close

Вход

Забыли?

вход по аккаунту

?

код для вставки
2,409,24?
Patented Oct. 15;, 1946
oNiso STATES PATENT orncs
2,409,247
POLYMERIZATION PROCESS
John W. Brooks, Wenonah, and Arlie A. O’Kelly,
Woodbury, N. 3., and Robert H. Work, Phila
delphia, Pa., assignors to Socony-Vacuum Oil
Company, Incorporated, a corporation of New
York
No Drawing. Application December 30, 1943,
Serial No. 516,243
7 Claims. (Cl. 2260-68315)
I
This invention relates to the polymerization of V
hydrocarbons, and is more particularly concerned
with the provision of a catalyst suitable for cata
lyzing the polymerization of hydrocarbons.
It is well known in the art, to effect a union
between molecules of an unsaturated hydrocarbon
to produce a compound, called a polymer, the
2
catalytically polymerizing ole?nic hydrocarbons.
A very important object of the present invention
is to afford a process capable of carrying out the
above objects by using a new polymerization cata
lyst. A more speci?c object is to provide a new
polymerization catalyst that can be readily and
efficiently prepared. Other objects and‘advan
tages of the present invention will become ap
molecular weight of which, is an even multiple of
parent to those skilled in the art from the fol
the molecular Weight of the original hydrocar
Icon. The operation is called polymerization and 10 lowing description.
Broadly stated, the present invention provides
the conditions of temperature, pressure, etc., are
a process for eiiecting the polymerization of ole
called polymerizing conditions. Under suitable
?nic hydrocarbons, which comprises contacting
conditions, the union may also take place among
the reactants in a reaction zone under polymeri
molecules of two or more different unsaturated
zation conditions, with the mixture resulting from
hydrocarbons, to produce compounds that repre
the action of anhydrous hydrogen ?uoride on
sent additions of the two or more hydrocarbons.
phosphorus pentoxide.
'
The compounds thus produced are referred to as
The new polymerization catalyst of our in
copolymers as distinguished from the compounds
vention, therefore, is the mixture of reaction
obtained when unsaturated hydrocarbons con
dense with themselves, and the operation is called 20 products obtained by reacting anhydrous hydro
fluoric acid with phosphorus pentoxide. The re
copolymerization. In the interest of brevity, poly
action produces what is believed to be a mixture
merization and copolymerization will be referred
of phosphoryl ?uoride and metaphosphoric acid,
to hereinafter, broadly as polymerization, and
and is believed to proceed in accordance with
the conditions of temperature, pressure, etc., will
‘
be referred to, accordingly, as polymerizing con 25 the following equation: .
ditions, it being clearly understood, that the na
ture of the union will become apparent to those
The reaction may be carried out in a number'of
versed in the art, from the character of the re
ways, but our preferred procedure is to pass an
actants used in any particular reaction.
hydrous hydrofluoric acid into phosphorus pent
As is well known to those familiar with the 30
oxide. Since much heat is evolved during the
art, polymerization reactions of the type referred
ensuing reaction, it is necessary to cool and stir
to hereinbefore, may be conducted at relatively
the mixture well during the addition of the hy
high temperatures and pressures; or may be car
drogen fluoride. The addition of a ‘saturated hy
ried out at lower temperatures and pressures, in
the presence of substances or of mixtures of sub 35 drocarbon or of a mixture of saturated hydro
carbons to the phosphorus pentoxide, before
stances, that facilitate the polymerization reac
the addition of hydrogen ?uoride, aids in the
tion. These substances are referred to as poly
preparation of the catalytic mixture. The hy
merization catalysts or copolymerization cata
drocarbon or hydrocarbon mixture forms a layer
lysts, depending on the type of reaction they
over the phosphorus pentoxide thereby prevent
catalyze; or in keeping with the terminology
ing contact between the phosphorus pentoxide
established herein, they may be referred to
and the moisture in the ambient atmosphere,
broadly, as polymerization catalysts. Several
whereby, formation of hard aggregates is elim
substances have been proposed as polymeriza
inated and stirring is facilitated.
tion catalysts, and among the most widely used
are phosphoric acid, sulfuric acid, hydrogen 45 The amounts of the catalytic mixture-used in
our process, vary between about 5% and about
?uoride, aluminum chloride and boron tri
?uoride.
We have now found that the mixture result
ing from the action of anhydrous hydrogen ?uo
ride on phosphorus pentoxide is an effective poly
merization catalyst.
It is an object of the present invention to pro
vide a process for catalytically effecting the poly
merization of unsaturated hydrocarbons. An
other object is to provide an efficient process for
50%, with respect to the weight of the hydro
carbon reactants in the charge. Larger amounts
may be used, if desired, although no additional
50 advantages seem to result therefrom.
V
The catalytic mixture resulting from the re
action between anhydrous hydrogen ?uoride and
phosphorus pentoxide may be used to catalyze
reactions involving polymerization or ,copoly
' merization of normally gaseous ole?nic hydro
