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Патент USA US2408330

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2,408,329
Patented Sept. 24, 1946
UNITED ‘STATES PATENT oFFicE
ALKYATION PROCESS
Jacob R. Meadow, Lexington, Ky., assignor to
Socony-Va'cuum Oil Company, Incorporated, a
corporation of New York
,‘No Drawing.
Original application October 9,
1943, Serial No.__505,661. Divided and this ap
plication May 23, 1945, Serial No. 595,492 '
5 Claims. (o1. zoo-683.45
2
This invention relates to the alkylation of par
a?inic hydrocarbons with ole?nic hydrocarbons,
and is more particularly concerned with the cat
alytic alkylation of isopara?inic hydrocarbons
with ole?nic hydrocarbons in the presence of hy-v
dro?uoric acid.
'
trifluoride and the like, of sulfuric acid, of phos
phoric acid, of metal phosphates, of activated
clays,’ and the like. In these processes, the alkyla
tion catalysts are used in amounts varying be
tween about 10% and 200% by weight, on the
charge, depending upon the alkylation catalyst
' It is well known in the art to eifect the union
and conditions used.
of parai?nic hydrocarbons and ole?nic hydrocar
bons by processes broadly called alkylation proc
esses. In alkylation processes, a charge including
that these and similar alkylation catalysts have
a mixture of a parai?nic hydrocarbon called the
However, it would seem
one or more de?nite disadvantages, among which
the most important are promotion of the afore
mentioned secondary reactions and loss oi?v alkyla
tion catalytic activity on the part of the catalyst,
para?inic reactant, and an ole?nic hydrocarbon
relatively rapidly. Notably, the metal halides
called the ole?nic reactant, is introduced into a
form additional compounds with olefinic reac
reaction zone under suitable reaction ‘conditions
of temperature and pressure, referred to as alkyl 15 tants, that ultimately degenerate into tarry
masses that represent loss of catalytic activity of
ating conditions, to yield a product called the hy-.
the alkylation catalysts and loss of potential ole
drocarbon alkylate, which comprises constituents
?nic reactant. Similarly, sulfuric acid causes the
of a saturated character. Since the alkylating
formation of various organic compounds that
conditions cause also polymerization of the ole?n
ic reactant, it is necessary to maintain a relatively 20 ultimately reduce the catalytic activity of the
acid necessitating periodic removal of the sulfuric
low concentration of the ole?nic reactant in the
acid contaminated with thesecompounds, and
charge. Generally speaking, the more severe the
replacement with fresh acid. It must be noted
alkylating conditions, i. e. the higher the tem
further, that sulfuricacid'is a powerful oxidizing
peratures and pressures, the higher the Yield of
hydrocarbon alkylate.v The only limit'to the pres 25 agent and its use, at temperatures above about‘ ‘
125° E, entails extensive undesirable secondary
sure used appears to be the feasibility of main
reactions that consume the acid and the valuable
taining high pressures.’ "On the other hand, the
hydrocarbon reactants. I
‘_ 'i
V
temperature used is limited by the degradation of
Concentrated hydro?uoric acid, when used as
the hyqdrocarbo-n reactants in the charge to low
molecular weight hydrocarbons, and the occur 30 an alkylation catalyst, apparently does not have
these disadvantages. It is a non-oxidizing‘and
rence of secondary reactions, including polymeri
non-reducing substance and hence, it may be
zation of the ole?nic reactant, under high tem
used at elevated temperatures without any of
perature conditions, that substantially reduce the
the undesirable results referred to hereinbefore.
purity of the product obtained,
Alkylation may be conducted at vhigh tempera
tures and pressures, on the order of over 900° F.
and over 4000. pounds per square inch, respec
tively; ormay be carried out at lower tempera
35 Several processes are known in the art for cat
alytically alkyiating para?inic hydrocarbons with
ole?nic hydrocarbons in the presence of hydro
?uoric acid. ‘Generally speaking, the process is
carried out with the hydrocarbon reactants sub
tures and pressures, in the presence of substances _
that facilitate the union‘ of para?inic hydrocar 40 stantially in liquid phase and in the presence of .
suf?cient amounts of hydrofluoric acid to effect
‘bons and ole?nic ‘hydrocarbons, hence called al
substantial saturation of the‘hydrocarbon liquid
kylation catalysts, thereby assuring a high yield
with hydrogen ?uoride.
