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Патент USA US2405995

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Aug. 2G,PROCESS
w46. FOR DEAROMATIZING
R. E. BURK
AN
D MODIFYING HYDRocAfíBoNswITH
HYDROGEN FLUORIDE AND BORON TRIFLUORIDE
Filed March 6, 1944
Patented Àug. 20, i946
2,405,995
STATI-:s PATENT OFFICE
UNlTE.
2,405,995
PROCESS FOR DEAROMATIZING AND MODI- `
FYING HYDROCARBON S WITH HYDROGEN
FLUORIDE AND BORON TRIFLUORIDE
Robert E. Burk, Cleveland Heights, Ohio, assign
or to The Standard Oil Company, Cleveland,
Ohio, a corporation of Ohio
l
Application March 6, 1944, Serial No. 525,300
15 Claims. (Cl. 19.6-9)
2
This invention relates to the dearomatization
the hydrocarbons in a liquid phase in the pres
of hydrocarbon fractions and the subsequent cat- .
ence of a catalyst in a liquid- phase.
alytic modification of the dearomatized fraction.
Another object of the invention is the provision
More particularly the invention relates to de
of a process in which fluorides containing the
aromatizaticn using primarily liquid hydrogen Ul impurities present in commercial grades may be
fluoride containing a minor proportion of boron
used as the catalyst.
trifluoride to remove the aromatics, following
Still a further object of the invention is the
which the dearornatized hydrocarbon fraction
provision of a process which may be carried out
may be modified catalytically using primarilyrhy
under conditions of temperature and pressure not
drogen fluoride promoted by a minor proportion
materially lower nor higher than can be obtained
of boron trifluoride as the catalyst. The inven
conveniently in ordinary plant and refinery oper
tion contemplates the use of the spent catalyst
ations such as currently practiced.
from the catalytic modifying reaction for the re
' The invention has as a further object the pro
moval of aromatics from the hydrocarbon frac
vision of a process in which the activity of the
tion to be catalytically modified.
catalyst, both in the dearomatizing action and in
A preferred and important embodiment of the
the catalytic modifying reaction, may be con
invention comprises the dearomatization of
trolled by variations in temperature, pressure and
stocks heavier than gasoline, following Which
other factors ordinarily available, and also can
these stocks are “averaged” with a light hydro
be controlled readily by means of variations in
carbon to form an intermediate hydrocarbon, 20 the amount of the boron trifluoride constituent of
such as gasoline, from a net consumption of both
the catalyst.
of said heavier and light fractions.
It is one of the objects of the invention to de
aromatize a hydrocarbon fraction, prior to modi
lowing description taken in connection with the
fying it catalytically, utilizing hydrogen fluoride
The invention will be understood from the fol
drawing which illustrates a preferred form of the
25 invention in a diagrammatical flow-sheet.
and a minor proportion of boron triñuoride to
Hydrogen fluoride boils at about 67° F. and is
remove aromatics, and without any subsequent
therefore a liquid at temperatures just under
treatment of the hydrocarbon fraction to remove
room temperature and may be kept liquid at
any of the fluorides that may remain in the frac
higher temperatures by moderate pressures. The
tion, prior to the catalytic treatment to modify 30 temperatures and pressures used are conveniently
the same.
those that maintain the hydrogen fluoride liquid.
A further object of the invention is to dearoma
Boron trifluoride boils at _150° F. and is a gas
tize a hydrocarbon fraction, prior to treating the
at the temperatures and pressures conveniently
same with a catalyst, utilizing the spent catalyst
employed in hydrocarbon treating processes,
from said catalytic treatment for dearomatizing 35 However, boron trifluoride dissolves in liquid hy
the said fraction.
drogen fluoride to a given extent and the amount
A further object of the invention is to accom
that dissolves at any given temperature depends
plish the dearomatization and catalytic modifica
on the partial pressure of boron trifluoride. At
tion in a countercurrent process in which the
higher partial pressures, a larger amount of boron
hydrocarbon feed is first contacted with the spent
trilluoride is dissolved.
catalyst exiting from the process, and last con
The boron trilluoride in the hydrogen fluoride
tacted with the catalyst entering the process,
in the liquid phase possibly may react at least to
whereupon the reaction of the hydrocarbons en
some extent, but an understanding of the chem
tering the process is primarily one of dearomati
istry involved is not necessary to practice the in
zation and the hydrocarbons leaving the process 45 vention, and I do not intend to be bound by any
is primarily one of catalytic modification, such
theory. At any event, the amount of the boron
as averaging.
trifluoride in the hydrogen fluoride is a function
Still a further object of the invention is to de
of the partial pressure of the boron triiluoride at
aromatize heavier hydrocar-bon fractions and then
any given temperature. The amount of boron
average the dearomatized fraction with a light 50 trifluoride dissolved in the hydrogen fluoride, at
hydrocarbon, such as butane, utilizing a material
any given temperature, may be expressed conven
of similar or identical composition to accomplish
iently in terms of the partial pressure of boron
both processes.
trifluoride. The Words “dissolved” and “solu
Still a further object of the invention is to
tion” are used as generic to both a physical ad
carry out all of the actions indicated above with 55 mixture and a reaction product,
2,405,995
3
It has been discovered that a wide variety of
hydrocarbons may be modiñed catalytically as to
4
cumulation of these hydrocarbons in the catalyst
decreases its activity to such an extent that it is
no longer economically feasible to continue using
the catalyst. This is particularly so if the stock
la1` weight may be altered or their chemical con
contains a significantly large amount of aro
figuration changed, or both, or they may be re
matics. If desired, the spent catalyst may be
acted with other hydrocarbons by subjecting the
regenerated by any of the processes described
hydrocarbons to a liquid catalyst comprising liq
hereinafter, that is the fluorides may be sepa
uid hydrogen fluoride
which is contained a
rated from hydrocarbons and the fiuorides re
minor proportion of boron trifluoride under a
positive partial pressure of Y boron trifluoride. 10 used.
their hydrocarbon content, that is their molecu
Such processes, for example, include “averaging" .