2,409,247
3
carbons, propene, butenes and pentenes, to pro
tween the diluents and the ole?nic hydrocarbons
duce polymers or copolymers, that boil within
involved in the polymerization operation. The
relatively low temperatures used in our proc
the boiling range of motor fuels. These prod
ucts are highly desirable in view of their high
ess, and the relatively high iodine number of
octane ratings, and accordingly, the use of our 5 the products obtained, are proof that very little
catalytic mixture in the polymerization processes
alkylation, if any, occurs.
for manufacturing high octane motor fuels, must
The amount of saturated hydrocarbon dilu
ent used, ordinarily varies between about 50%
and about 95%, with respect to the weight of
The ole?nic hydrocarbons to be used in our 10 the ole?nic hydrocarbons in the charge.
be considered a preferred embodiment of our
invention. -
process may be derived from any suitable source,
as is well known in the art. A conventional and
preferred source of the hydrocarbons used in the
In our process, the polymerization operation
may be carried out in several ways. For exam
ple, when the reaction involves copolymerization,
preferred operation of manufacturing motor fuels,
one of the ole?nic reactants may be pumped into
is the ?xed gases obtained around petroleum
a mixture of the catalytic mixture, the other ole
?nic reactant, and a saturated hydrocarbon di
re?neries, as is well understood in the art. These
hydrocarbons may be used either in the pure
luent, where desirable; or, a mixture of the ole
state or in admixture with other constituents not
?nic reactants may be pumped into a mixture
of .our catalytic mixture and a mixture of sat
undesirable. In this connection, it must be noted
that when the polymerization reaction involves
urated hydrocarbon diluents; or, a mixture of
for example, polymerization or copolymerization
the ole?nic reactants and diluent may be pumped
of the normally gaseous ole?nic hydrocarbons in
into a reaction zone containing the catalytic mix
the preferred embodiment of our invention, the
ture.
manufacture of motor fuels, under the polymeriz
In the process of our invention, the tempera
ing conditions extant in the reaction zone and 25 ture to be used usually varies between about 0°
in the presence of our catalytic mixture, it is
C. and about 60° C., and preferably, between
difficult to control the degree of polymerization
about 18° C. and about 30° C. The pressure to
or copolymerization, with the result that the prod
be employed depends upon the temperature used,
uct obtained contains large amounts of polymers
and ordinarily, a pressure su?‘lcient to maintain
and copolymers, that have boiling points outside 30 the reactants in the liquid phase at the tempera
the boiling range of motor fuels.
ture employed, is adequate. The reaction pe
riod, whether the condensation operation in
We have found also, that the degree of poly
volves polymerization 0r copolymerization, de
merization or'of copolymerization of the ole?nic
hydrocarbons in the presence of our novel poly
pends, of course, upon the temperature, and to a
merization catalyst, may be controlled through
certain extent, upon the pressure. Ordinarily,
a reaction period varying between about one min
the use of a saturated hydrocarbon diluent, there
by insuring a product that will contain predomi
ute and 30 minutes is satisfactory.
nantly, constituents that boil Within the boiling
It must be understood, of course, that the re
range of motor fuels. Accordingly, the charge
action variables are more or less interdependent,
stock of our process may consist of a re?nerv 40 hence, when one is arbitrarily ?xed, the limits
within which the others may be varied are some
C4-cut, containing 44% isobutene, 13.4% 1- and
2-butenes, 1% propene. and the balance mainly
what restricted. In any particular instance, the
normal butane and isobutane. In general, com
most desirable conditions can be readily ascer
pounds or mixtures of compounds that are inert
tained by one skilled in the art, the working
under the polymerizing conditions of our proc 4 ranges of these variables in the preferred op
ess, and that can be easily separated and re
moved from the product, if desired, are suitable
eration of our process for the manufacture of mo
tor fuels, having been indicated hereinbefore.
diluents. Accordingly, parafiinic hydrocarbons
Numerous experimental data could be adduced
have been found to be very effective diluents of
to indicate the results obtainable in accordance
this type. Para?lnic hydrocarbons that are suit 50 with the process of the present invention, but the
able diluents in the preferred embodiment of
following runs are sufficiently characteristic:
our invention, i. e., the manufacture of motor
Example 1
fuels, comprise propane, normal butane, isobu
A mixture of 300 grams of mixed amylenes and
tane, normal pentane and isonentane, and mix
ture thereof. It must be understood, of course, 55 200 grams of catalytic mixture was placed in an
that para?inic hydrocarbons such as hexane. hep ' autoclave and stirred. The temperature of the
mixture increased rapidly and could not be con
tane, octane and the like, may be used if desired;
however, and by way of example, if the product
trolled. The product consisted predominantly,
of high-boiling unsaturated hydrocarbons.