I
of desired hydrocarbon alkylate by avoiding ex
In some instances, the alkylation catalyst con
tensive degradation of the reactants, the occur
rence of secondary reactions, and appreciable 45 sists of two 'or ‘more of‘ the alkylation catalysts
referred to. Thus, it is known to effect the alkyla- _
polymerization of the ole?nic reactants. The two
tion of paraf?nic hydrocarbons with ole?nic hy
methods are known as thermal alkylation "and
drocarbons in the presence of alkylation catalysts '
as Several
catalyticmethods
alkylation,
arerespectively.
known for the catalytic
consisting of mixtures of sulfuric acid/and hydro
alkylation of para?inic hydrocarbons with ole?nic 50 ?uoric acid, or of mixtures of sulfuric acid and
hydrochloric or hydrobromic acids, or of mix
hydrocarbons. Thus, it is known to carry out the
tures of a metal halide‘ and the corresponding I
alkylation of parai?nic hydrocarbons with ole-'
hydrogen halide.
‘
.
v
'
?nic hydrocarbons in the presence of alkylation
It is also known that certain substances called
catalysts consisting essentially of metal and non
promoters, promote .the catalytic action of al
metal halides, such as aluminum chloride, boron
3
4
kylation catalysts, particularly those consisting
60% of the total charge, on a liquid volume basis‘.
Aqueous solutions of hydro?uoric acid in Which
essentially of metal halides. Accordingly, sev
eral processes have been proposed wherein small
amounts of these promoters, on the order of about
0.5 to 3% by weight, on the charge, are added to
the alkylation catalysts to promote their alkyla
tion catalytic activity.
hydrogen ?uoride is present in concentrations
greater than 80% may be used, but the use of
95% to 100% hydro?uoric acid is to be preferred,
and substantially anhydrous hydro?uoric acid or
hydrogen ?uoride is very effective aS‘an alkyla
'
tion catalyst in the process of my invention.
I have now found that the alkylation catalytic
The reaction temperature may be varied over
activity of anhydrous hydrogen ?uoride may be
appreciably enhanced through the addition of or ,10 a wide range depending upon the paraf?nic re
actant used in the reaction. Generally speaking
ganic or inorganic halogen compounds, excluding
the temperature of reaction varies between about
?uorides, or of elemental halogens, excluding,
0° F. and about 400° F., lower temperatures being
?uorine.
used when the more reactive para?imc or ole
It is an object of the present invention to pro
vide an efficient process for catalytically alkylat
15 ?nic reactants are employed and higher tem
ing para?’lnic hydrocarbons with ole?nic hydro
carbons. Another object of the‘ present inven
peratures becoming necessary when the less re
active paraf?nic or ole?nic reactants are em
tion is to provide an efficient process for cata
ployed. For instance, when the paraf?nic react
ant is isobutane or isopentane, and when the
ole?nic reactant is propylene or butylene, alkyla
ole?nio hydrocarbons in the presence of hydro
tion may be readily effected at temperatures
?uoric acid. A more speci?c object is to provide
varying between about 35° F. and about 100° F.
a process for catalytically alkylating para?inic
Ordinarily, alkylation in the presence of hydro
hydrocarbons with ole?nic hydrocarbons to pro
?uoric acid as ‘the alklation catalyst, is carried
duce high yields of high-octane ‘blendingr agents
for the manufacture of improved motor fuels. A 25 out under super atmospheric pressure, and pres
sures varying between about 20 pounds per square
very important object of the present invention is
inch and 500 pounds per square inch have been
to afford a process capable of carrying out the
found ample in most instances. As a general .
above objects by carrying out the reaction in the
rule, the most suitable pressure is more or less
presence of halogens, other than ?uorine, or of
halogen compounds, other than ?uorides. Other .30 dependent upon the particular temperature in
volved and when high temperatures are em
objects and advantages of the present invention
ployed, pressures as high as 2000 pounds per
will become apparent to those skilled in the art
square inch may ‘be employed, if desired.
from the following description.