In accordance with the invention, it is possible
to use substantially the same material that is
used as a catalyst in the averaging reaction to act
kerosene or higher naphtha, may be reacted with
as an extracting material for the removal of aro
a. light hydrocarbon, such as a butane, to produce
hydrocarbons intermediate said light and heavier 15 matics from the heavier hydrocarbon fraction
being used in the averaging reaction. In accord
hydrocarbon fractions, such as gasoline, and
ance with this operation the heavier fraction is
which results from a net consumption of both
subjected >to a liquid material comprising liquid
fractions. Other reactions that may be accom
in which a heavier hydrocarbon fraction, such as
plished include, for example, isomerization,
hydrogen fluoride containing dissolved boron tri
cracking, alkylations, etc. The process of aver 20 fluoride, under pressure, temperature and other
lconditions to be pointed out more particularly
aging is typical of a catalytic reaction in which
hereinafter. Following this the mixture is set
tled and the dearomatized heavier fraction will
comprise the upper laye1` and the lower layer will
25 comprise the iluorides in the liquid phase in which
the aromatics are contained. These two layers
In carrying out the averagingïreactiona higher
can be settled, and the dearomatized heavier
boiling fraction, such as kerosene, and the lower
fraction may then be transferred to the averaging
boiling fraction, such as a butane fraction, are
reaction zone.
contacted with each other in the presence of the
liquid catalyst under conditions of temperature 30 Y A small amount of the fluorides may be soluble
in the upper hydrocarbon layer. It is significant
and pressure for a length of time and under other
the liquid fluoride catalyst may be used, andîwill
be further referred to as illustrative in connec
tion with a more detailed explanation of. the in
vention.
'
’
,
,
conditions as will be pointed out more particu
larly hereinafter. At the conclusion of the treat
ment, the hydrocarbons >and the liquid catalyst
to note that it is not necessary to remove these
prior to the treatment of the heavier fraction
in the averaging reaction, since the same ma
may be settled in two phases. 4The hydrocarbons 35 terial is there used as the catalyst. This is to
be distinguished from processes where another
comprise the upper or lighter layer. The liquid
material may be used as a catalyst, which would
catalyst comprises the heavier layer; because it
be adversely affected by the presence of the ñu
separates as the lower of the two layers, it is often
orides; it is also to be distinguished from proc
referred to hereinafter as the “lower layer.”
In the catalytic hydrocarbon modifying proc 40 esses in which another material may be used for
extracting aromatics which would adversely affect
esses, such as averaging, where one or more or
the later catalytic reaction or the ñuorid‘es if
all of the hydrocarbon fractions entering into the
not completely removed from the raffinate.v
reaction contains aromatics, the catalyst is de
In accordance with the preferred embodiment
activated by any substantial amount of aromatics
of the process, it has been discovered that al
present. This is particularly troublesome since
though the spent catalyst from the averaging re
kerosene and Vnaphtluas, whichare often used in
action may be deactivated during averaging inso
averaging, may contain a suiiiciently large pro
far >as the averaging reaction is concerned, it-is
portion of aromatics to deactivate the catalyst
still active for extracting aromatics from the
'during the averaging process. Extended studies
have shown that the aromatics present in an Illi 50 heavier hydrocarbon fraction. In accordance
with this embodiment, therefore, it is possible to
‘ nois kerosene to the extent of 17% greatly retard
Yuse the fresh catalyst for the averaging of de
the averaging reaction. While this can be over
aromatized kerosene and butano, for example,
come for some purposes by using a larger amount
until the catalyst becomes deactivated for the
of the catalyst, i. e., so that there will be suffi
cient catalyst to accomplish the catalytic opera 56 averaging reaction to an extent which justifies
its replacement. This spent catalyst may then
_ tion in addition to that which is deactivated by
be used for the treatment of the heavier hydro
the aromatics, this procedure is not as desirable
carbon fraction feed stock containing aromatics,
in many instances as a preliminary dearomatiza
in order to dearomatize the same, and the feed
tion of the stock containing the aromatics. The
stock thus dearomatized may then be fed to the
aromatics for the most part leave the hydrocar
averaging reaction zone. It will be readily ap
bon phase and go into the lower layer.
During the averaging reaction, hydrocarbons
_ tend to accumulate in the catalyst phase.
These
are thought to comprise primarily unsaturates
parent that such a. process may be carried out
conveniently in a countercurrent operation, either
of a truly continuous type, or in a semi-contin
uous process, involving a plurality of stages.
The catalyst phase left from the dearomatiza
light fraction feeds, or unsaturates which may be
tion, irrespective of whether it was fresh ñuo
formed during the averaging process, and which
rides or the spent catalyst from the averaging
go into the catalyst `phase rather than react in
reaction, in which the aromatics have accumu
the averaging reactions. I_f the stock is not suf
iiciently dearomatized, aromatics may also ac 70 lated during the dearomatization, may be regen
erated by separating the iiuorides from the hy
cumulate in the catalyst phase. The presence of
drocarbons in accordance with any of the regen
any aromatics, and the presence of unsaturates
erating methods described hereinafter. The re
beyond the point where they function as an ac
which may be present in either the heavier or
generated _ñuorides may be recycled either to the
tivator, in the catalyst phase has a poisonous, ef
fect upon the catalyst and eventually theV ac--y 75 4averagingV or dearomatization. The hydrocar
alioaoos
Y
6
n
bons separated duringV the regeneration may be
0.8% of hydrocarbons lighter than C4, 53.2% bu
processed such as by cracking, hydrogenation,
tanes of which 54.4% was isobutane.
etc., or used as fuel.
drocarbons boiling within the range of 70° to300°
F. amounted to 21.6%. The hydrocarbons boil
ing within the range of 300° to 400° F. amounted
t0 3.4%, and those boiling above 400° F. amount
.
The action of the iiuorides in removing the
aromatics, strictly speaking, is not one of ca
talysis. The process is more in the nature of
an extraction.. For convenience, however, the
The hy
liquid hydrogen fluoride containing boron tri
ed to 10.2%. 8.6% of hydrocarbons was found
in the catalyst phase. Experimental loss in the
fluoride is referred to herein as a catalyst even
handling of the material, amounting to 2.2%, is
10 unaccounted for. Calculations showed that about
when used for dearomatization.
The following examples are given merely as
11% of the butane feed entered into the reac
tion. The recovered butane fraction and the
illustrative of the manner in which a heavier
fraction boiling above 300° F. may be recycled to
fraction maybe dearomatized prior to averaging
the averaging zone, resulting in a net consump
with butane. 'I‘he percentage of arcmatics is that
tion of 39.2% of the charge. Of this, 55% is
converted into hydrocarbons in the gasoline range.
determined by the Kattwinkel test.
