel, which comprises contacting iso
butane with ethylene, in gaseous phase and in
95+
in gaseousphase and in a reaction zone under al
,
TABLE II
‘
Alkylation of isobutane with‘ propylene to produce
triptane
‘
Continuous operation
Run No
1
2
kylating conditions including a, temperature
varying between about 590° F. and about 850° F.‘
55 and a pressure of at least 500 pounds per square
inch, in the presence of a mixture of carbon di
oxide and water, said carbon dioxide and said
water each being present in amounts varying
between about 3 per cent and about 50 per cent
60 by weight based on the hydrocarbon charge, and
maintaining said alkylatable paraf?nic hydro
carbon in excess over said ole?nic hydrocarbon ’
Temperature, ° F __________ _-
800
Pressure, lbs. per sq. in .... __
4,500 '
Contact time, minutes _____ _.
-._
806
4,600
15.3
16.8
charge.- _________ __‘ ____________________________ __
0
7.0
Water. per cent by weight of hydrocarbon charge _
0
11.5
10.3
10.1
21.5
48.0
Carbon dioxide, per cent by weight of hydrocarbon
'
Propylene, per cent by weight of hydrocarbon
~
charge ___________________________________ __' ____ __
Volume peé cent of alkylate boiling between 76° C.
> and 86°
____________________________________ _-
Volume per cent triptane in 76»86° C. out of
alkylate ___________________________________ __>____
-
-
in said reaction zone, so that aikylation is the
principal reaction.
6. The process of manufacturing a high-oc
tane motor fuel, which comprises contacting an
alkylatabie normally gaseous isopara?inic hydro
carbon with a. normally gaseous olefinic hydro- -
.
11
‘ 6
carbon, in gaseous phase and ma reaction zone
70 under alllrylating conditions including a temper
ature varying between about 590° F. and about
This application is a continuation-in-part ofv
my copending application Serial No. 523,727, ?led
February 24, 1944.
850° F. and a pressure of at least 500 pounds per 7 ~ I
squareinch, in the presence of a mixture of car
bon dioxide and water, said carbon dioxide and
The present invention may be embodied in 75 said water each being present in amounts vary-v
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