In carrying out alkylation of para?inic hydro
Broadly stated, the present invention provides
a ‘process for alkylating para?im'c hydrocarbons .35 bons with ole?nic hydrocarbons, it is well known,
as stated hereinbefore, to maintain a relatively
with ole?m'c hydrocarbons, which comprises con
low concentration of the ole?nic reactant in the
tacting a paraf?nic hydrocarbon and an ole?nic
reaction zone, in order to preclude extensive
hydrocarbon in a reaction zone under alkylating
polymerization of the ole?nic hydrocarbon. Ac
conditions, with an alkylation catalyst consist
ing essentially of anhydrous hydrogen ?uoride, in 40 cordingly, it is advisable to maintain the ole?nic
hydrocarbon concentration in the reaction zone
the presence of organic or inorganic halogen
below about 25% by volume, and preferably, be
compounds, excluding ?uorides, or of elemental
lytically alkylating para?inic hydrocarbons with
halogens, excluding ?uorine.
While it is well known that hydro?uoric acid
.tween about 7% and about 12% by volume. In
continuous operation, this is effected by introduc
is a good alkylation catalyst, see U. S. Patent No.
ing the ole?nic reactant over a period of time
corresponding to the reaction period.
The “reaction period duringwhi-ch the ole?nic
2,267,730, my invention indicates very de?nitely
that halogen compounds, other than ?uorides and
elemental halogens, other than ?uorine, improve
the quality and quantity of the hydrocarbon a1
reactant is introduced into the reaction zone
to react with the paraf?nic reactant to produce
kylate, when these compounds or elemental halo- , ,
the hydrocarbon alkylate, depends upon the
gens are added to the hydrogen ?uoride, before
the alkylation operation is carried out.
temperature, and to a certain extent, upon the
pressure. Ordinarily, a reaction period varying
between 15 minutes and 2 hours is satisfactory.
When a mixture of a paraf?nic hydrocarbon,
At higher temperatures, the time of reaction may
bon such as isobutane, anhydrous or concentrated 55 be as low as 5 minutes and even lower, while at
lower temperatures, the time of reaction may be
hydro?uoric acid, and an olen?nic hydrocarbon
‘as high as 5'hours.
such as isobutylene, is maintained at a reduc
It must be understood, that the reaction vari
tion temperature, a union takes place between the
ables are‘ more or less interdependent, hence
para?inic hydrocarbon and the ole?nic hydro
‘when one is arbitrarily ?xed, the limits within
carbon to produce a higher boiling para?inic hy
which the others may bejvaried, are somewhat
drocarbon which generally represents structural
particularly a low-boiling isopara?‘inic hydrocar
restricted. In any particular instance, the most
desirable conditions can be'readily ascertained
ly, the addition of the ‘original hydrocarbon re
actants. Valuable high-octane blending agents
by one skilled in the art, the preferred ranges of
for the manufacturing of improved motor fuels
may be thus produced. For example,
765 these variables having been indicated hereinbe
0H3
,
l
H
l
CH3
2:
'
HF
CH3 H
CH3
l
CH3—(IJ—H + (‘3: —CH3 -—> CHa—C—-— — -—CH3
CH3
Isobutane
H
Isobutylene
CH3
H
Isooctane
In carrying out the alkylation of para?inic hy
drocarbons with olefinic hydrocarbons in the
presence of hydro?uoric acid as alkylation cata
lyst, the hydro?uoric acid should be used in
70
fore.