Example 1
Eœample 5
A kerosene containing 18% aromatics was
treated with 10 volume per cent of hydrogen flu
oride and an amount of boron trifluoride to pro
vide a partial pressure of 150 pounds per square
A kerosene containing 16-18% aromatics was
treated with 16 volume per cent of liquid hydro
gen fluoride based upon the kerosene and an
amount of boron trifluoride to provide a partial
pressure of 150 pounds per square inch. The
treatment was continued for 15 minutes with
agitation at a temperature of 90° F. The raffinate
was found to contain 6% aromatics. The raf
inch. The treatment was continued at 90° F.
for a period of 15 minutes. The hydrocarbon
phase was separated from the fluoride phase.
The amount of aromatics in the raiiînate was
reduced to 6%.
ñnate from the above dearomatization, without
Example 2
any removal of fluorides dissolved or otherwise
contained therein, was then mixed with a butane
The same kerosene stock was treated with 20
volume per cent of hydrogen fluoride and an *
amount of boron trifiuoride to provide a partial
pressure of 50 pounds per square inch. The ac
tion was continued for 15 minutes at 90° F. The
raflinate contained 7% aromatics.
Example 3
fraction in the proportions of 57% by weight
of the butane fraction and 43% of the raíiinate.
The amount of isobutane in the butane fraction
was 52.6%. All of the rañ'inate boiled above 300°
F. The mixture was subjected to a catalytic
35 treatment with 100 volume per cent of hydro
gen fluoride (based on the hydrocarbons) and an
amount of boron trifluoride to provide a partial
pressure of 150 pounds per square inch. The
cent hydrogen fluoride and boron trifluoride in
total pressure was 250 _pounds per square inch.
an amount to provide a partial pressure of 150 40
The reaction was continued for 15 minutes at a
pounds per square inch. The treatment was
temperature of 120° F. The hydrocarbons were
continued for 15 minutes at 90° F. and the raf
separated from the catalyst phase and upon frac
ñnate was found to contain 3% aromatics.
tionation were found to contain 0.4% of C3 or
The above examples illustrate an embodiment
lower hydrocarbons,55.3% butanes, of which about
of the invention using fresh ñuorides in the de
60% was isobutane, 15.4% boiling in the gasoline
arornatization. From these examples it will be
range (from isopentane to 300° F.) and 20.8%
seen that thearnount of hydrogen iiuoride and
boiling above 300° F. The catalyst phase com
the partial pressure of the boron trifluoride may
prised 8.1%. Based upon the rafiînate charged,
be adjusted to reduce the aromatic content of
the hydrocarbons to the various levels as found 50 the yield of gasoline was 36%. If desired, the
The same stock is treated with 30 volume per
desirable in the catalytic operation using the de
aromatized kerosene. Depending upon the eco
nomics involved, a point will be reached where
the increased amount of catalyst required to re
duce further the aromatics is not reflected in an 55
improvement in the catalytic reaction.
Example 4
unreacted butanes and the products boiling above
_300° F. may be recycled. Based upon the hydro
carbons not recyclable, the yield of gasoline was
64%.
Example 6
The same kerosene was dearomatized in accord
-ance with the same process as that described in
'Example 5 and averaged With butane under the
same conditions, except that the reaction time
A butane fraction containing 15.7% isobutane
was averaged with a Pennsylvania kerosene de 60 was 30 minutes and the total pressure was 260
pounds per square inch. The butane fraction
aromatized by any of the above processes and
charged was 58.4%, of which 50% of this frac
containing about 2% aromatics. The Volume of
tion was isobutane. The raffinate charged was
the butane' fraction based on the kerosene was
41.6%, all of which boiled above 300° F. Of
200% and the weight of the kerosene based on
the products obtained, 1.0% was Cs or lowerhy
the total hydrocarbon charge was 40.6%. The
amount of the hydrogen ñuoride based on the ~ drocarbons, 57.4% were butanes, 58% of which
total hydrocarbon charge was 33.7 volume per
was isobutane. The fraction boiling in the gaso
line range was 16.6% and the hydrocarbons boil
cent, and the amount of the boron triiiuoride
was such as to provide a partial pressure of 150
ing above 300° F. amounted to 17.1%. The cata
pounds per square inch. The total pressure was 70 lyst phase contained 7.9%.
200 pounds per square inch. The hydrocarbons
The yield of gasoline, based on the rañinate
and the catalyst were agitated under these con
used was 40%, and the yield of gasoline, based
ditions at a temperature of 90° F. for one hour.
on the hydrocarbons, not recyclable to the aver
The hydrocarbon phase, upon its separation from
aging reaction zone in a continuous process,
the catalyst was found to contain, by weight, 75 amounted to 65%.
'
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2,405,995
7
Example 7
As illustrative of a continuous process in which
the spent catalyst from the averaging reaction is
used to dearomatize the heavier hydrocarbon feed
stock for an averaging process, a fraction of
V The proportions of the heavier and light frac
tions should be one mol of the heavier fraction
to at least one Kmol of the light fraction. When
using butanes, 2 to 4 mols of butane per mol of
the heavier fraction is preferred. No appreciable
economic advantage accrues from the use of more
than V6 mols of butano, although as high as 10
crude, boiling between 50° and 550° F. and con
taining 10% aromatics. was utilized as the heav
mols or more may be used if desired for other
ier fraction. To start the process, the crude was
extracted with 10 volume per cent liquid hydro 10
The unreacted light fraction may be recycled
gen fluoride and an amount of boron trifluoride
to the averaging reaction zone and the net feed
lto provide a partial pressure of 150 .pounds per
of'the light fraction need be only that consumed
square inch. Dearomatization was continued for
in the reaction. This may be a normal hydrocar
15 minutes at 90° F. and the amount of aromatics
bon. The light hydrocarbon which does not enter
in the raiiinate was reduced to 5 % .
