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Патент USA US2405997

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2,405,997
Patented Aug. 20, 1946
UNITED STATES PATENT OFFICE
2,405,997 '
AVERAGING WITH PENTANE
Robert E. Burk, Novelty, Ohio, assignor to The
Standard Oil Company, Cleveland, Ghio, a cor
poration of Ohio
No Drawing. Application August 9, 1944,
-
Serial No. 548,807
10 Claims.
(Cl. 260—-683.4)
1
This invention relates to the treatment of a
heavier molecular weight hydrocarbon fraction
and a lighter hydrocarbon fraction comprising
normal pentane with a catalyst comprising pri
marily hydrogen ?uoride promoted by a minor
proportion of boron tri?uoride to produce hy
‘drocarbons of intermediate molecular weight, a
process termed “averaging.”
A preferred and important embodiment of the
2
,.
carbons as well as converted to isobutane which
may be fractionated and used in other processes
such as alkylation.
Still another object of the invention is to
carry out the averaging reaction in the presence
of an amount of the lighter hydrocarbon frac
tion in excess of that entering into the reaction,
and in which the excess of the lighter hydrocar
bon fraction may be recycled to the averaging re-
invention comprises the use of a normal pentane 10 action in a continuous or semi-continuous
process.
containing fraction as the lighter hydrocarbon,
A further object of the invention is to carry
and a liquid hydrocarbon boiling above the gaso
out the above process, utilizing a pentane frac-.
line range as the heavier hydrocarbons, to pro
tion containing normal pentane in excess of that
duce gasoline of desirable properties.
It is one of the objects of the invention to 15 entering into the reaction, fractionating the ex
cess to remove all or a portion of isobutane or
utilize normal pentane as one of the raw mate
isopentane which is formed during the averaging
rials in making more valuable hydrocarbon
reaction if desired and recycling the balance of
products.
the lighter fraction to the reaction zone.
,
A further object of the invention is to utilize
Still a further object of the invention is to
heavier hydrocarbon fractions, such as kerosene 20
carry out the above reactions in the liquid .phase
or naphthas, in the formation of hydrocarbons
in the presence of a liquid catalyst comprising
of lower molecular weight, such as gasoline,
primarily hydrogen fluoride and promoted by a
without the production of large amounts of un
minor proportion of boron tri?uoride, and if de
saturated hydrocarbons or ?xed gases, and also
without the destructive in?uences and losses in 25 sired, also promoted by the presence of an un
saturated hydrocarbon.
.
cident to conventional methods of cracking.
Another object is the provision of a process in
An additional object of the invention is to
which ?uorides containing the impurities pres
utilize both a pentane containing hydrocarbon
ent in commercial grades may be used.
fraction and a heavier hydrocarbon fraction
An additional object of the invention is to
simultaneously in a single reaction to produce 30
carry out the pentane averaging process under
valuable products intermediate said fractions re
conditions of temperature and pressure not lower
sulting from a net consumption of both of them
nor higher than can be obtained conveniently
at the same time.
An additional object of the invention is to
provide a process in which a mixture of butanes 35
and pentanes may be used as the lighter fraction
in ordinary plant operations.
.
The invention has as a further object the pro
vision of a process of the character described in
which the activity of ‘the catalyst, in addition to
being controlled by variations in temperature,
.sumption of normal pentane to form more valu
pressure and other factors ordinarily employed
able hydrocarbons.
,
Still a further object of the invention is the 40 in catalytic operations, also can be controlled
readily by means of the partial pressure of the
provision of a process in which a butane and
boron tri?uoride constituent of the catalyst.
pentane containing lighter fraction may be used
in an averaging process resulting in a net con
Still a further object is the provision of a
as the lighter hydrocarbon in an averaging re
process of averaging as described in which the
action and the proportions adjusted so as to re
sult in .a net consumption of the butanes along 45 catalyst can be readily recovered and reused.
with the pentanes.
A further object is to provide a process in’
which the normal pentane in the lighter fraction
is used in the manufacture of higher hydro—
Other objects of the invention will appear from
the following description.
In carrying out the process of the invention,
a lighter hydrocarbon fraction comprising normal
2,405,997 '
3
4
pentane is mixed with the heavier boiling frac
tion, such as a normally liquid hydrocarbon.
tain normal hydrocarbons, isomers, napthanes
carbon and lighter than the heavier hydrocarbon
starting materials. At the conclusion of the
phase and may be fractionated, and the catalyst
is separated as another phase. The catalyst phase
stock boiling from 70° to above 400° F., or crude
oil or reduced crude as such, may be used in the
averaging reaction.
The presence of aromatics in the feed stocks,
particularly in the heavier fraction where they
may be reused as such or may be regenerated and
reused.
are more apt to be present, is undesirable be
cause these aromatics tend to form a complex
or small amounts of hydrocarbons other than
These are caused to react preferably in a liquid
normal or unsaturated hydrocarbons. The lat
state, in the presence of a liquid catalyst and un
ter may be bene?cial as mentioned heretofore.
der conditions of temperature and pressure as 5
In some instances both the light and the heav
will be pointed out more particularly hereinafter,
ier fractions to be reacted in the process may be
to produce products heavier than the light hydro
in the form of a single fraction. For example, a
treatment the hydrocarbons are separated as one
The light hydrocarbon may be normal pentane
or a mixture of normal and isopentane.
