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Патент USA US2403649

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Patented July
1946
2,403,649
`
UNITED STATI-:sf PATENT OFFICE; f
HYDROCARBON RECONSTRUCTION
Frederick E. Frey, Bartlesville, Okla., vassigner to
. Phillips Petroleum Company, a corporationof
Delaware .
Application January 13, v1942, Serial No. 426,627
18 Claims.v (Cl. 260-683.5)-
2
1
compounds; (6) conversion of noncyclic hydro
vThis invention relates to the conversion of hyv
drocarbons. More particularly, Y ity relates fto'
chemical reconstruction of hydrocarbons-in the
carbons to cyclic compounds. When the initial
material has a considerable proportion of naph
presence of hydrofluoric acid as a catalyst. This
thenes,disproportionationofV these to paraflins
application is a continuation in part of my co 5 and aromatics appears to occur, especially at rela
pending application Serial No. 323,443, filed March
11, 1940, now Patent 2,317,901, issued April 27,
tively drastic conditions oi 'time and 'tempera
1943.
ture.
The y production
.
of these effects indicates>
, that
several different types of Vchemical reactions may
beiin'volved vin-the present 'process'.ffor; recon
struction of hydrocarbons.
v Y
The `predominating
I have discovered that, in the presence of `sub
stantial proportions _of khydroi‘luoric «acid andv 10
under suitable conditions of time and/or'temper
Iature, hydrocarbons cany be catalytically recon
structed to hydrocarbons of differentA lcarbon
vskeleton arrangement and/or., different vboiling
point, thereby effecting an improvement in yprop
t
reaction types, as deduced `from 'a consideration „
of reactants, products, operating conditions,fand
theoretical aspects relating to the invention, may
be exemplified as follows:
Y
" Y
erties and in usefulness for specific purposes.
Parañinic hydrocarbons boiling in the motor
,<0 .
fuel range, for example, undergo conversioni-,o
isomers and to hydrocarbons of both lower and
y
'
higher molecular> weights and correspondingly 20'(2)
y
.
Y
suitable reaction temperature and pressure and
'
.
’
,
j
,HF
30
..
Y
'
`-
2C1H1ß
`
HF
'
,_>
(heptanevs)
-l-_> 2041110
(cyclohexane)
'
06H12
06H12
(butanes) '
H
-_->«
(cyclohexane)_ ,
for a time suflicient to eii’ect the desired extent
'(octanes)
-
y(b) :_1-butano- --> Isobutane
Í
(4)
hydrocarbons to the action of a substantial'pro
vportion ofconcentrated- hydrofluoric'acid at a
HF
(a) n-heptane 1_» branched heptanes ,
’,
higher-boiling products. Accordingly, the pres 25 (3)
ent invention comprises subjecting hydrocarbon
material consistingk predominantly of saturated
Y (hexanes)
‘
lower and higher boiling temperatures. Similarly,
motor-fuel fractions containing minor propor
tions of unsaturates are converted into complete
ly saturated materials containing some lower-and
(heptanes)
.
t
CHaCtHa
(methyl cyclopentane)
The ñrst two reactions, namely, reconstruction to
produce both higher-and lower-boiling parafñns,
of conversion. Recycling of unreacted hydrocar
'and isomerization, respectively, predominate un
bons and/or of selected fractions of the product
der relatively mild treating conditions. "The
may be practiced. By the term “saturated” l
yields of cyclics, exemplified' in thethird equation
intend to exclude unsaturated hydrocarbons such 35 by cyclohexane, is increased by increasing theV
as oleiins, dioleiins, acetylenes, and the like.
temperature and/or the timeofu reaction. A
In general, this invention may be Íused to con
vfourth ytype. of reaction' is believed to account for
vert or improve hydrocarbon materials compris
the increase in saturation and stability that oc
ing substantially entirely saturated hydrocar
curs when motor fuel comprising some unsatu
bons; although minor proportions of unsaturated 40
rated material is treated. By this reaction, ole
ñns arey converted to cycloparañins such as cyclo
heXane and its derivatives. _This reaction may
hydrocarbons initially present can be tolerated,
it is not intended that my invention Ashall include
a process'only for the alkylation- of saturated
hydrocarbons by reaction with unsaturated hy,
be exempliñed as follows: l
‘
drocarbons. The specific effect-„produced in any 45
particular case is usually one or more of the fol
lowing: (1)' increased octane number of motor
fuel range hydrocarbon materials; (2)V enhanced
susceptibility to antiknock improvement by the
addition of tetraethyl lead to hydrocarbon ma
__)
(heptylene)
" C eHuC Ha
‘ (methyl cyclohexane)
Several other types of reactions undoubtedly oc
50 cur in the reconstruction process; however, the
terials; k(3) ' conversion of hydrocarbons to hydro
above-mentioned kñve types appear to accountl for
carbons of higher and/or lower molecular
most of the effects which are produced. The gen
eral term “reconstruction” is used herein to de
weights; (4) decreased content of unsaturates in
noteV the production of one or more of the above- „
hydrocarbon materials; (5) conversion of hydro
carbons to relatively highly branched isomerio 55 mentioned effects and/or of other inherent ad- '
U
2,403,649
3
4
vantageous effects which result from the practice
production capacity of equipment of any given
size; however, proportions outside of the pre
of my invention.