15 into the averaging reaction may be isomerized to
The raflinate was then averaged with butane,
a large extent and the recycle stock may be
the amount of butane charged being 58.4% and Y
predominately vthe isomer. This is advantageous
the amount of raninate charged being 41.6%.
under some conditions. A portion or all of the
The butane fraction comprised 29% isobutane.
isomer may be withdrawn and the balance re
The reaction Was continued for V30 minutes at a 20 cycled. The withdrawn portion may be replaced
temperature of 90° F. The catalyst used com
by fresh feed which may be a normal hydrocar
prised 100 volumes per cent hydrogen fluoride
bon. Thus, normal butane may be isomerized
(based on -the hydrocarbons) and an amount
simultaneously with the averaging.
of boron trii‘luoride to provide a partial pressure
An oleñn may be included in a small amount
of 150 pounds per square inch. The total .pres 25 in either fraction and Jthe presence of the same
sure was 250 pounds per square inch. The mix
in an amount of 1 to 10%, and not over 25%,
ture was settled and the hydrocarbon phase was
based on the total hydrocarbons acts as a pro
found to contain 57% butane, and 0.7% of C3 or
moter. Too large an amount acts to poison the
lower hydrocarbons. 'I'he fraction boiling in the
catalyst.
gasoline range (isopentane to 300° F.) amounted 30
The conditions under which the dearomatiza
to 25.1%. Of .this fraction 13.5% was isopentane,
tion and the averaging or other catalytic opera
although none was contained in the dearomatized
tions are carried out, may overlap to a large ex
crude. The fraction boiling above 300° F. was
tent and under some conditions may cover about
reasons.
14.2%. The catalyst phase contained 3.0%.
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'
i
the same range. In general, the averaging tem
’ The spent catalyst from the above averaging 35 perature may vary from -30° to 400° F. and the
reaction was utilized to dearomatize an addi
dearomatizing temperature from -30 to 300° F.
tional quantity of the same crude stock, boiling
Preferably the same or different temperatures
between 50° and 550° F. and containing 10% aro
within the range of 32° to 212° F. may be used
matics. The crude was treated with the spent
in rthe dearomatizing and averaging. It is an
catalyst at a temperature of 90° F. for a .period 40 advantage that extreme temperatures in either
of 15 minutes in the presence of suiiicient boron
direction are not necessary. The temperature
trii'luoride to provide a partial pressure of 150
should be adjusted with reference to the amount
pounds per square inch. The aromatics were re
of catalyst, and the partial pressure of boron tri#
duced from 10 to 3%. The fraction dearomatized
fiuoride and other conditions. A single tempera
with the spent catalyst was then averaged with 45 ture may be used in the averaging and in the
butane under conditions indicated heretofore in
dearomatizing, or it may be varied during either
the example.
or both of these actions. The temperature also
In the dearomatizing process, any fraction may
may be dependent upon the activity of the cata
be treated which contains aromatics, i. e., a frac
lyst. For example, a fresher catalyst in the aver
tion with constituents boiling above about 175° F. 50 aging or one having a higher boron trifluoride
For the most part, such fractions are formed
content may be used with' a lower temperature.
from parañins but they may contain naphthenes,
In the dearomatizing the temperature may be
unsaturates, etc., as Well as aromatics. The
adjusted with reference to the extent to which
exact chemistry involved in the removal of the
the catalyst is spent and the amount of aromatics
aromatics is not entirely understood, but it is
to be removed.
thought that the aromatics form a loose chemical
The amount of fluorides employed must be con
complex with the ñuorides at the temperatures
sidered with reference to both of the fluoride in
used which is miscible in the liquid fluoride layer.
gredients. The amount of hydrogen iiuoride may
The complex can be dissociated at high ytempera
be from 5 to 300 volume per cent, based on the
tures and the iluorides liberated.
hydrocarbons to be treated and the other condi
The .conditions under which the dearomatiza
tions, preferably an amount of 10 to 100 volume
tion can be accomplished are pointed out here
per cent. The amount may also be gauged with
inafter, and also in Patents Nos. 2,343,744 and
2,343,841 to be granted on March 7, 1944, any
reference to the nature of the materials being
treated. In the averaging reaction the amount
necessary part of the disclosures in which are
may depend upon the reactivity of the stocks and
incorporated herein by reference.
their nature. In the dearomatizing reaction the
The averaging reaction may be carried out with
amount used may be lower but this depends on
a heavier fraction predominately Ce Yand higher
the amount of aromatics to be removed and the
hydrocarbons, preferably boiling above the gaso
degree to which' a catalyst has been used. The
line range. The light fraction may be prefer 70 amount of boron triñuoride used, as expressed in
ably butane or butanes, although .propane and
terms of partial pressure, may be from a, :few
pentane can be used in some cases. The butane
pounds toA 550 pounds per square inch, preferably
vfraction may comprise normal butane and the
50 to 250 pounds per square inch. This must be
normal butane’may be the net product consumed
related to the amount of hydrogen fluoride used,
in the averaging.
l '
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75 `the reaction time and temperature. Under no
2,405,995
circumstances should the amount exceed 50 mol
per cent of the fluoride. In the dearomatization
fthe use of a higher partial pressure of boron tri
fluoride permits the use of a smaller amount of
hydrogen iiuoride and vice versa.
One of the advantages of the process of the
invention is the ability to control the activity of
the catalyst through control of its composition.
This may be accomplished by varying the partial
pressure of the boron triñuoride, because a
change in this partial pressure results in a change
in the amount of boron trifluoride dissolved. If
the partial pressure of the boron tri?luoride is in
creased, by admitting boron trifluoride from a
high pressure source of supply, the activity of the
catalyst is greater and it has a greater ability to
dearomatize under conditions otherwise the
same. If this partial pressure is decreased, by
bleeding boron triñuoride, the activity is reduced.
The temperature, composition of the catalyst,
time of Contact, and other factors mentioned
heretofore, are more or less interdependent. The
ranges described heretofore are not intended to
mean that any temperature may be used with any
length of time or any composition of catalyst to
obtain the identical result. For example, if a
lower temperature is used, a somewhat larger
amount of catalyst may be present or a some
what higher partial pressure of boron triiluoride
may be used, or the treating time may be longer,
or any or all of them, to obtain about the same
result that would be obtained with a higher tem
perature and with a lesser amount of catalyst,
or a lower partial pressure of boron trifluoride, or
with a shorter treating time.
Thus, for example,
any temperature within the range may be em
ployed and the other variables may be adjusted
within their ranges so as to obtain averaging.
The hydrogen fluoride and boron trifluoride
The temperature may affect the rate of the re
may be the available commercial grades. It is
action as well as the equilibrium point and should
not necessary to have chemically pure fluorides.
be selected with this in view.