It may
also be a mixture of normal (or normal and iso-)
pentane with normal butane or a mixture of nor
mal and isobutane. Normal pentane is readily
reacted in accordance with the invention and
with the catalyst and decrease its activity. For
this reason it is desirable that the feed stock
should contain a minimum of aromatics. While
it is not essential that the stock be free from
aromatics if other conditions are adjusted suit
ably, it will be generally preferable at least to
since it is not of great value in itself as a motor
reduce the aromatic content of the stock some
fuel, the invention assumes particular importance
what by a dearomatization process if the stock
with reference to its use as the lighter reacting
is high in aromatics. This may be done by any
component.
means conventional in the art, such as solvent
The lighter hydrocarbon fraction may be ob 25 extraction, or the fluorides may be used for de
tained from any re?nery operation; it is imma
terial if it contains small amountsof other con
stituents, and for this reason it need not be highly
puri?ed. It is also immaterial, and in fact it is
aromatizing in accordance with the process de
scribed in my Patent No. 2,343,744, granted
March 7, 1944.
p
>
The ratio of the light to the heavier fraction
an advantage as pointed out later, if it contains a 30 may vary over a relatively wide range. Gener
ally it is preferred to have at least i mol of the
small amount of unsaturated hydrocarbons. For
this reason it is not necessary to fractionate the
unsaturated hydrocarbons and other ingredients
from the lighter fraction. Generally the normal
pentane is found mixed with‘ some isopentane
and no harm is done if the latter is present. Un
lighter fraction per mol of the heavier fraction.
Two to 6 mols of the light fraction per mol of the
heavier fraction is the preferred range. There is
no object in having present more of the lighter
fraction than will re?ect an improvement, since
der some conditions the reaction may be facil
there is no point in recycling a larger excess of
itated by the presence of isopentane. However,
this fraction than can accomplish a corresponding
since isopentane is more useful in itself as a
improvement in the reaction.
motor fuel, the ability to use normal pentane 40
The catalyst used in the process comprises hy
as a raw- material in the averaging process is of
drogen ?uoride promoted with a minor propor
great importance. If the lighter fraction contains
tion of boron tri?uoride therein, and in some
butanes, as it may especially in a continuous
instances with an ole?n. It is used preferably
process, the presence of the latter does not in
in the liquid phase.
'
terfere with the net consumption of the normal 45
Hydrogen ?uoride boils at about 67° F. and is
pentane.
therefore a liquid at temperatures just under
In ‘a continuous operation in which an excess
room temperature and may be kept liquid at
of the lighter fraction is used, a part of the nor
higher temperatures by moderate pressures. The
_mal pentane may be isomerized to isopentane and
temperatures and pressures used in the process
a part converted to isobutane. When the ex 50 of the invention are conveniently those that
cess of the lighter fraction is recycled the amounts
maintain the hydrogen ?uoride liquid. Boron
of the isopentane and/orisobutane in the re
tri?uoride boils at ~l50° F. and is a gas at the
cycled fraction may be varied and this becomes
temperatures and pressures conveniently em
a controllable variable.
ployed in hydrocarbon treating processes. How
The heavier fraction, in general, should be a 55 ever,,boron tri?uoride dissolves in liquid hydro
heptane or heavier hydrocarbon. While the heav
gen fluoride to agiven extent and the amount
ier fraction may be a pure hydrocarbon, gen
which dissolves at any given temperature depends
erally it will be a mixture, such as naphthas
on the partial pressure of boron tri?uoride. At
(250-400" F), kerosenes (350-550° F), light gas
higher partial pressures, a larger amount of boron
oils MOO-625° F), heavy gas oils (SOD-710° F),
tri?uoride is dissolved.
mixtures of light and heavy gas oils (LlOO-‘l'lOo
The boron tri?uoride in the hydrogen ?uoride
F), deasphaltized and dearomatized residues
in the liquid phase possibly may react at least
(above 700° F), the portion of crude boiling to
to some extent, but an understanding of the
550° F., the portion of crude boiling to 700° F.,
chemistry involved is not necessary to practice
the portion of crude oil boiling between 250-710” " my invention, and I do not intend to be bound
F., mixtures of naphthas with kerosenes, and
by any theory. At any event the amount of the
fractions boiling higher than 825° F. In these
boron tri?uoride in the hydrogen ?uoride, which
stocks the presence of hydrocarbons lower than
controls the activity of the catalyst, is a function
heptanes is no disadvantage. Other stocks that
of the partial pressure of the boron tri?uoride.
may be used are Fischer-Tropsch (Hz-l-CO‘Y 70
The amount of boron tri?uoride dissolved in
stock, Houdry cycle stock and thermal cycle
the hydrogen ?uoride, at any given temperature,
stock. Some of the above fractions may require
may be expressed conveniently in terms of the
partial pressure of boron tri?uoride. This may
vary, in accordance with the invention, from .5
aromatic extraction because the stock should be
relatively low in aromatics as explained herein
after. The heavier fractions described may con
to 1000 Pounds per square inch; generally about
2,405,997
5
50 to ‘300 pounds .per square inch will be ‘used.