Insofar as I have been able to determine, .the
actual catalyst which promotes the reconstruc
tion reaction, or reactions, is concentrated hydro
ñuoric acid. Other materials may be present
which will exert a slight promoting effect, such
as compounds fortuitously formed in minor
amounts by reaction of hydroñuoric acid with
Walls of reaction vessels, but the presence of
such compounds does not alter the fact that hy
drofluoric acid is the catalyst. Agents which
ferred range should not be excluded from the
scope of this invention. Mixing of the hydro
fluoric acid and the hydrocarbon material may
be effected by any of a number of methods, as by
the use of a special mixer or emulsiñer, or by
maintaining high linear velocities in conduit I3;
devices such as sharp bendsI or constrictions in
conduit I3 are advantageous in some instances. `
The resulting mixture is passed to heater I?,
wherein it is heated to a suitable reaction tem
perature. Heater I1 preferably consists of a tube
cOil surrounded by hot gases or liquids. In some
promote the action of the hydrofluoric acid may
be added in many instances without changing
the character of the reaction nor exceeding the 15 instances, as When the desired reaction tempera
ture is atmospheric, or only slightly above, heater
scope of the spirit of the invention and of the
I'I is unnecessary and may be ‘oy-passed or. re
disclosure. The> reaction may take place in the
presence of relatively or essentially inert solids
moved from the system.
Depending somewhat .upon the character of the
of large surface area such as activated charcoal,
initial hydrocarbon material, the reaction tenu
bauxite, etc. which will tend to adsorb and con
perature may vary from about 50 to about 1090o
centrate hydrofluoric acid in an active state.
F.; a temperature in the range of 250 to 800D F. is
’When it is desired to maintain hydroñuoric acid
usually preferred. The pressure may vary from
in a liquid phase at higher reaction tempera
about atmospheric to 5000 pounds »per square
tures, this effect may be aided by incorporating
with the hydrofluoric acid inorganic salts which 25 inch, or more. The reaction time may vary from
about one minute to twenty hours or more, high
are soluble in hydro?luoric acid, especially the
values applying to relatively low reaction tem
iiuorides of alkaline materials and of alkali-earth
peratures or to highly refractory reactants, and
metals.
i
low values applying to relatively high operating
' An object of this invention is to provide a new
process for catalytically reconstructing hydro 30 temperatures or to highly reactive reactants. De
pending upon the particular hydrocarbon mate
carbon material.
rial being treated and upon the region of tem
lA further object is to produce hydrocarbons
perature and pressure under which the recon
of -loWer and/or higher molecular weight and of
structing reaction is conducted, the mixture of
correspondingly lower and/or higher boiling
hydrocarbons and catalyst may be in a wholly
points than those of the material treated.
gaseous phase, in a partially liqueñed condition,
A specific object is to treat motor fuel so as to
or in a Virtually wholly condensed condition. The
enhance its susceptibility to improvement of its
extent of conversion increases with increase in
antiknock rating by the addition of tetraethyl
temperature, time, and/or catalyst concentration.
lead.
Another speciiic object is the production of sat 40 Changes in pressure appear to affect the nature
of the reaction appreciably, particularly at high
urated hydrocarbons boiling in the motor-fuel
temperatures. In general, an increase in pressure
range and having increased unleaded and leaded
retards the formationof lower-boiling hydrocar~
octane numbers as compared with the original
4bons and increases the formation of higher-boil
material or corresponding fractions thereof.
Another specific object is to improve hydrocar- -» ing- hydrocarbons; also, increase in pressure tends
to increase the rate of conversion, particularly
bons, such as those obtained by petroleum reñnery
under gas-phase operating conditions. Over-re
operations, and especially those boiling in the
acting may lead to the formation of some heavy
motor-fuel range, by increasing the degree of
oils, usually of relatively low value, and of some
saturation and, consequently, the stability, when
a small but undesirable proportion of unsaturates 50 organic iiuorine-containing compounds of high
molecular weight, which usually remain mostly
are originally present.
dissolved in the hydroñuoric acid when the pro
Another specific object is to convert normal or
portion of acid is large enough for a separate
slightly branched aliphatic hydrocarbons to more
liquid acid phase to be produced upon cooling
highly branched aliphatic hydrocarbons.
the reaction mixture.
A further object is to convert normal paraffins
The optimum operating conditions in any
into corresponding isoparafñns.
specific case are dependent upon the nature of
Other objects and advantages of my invention
the feed material aswell as upon the extent of
will be apparent from the accompanying disclo
reconstruction desired. For example, in treating
sure and discussion.
An understanding of some of the many aspects 60 a lube oil to decrease unsaturation or to modify
such properties as the pour point, the viscosity,
of the invention may be aided by the accompany
or the like, relatively mild reconstructing condi
ing drawing, which is a flow-diagram illustrating
tions are used. By contrast, in reconstructing
a preferred arrangement for practicing the in
relatively refractory materials, such as normal
vention.
~
butane or normal pentane, to produce isomers
A suitable hydrocarbon material, admitted tov
the system through inlet I0, pump II, and valve
I2, is mixed in conduit I3 with concentrated, prei
erably anhydrous, hydrofluoric acid, which is ad
mitted through inlet I4, pump I5, and valve I6.
The proportion of hydro?luoric acid is preferablyy
in the range from 0.2 to ‘l times by weight of the
total l hydrocarbon
fluids.