The impurities in the commercial grades, includ~
It is a particularly important part of the proc
ing water, which are generally present in an
ess that in addition to varying the time of con-Y
amount of about 1/4 to 5 per cent, do not interfere 25 tact, the amount of catalyst, and the tempera
materially with the operation of the catalyst.
ture, which are the variables with which the prior
In view of the economic advantage of using the
art has had to work, it is possible, in accordance
commercial grade, it is preferred, and was used
with the process to vary the composition of the
in the foregoing examples. Reference to the flu
catalyst by varying the partial pressure of the
orides hereinafter is intended to include such 30 boron fluoride. If the effective ingredient for
commercial grades and their normal impurities or
catalyzing averaging or removing aromatics is
their equivalent in composition.
viewed as the combination of the'two fluorides,
The total pressure in each instance should be
the amount of said ingredient will be dependent
sufficient to keep the hydrogen fluoride in the
on the partial pressure of the boron trifluoride.
liquid phase in both the averaging and the de 35 Thus, for any given temperature, time of con
aromatizing and preferably also to keep all of the
tact, etc., at which it is desirable to operate be-hydrocarbons in the liquid phase. The pressure,
cause of plant equipment or economic reasons,
of course, must exceed the partial pressure of
the rate of the reaction and the activity forvthe
boron tri?luoride used and may be in excess of
catalyst can be varied simply by adjusting the
the sum of the partial pressures of the boron tri 40 partial pressure of the boron trifluoride.
iluoride, hydrogen fluoride, hydrocarbons, if other
The relation of the conditions is also dependent
materials, for example, hydrogen, are present. It
upon the nature of the hydrocarbons being
is an advantage of the process, however, that
treated. It might seem somewhat paradoxical
high pressures are not required.
that substantially the same conditions could be
The time of contact between the hydrocarbon 45 used for averaging as could be used for dearo
and the iiuorides will vary with the temperature,
matization. However, in the dearomatization
thoroughness of contact or mixing, the composi
process the aromatics in the stock treated which
tion of the fluoride mixture, and other factors.
go into the catalyst phase deactivates the cata
The dearomatization can generally be accom
lyst so that it is not sufficiently strong to accom
plished in a much shorter time as the formation 50 plish much averaging or other catalytic modifica
of a complex with the aromatics appears to pro
tion, even though the materials present in the
ceed quite rapidly.
If the dearomatization is
carried out under conditions which are not con
remaining hydrocarbon layer are those which
could be reacted in averaging. When the rafñ
nate is treated with the same catalyst under the
ductive to other reactions, it is not material if the
time is extended somewhat beyond the period 55 identical conditions, the averaging reaction takes
necessary to dearomatize. If some other reac
place and this is accounted for by the fact that
tion is to take place in the dearomatizing step, the
the treated stock is substantiallyffree from aro
time should be selected with this in mind. The
matics and the catalyst is not deactivated to an
time in the averaging reaction should be selected
extent to interfere with the averaging or other
to give the optimum yield of the desired products 60 modifying reaction.
and this may vary from 5 minutes to 3 hours, de
It will be apparent that the control of the proc
pending upon the reactivity of the hydrocarbons,
ess is an important aspect of the invention _and
temperature used, composition of the catalyst,
that it is not possible to interrelate the variables
and in particular, upon the thoroughness of mix
mathematically. However, it is believed that
ing. With the thoroughness of contact available
one skilled in the art, in view of the disclosure
in this application, will be able to adjust the
with the best commercial mixing apparatus, and
at the optimum temperatures, the time might be
conditions without difficulty so as to obtain the
reduced to an order of a few minutes.
At Very
desired new results.
low temperatures a longer time is required.
These processes are adapted either for batch
The agitation may be accomplished with any 70 operation or for continuous operation. In a
type of a mechanical agitator or stirrer, or it
batch operation the hydrocarbons and the fluo
may be accomplished by inducing flow such as
rides are brought together in desired amounts in
would result from the introduction of one of the
aclosed container or autoclave, or they are prefer
ingredients into the reaction zone through an
ably subjected to agitation and maintained under
orifice under high pressure.
the desired temperature, pressure and other con
2,405,995
ll
12
ditions for the required length of time. The mix
ture is settled and the two layers separated. The
operation would be much the same either for
dearomatization or averaging. The process is
well adapted for a continuous operation, and in
view of the desirability of continuous and semi
material may be an oxyfiuoboric acid, such as
continuous processes, on a commercial scale, the
adaptability of the invention to these processes is
important. In such a continuous process the flu
orides and the hydrocarbons to be treated are
fed to a continuous type mixer, which may have
one or more stages, and maintained under the
desired conditions during the mixing. The now
H3BF202 0r H4BF302.
‘
Another alternative is to distill olf a part or
most of the iiuorides from the lower layer at a
relatively lower temperature and remove the rest
of the fluorides by extraction with such a ma
terial. Substantially all of the ñuorides can be
recovered by any of these processes and reused in
either the averaging or dearomatizing processes.
The hydrocarbons in the upper layer also can
be treated with a material such as an oxyñuo
boric acid, to extract iiuorides therefrom if this
is desired.
The reference to a “hydrocarbon fraction” is
through the mixerv may be continuous or inter
mittent and may be at a rate so that the hydro 15 intended to refer to a pure- hydrocarbon as well
as a mixture of hydrocarbons.
carbons are in contact with the catalyst for the
It will be apparent that the invention is ca
desired length of time. After the hydrocarbons
pable of many applications and variations and I
and the catalyst have been mixed under the se
intend all of them to be included as are within
lected conditions the agitation maybe discon
tinued, as for example, by discharging hydrocar 20 the following claims.
VI claim:
bons and the catalyst from a mixer into a sepa
l. A process which comprises treating a hydro
rator, where two layers will form. The upper
carbon' mixture containing aromatic and non
layer, if it is from the dearomatizing process,- may
aromatic hydrocarbons with a composition com
then be sent to the averaging reaction zone and
the lower layer may be sent to the catalyst re 25 prising liquid hydrogen ñuoride containing boron
trifluoride dissolved therein, whereupon aromatic
generating system if its ability to extract aro
hydrocarbons form a complex with said fluoride
matics is spent. Otherwise, it may be used to
composition as the principal action; separating
dearomatize an additional amount of feed stock
before being regenerated. The flow ofthe feed . said fluoride composition containing said aro
stock and catalyst, either fresh or spent, in the 30 matic-fluoride complex as a heavier layer, and
the hydrocarbons from which aromatics have
dearomatizing process may be countercurrent in
order to utilize Vfully theV capacity of the catalyst
for extracting aromatics.