However, the partial pressure should under no
circumstances be such that the amount of boron
tri?uoride exceeds 50 mol per cent of the'?uo
This may enable a reduction in the amount of
catalyst per unit of the product formed, and
may also have a bene?cial effectin causing some
of the hydrocarbons to shift from the catalyst
phase of the ‘reaction to the hydrocarbon phase.
The amount of the catalyst employed must be
rides' With the partial pressures usually used
the amount does not exceed 25 mol per cent.
The words “dissolved” and “solution” are used
considered with reference to both of the ?uoride
as generic to both a physical admixture and a
ingredients comprising :it. The amount of the
hydrogen ?uoride may be 5 to 1300 volume per cent
One of the advantages of the process of the v10 based on the hydrocarbons to be treated when
in liquid form, preferably-the amount should be
invention is the ability to control the reaction
about 15 to 1.00 volume per cent. Amounts as
by adjusting the activity of the catalyst through
low as 1 volume per cent may be used in a multi
control of its composition. This may be accom
reaction product.
plished by varying the partial pressure of the
boron tri?uoride, because a change in this partial
pressure results in a change in the amount of
boron tri?uoride dissolved. If the partial pres
sure of the boron trifluoride is increased, by ad
mitting boron tri?uoricle to the reaction zone
from a high pressure source of supply, the activ
ity of the catalyst is greater under conditions
otherwise the same. If this partial pressure is
decreased, vby bleeding boron tri?uoride, the ac.
tivity of the catalyst is reduced.
If an ole?n is added, or is present in the re
action zone in an amount less than that which
acts as a poison, the ole?n appears to act as
stage treatment in which the total ‘would be at
least 5%. The use ,of larger amounts increases
the rate of conversion and the yield in- a‘ given
time under conditions otherwise the same. The
amount used may depend. to a large extent upon
the economics involved and the maximum con
version desired per pass .of the material. The
total amount necessary ‘may also be less if it is
supplied in increments'during the reaction. If
desired the used catalyst may be removed before
the next increment is supplied. ~No more-is used
than is necessary to ve?ect the desired ‘reaction
in the desired time since to use more would only
add to the amount to be recovered or regener
a promoter. The available evidence indicates
The amount of the ‘boron ?uoride used, as ex
that the ole?n acts as ;a “hydrogen acceptor” and
that the hydrogen ?uoride-boron tri?uoride so 30 pressed in termso-f partial pressure, has been,
indicated ‘heretofore in describing the composi
lution or the reaction product may form a new
tion of the catalyst.
compound or chemical complex with the ole?n.
ated.
Since ole?ns may be formed in the process, espe
cially when heavier stocks are used, the addition
'
I
When an ole?n is added ‘separately as an in
gredient it may vary from extremely small
of an ole?n as a separate addcd'ingredient to the 35 amounts to 100 or more mol per cent based on the
stocks may not re?ect a separate improvement.
The catalyst to be used in practicing the in
vention, therefore, may be viewed as hydrogen
?uoride promoted by a minor proportion of
amount of the boron tri?uoride dissolved in the
hydrogen fluoride. ‘Expressed in practical terms,
the amount of the ole?n may be % to 125% based
on the hydrocarbons being treated.
The total pressure .should be .suf?cient to keep
boron tri?uoride; or it may be viewed as hy 40
the hydrogen ?uoride in the liquid phase, and
drogen ?uoride promoted by ‘both boron tri
preferably also to keep all the hydrocarbons in
?uoride and an ole?n; or a combination of ‘both
the liquid phase. It must, of course, exceed the
?uorides promoted by the ole?n. ' The presence
partial pressure of the boron tri?uoride. The
of an ole?n generally gives somewhat better re
sults.
The hydrogen ?uoride and boron tri?uoride
may be the available commercial grades. It is
not necessary to have chemically :pure ?uorides.
45 total pressure may vary up to 1000 pounds per
square inch, such as might be obtained ‘by the
presence of an inert gas, but generally no ad
vantage is gained 5(un'less hydrogen is used as .de
scribed later) by ~having a total pressure greater
The impurities in the commercial grades, in
cluding water, which are generally present in 50 than the sum .of the partial pressure of the boron
tri?uoride and the partial ‘pressures of the hy
drogen ?uoride and the hydrocarbons at the tem
fere materially with the operation of the catalyst.
perature utilized.