Proportions
much
smaller than this are sometimes insuiiicient to
>effect the desired degree of conversion, whereas
much larger proportions vdecrease undesirably the
and higher-and/or lower-boiling hydrocarbons,
relatively drastic conditions are required. For re
constructing normal butane to produce isobutanc,
the preferred conditions are a temperature in
the range of 400 to 800° F., a pressure in the range
of 250 to 2500 pounds per square inch, and a re
action time in the range of 1 to 100 minutes; but
` conditions outside of these ranges may at times œ
used, in accordance with the principles of the
invention. The reconstructing reactions to im
‘2,403,649
.
‘
5
V6
prove the rantikno'ck"characteristics of' motorffuel
i'acid phase, wherein most of the reaction takes
what less drastic conditions than those preferred
upper layer _from the acid, from which it maybe
withdrawn. Acid passing out of solution on cool
place;V Converted hydrocarbonseparates as 'an .
hydrocarbons are usually carried-out under some
for the reconstruction of normal butane. For any
rparticular case, the optimum;k conditions are read
ing may be allowed to return to the column of
ily determinable’by trial "by one skilled in the
art in the light ofthe present disclosure and dis
cussion.
'
'
-
acid.
l
f
Y
' '
'
The eliiuent mixture from reactor 23 is passed
l Vthrough conduit 28 havingvalve 29 to separator
f
20 Ywherein it is separated into two liquidphases, `
When the requisitereaction time is relatively
as
lby ‘cooling and gravitation or centrifugal
10
short, such as about one to about ten minutes, the
means. The lighter' 'or hydrocarbon phase is
reaction may be carried out preferably wholly in
passed vthrough conduit 30 Vhaving valve 3| to
tu-be heater I1, from which the reaction mixture
fractionator32. The heavier or hydrofluoricacid
is conducted via pipe I8 and vvalve I9 directly to
phase ’ may be recycled via conduit`33 _having
cooler and 'separator 20. -When the requisite re`~
>action time is relatively long, it is advantageous 15 valve 34 to pump> I5; however, preferably at least
part of it is passed through valve 35 and con
>to pass the heated, mixture from heater rI'l
duit
36'to acid fractionator 31, wherein it is puri
through valve> 2| and conduit 22A >to reactor 23,
ñedbefore being reused.
wherein the mixture isdigested at the reaction
From -fractionator 32 is passed a comparatively
temperature and pressure for a time sufficient to
minor
overhead fraction, which comprises free
effect the desired conversion. Such digestion may
hydrogen fluoride and relatively low-boiling- hy
need AtoA be accompanied by vigorous agitation
drocarbons, through valve 38 and conduit 39‘ to
when relatively immiscible liquid phases are pres
separator 4ll.V The rremaining or major portion
ent. When liquid-phase or mixedfpha'seroperat
of material, which comprises substantially pure
ing conditionsl are used, means for effecting agi
hydrocarbons with very small proportions of or
tation or miXingrin reactor 23 are usually desir 25 ganic fluorine compounds, is passed through valve
able, Y because liquid hydrocarbon-hydrofluoric
4| -and conduit 42 to deñuorinator or i'luorine re
acid'mixtures tend to separate into two layers.
mover 43.
Mixing may be effected by any well-known means,
` Fluoriner remover 43 comprises a chamber con- ,
such as mechanical stirrers, relatively constricted
taining a contact mass having hydrogenation '
.30
orifices or zones` through which the mixture is
and/ or dehydrogenation properties, such as baux
passed at high linear velocity, or the like; it may
ite, alumina, or other similar material. Usually
be aided by recirculation, las through circuit 24,
suitable operating conditions are a temperature
pump 25, and valves 26 and 21. If all components
in the range of 75‘to 250° F. and a space velocity
of the reaction mixture are in a single phase,
Yin the range of 1 to 50 volumes of liquid hy.
no means of agitation willgenerally be required.
drocarbon material per volume of contact mass
Usually the heat of reaction is relatively small
per hour. Under such conditions, which may. be
particularly selected in accordance with a trial,
organically combined ñuorine is substantially
and does not markedly affect the temperature of .
the reacting mixture. Preferably, reactor 23 is
,operated adiabatically; but, if desired, auxiliary
completely removed from the hydrocarbon ma
heating or cooling devices may be incorporated in 40 terial, which then is `passed through valve 44
reactor '23,. although control of the temperature
4and conduit 45 to fractionator 46. Such deflu
therein is more suitably effected by controlling
orination'is more completely disclosed, and is
the heat input in heater l1.
, ì
claimed, in my copending application Serial No.
YI have found that the solubility of saturated
398,361, filed June 16, 1941. This is now Patent
hydrocarbons in hydrogen fluoride, and the solu
2,347,945, issued May 2, 1944. When organic flu
bility of _hydrogen ñuoride in 'such hydrocarbons
increases with elevation in temperature. At tem
peratures near but below the critical for hydro
gen fluoride, under supercritical pressures Ihave
found it convenient to operate with a liquid hy- ~
drogen iluoride phase containing a _high content
vof dissolved hydrocarbon. ~ rIn such instances ag1
tating means are sometimes unnecessary, during
the digestion period in which the reaction is ef-`
fected, a's discussed. Similarly, I may operate in
the sub-critica1 temperature region with respect
>to a hydrocarbon phase carrying in solution a
high proportion pf hydrogen fluoride or acid.
Reaction may be effected in acid rich liquid phase
by contacting the hydrocarbon to be converted
with liquid hydrogen fluoride at elevated tem
perature, thereafter separating the acid phase,
now containing the reactant hydrocarbon in so
lution, and then subjecting the solution to reac
tion conditions. The acid rich effluent from such
a step may be distilled to recover the volatilizable
hydrocarbons together with a part of the acid,
orine compounds are not present or harmful, ory
are to be removed by treating only a part of the
material present, the hydrocarbon material can .