'
From the settler for the averaging reaction,
the upper hydrocarbon phase may be Vfraction
ated to obtain the wanted products and the re
mainder of higher and/or lower boiling materials
may be recycled Ato the averaging reaction Zone.
The spent catalyst from the averaging reaction
zone may be regenerated or used to extract aro
matics from the feed stock, as explained here
tofore.
,
~
Preferably the separating operation, when yap
thus been removed as a lighter layer; and then
subjecting said dearomatized hydrocarbons, with
out the removal of any fluorides remaining there
in, to the action of a catalyst comprising liquid
hydrogen fluoride containing boron trifluoride
dissolved therein which acts to modify the chem
ical structure of the non-aromatic hydrocar
bons.
2. A process which comprises treating a hydro
carbon mixture containing aromatic and non
aromatic hydrocarbons with a composition com
prising liquid hydrogen fluoride containing boron
trifluoride dissolved therein, whereupon aromatic
plied to either a batch or continuous operation, is 45 hydrocarbons form a complex with said nuoride
carried out under the pressure used in effecting
composition as the principal action and deactivate
the reaction. Alternatively, vii“ the pressure is
said fluoride composition as a catalyst; separat
reduced some ofthe lower layer may redissolve
ing said fluoride composition containing said aro
and most of the boron trifluoride and some of
matic-fluoride complex as a heavier layer, and
the other light components may be released.
the hydrocarbons from which aromatics have
After _the catalyst has been used in either the
thus been removed as a lighter layer; and then
averaging or dearomatizing process it may be
subjecting said dearomatized hydrocarbons, with
regenerated by withdrawing apart or all of the
out the removal of any ñuorides remaining dis
used or reused catalyst at any stage of the op
solved therein, to the action of a catalyst com
eration and subjected to a relatively high tem
prising liquid hydrogen fluoride containing boron
perature, for example 250-600° F. vThis may be
trifluoride dissolved therein which acts to modify
by way of a pot still, or by means of flash dis
the chemical structure of the non-aromatic hy
tillation. At this temperature substantially all
drocarbons.
of the ñuorides are liberated as gases. These can
3. A process of dearomatizing a hydrocarbon
be collected and condensed and/or compressed 60 fraction and catalytically modifying the hydro
and returned to the mixing zone or stored or
carbons in the dearomatized fraction, which com
otherwise used. Two stage regeneration is de
prises adrnixing an aromatic-containing hydro
sirable, the ñrst stage being a flash distillation
carbon fraction with a spent catalyst comprising
operated at a fairly low temperature to remove
liquid hydrogen nuoride containing a minor pro
a major portion of the iiuorides, following which
portion of boron triñuoride that has been used
the balance may be removed in' a stripper at a
in the catalytic modification of hydrocarbons, to
higher temperature.
'
form hydrocarbon and spent catalyst phases un
Alternatively, instead of distilling the ?luorides,
der a pressure to maintain the hydrogen fluo
the lower layer or catalyst phase may be treated
ride liquid and conditions such that the primary
with a. material which exerts a solvent action on
action is the transfer of aromatics from the hy
the ñuorides and which is immiscible with the
drocarbon fraction into the spent catalyst phase,
hydra arbons in the lower layer, or which forms
separating the hydrocarbon fraction as one phase
a chemical compound or complex with the iluo
and the aromatic-containing spent catalyst as
rides and from which the iluorides may be re
another phase, catalytically modifying the hy
leased later, for example .by heating. Such a 75 drocarbons in said dearomatized fraction by
2,405,995
I3
treating it With> a liquid catalyst comprising liq
14
fraction as one `phase and the catalyst as another
phase.
uid hydrogen fluoride in which is dissolved a
minor proportion of boron trifluoride under a
6. A process of dearomatizing a heavier hydro
pressure to maintain the hydrogen fluoride liq
carbon fraction boiling above gasoline and cata
uid and conditions such that the primary action
lytically modifying the hydrocarbons in the de
is the catalytic modiiication of the hydrocarbon
aromatized fraction in the presence of a butane
in said fraction, separating the modified hydro
which comprises admixing an aromatic-contain
carbon fraction as one phase and the catalyst
ing hydrocarbon fraction boiling above gasoline
after it is spent in the above catalytic modifying
with a spent catalyst comprising liquid hydrogen
process as another phase, and using the spent 10 fluoride containing a minor proportion of boron
catalyst t0 dearomatize the aromatic-containing
triiiuoride -that has been used in the catalytic
hydrocarbon fraction in accordance with the first
modification of hydrocarbons, to form hydrocar
steps of the process.
bon and spent catalyst phases under a pressure
4. A process of dearomatizing a hydrocarbon
to maintain the hydrogen fluoride liquid and con
fraction and catalytically modifying the hydro 15 ditions such that the primary action is the trans
carbons in the dearomatized fraction, which com
fer of aromatics from the hydrocarbon fraction
prises admiXing an aromatic-containing hydro
into the spent catalyst phase, separating the hy
carbon fraction with a spent catalyst compris
drocarbon fraction as one phase and the aro
ing liquid hydrogen fluoride containing a minor
matic-containing spent catalyst as another phase,
proportion of boron trifluoride that has been used 20 catalytically modifying said dearomatized heav
in the catalytic modification of hydrocarbons, to
ier hydrocarbon fraction by treating it in the
form hydrocarbon and spent catalyst phases un
presence of a butane with a liquid catalyst com
der a pressure to maintain the hydrogen fluo
prising liquid hydrogen fluoride in which is dis
ride liquid and conditions such that the pri
solved a minor proportion of boron triiiuoride
mary action is the transfer of aromatics from 25 under a pressure to maintain the hydrogen iiuo
the hydrocarbon fraction into the spent catalyst
phase, separating the hydrocarbon fraction as
one phase and the aromatic-containing spent
catalyst as another phase, regenerating the fluo
rides from the last mentioned phase; and in 30
the presence of any fluorides that may be con
tained in said dearomatized fraction, catalyti
cally modifying said hydrocarbon fraction by
treating it with a liquid catalyst comprising liq
uid hydrogen fluoride in which is dissolved a f
minor proportion cf boron trifluoride, at least
some of said fluorides being said regenerated iiuo
rides, under a pressure to maintain the hydro
gen fluoride liquid and conditions such that the
primary action is the catalytic modification of
ride liquid and conditions such that the primary
action is the catalytic modification of the heavier
hydrocarbons in said fraction to form hydrocar
bons lighter than in said fraction, separating the
modified hydrocarbon fraction as one phase and
the catalyst after it is spent in the above cata
lytic modifying process as another phase, and
using the spent catalyst to dearomatize the aro
matic-containing heavier hydrocarbon fraction
in vaccordance With the first steps of the process.