contains cv-ole?nic hydrocarbons, the diluent, if
heptane, can be separated and removed there 60
Example 2
from with dif?culty. On the other hand, if not
objectionable. the diluent or diluents may be left
300 grams of mixed amylenes were pumped
in the product. In commercial applications of
over a period of one hour, into an autoclave con
our process, the charge stock containing the ole
_ taining a mixture of 1206 grams of isobutane and
?nic hydrocarbons to be polymerized or copoly 60 200 grams of catalytic mixture, while the mixture
merized, may contain also the necessary diluent
was being stirred. Stirring was continued for 30
or diluents. Thus, in a charge stock containing
minutes after the amylene was added. The tem
light ole?nic hydrocarbons and higher paraf?nic
perature of the reaction was kept at 18° C.-24° C.
hydrocarbons, the higher para?inic hydrocarbons
The debutanized product weighed 300 grams. 5%
will act as the diluent and if not objectionable 70 of the debutanized product boiled below 41° C.,
for the intended use of the product of the poly
85% boiled between 41° C. and 210° C., and 15%
merization operation, may be left in the product.
above 210° C. The iodine number of the fraction
It must be observed, that the desirable effect
boiling between 41° C. and 210° C. was about 200
produced through the use of these diluents, is
and had an octane number of 97.2, by the re
not to be attributed to an alkylation reaction be 75 Search method.
>
2,409,247
6
5
ing normally gaseous ole?nic hydrocarbons with
said reaction mixture, in the presence of paraf
The present invention may be embodied in
other specific forms without departing from the
spirit or essential attributes thereof, and it is
therefore desired that the present embodiments
?nic hydrocarbon material, in said reaction zone
under polymerizing conditions including temper
atures varying between about 18° C. and about
30° C.
be considered in all respects as illustrative and not
restrictive, reference being had to the appended
claims rather than to the foregoing description
to indicate the scope of the inventiorn
We claim:
1. The process of polymerizing ole?nic hydro
carbons, which comprises establishing a reaction
zone; reacting outside said reaction zone, anhy
drous hydro?uoric acid with phosphorus pentox
ide, to yield a reaction mixture; and contacting
ole?nic hydrocarbons with said reaction mixture,
in said reaction zone under polymerizing condi
tions including temperatures varying between
about 0° and about 60° C.
2. The process of polymerizing ole?nic hydro
carbons, which comprises establishing a reaction
zone; reacting outside said reaction zone, anhy
drous hydro?uoric acid with phosphorus pentox
5. The process of manufacturing high-octane
motor fuel, which comprises establishing a reac
tion zone; reacting outside said reaction zone, an
10
hydrous hydro?uoric acid with phosphorus pent
oxide, to yield a reaction mixture; and contacting
normally gaseous ole?nic hydrocarbons with said
reaction mixture, in the presence of para?inic hy
drocarbon material selected from the group con
sisting of propane, butane, pent-ane, isobutane
and isopentane, in said reaction zone under poly
merizing conditions including temperatures vary
ing between about 0° C. and about 60° C‘.
6. The process of manufacturing high-octane
motor fuel, which comprises establishing a reac
tion zone; reacting outside said reaction zone, an
hydrous hydro?uoric acid With phosphorus pent
oxide, to yield a reaction mixture; and contacting
ide, to yield a reaction mixture; and contacting
normally gaseous ole?nic hydrocarbons with said
ole?nic hydrocarbons with said reaction mixture,
in said reaction zone under polymerizing condi 25 reaction mixture, in the presence of paraffinic hy
drocarbon material selected from the group con
tions including temperatures varying between
sisting of propane, butane, pentane, isobutane ’
about 18° C. and about 30° C.
and isopentane, in said reaction zone under poly
3. The process of manufacturing high-octane
merizing conditions including temperatures vary
motor fuel, which comprises establishing a reac
ing between about 18° C. and about 30° C.
tion zone; reacting outside said reaction zone, an
'7. The process of manufacturing high-octane
hydrous hydro?uoric acid with phosphorus pent
motor fuel, which comprises establishing a reac
oxide, to yield a reaction mixture; and contact
tion zone; reacting outside said reaction zone, an
ing normally gaseous ole?nic hydrocarbons with
hydrous hydro?uoric acid with phosphorus pent
said reaction mixture, in the presence of paraf
?nic hydrocarbon material, in said reaction zone 35 oxide, to yield a reaction mixture; and contacting
a Ctr-re?nery cut with said reaction mixture, in
under polymerizing conditions including temper
said reaction zone under polymerizing conditions
atures varying between about 0° C. and about
including temperatures varying between about 18°
60° C.
C. and about 30° 0.
4. The process of manufacturing high-octane
JOHN W. BROOKS.
motor fuel, which comprises establishing a reac
ARLIE A. O’KELLY.
tion zone; reacting outside said reaction zone, an
ROBERT H. WORK.
hydrous hydro?uoric acid with phosphorus pent
oxide, to yield a reaction mixture; and contact
Документ
Категория
Без категории
Просмотров
0
Размер файла
439 Кб
Теги
1/--страниц
Пожаловаться на содержимое документа