'be passed directly to fractionator 46, entirely or
vin,pa.r1'.,fiîrom conduit 42 through conduit 69 and
valve 1K0, valves 4I and 44 being partially or com
pletely closed.
'
'
‘
'
'
Fractionator 46 effects'a separation of the hy
drocarbon mixture into the desired products, by
products, and recycle fractions. For exam-ple, if
' the principal product is motorfueljthe follow
ing four fractions may be obtained: (l) a >by
product fraction comprising chiefly isoparañ‘ins
60 boiling below the motor-fuel range, whichis with
drawn through outlet 4l having valve 48, and
which may be used as conversion stock in an al
kylation process;
(2‘)
a motor-fuel fraction,
which is withdrawn‘through outlet 49 having
valve 50; (3) a fraction vboiling above the motor
fuelrange, which may be recycled by way of valve
5I and conduit 52’ to pump Il; and (4) a bottom
fraction comprising a high-boiling hydrocarbon
residue, which may be Withdrawn through outlet
may be used again in the conversion Step. In an
other modiñcation hydrocarbon material may be 70 53 having valve 54. If desired, the motor-fuel
fraction withdrawn may be limited to a relatively
.introduced into the lower end of a column'of y
narrow-boiling range in order to obtain relatively
liquid acid maintained at reaction temperature
concentrated
specific materials, such as, for ex
through which the hydrocarbon ascends by vir
ample, highly-branched octanes, while‘other hy
tue of its lower density, undergoing as it ascends
While the residue of hydrocarbon-depleted acid
y
-partitionwith the hydrocarbon dissolved in the
drocarbons boiling in the motor fuel range are
2,403,649
7
vseparately-recovered, by means *not shown '_or
thereaction mixture in th'efliquid phase. The
through 53, and/or passed tothe conversion zone
reaction> mixture was then cooled to 32° F. and
through' conduit 52.
was allowed to stand for a few minutes, Where
upon two liquid phases separated out. The upper
or hydrocarbon phase was equivalent to»93 per
.-
. .
.
»
The overhead effluent from fractionator 32'is
separated into two phases in separator 40, as by
cooling and centrifugal or gravitational means.
»The lighter or hydrocarbon phase is withdrawn
through outlet 55 having valve VV55; and theheavier or hydroiiuoric acid phase is recycled
cent by weight ofA theV Aoriginal hydrocarbon
charge. 'I'h‘ishydrocarbon product'was found to
have approximately the following composition, in
per cent by weight: propane, 1,2; isobutane, 4.1;
through conduit 1l and valve 51 to conduit 33 10 pentane, 2.3;v hexanes, 1.2; highly branched >hep
and to pump I5. f Part> or all of the light hy
drocarbon material passed through conduit 55
may be returned to fractionato-r 32 through con
duit 61 controlled >by valveI 58 in which case light
hydrocarbons . mayv be
through conduity 41.
completely
discharged
Such an operation is more ’
fully disclosed, and is claimed, in’my copending
application Serial No. 315,063, Filed March 11,
1940, now Patent 2,322,800, issued June 29, 1943.
Fractionator 31 separates the acid eiiiuent from ,
separator 20 into an overhead fraction compris
ing anhydrous hydrogen fluoride and small pro
portions of hydrocarbons, which is passed by way
of valve 58 and conduit 50 to separator 60, and
into a bottom or sludge fraction comprising flu 25
oro-organic material, tar, etc., which is with
drawn through outlet 5! having valve 52.
tanes, 18.4; hydrocarbons boiling in the range of
93.5 to 100° C., 43.0, which appeared to be com
posed of normal heptane, isooctane, and cyclics;
hydrocarbons boiling above 100°’ C., 11.4. This
product was found to havev an ASTM- octane num
ber of 54.6 and a lead susceptibility of 12.5; it
contained virtually no oleñnic unsaturation (by
bromine titration).
~
,»
,
Material of thefcharacter produced in this'ex
ample is suitable for blending in ordinary motor
fuel.. Preferably, however, an aviation-gasoline
cut, such as an isooctane fraction, is separated
out, and part of the remainder is recycled to the
treatment with‘vhydrogen ñuoride, and/or, 'op
tionally, part is used for conversion stock in other
hydrocarbon-conversion processes. For example,
the isobutane fraction is particularly advanta
In separator 60, the overhead effluent from
geous for use in alkylation processes; thefrac
tions boiling above the aviation-gasoline range
las by cooling and centrifugal or gravitational 30 are suitable for cracking stock to produce cracked
means; a hydrocarbon phase which is withdrawn
gasoline; and the relatively low-octane fractions
through outlet 63 havingvalve 04, and a con
boiling within the gasoline range are suitable for
centrated hydroiiuoric acid phase which is re
recycling to my process.
' ’
cycled by way of va1ve55 and conduit `(it to
Example II
acid fractionator 31 is separated into two phases
pump I5. Any hydrocarbon -phase may, if de 35
A substantially pure isooctane fraction was ag
sired, be passed from conduit 63 through conduit
itated for one hour at a temperature of 70° F.
r‘l2 and valve 'F3 to conduit I8 and separator 20.
with an equal volume of concentrated hydroflu
If desired, the sludge formed at the bottom of
fractionator 31 may be subjected to thermal de
oric acid. The reaction mixture was Withdrawn
and was separated, by settling and decanting, in
composition, whereby free hydrogen fluoride is
to an acid phase and a hydrocarbon phase. The
liberated, and the resulting recovered hydrogen
fluoride may be recycled to pump I5. The ther
mal decomposition may be effected in fractionator
31 itself, if a-suitably high bottom temperature
is emp1oyed,ror it may be effected in a separate
means, not shown.