7. A process of dearomatizing a heavier hydro
carbon fraction boiling above gasoline and cat
alytically modifying the hydrocarbonsl in the de
aromatized fraction in ’the presence of a butane
which comprises adrnixing an aromatic-contain
the hydrocarbons in said fraction, separating the
ing hydrocarbon fraction boiling above gasoline
modified hydrocarbon fraction as one phase and
with a spent catalyst comprising liquid hydro
the catalyst after it is spent in the above
alytic modifying process as another phase,
using the spent catalyst to dearomatize the
matic-containing hydrocarbon fraction in
cordance with the first steps of the process.
cat
gen fluoride containing a minor proportion of
and
boron trifluoride that has been used in the cat
aro 45 alytic modification of hydrocarbons to form hy
ac
drocarbon and spent catalyst phases under a pres
sure to maintain the hydrogen fluoride liquid
5'. A process of dearomatizing a heavier hydro
and conditions such that the primary action is
carbon fraction containing primarily hydrocar
the transfer of aromatics from the hydrocarbon
bons having at least six carbon atoms and ca't- ,
fraction into the spent catalyst phase, separating
alytically modifying the hydrocarbons in the de
Ithe hydrocarbon fraction as one phase and the
aromatized fraction in the presence 0f a light
aromatic-containing spent catalyst as another
phase, regenerating the fluorides from the last
hydrocarbon fraction, which comprises admixing
an aromatic-containing heavier hydrocarbon
fraction with liquid hydrogen fluoride contain
mentioned phase; and in the presence of any
fluorides that may be contained in said dearo
ing a minor proportion of boron trifluoride to
matized heavier fraction, catalytically modify
ing said fraction by treating it in the presence
form hydrocarbon and fluoride phases under a
of a butane with a liquid catalyst comprising
pressure to maintain the hydrogen fluoride liq
liquid hydro-gen fluoride in Which is dissolved
uid and conditions such that the primary action
is the transfer of aromatics from the hydrocar 60 a minor proportion of boron trifluoride, at least
some of said fluorides being said regenerated fluo
bon fraction into the iiuoride phase, separating
rides, under a pressure t0 maintain the hydro
the hydrocarbon fraction as one phase and the
gen'fluoride liquid and conditions such that the
aromatic-containing fluorides as another phase,
primary action is the catalytic modification of
catalytically modifying said dearomatized heav
ier hydrocarbon fraction without the removal ' the heavier hydrocarbons in said fraction to form
of any iiuorides remaining therein, by treating
hydrocarbons lighter than in said fraction, sep
it in the presence of a light hydrocarbon frac
arating the modified hydrocarbon fraction as one
phase and the catalyst after it is spent in the
albove catalytic modifying process as another
tion with a liquid catalyst comprising liquid hy
drogen iiuoride in which is dissolved a minor pro
portion of boron trifluoride under a pressure to 70 phase, and using the spent catalyst to dearomatize
maintain the hydrogen fluoride liquid and condi
tions such that the primary action is the catalytic
modification of the heavier hydrocarbons in said
fraction to form hydrocarbons lighter than in
said fraction, and separating the hydrocarbon
the aromatic-containing heavier hydrocarbon
fraction in accordance with the first steps of the
process.
'
8. A process which comprises treating al hydro
carbon mixture containing aromatic and non
2,405,995
15
16
to dearomatize the aromatic-containing heavier
hydrocarbon fraction in accordance with the ñrst
aromatic hydrocarbons with a composition com
prising liquid hydrogen iluoride containing boron
triiiuoride dissolved therein, whereupon aromatic
steps of the process.
l1. A process of dearomatizing a heavier hy
drocarbon fraction boiling above gasoline and
catalytically averaging the hydrocarbons in the
dearomatized fraction with a butane fraction,
which comprises admixing an aromatic-contain
hydrocarbons form a complex with said fluoride
composition as the principal action; separating
said ñuoride composition containing said aro
matic-iluoride complex as a heavier layer, and
the hydrocarbons from which aromatics have ‘thus
been removed as a lighter layer; and then sub
ing hydrocarbon fraction boiling above gasoline
jecting said dearomatized hydrocarbons, without 10 with liquid hydrogen fluoride containing a minor
proportion of boron trifluoride to form hydrocar
ythe removal of any fluorides remaining therein,
to the action of a catalyst comprising liquid hy
bon and fluoride phases under a pressure to
maintain the hydrogen fluoride liquid and con
drogen ñuoride containing boron triiiuoride dis
ditions such that the primary action is the trans
solved therein, and in the presence of a normally
gaseous hydrocarbon Ito form hydrocarbons hav 15 fer of aromatics from the hydrocarbon fraction
into the fluoride phase, separating the hydro
ing a boiling point between the dearomatized hy
carbon fraction as one phase and the aromatic
drocarbons and the normally gaseous hydrocar
containing ñuorides as another phase, regenerat
bon.
.
ing the iluorides from the last mentioned phase,
9. A process of dearomatizing a heavier hydro
carbon fraction containing primarily hydrocar
bons having at least siX carbon atoms and cat
alytically averaging the hydrocarbons in the de
aromatized fraction with light hydrocarbons,
which comprises admixing an aromatic-contain
ing hydrocarbon fraction with liquid hydrogen
20
catalytically averaging said heavier hydrocar
bons in said dearomatized fraction, without the
removal of any ñuorides remaining therein, with
a butane fraction by treatment with a liquid cat
alyst comprising liquid hydrogen fluoride in which
is dissolved a minor proportion of boron triiiuo
ride under a pressure to` maintain `the hydrogen
fluoride containing a minor proportion of boron
fluoride liquid and conditions such that the pri
trifluoride t0 form hydrocarbon and iluoride
mary action is the formation of the hydrocarbons
phases under a pressure to maintain the hydro
between butane and said heavier hydrocarbons,
gen iluoride liquid and conditions such that the
primary action is the transfer of aromatics from 30 separating the hydrocarbon fraction as one phase
and the catalyst as another phase.