In view of the economic advantage of using the
The time of contact ‘between the pentane and
commercial grade, .it is preferred, and was used
in the following examples. Reference to the 55 other hydrocarbons and the catalyst may vary
with the temperature, thoroughness of contact
?uorides hereinafter is intended to include such
or mixing between the hydrocarbon and the cat
commercial grades and their normal impurities
alyst, and other factors. Depending upon such
or their equivalent in composition.
other factors, the time should be selected to
The conditions under which the process is car
give
optimum yields. ‘This may be from ‘5 min
60
ried out are selected within convenient ranges
utes
to
13 hours, although in the higher tempera
so as to produce maximum yields. In general
an amount of about 1A; to 5 per cent, do not inter
ture ranges and with very thorough mixing, as ~
the temperature may ‘vary from —30° to 400° F.,
might be accomplished with the ‘best commercial
preferably from about 20° to 212° F. Averaging
mixing apparatus available, the time ‘might ‘be re
with kerosene as the heavier stock shows that
the process can be carried out conveniently at 65 duced to the order of a minute. ‘In a commercial
operation, it is desirable, of course, to ‘keep the
a temperature within a range of about 32° to
reaction
time as short as possible since this de
150° F. It is an advantage of the process that
creases the size of the reactor necessary to pro
extreme temperatures in either direction are not
duce a given amount of product. Observations
necessary. A single temperature may ‘be used
indicate .that the reaction proceeds quite quickly,
throughout the reaction, or it may be varied dur
and readily reaches :a condition where more time
ing the reaction. If the catalyst is reused a some
does not materially alter the distribution ‘of the
what higher temperature may be desirable than
products to such an extent that it .is of economic
is the case when the catalyst is ‘fresher. It may
be desirable, for this reason, to operate with
ascending temperatures in the direction of ?ow.
advantage to continue the reaction longer.
The .agitation may be accomplished with any
2,405,997
7
8
type of a mechanical agitator or stirrer, or it
or absorbed in ‘the ?uorides. If hydrogen is to be
used, thismay' be introduced from a separate
high pressure source of the supply.
The order of mixing the components is not
critical. The pentane-containing fraction and
heavier hydrocarbons may be fed separately or
.mixed and introduced into the ?uorides or vice
may be accomplished by induced ?ow suchas by
the introduction of one vof the ingredients from
an'ori?ce under high pressure.
‘ 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
versa. Alternatively the pentane-containing
mean that any temperature may be used with
component may be mixed with the ?uorides and
any length of time or any composition of cat 10 this mixture fed gradually to the heavier hydro
alyst to obtain the identical result. For example,
if a lower temperature is used, a somewhat larger
carbons or vice versa in one or more stages. In
I either a batch or continuous process, the ?uo
amount of catalyst may be present or a some
rides may be introduced in increments at differ
what higher partial pressure of boron tri?uoride
ent intervals during the total reaction period.
may be used, or the treating time may be longer, 15 When using a continuous mixer having a plural
or mixing better, or any or all of them, to obtain
ity of stages, the ?uorides may be introduced at
about the same result that would be obtained
each stage. The operation may be countercur
with a higher temperature and with a lesser
rent or concurrent.
'
amount of catalyst, or a’ lower partial pressure
In a multiple treatment process the ?rst treat
of boron trifluoride, or with a, shorter treating 20 ment with the catalyst may be largely or in part
‘time. Thus, for example, any temperature within
one of dearomatizing, and subsequent treatments
the range may be employed and the other vari
may be responsible for the major portion of the
ables‘ may be adjusted within their ranges so as
pentane averaging reaction. Although the cat
“to obtain, averagingiwith pentane.
It is a particularly important part of the proc
ess that in addition to varying the time of con
alyst may be reduced in activity during the av-,
25 eraging reaction so as to render it ineffective for
further reacting pentane, it may still be used
tact, the amount of catalyst, and the temperature,
to dearomatize and the. dearomatization of the
which are the variables with which the prior art
heavier fraction feed stock with the used cata
hasv had to work, it is possible, in accordance with
lyst from the pentane averaging reaction is an
thef process to vary the composition of the cat 30 important aspect of the invention. This could
alyst by. varying the partial pressure of the boron
be accomplished, for example, in a two-stage
?uoride. Thus, for any given temperature, time
countercurrent treatment. The catalyst con
of contact, etc., at which it is desirable to oper
taining the aromatics may then be subjected to
ate because of plant equipment or economic
a regenerating action in accordance with any of
reasons, the activity of the catalyst and the rate
the processes indicated heretofore, and the ?uo
of the pentane averaging reaction can be varied
rides returned to the averaging zone.
simply by adjusting the partial pressure of the
The following examples are given merely as il
boron trifluoride.
lustrative of the results that may be accom
It will be apparent that the control of the
plished when the invention is practiced on a lab
process is an important aspect of the invention 40 oratory scale. This may be transferred to a com
and that it is not possible to interrelate the vari
mercial basis with the incident improvements as
ables mathematically. However, it is believed
described heretofore.
that one skilled in the art, in view of the disclo
Example 1
sure in this application, will be able to adjust
the conditions without difficulty so as to obtain
An Illinois kerosene, containing 16% aromatics
the desired new results.