The process of this invention is applicable to
hydrocarbon phase wasequivalent by Weight to
94.1 per cent of the original hydrocarbon charge.
It had the following composition in mol per cent;
isobutane, 29.2'; Pentanes, 9.1;'hexanes 4.8; hep
tanes, 4.5; hydrocarbons boiling higher than hep
tanes, 52.4. The composition of the normally liq
many different specific hydrocarbon feed mate
uid portion of the product, in per cent by weight,
rials, and it may be employed to produce several
was as follows: pentanes and h'exanes, 15.5; hep-k
desirable effects. For example, in the produc
tanes, 6.8; octanes, 34.2; nonanes, 9.3;` decanes,
tion of isoparaffins of five toten carbon atoms 50 10.9; undecanes and dodecanes, 15.0; hydrocar
per molecule, suitable for use in aviation gasoline,
bons boiling higher than dodecanes, ,8.3.
fractions of straight-run gasoline or natural gas
This example illustrates the formation of hy
drocarbons having higher and lower boiling points
oline are suitable; these fractions may be ob
tained by many known means, such as fractional
and correspondingly higher and lower molecular
distillation, selective extraction, and the like.
lsopentane, when reconstructed by hydrogen `flu
weights than those of the original material. " The
lower boiling compounds, particularly isobutane,
oride, yields, besides some isobutane, considerable
amounts of `hexanes and heptanes, mainly of
rather highly branched structure, that are suit
are suitable for conversion stocks in alkylation
processes for producing aviation gasoline; the
higher-boiling compounds, such as undecanes and
60 higher, may be advantageously recycled within
able for inclusion in aviation fuel.
A few of the many aspects of my invention
my process, or they may be used, for examplaas
are illustrated in the following examples, which
conversion stock in cracking processes to produce
are purely illustrative and not necessarily limi
aviation gasoline. The middle-range hydrocar
tative of the invention.
Example I
A fraction fromV natural gasoline that boiled in
the methylhexane range was found to have- a
clear ASTM octane number of 46.9 and a lead
susceptibility of 11.7 octane numbers for 1 cc. of
tetraethyl lead per gallon. A portion of this ma
terial was agitated with one third of its volumne
of concentrated hydrogen fluoride for 26 hours at
an average temperature of 270° F. anf‘ under
pressure suñìcient to maintain all components of
bon material, such'as pentanes t0 decanes, in
clusive, is suitable’ for use- as aviation motor fuel.
Example III
In a process for'manufacturing-aviation gaso
line, a by-product motor-fuel-range hydrocarbon
mixture is produced that has an octane number
of about 63 and a tetraethyl‘lead response of '7.5
octane numbers for 1 cc. of tetraethyl lead per
gallon. This material is treated, in accordance
with’ the principles of my invention, with an equal
volume of concentrated hydrofluoric acid. The
2,403,649;
10
conditions are: temperature 350° F.; pressure,
shaken 4continuously by a Ymechanical rocker.,
equivalent to the vapor pressure of the reaction
The reaction mixture -was then withdrawn, and a _»
mixture; time, 40 minutes; and rapid agitation.
The reaction mixture isV partly in the vapor, phase.
On being cooled, as to about V40 to 80° F., there
hydrocarbon phase was recovered by decanting.`
It V_was found by fractional analysis to have the
followingl composition in per cent by liquid
sulting Ymixture is separated into . two ,liquidV
volume.
phases. From the hydrocarbon' phase, which is`
equivalent by weight to about 86 percent of ythe*
.
.Y
Y.
~
~ Lower-boiling _`_____________v_____________ Tracel
original charge, is separated an aviation-gasoline f
Butanes _ ______________________________ __
8.5
70.2
fraction having an octane number of 85 and a 10 Isopentane
lead lresponse of 12.5. e A relatively low-boiling _
N-.Pentane ______ __ ____________________ __
fraction comprising mostly isobutane is used as
feed to an alkylation process for producing avia
tion gasoline, and a relatively high-boiling frac
Hexanes
'
High bniling
____ ___
tion is subjected to a cracking process for produca 15
ing cracked gasoline.
Y
100.0
Example VII
anhydrous l hydrofluoric
acid.
`
Toa steel bomb of 400 cc. capacity were charged
84 grams of anhydrous hydroñuoric acid and43>
Asteel bomb was almost ñlled with' 28 grams
of C. P. normal butane and 60 grams of substan
grams of C. P. normal pentane. The'bomb was
heated to` 572° F. »and was maintained at that
temperature for A30 minutes. vIt >was then cooled,
and the products were withdrawn. It was found
Suitable
means for heating the bomb, maintaining the
contents in intimatemixture, and for measuring
the internal temperatureand `the pressure were
by fractional'analysis that approximately 10l per
centofiv the >normal pentane had reacted to give
the following products in the proportions shown:
provided. The temperature was raised to 350°F.,
and the pressure rose to 3700 pounds per square
inch.
0.6
AY small proportion of .l
tarry residue is withdrawn fromthe system.
El‘ample IV
tially
,
8.3
12.4
After 3 hours th'e heatv was turnedroiî, and ,
the bomb was rapidly cooled.y The products were
wtihdrawn and separated by decantation. The
recovered hydrocarbon layer weighed 20.3 grams; ,
it was treated with alkaline solution to'remo've.