, The paraf?nic and. ole?nic hydrocarbons to be
used in my process may be derived from any suit
,able source, as is well known in the art, and may
be usedeither in the pure state or, in admixture
with other constituents not undesirable. The
,paraf?nic and ole?nic hydrocarbons usually em
ployed in the preferred operation of manufac
turing motor fuels will be the normally gaseous
amounts of at least about 10% and up to about 175 para?inic hydrocarbons, except methane and
72,408,329
5
6
ethane, and the normally gaseous ole?nlc hy
5% and ab.out'50% with respect to the amount of
hydrogen _ ?uoride employed. Larger' amounts
~ drocarbons, propylene, butylene‘ and pentene, as
appear to be unnecessary; however, it must be
is well understood in the art. A conventional and
noted thatthey may be employed if desired, al
preferred source of para?inic and ole?nic hydro
carbons is the ?xed gases obtained around petro- 5 though no additional advantages result there
from. The amounts of hydrogen vfluoride addi
leum re?neries. .These ?xed gases may furnish
tives used may be smaller, on the order of 1% to
substantially all the desired para?inic and ole
about 5%, when larger amounts of hydrogen ?uo~
?nic hydrocarbons, or it may be necessary or
ride catalyst are employed. _
'
desirable to obtain additional supplies, as is well
understood. ; Additional ole?nic hydrocarbons, if 10 Numerous experimental data could be-adduced
to'indicate the results obtainable by employing
required, may be formed from a portion of the
para?inic hydrocarbons.
the hydrogen fluoride additives of the present in
vention in the catalytic alkylation of para?inic
hydrocarbons with cle?nic hydrocarbons in the
On the other hand,
' additional amounts of para?inic hydrocarbons
may be admixed in order to increase the concen
~ tration of para?inic hydrocarbons to 2. _desired 15 presence of hydrogen fluoride, but the following
magnitude.
-
examples are su?iciently characteristic:
.
Runl
B11112
Run3
275.
87.
Isobutane, weight in grams ____________________ ._
Isobutylene, weight in grams ____________ __
__
_.
Hydrogen ?uoride, weight in grams _____ ._
Hydrogen ?uoride additive, weight in gram
‘Rum
35.
_ T_butyl-bromide 18.
___
25-30.
Temperature, ° 0
Pressure in pounds per square inch ____________ __
Hydrocarbon alkylate, weight in grams ________ __
. Total octanes 90° C.—l25° 0., weight in grams“.
Isooctane 98° O.—101° 0., weight in grams _____ ._ 39
The‘ octane fraction of the hydrocarbon alkyl
ate produced by my process contains 2,2,4-tri;
methylpentane in predominant amounts, and the
The organic and inorganic halides, other than
?uorides, and the elemental halogens, other than
?uorine, that are used in accordance with the
process of my invention, may be solids, liquids
or gases under normal conditions. It is suspected
that the improved results obtained with those
substances, is probably due more to an ultimate
activation of the ole?nic reactant during the
alkylation operation, than to promoter action on
the hydrogen ?uoride catalyst, although the lat
ter should not be excluded'altogether.‘ What
ever the function of these substances is, the qual
ity and quantity of the hydrocarbon alkylate
are substantially improved through their use. In
view of the relative uncertainty ofthe' n'ii‘nner in
which these substances'function during the al
results of infra-red analysis indicate the presence
also of 2,3,3-trimethylpentane. This octane is
not present in the hydrocarbon alkylates ob
_ tained when the alkylation is conducted in the
3" absence of vmy hydrogen ?uoride additives and
under the conditions outlined hereinbefere. In
fra-red analyses also indicate that the hydrocar
bon alkylates obtained when alkylation is carried
out in the absence of the hydrogen ?uoride addi
40 tives of my invention and under conditions out
lined in the preceding table, contain appreciable
concentrations of unsaturates whichare not pres
ent in the hydrocarbon alkylates obtained in the
process of my invention.
kylation operation, these substances may be re
The present application is a division of copend
ferred to more correctly, as hydrogen ?uoride 45
ing application Serial Number 505,661, ?led Oc
additives, rather than as promoters or as activa
tors.
tober 9, 1943.
.