I The process may also be carried out in the
presence of hydrogen, which may be introduced
into the reaction in an amount to provide a par
was used as the heavier stock for averaging with a
pentane fraction. Five per cent of the kerosene
boiled below 360° F. and 50% below 425° F.; the
tial pressure of hydrogen of 100 to 1000 pounds 50 end point was 551° F. ' The process was carried
out in a two stage treatment. In the ?rst stage
per square inch. This tends to minimize the
the kerosene was treated with 15 volume per cent
amount of hydrocarbons entering the lower layer.
of liquid hydrogen ?uoride (based on the volume
The process is adapted either for batch oper
of the kerosene) in which boron tri?uoride was
ation or for continuous operation. In either type
dissolved in an amount to provide a partial pres
of operation the feed stocks may be dried, if de
sure of 150 pounds per square inch. The reac
sired, by suitable driers. In a batch operation
tion was continued for 15 minutes at 90° F. by
the pentane-containing fraction and the higher
agitating the kerosene and the catalyst. After
hydrocarbons are brought together with the ?u
the kerosene and the catalyst have been mixed
orides in the desired amounts in a closed con
under the above conditions for the stated time,
tainer or autoclave where they are preferably
the agitation was discontinued and the catalyst
subjected to agitation and maintained under the
phase and the hydrocarbon phase, being mutu
desired temperature and pressure for the re
ally insoluble in each other, was separated by
quired length of time. In a continuous process
gravity. If desired, forces greater than gravity,
the ?uorides and the hydrocarbons to be treated
such as centrifuging, could be used in effecting
are fed into a continuous type mixer, for exam
the separation. The lighter or upper layer con
ple, a three-stage mixer, and maintained at the
desired temperature and under the appropriate
tains the hydrocarbons and the lower layer com
pressure. The ?ow through the mixer may be
prises the catalyst phase. This separating op
intermittent or continuous and may be adjusted
eration was carried out under the pressure used
so that the hydrocarbons are in contact with the 70 in effecting the reaction.
catalyst for the desired length of time.
7 The upper layer and 400 volume per cent of
In either the batch of continuous operation, if
a pentane fraction was placed in the second
an ole?n is to be added as a promoter, this may
stage reaction vessel in the presence of 100 vol
be contained in either of the pentane or other
ume per cent of liquid hydrogen ?uoride (based
'raw materials or may be introduced separately 75 , on the volume of the kerosene) in which boron
2,405,997
9
10
trifluoride was dissolved in an amount to pro-‘
vide a partial pressure of 150 pounds per square
inch under the reaction conditions. The mixture
.is agitated at a temperature of 90° F. for a pe
riod of 60 minutes.
low 300°‘F. and about 31% boiling below 400° F.»
The results are as follows:
Hydrocar
bons pro
At the conclusion of the reaction, the upper
bHydilrlocar-d
(weig
ducgcti, 11er
in g
ons c arge
.
layer containing the averaged hydrocarbons and
Hydl ocmbon
any unreacted hydrocarbons, was separated and
its constituents determined.
hydrocarbons charged, are as follows:
Hydrocar
produc
Hydrocar bons
ed
bons charged per(weight
cent of
(weight per
cent)
Propane and lighter _____ __1___\___- ____ __
total hydro
carbons
charged)
0
0. l
_._
35. 9
42. 3
_
4. 9
9. 3
Isopentane _____ ..
25.‘ 6
l5. 5
Normal pentane..
8.0
3. 3_
l. 2
15.0
Isobutane _____ __~ ____ __
Normal butane
Hexane to 300° F_
15
Propane and lighter
cent of the
cent)
-
The composition of the hydrocarbons charged 10
to the over-all two stage process in weight per
cent, and the hydrocarbons resulting from. the
process, expressed in weight per cent of the total
Hydrocarbon
(weight per-
300° to 400° F ____ __~___
_
___
7.9
Above 400° F _______________________ ._
__
__
l6. 5
Hydrocarbons in catalyst phase.
2. 4‘
8. 2
3. 9
It will be seen that there is a net production
the total
hydrocarbons 20 of hydrocarbons boiling in the hexane to 300° F.
charged)
range and a substantial net consumption of the
kerosene and a net consumption of the pentane
fraction, particularly of the normal pentane.
While there is an increase in the amount of
25 butanes from 40.8%. to 51.6%, this increase‘ is
less than the amount of the heavier fraction and
the lighter fraction consumed, indicating the
the accomplishment of averaging.
By extrapolation of- the data from the above
two examples, and by further research, it has
From the above reaction it will be seen that 30 been ascertained thatupon recycling the‘ entire
Hydrocarbons in catalyst phase ____ -I:
there is a net production of 14.3% boiling within
the range of hexane to 300° F. There is a sig
ni?cant consumption of kerosene and a large
consumption of the pentane fraction, particu
larly anet consumption of the normal pentane
to result in these valuable intermediate boiling
hydrocarbons.
The fraction boiling above 300° F. comprising
lighter fraction the amount of butanes may be
expected» to increase until they represent about
80% of the lighter fraction. At this stage there
' will be a net consumption of both the butanes
and the pentanes in‘ the averaging.
The above examples are given merely as illus
trative of the results that may be accomplished
and not as a limitation upon the scope of the
21.8% can be recycled to the reaction zone as 40 invention as described heretofore.
well as the pentanes and butanes, if desired.