Mol
'
30
Product:>
Y
'~
Lower boiling ______ _____ _______ __ ____ __.'I‘race
Propane
` I_ 17.3
hydrogen fluoride. The resulting hydrocarbon
Isobutane
product was found by fractional analysis to have
Normal lontane
31.5
‘
the following composition, in per cent by weight: 35 Isopentane
`Propane
___________ __ _________________ __
Isobutane
>
Normal butane
Hexane
3.2
4.3
ì
6.0
Higher-boiling _.-_____ _______________.___'___ _3.0
n
2.5
40
Y
19.7
_ 22.5"
90.0
Isopentane ________ __ __________________ __
'
percent
100.0
Example VIII-
'
100.0
Ezramplel V
To a steel bomb were charged 92.4 grams of
In- an> experiment similar to that of `Example ` concentratedhydroiluoric acid‘and 50.6 grams of
IV, 64y grams'of C. _P." normal butane and 188 45 normal pentane. The bomb was surrounded byV
an electrical heating jacket, and was heated to
grams of substantially pure hydroiluoric acid
570° F. in 70 minutes, as follows: up to 356° F, in
were chargedto a steel bomb having a capacity
30 minutes, from 356 to 453° F. in> 17 minutes, and
of 400 cc. During aperiod of two hours and
from 453 to 570° F. in 23 minutes. At 570° F. a
twenty minutes, the temperature was gradually
raised to 520° F., at which temperature the pres 50 pressure gage attached to the bomb registered
4,240 pounds per square inch. The bomb was
sure was 3400 pounds per square inch. The
maintained at this temperature for 4 hours; and
bomb was then cooled rapidly, and the contents
was then cooled to 212° F. in 14 minutes. 'I'he
were removed for examination. The resulting
hydrocarbon material recovered from kthe bomb
hydrocarbon material was. found by fractional
analysis to have the following composition, in per 55
cent by weight:
`
hadA the following analysis.
Lower-¿boiling
Methane
__
0.6
Propane
10.1 v
Norma1 butano
ì-Cï4Hio
50.8 60
Isopentane _____ ______ __________ __ _____ __
8.1
__________________ __ ________ ____
_
'
____________ __ _________ __ Trace
---__ ________________ __dO...... __
n-C4H1n
"
`
~
i-CsHiz f __
n-C5H12
Norma1pentane_ _______________________ __ _2.0
Hexanes
~
CsHa _________ __»____ __Per cent by weight...` V2.7
Isobutane ___________ __T _______________ __, 25.9
Heptanes
'
'
06H14
2.0
'
~
Higher-boiling
l `
4-.6
d0
3.0
do
10.5
do
76.6
dn
______________ __do ...... __
1.7
0.9
0.5
65
100.0
The fextent of isomerization of normal butane to
isobutane was considerably more than that ob
tained in Example IV, as was also the conver->
sion to _isopentane and lhigher-boiling parañ‘ìns.
v 'Approximately equal proportions by volumeof`
isopentane andv yanhydrous hydrogen fluoride
were charged to a steel bomb. For a period of 28
y
,y
VExample IX
Y
.
100.0
l
To arsteel bomb were charged 165.0 grams of
concentrated hydrofluoricacidand 74.4 grams Yof
normal butano, the bomb being agitated by ‘a
platformV shaker. The ‘bomb VIwas heated from
145° F..up toV 302° F.; in"1_l"1our,iand,maintainedv
daysl the ‘boint'ßv was maintained 'at atemperaturef '15 at 302° F. for vv2 hours. ’ »After.this,Y theìboinb was?
cooled to >140°!F.fin 15 minutesz: YThe hydroc‘zar-'YV
of 175° F. by'v an electric heating coil and‘wasï
2,403,649
1i*
position.
'
by weight
____ __ ___________________ __
i
tion in the liquid-phase-‘while intimately mixed
Per cent
Lower-boiling
12
,
bon material recovered had the following com
0.0
í-C4H1o _______________________________ __ 13.
n-C4H1o _______________________________ __ 82.4
05H12 (and4 heavier) ____________________ __' 4.2.
with 0.2 to 4 times by weight of coneízentratedr
liquid hydroi’iucri'c acid as the eiTecti-ve vcatalyst
at a reaction temperature ofvat `least-59" F. for a
time sufficient to effect alteration of the struc~
ture of saturated hydrocarbons present tol form
other saturatedY> hydrocarbons, and subsequently
recovering from eiiluents of said treatment satu-V
rated 'hydrocarbons' boilingin-the motorîfuel
100.0 10
` 4. A process of `converting a saturated hydroIt Will 'be understood that Various parts Of the
carbon
material of" at least four carbon* atoms
eflluent from theprocess may -be recycled. For
per molecule into other saturated hydrocarbons,
example', any ofthe fractions obtained from frac
which comprises subjecting such a ¿material- to
tionator 46, preferably the light-isoparafñn frac
15 reaction at an elevated temperature and pressure
tion boiling below the motor-fuel range, may be
while Vintimately mixed with 0.2'to-4 times ïby
advantageously recycled to coil I3 and/ or reactor
range so produced.j
23 by means not shown that can be readily sup
plied by those skilled- in the art; thereby the yield
of hydrocarbons of adesired boiling range or of a
v
'
`
'
’
weight of concentrated hydroiluoric acidasthe
effective catalyst for a time >such as to eiTect a
material alteration in the structure of saturated
20 hydrocarbons in said hydrocarbon material into
desired carbon-skeleton structure is increased.