the hydrocarbon fraction into the ñuoride phase,
12. A process of dearomatizing a heavier hydro
separating the hydrocarbon fraction as one phase
carbon fraction boiling above gasoline and cataly
and the aromatic-containing ñuorides as another
tically averaging the hydrocarbons in the dearo
phase, catalytically averaging said heavier hy
drooarbons in said dearomatized fraction, with 35 matized fraction with a butane fraction, which
comprises admixing an aromatic-containing hy
out the removal of any iluorides remaining there
in, with light hydrocarbons by ltreatment with
a liquid catalyst comprising liquid hydrogen fluo
drocarbon fraction boiling above gasoline with liq
the hydrogen fluoride liquid and conditions such
that'the primary action is the formation of hy
drocarbons between said heavier and light hydro
carbons, separating the hydrocarbon fraction as
the hydrogen fluoride liquid and conditions such
uid hydrogen ñuoride containing a minor prop
portion of boron trifluoride, to form hydrocarbon
ride in which is dissolved a minor proportion of
boron trifluoride under a pressure to maintain 40 and fluoride phases under a pressure to maintain
that the primary action is the transfer of aro
matics from the hydrocarbon fraction into the
fluoride phase, separating the hydrocarbon frac
45 tion as one phase and the aromatic-containing
one phase and the catalyst as another phase.
fluorides as another phase; catalytically averag
l0. A process of dearomatizing a heavier hy
ing said heavier hydrocarbons in said dearomat
drocarbon fraction containing primarily hydro
ized fraction, without the removal of any fluo
carbons having at least six carbon atoms, and
catalytically averaging the hydrocarbons in the
rides remaining therein, with a butane fraction
dearomatized fraction with light hydrocarbons, 50 by treatment with a liquid catalyst comprising
liquid hydrogen fluoride in which is dissolved a
which comprises admixing an aromatic-contain
minor proportion of boron triñuoride under a
ing hydrocarbon fraction with a spent catalyst
pressure to maintain the hydrogen fluoride liq
comprising liquid hydrogen fluoride containing a
uid and conditions such that the primary action
minor proportion of boron trifluoride that has
been used in the catalytic modification of hydro 55 is the formation of the hydrocarbons between
butane and said heavier hydrocarbons, separat
carbons, to form hydrocarbon and spent cat
ing »the hydrocarbon fraction as one phase and
alyst phases under a pressure to maintain the
the catalyst as another phase.
hydrogen fluoride liquid and conditions such that
13. A process of dearomatizing a' heavier hydro
the primary action is the transfer of aromatics
from the hydrocarbon fraction into the spent cat 60 carbon fraction boiling above gasoline and cat
alytically averaging the hydrocarbons in the de
alyst phase, separating the hydrocarbon fraction
as one phase and the aromatic-containing spent
aromatized fraction with a butane fraction, which
comprises admixing an aromatic-containing hy
catalyst as another phase, catalytically averag
drocarbon fraction boiling above gasoline with
ing said heavier hydrocarbons in said dearomat
ized fraction with light hydrocarbons by treat 65 a spent catalyst comprising liquid hydrogen iluo
ride containing a minor proportion of boron
ment with a liquid catalyst comprising liquid hy
trifluoride that has been used in the subsequent
drogen fluoride in which is dissolved a minor
ly mentioned catalytic averaging of hydrocar
proportion of boron trifluoride under a pressure
bons, to form hydrocarbon and spent catalyst
to maintain the hydrogen fluoride liquid and con
ditions such that the primary action is the for 70 phases under a pressure to maintain the hydro
gen fluoride liquid and conditions such that the
mation of hydrocarbons between said heavier and
primary action is the transfer of aromatics from
light hydrocarbons, separating the hydrocarbon
the hydrocarbon fraction into the spent catalyst
fraction as one phase and the catalyst after it
phase, separating the hydrocarbon fraction as
is spent in the above catalytic averaging process
one phase and the aromatic-containing spent
as another phase, and using the spent catalyst
17
2,405,995
18
catalyst as another phase; and in the presence
said iiuoride composition containing said aro
of any fluorides that may be contained in said
matic-fluoride complex as a heavier layer, and
the hydrocarbons from which aromatics have
thus been removed as a lighter layer; and then
dearomatized fraction, catalytically averaging
-said heavier hydrocarbons in said dearomatized
fraction with a butane fraction by treatment
with a liquid catalyst comprising liquid hydro
gen fluoride in which is dissolved a minor pro
portion of boron trifluoride under a pressure to
maintain the hydrogen ñuoride liquid and con
ditions such that the primary action is the for
" mation of the hydrocarbons boiling between bu
subjecting said dearomatized hydrocarbons, With
out the removal of any fluorides remaining there
in, to the action of a catalyst comprising liquid
r hydrogen fluoride containing boron triñuoride
dissolved therein under conditions which cata
lytically crack the dearomatized hydrocarbons as
a principal reaction.
15. A process of dearomatizing a hydrocarbon
tane and said heavier hydrocarbons, separating
the hydrocarbon fraction as one phase and the
fraction, which comprises admixing an aromatic
catalyst after it is spent in the above catalytic
containing hydrocarbon fraction with a spent cat
averaging process as another phase, recycling 15 alyst comprising liquid hydrogen ñuoride contain
the unreacted butane fraction to the averaging
ing a minor proportion of boron trifluoride that
reaction, and using the spent catalyst »to deare
has been used in lthe catalytic modiñcation of
matize the aromatic-containing heavier hydro
hydrocarbons, to form hydrocarbon and spent
carbon fraction in accordance with the ñrst steps
catalyst phases under a pressure to maintain the
of the process.
20 hydrogen fluoride liquid and conditions such that
14. A process which comprises treating a hydro
the primary action is the transfer of aromatics
carbon mixture containing aromatic and non
from the hydrocarbon fraction into the spent cat
aromatic hydrocarbons with a composition com
alyst phase, and separating the hydrocarbon frac
prising liquid hydrogen ñuoride containing boron
tion as one phase and the aromatic-containing
trifluoride dissolved therein, whereupon aromatic 25 spent catalyst as another phase.
hydrocarbons form a complex with said iluoride
composition as the principal action; separating
ROBERT E. BURK.
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