In the above examples the upper layer com
Since this stock is substantially aromatic free
prising the hydrocarbons may be sent to a pri
there would be less lower layer hydrocarbon in
mary fractionating column and the excess of
such a continuous process.
lighter fraction and any ?uorides dissolved in
If desired, the fraction boiling from isopentane 46 the upper phase may be separated at the top
to 300° F. may be separated. This amounts to
of the column and recycled to the reaction zone.
39% of the hydrocarbons charged and is a good
‘Since an excess of the lighter fraction in the re
grade of gasoline in View of the small amount
action zone is preferable, a part of the feed for
of normal pentane. The butane fraction may
for the reaction in a continuous process may
be used in alkylating or may be recycled to the
comprise the recycled lighter fraction and fresh
reaction zone and mixed- with the fresh charge 50 pentane feed. The amount of the fresh feed
of pentanes.
stock need be only equal to that which is con
The consumption of kerosene is not as large
sumed in the averaging reaction and it- may be
as in the- following examples, but the process is a
all normal pentane.
desirable one in making a hexane to 300° F.
During the averaging process the normal pen
65
gasoline from pentanes. The incidental iso
tane fed into the averaging reaction zone may
butane formation is desirable since it is a valu
become at least partially isomerized and also
able intermediate product.
converted to butanes as shown in the examples.
The
lighter components that are taken from the
Example 2
60 top of the primary fractionating' column may be
If the entire butane-pentanes fraction from ' further fractionated in one or more secondary
fractionating columns to separate a portion or
Example 1 is to be recycled or if the butanes are
all of the isobutane for use in other processes,
to be recycled with the addition of a fresh charge
such as alkylation, and the remainder of the
of pentane, the results that may be obtained are
excess of the lighter fraction may be returned
indicated in this example, in which a mixture of 65 to the averaging zonep When they alkylation is
butanes and pentanes (approximating the
to‘ be accomplished" with the same catalyst it is
butanes-pentanes fraction from Example 1) is
not necessary to separate any fluorides that may
used as the light stock. This light fraction, in an
distill with the isobutane. Similarly isopentane
amount of 400 volume per cent (based on the 70 may be fractionated if it is not to be recycled or
kerosene) is averaged with a kerosene, with the
taken off in the gasoline fraction. Thus the in
same catalyst and in the same amount, and for
vention contemplates the ability not only to
the same length of time as in Example 1. The
utilize the normal pentane and convert it into
a higher molecular weight hydrocarbon, but at
kerosene used contains about 6% aromatics,
about 5% of the total hydrocarbons boiling be 76 the same time to ‘convert normal pentane to:
2,405,997
11
12
isopentane and isobutane, -a portion-of which
may be withdrawn and used in other reactions.
The lighter fraction separated for recycling
may be depropanized by fractional distillation,
be collected and condensed and/or compressed
absorption, or any other fractionation or suit
able method before recycling, if the propane
builds up to an undesirable level.
-
The wanted products may be withdrawn fro
intermediate plates in the primary fractionating
and returned to the mixing zone or stored or
otherwise used.
Alternatively, instead of distilling the ?uorides,
5
the lower layer or catalyst phase may be treated
with a material which exerts a solvent action on
the ?uorides and which is immiscible with the
hydrocarbons in the lower layer, or which forms
a chemical compound or complex with the ?uo
rides, and from which the ?uorides may be re
column.
The heavier unconverted products may be
leased later, for example, by heating.
withdrawn from the bottom of the column.
Fluorides can be extracted from the upper or
These may or may not be recycled to the reaction
lower layers, for example, with an oxy?uoboric
zone, depending upon their character, or they
acid, such as H3BF2O2 or H4BF'3O2.
may befurther fractionated and a part returned 15
The reference .to a “hydrocarbon fraction” is
to the reaction zone.’
'
If desired, a single product, such as isopen
tane or neo-hexane or a mixture boiling from
about 75° to 141° F. (since only a small amount
intended to refer to a pure hydrocarbon as well
as a mixture of hydrocarbons.
It will be apparent that the invention is capa
ble of many applications and variations and I
of normal pentane remains after the reaction 20 intend all of them to be included as are within
the following claims.
process) may be withdrawn from the fractionat
This application is a continuation-in-part of
ing column and all of the lighter (butanes) and
all of the heavier (normal hexane and heavier)
applications Ser. No. 422,744, filed December 12,
materials maybe recycled to the averaging re
1941; Ser. No. 451,216, ?led July 16, 1942, and
action zone. This will shift the conditions in the 25 Ser. No. 529,681, ?led April 5, 1944.
averaging reaction so as to form primarily the
I claim:
1. A process of catalytically averaging hydro
product being withdrawn. The pentane averag
ing process thus may be used essentially for mak
carbons which comprises reacting a normally liq
uid hydrocarbon fraction comprising para?inic
ing a single wanted product with the return of
all other products as raw materials.