I
The present invention may be embodied in
The hydrogen ?uoride additives of my inven
other speci?c forms without departing from the
tion include various metallic chlorides, bromides
and iodides, for example, anhydrous calcium '50 spirit or essential attributes thereof, and it is
therefore desired that the present embodiments
chloride; organic halogen compounds, excepting
be considered in all respects as illustrative and
?uorides, such as alkyl chlorides, bromides and
not restrictive, reference being had to the ap
iodides, especially secondary and tertiary halides;
pended claims rather than to the foregoing de
aralkyl halogen compounds, excepting ?uorides;
aliphatic and aromaticiacid chlorides, bromides 55 scription to indicate the. scope of the invention.
and iodides; non-metallic halides, excepting ?u- '
orides, such as phosphorus and sulfur chlorides,
bromides and iodides; hydrogen halides, except
ing of course hydro?uoric acid; and ?nally, the.
halogens themselves, excepting ?uorine.
I claim:
_
1. In a process for alkylating a paraf?nic hy
drocarbon having at least three carbon atoms
with an ole?nic hydrocarbon having at least three
60 carbon atoms, which includes contacting said
I especially prefer to use, as hydrogen fluoride
paraf?nic hydrocarbon with‘ said ole?nic hydro
additives, alkyl chlorides and bromides, particu
larly tertiary alkyl chlorides and bromides and
secondary alkyl chlorides and bromides, hydro
carbon in a reaction zone under alkylating con
ditions, in the presence of a hydrogen ?uoride
alkylation catalyst, and maintaining said paraf
gen halides other than hydro?uoric acid,‘ and hal- 65 ?nic hydrocarbon in excess over said ole?nic hy
ogens other than ?uorine. Speci?c and preferred
hydrogen ?uoride additives. that may be men
tioned by way of non-limiting examples are:
drocarbon in said reaction zone so that alkyla
tion is the principal reaction; the improvement
which comprises contacting said para?inic hy
drocarbon and said ole?nic hydrocarbon with a
tertiary butyl chloride, tertiary butyl bromide,
tertiary amyl chloride, tertiary amyl bromide, iso- 70 hydrogen ?uoride alkylation catalyst in said re
action zone, in the presence of a material selected
propyl chloride, isopropyl bromide, propylene
‘from the group consisting of chlorine, bromine,
chloride, propylene bromide, hydrogen chloride,
and iodine.
I
hydrogen bromide, chlorine and bromine.
The amounts of hydrogen ?uoride additives or
dinarily used in my process, vary between about 75
2; The process of manufacturing high-octane
gasoline, which'comprises contacting a normally
"£408,329
8
gaseous isopara?inic hydrocarbon and a nor
gaseous ole?nic hydrocarbon in said reaction
mally gaseous ole?nic hydrocarbon having at
zone so that alkylation is the principal reaction.
4. The process of manufacturing high-octane
least ‘three carbon atoms in a reaction zone un
der alkylating conditions, with a hydrogen ?uo
ride alkylation catalyst, in the presence of ch10
rine, and maintaining said normally gaseous iso
para?inic hydrocarbon in excess over said nor
mally gaseous ole?nic hydrocarbon in said reac-_
tion zone so that alkylation is the principal
reaction.
3. The process of manufacturing high-octane
gasoline, which comprises contacting a normally
gaseous isoparamnic hydrocarbon and a normally
gaseous ole?nic hydrocarbon having at least
three carbon atoms in a reaction zone under
alkylating conditions, with a hydrogen ?uoride
alkylation catalyst, in the presence of bromine,
and maintaining said normally gaseous isoparaf
?nic hydrocarbon in excess over said normally
gasoline, which comprises contacting isobutane
and isobutylene, in a reaction zone under alkyl
ating conditions, with a hydrogen ?uoride alkyla
tioncatalyst, in the presence of chlorine, and
maintaining said isobutane in excess over said
isobutylene in said reaction zone, so that alkyla
tion is the principal reaction.
5. The process of manufacturing high-octane
gasoline, which comprises contacting isobutane
and isobutylene, in a reaction zone under alkyl
ating conditions, with a hydrogen ?uoride alkyl
ation catalyst, in'the presence of bromine, and
maintaining said isobutane in excess over said
isobutylene in said reaction zone, so that alkyla
tion is the principal reaction.
JACOB R. MEADOW.
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