other saturated hydrocarbons, passing eiiluents of
It valsowill -be understood that the equipment
said treatment to a separating Zone wherein a hy
used for this process may be of corrosion-resist
drocarbon phase is separated from a liquid hy
ant> steels, Monel metal, nickel alloys, aluminum
drofluoric acid phase, subjecting said hydrocar
and/or magnesium alloys, copper, copper alloys,
bon phase to fractional distillation to remove
orthe like, Since hydro?luoric Yacid is relatively
residual amounts of hydrofluoric acid contained
inert to metals in the absence of moisture, corro
in said hydrocarbon phase, and >recovering from
sion may be minimized by using substantially
remaining hydrocarbons a fraction containing
completely anhydrous hydroñuoric acid and by
saturated hydrocarbons of atleast four carbon
drying `the hydrocarbon material fed to the proc
atoms per molecule and of altered structure Vs0
ess.-`
’
~
My invention provides a new catalytic process
for » reconstructing hydrocarbon materials. It
provides a new process for improving the anti
knock characteristicsnand the degree of satura
tion of motor-fuel hydrocarbons, It further pro
vides a novel process for producing lhydrocarbons
of higher and/or lower molecular weight than
produced.
5. A process of converting a saturated hydro
carbon material of at least four carbon atoms
per molecule, which comprises subjecting such a
35 material to reaction at an elevated temperature
and pressure whileintimately mixed with 0.2 to 4,
times by weight of concentrated hydroiluoric
acid as the _effective catalyst for a time such as
that of the original material. Still further, it
to effect a material` alteration in the structure of .
provides a process wherein normal and slightly
branched aliphatic hydrocarbons may be con 40 saturated hydrocarbons in said hydrocarbon ma
terial, passing effluents of said treatment to a
verted t0 relatively highly branched aliphatic
separating Zone wherein a hydrocarbon phase is
hydrocarbons.
separated from a liquid hydroiluoric acid phase,
My process is especially advantageously ap
subjecting said hydrocarbon phase to -fractional
plicable' to treatment of all hydrocarbon mate
distillation to remove residual amounts of hydro
rials which comprise predominantly saturated
fluoric acid contained in said hydrocarbon phase,
hydrocarbons having four or more carbon atoms
separating low-boilingk material so ,removed into
per molecule. Because of the variety of mate
a hydrocarbon phase and a hydroñuoric acid
rials and the plurality of vpurposes to which my
phase, returning said hydrofluoric acid to said re
invention is applicable, there -are a large number
of modifications and variations of my invention, 50 action, returning said hydrocarbon phase to said
distillation, removing as a high ‘boiling product
of which only a very few are specifically described
of said distillation a hydrocarbon material essen
in this speciñcation. Additional equipment such
tially free of hydro?luoric acid but containing
as pumps, valves, coolers, fractionators or the
minor amounts of organic iluorine compounds,
like, such as are well-known to those skilled in
passing said hydrocarbon material to the action
the art, may be used in my process wherever
of granular bauxite to remove said organic fluo
needed or convenient. It is not intended that
rine compounds and. to. produce a substantially
mention herein of specific apparatus, materials,
liuorine-free eiiluent, and recovering from the hy
conditions, theories, reactions, or purposes should
drocarbon material so purified a normally liquid
unnecessarily limit the scope of my invention.
What I claim is:
,
l. A process of isomerizing a normal parañin
60 hydrocarbon .fraction boiling _in the: motor-fuel
range.
„
l
6. AY processY for converting hydrocarbons by
having at least four carbon atoms per molecule,
reactions -comprising isomerization and dispro
which comprises subjecting said normal parañ‘ìn
portionation,A which comprises subjecting a nor
to the catalytic action of 0.2 to 4 times by Weight
of Vconcentrated hydroiiuoric acid as the effective 05 mally liquid parañin hydrocarbon to a reaction
temperature in the presence and intimately ad
catalyst at an elevated temperature in the range
miXed with 0.2 to 4 times by weight of liquid con
of about 50 to 1000? F. for a time Suñicient to ef
fect a substantial extent of isomerization of said
normal paraiiin.
v
~ 2.l The process of olai
l, in which .said normal
` paraflin isnormal butane.
3. A process for improving the antiknock char
acteristics of a saturated hydrocarbon material
boiling in the motor ¿fuelrange which comprisesv
subjecting such a hydrocarbonmaterial to reac-Vr
centrated hydro?luoric acid as the sole catalyst
`for a time su?icient to convert saidparafün hy
drocarbon in part to isomeric paraffin hydrocar
bons of Vthe same molecular weight and in part
to parailins of higher and of lower molecular
weights.
M
Y
K
Y
'LA process »for converting hydrocarbons ¿by
reactions comprising isomeriaation . and dispro
2,403,649
13
14
ly recovering from eilluents of said reaction a
fraction comprising at least one of said paraffin
hydrocarbons so produced.
l
carbons of the same molecular Weight and in part
to parañìns of higher and of lower molecular
-
i
13. A process for isomerizingl normal pentane
to produce isopentane, which comprises subject
ing normal pentane to isomerization under isom
hydrocarbon in part to isomeric paraffin hydro
Weights.