,
30 hydrocarbons having at least seven carbon atoms
The lower layer or catalyst phase is separated
and a lighter hydrocarbon fraction comprising
from the hydrocarbons at such a temperature
normal pentane, in the presence of a liquid cata
lyst the inorganic ingredients of which comprise
and pressure that the catalyst remains as a dis
tinct liquid phase, in accordance with the pre
essentially liquid hydrogen ?uoride in which is
ferred embodiment, the catalyst phase may be 35 dissolved not over 50 mol per cent of boron tri
recycled and reused for the treatment of a fresh
?uoride, and continuing the reaction under a
pressure to maintain the hydrogen fluoride liq
current system for dearomatizing mentioned
uid and at a temperature and for a period of
heretofore. The used catalyst phase may also be
time while regulating the activity of the catalyst
employed in other averaging operations which 40 by adjusting the partial pressure of the boron
require a less active catalyst. For example, the
tri?uoride to result in a net production of hy
catalyst may be used initially on a stock which is
- drocarbons intermediate said liquid hydrocarbon
di?icult to react and after separation from said
fraction and said normal pentane.
stock, it may be reused with stocks that are.
2. A process of catalytically averaging hydro
easier to react. Alternatively the used catalyst 45 carbons, which comprises reacting a normally
phase may be used as an alkylation catalyst where
liquid petroleum fraction boiling higher than
a less active catalyst is required.
gasoline, and a hydrocarbon fraction compris
Certain hydrocarbons, notably unsaturates and
ing normal pentane, in the presence of a liquid
aromatics, tend to accumulate in the catalyst
catalyst the inorganic ingredients of which com
phase in the form of a complex during the aver 50 prise essentially liquid hydrogen ?uoride in which
aging reaction. In the above examples it will
is dissolved not over 50 mol per cent of boron
be noted that the catalyst phase contains a
trifluoride, and continuing the reaction under a
slight amount of hydrocarbons. A small amount
pressure to maintain the hydrogen'?uoride liquid
of a complex with an unsaturate in the catalyst
and at a temperature and for a period of time
phase is thought to be helpful as a promoter, and
while regulating the activity of the catalyst by
for this reason the presence of an ole?n has been
adjusting the partial pressure of the boron tri
indicated as desirable. But the accumulation of
?uoride to result in a net production of hydro
too much hydrocarbon in the catalyst phase ex
carbons intermediate said liquid petroleum frac
erts a poisoning effect. Therefore, if the amount
tion and said normal pentane.
of hydrocarbon in the catalyst phase is keptat 60
3. A process of catalytically averaging hydro
supply of raw materials or such as in the counter
the optimum value, the reaction will proceed
carbons, which comprises reacting kerosene and
more rapidly and less of the catalyst will be re
a hydrocarbon fraction comprising normal pen
tane and isopentane, in the presence of a liquid
quired.
To overcome this poisoning effect, a part or
catalyst the inorganic ingredients of which com
all of the used or reused catalyst may be with 65 prise essentially liquid hydrogen ?uoride in which
drawn and subjected to a relatively high tem
is dissolved not over 50 mol per cent of boron
perature, for example, 250-600° F. This may be
tri?uoride, and continuing the reaction under
by way of a pot still, or by means of ?ash distil
a pressure to maintain the hydrogen ?uoride liq
lation. Preferably a two-stage treatment ‘is em
uid and at a temperature and for a period of
ployed, the ?rst stage using a ?ash distillation 70 time while regulating the activity of the catalyst
at a somewhat lower temperature, preferably at
by adjusting the partial pressure of the boron
system pressure followed by distillation in a
tri?uoride to result in a net production of hydro
stripper at a higher temperature and lower pres
carbons intermediate said kerosene and said pen
sure. At this temperature substantially all of
tanes.
4. A process of catalytically averaging hydro
the ?uorides are liberated as gases, These can 75
13
2,405,997
14
carbons, which comprises reacting a normally
liquid hydrocarbon fraction comprising paraf?nic
catalyst phase from the hydrocarbon phase, frac
tionating the hydrocarbon phase and recycling
hydrocarbons having at least seven carbon atoms
and a butanes-pentanes hydrocarbon fraction
comprising normal pentane, in the presence of
a liquid catalyst the inorganic ingredients of
at least part of the unreacted lighter hydrocar
bon fraction to the reaction zone.
8. A process of catalytically averaging hydro
carbons, which comprises reacting a lighter hy
drocarbon fraction comprising normal pentane
which comprise essentially liquid hydrogen ?uo
ride in which is dissolved not over 50 mol per
and a heavier hydrocarbon fraction comprising
cent of boron tri?uoride, and continuing the re
primarily hydrocarbons having at least seven
action under a pressure to maintain the hydro 10 carbon atoms in a reaction zone in the presence
gen ?uoride liquid and at a temperature and for
of a liquid catalyst, said catalyst comprising es
a period of time while regulating the activity
sentially liquid hydrogen ?uoride in which is dis
of the catalyst by adjusting the partial pressure
solved less than 50 mol per cent of boron tri
of the boron tri?uoride to result in a net con
?uoride as the primary inorganic catalytic in
sumption of said liquid hydrocarbon fraction and 15 gredients, and continuing the reaction under a
said normal pentane, and to produce hydrocar
bons intermediate said liquid hydrocarbon frac
pressure to maintain the hydrogen ?uoride and
the hydrocarbons liquid and at a temperature
and for a period of time while regulating the
tion and said pentanes.
5. A process of catalytically averaging hydro
activity of the catalyst by adjusting the partial
carbons, which comprises reacting a petroleum 20 pressure of the boron tri?uoride to result in a
fraction boiling higher than gasoline and a bu
net production of isopentane and hexanes, sep
tanes-pentanes hydrocarbon fraction comprising
arating the catalyst phase and the hydrocarbon
a normal pentane, in the presence of a liquid
catalyst the inorganic ingredients of which com
prise essentially liquid hydrogen ?uoride in which 25
is dissolved not over 50 mol per cent of boron
tri?uoride, and continuing the reaction under a
pressure to maintain the hydrogen ?uoride liquid
phase, iractionating the hydrocarbon phase to
separate a single wanted fraction boiling between
isopentane and hexane isomers, and recycling at
least part of the remaining heavier hydrocar
bons to the reaction zone.
9. A process of catalytically averaging hydro
and at a temperature and for a period of time
carbons, which comprises reacting a lighter hy
while regulating the activity of the catalyst by 30 drocarbon fraction comprising normal pentane
adjusting the partial pressure of the boron tri
and a heavier hydrocarbon fraction comprising
?uoride to result in a net consumption of said
primarily hydrocarbons having at least seven
petroleum fraction and said normal pentane, and
carbon atoms in the presence of a liquid catalyst,
to produce hydrocarbons intermediate said petro
said
catalyst comprising essentially liquid hydro
leum fraction and said pentane.
35 gen ?uoride in which is dissolved less than 50
6. A process of catalytically averaging hydro
mol per cent of boron tri?uoride as the primary
carbons, which comprises reacting a lighter hy
inorganic catalytic ingredients, and continuing the
drocarbon fraction comprising normal pentane
reaction under a pressure to maintain the hydro
and a heavier hydrocarbon fraction comprising
gen ?uoride and the hydrocarbons liquid and at
primarily hydrocarbons having at least seven 40 a temperature and for a period of time while
carbon atoms in a reaction zone in the presence
regulating the activity of the catalyst by adjust
of a liquid catalyst, said catalyst comprising es
ing the partial pressure of the boron tri?uoride
sentially liquid hydrogen ?uoride in which is
to result in a net production of isobutane and
dissolved less than 50 mol per cent of boron tri
hydrocarbons intermediate the pentane and said
?uoride as the primary inorganic catalytic in
heavier fraction, separating the catalyst phase
gredients, and continuing the reaction under a
pressure to maintain the hydrogen ?uoride and
the hydrocarbons liquid and at a temperature
and for a period time while regulating the activ
ity of the catalyst by adjusting the partial pres
sure of the boron tri?uoride to result in a net
production of hydrocarbons intermediate said
normal pentane and said heavier fraction, sep
arating the catalyst phase from the hydrocar
and the hydrocarbon phase, fractionating the
hydrocarbon phase to separate isobutane as one
fraction and said intermediate hydrocarbons as
50
another fraction.
10. A process of catalytically averaging hydro
carbons which comprises reacting a butanes
pentanes hydrocarbon fraction comprising nor
mal pentane and a petroleum fraction boiling
above gasoline in a reaction zone in the presence ,
bons, separating the ?uorides from the catalyst 55 of a liquid catalyst, said catalyst comprising es
phase, and recycling the separated ?uorides to the,
sentially liquid hydrogen ?uoride in which is dis
reaction zone.
solved less than 50 mol per cent of boron tri
7. A process of catalytically averaging hydro
?uoride as the primary inorganic catalytic in
carbons, which comprises reacting a lighter hy
gredients, and continuing the reaction under a
drocarbon fraction comprising normal pentane 60 pressure to maintain the hydrogen ?uoride and
and a heavier hydrocarbon fraction comprising
the hydrocarbons liquid and at a temperature
primarily hydrocarbons having at least seven car
and for a period of time while regulating the ac
bon atoms in a reaction zone in the presence of
tivity of the catalyst by adjusting the partial
a liquid catalyst, said catalyst comprising essen
pressure of the boron tri?uoride to result in a net
tially liquid hydrogen ?uoride in which is dis 65 consumption of said normal pentane and said
solved less than 50 mol percent of boron tri?uo
petroleum fraction, and to produce hydrocarbons
ride as the primary inorganic catalytic ingredi
intermediate said normal pentane and said pe
ents, and continuing the reaction under a pres
troleum fraction, separating the catalyst phase
sure to maintain the hydrogen ?uoride and the
from the hydrocarbon phase, separating ?uorides
hydrocarbons liquid and at a temperature and for 70 from the catalyst phase and recycling the sepa
a period of time while regulating the activity of
rated ?uorides to the reaction zone, fractionat
the catalyst by adjusting the partial pressure of
ing the hydrocarbon phase and recycling to the
the boron tri?uoride to result in a net production
reaction zone at least part of the hydrocarbons
of hydrocarbons intermediate said normal pen
lighter than said intermediate hydrocarbons.
tane and said heavier fraction, separating the 75
ROBERT E. BURK.
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