„
forming paraffin hydrocarbons having fewer and
morecarbon atoms per molecule, and subsequent
portionation, which comprises subjecting a nor
mally liquid paraífln hydrocarbon to a reaction
temperature in the presence and intimately ad
mixed with 0.2 to 4 times by Weight of liquid con
centrated hydrofluoric acid as the effective cata
lyst for a time suii'icient to convert said'parafjn
erization conditions in the presence of liquid
10 concentrated hydrofluoric acid as the essential
8. A process for converting saturated hydro
carbons contained in a saturated hydrocarbon
isomerization catalyst to form isopentane, and
recovering from eiiiuents of said isomerization
material by reactions comprising isomerization
and disproportionation, which comprises subject
>isopentane so produced.
ing a saturated hydrocarbon material to the cata
lytic action of 0.2 to 4 times by Weight of inti
f
14. A process for isomerizing a saturated hy
15 `drocarloon having at least four carbon atoms per
molecule, which comprises subjecting such a sat
urated hydrocarbon to isomerization under isom
mately admixed liquid concentrated hydrofluoric
erization conditions in the presence of 0.2 to 4
acid as the effective catalyst at a conversion tem-4
times by weight of intimatelyïadmixed liquid con
perature for a time sufficient to effect a> substan
tial conversion of saturated hydrocarbons con 20 centrated hydrofluoric acid as the essential isom
erization catalyst to form a saturated hydro
carbon isomeric with the ñrst said saturated hy
drocarbon, and recovering from eiliuents of said
tained in said material into other saturated hy
drocarbons including at least one isomer of a
saturated hydrocarbon so converted.
f
9. A process for converting saturated hydro
carbons contained in a saturated hydrocarbon
isomerization a saturated hydrocarbon fraction
material by reactions comprising isomerizationA
and disproportionation, which comprises subject
so produced.
l5. A process of isomerizing a paraiîin having
at least four carbon atoms per molecule, which
comprising said isomeric saturated hydrocarbon
ing a saturated hydrocarbon material to a con
Version temperature in the presence vof 0.2 to 4 y
comprises subjecting said paraiiin to the catalytic
times lby-Weight of intimately admixed concen
trated liquid hydroñuoric acid as the sole cata
action of 0.2 to 4 times by weight of concentrated
hydro?luoric acid as the effective catalyst at an
lytic material for a time sufficient to elîect a con-Y
elevated temperature in the range of about 50 to
version of saturated hydrocarbons into other 'sat
urated hydrocarbons including at least one iso
tial extent of isomerization of said paraffin.
mer of a saturated hydrocarbon so converted.
10. A process for converting a _paraffin hydro
carbon contained in a saturated hydrocarbon ma
1000° F. for a time sufficient to effect a substan
35
16. A process of isomerizing a saturated hydro
carbon having at least four carbon atoms per
molecule, which comprises subjecting said satu- f
terial, -Which comprises subjecting a liquidsatu
rated hydrocarbon material containing at least
rated hydrocarbon to the catalytic action of 0.2
to 4 times by Weight .of concentrated Vhydroiluoric
one paraffin hydrocarbon of atleast four carbon
atoms per molecule to a conversion temperature
in the presence of 0.2 to 4 times by weight of in
acid as the eifective catalyst at an elevated tem
perature in the range of about 50 to 1000a F. for
a time suñîlcient to effect a substantial extent of
isomerizationV of said saturated hydrocarbon.
17. A process of isomerizing a cycloparaflin hy
oric acid as the essential catalyst for a time suffi
cient to convert said parañin hydrocarbon into an 45 drocarbon having at leastsix carbon atoms per
timately admixed liquid concentrated hydroflu
>isomeric parafûn hydrocarbon.
molecule, which comprises subjecting said cyclo
paraffin hydrocarbon to the catalytic action of
11. A process for converting normal pentane
0.2 to 4 times by weight of concentrated hydro
into isobutane, isopentane, and isohexanes, which
ñuoric acid as the effective catalyst at an ele
comprises subjecting liquid normal pentane at a
conversion temperature to the catalytic action of 50 vated temperature in the range of about 50 to
about 1000o F, for a time sufñcientto eiïect Ia
liquid hydrogen fluoride as the essential catalyst
substantial extent of isomerization of said cyclo
for a time sufficient to effect ra substantial con
paraíi‘in hydrocarbon.
version of normal pentane to isobutane, isopen
18. A process for isomerizing a cycloparaiìn
tane and isohexane, and subsequently recovering
from eñiuents of said conversion a fraction com 55 hydrocarbon having at least six carbon atoms per
molecule, which comprises subjecting such a
prising at least one of said isoparaflins so pro
cycloparañln hydrocarbon to isomerization under
»
isomerization conditions in the presence of 0.2 to
12. |A process for effecting disproportionation
4 times by Weight of intimately admixed liquid
of a paraffin hydrocarbon having at least ñve
carbon atoms per molecule, which comprises sub 60 concentrated hydroñuorie acid as the essential
isomerization catalyst to form a cycloparafûn hy- '
jecting a liquid saturated hydrocarbon material
drocarbon isomeric with the ñrst said cyclo
comprising such a paraffin hydrocarbon at a re
parañin hydrocarbon, and recovering from eillu
action temperature to the catalytic action of 0.2
`ents of said isomerization a hydrocarbon frac
to 4 times by weight of intimately admixed liquid
tion comprising said isomeric cycloparaflin hydro
hydrofluoric acid as the essential catalytic mate
duced.
rial for a time sufficient to eiïect a substantial
disproportionation of said parañ‘in hydrocarbon,
65 carbon so produced.
`
FREDERICK E. FREY.
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