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Nov. 26, 1946.
w. E. Ross ETAL
2,411,835
ISOMERIZING HYDROCARBONS
Filed March 14, 1944
CaTlqsT
Inven‘korsi William E. Ross
'
?eorqe J. Carlson
Patented Nov. 26, 1946»
‘ 2,411,835‘
UNITED STATES PATENT QFEIQE
2,411,835
ISOMERIZING HYDROCARBONS
William E. Ross, Berkeley, and George J. Carlson,
El ‘Cerrito, Calif., assignors to Shell Develop
ment Company, San Francisco, Calif., a corpo
ration of Delaware
Application March 14, 1944, Serial No. 526,406
.9 Claims. (01. 260-6835)
2
1
true mixed molten salt catalyst. Particularly
suitable molten salt type aluminum halide-con
taining catalysts comprise a molten mixture of
This invention relates to the isomerization of
hydrocarbons and relates more particularly to
the isomerization of hydrocarbons having from
aluminum halide and a halide of antimony, for
example a melt comprising aluminum chloride
dissolved in antimony trichloride, a molten‘mix
‘ 5 to 10 carbon atoms to the molecule and hydro
carbon fractions comprising them.
Feasibility of executing the isomerization of
paraffin hydrocarbons with the aid of catalysts
comprising metal halides of the Friedel-Crafts
ture of an aluminum halide and at ‘least one
halide sale of an alkali or alkaline earth metal,
etc. Of these various ?uid type isomerization
catalysts, those of the molten salt type are often
type on a practical scale is governedto no small
degree by the ease with which the tendency of
these catalysts to promote undesirable side re
somewhat preferred.
. I
i
1»
However, in processes available heretofora'uti
lizing catalysts of the ?uid type, difficulties in
actions can be overcome and the isomerization re
action be made to dominate. The degree to which
herent in the use of these catalysts are often ag
this problem in?uences the ‘particular process
is dependent upon the nature of the hydrocarbon 15 gravated by the degradation of the para?inic
hydrocarbons having from 5 to 10 carbon atoms
charge. 'The' more stable hydrocarbons, such as,
to the molecule, thereby presenting problems
for example, the butanes, can be readily isom
which detract materially from the full realiza
erized in the absence of these difficulties ‘with the
tion of the advantages to be derived from the
aid of any of the available isomerization cata
lysts. The isomerization of these more stable hy 20 use of these catalysts. One of these dii?culties
is the maintenance of the ?uid catalyst ‘within
drocarbons is readily accomplished in either the
the ‘system at the optimum conditions of compo
vapor or liquid phase with isomerization cata
sition enabling efficient conversion to the de
lysts of the solid type comprising the metal halide
sired product in the absence of any substantial
per se, optionally in combination with a suitable
solid diluent or support material which may or 25 hydrocarbon decomposition. Localized concen
tration of the active metal halide constituent,
may not exert a promoting eiTect upon the cata
even for the relatively short time between its
lyst. The more readily degraded hydrocarbons
introduction into the system and its dispersion
comprising those having from 5 to 10 carbon
through the catalyst mass, often results in sub
atoms to the molecule, particularly the pentanes,
stantial degradation ‘of hydrocarbons and con
branched hexanes, and hydrocarbon fractions
sequent formation of inactive sludgy catalyst‘ma
comprising them, are more di?icult to isomerize
terial resulting not only in a loss of valuable cata
economically on a large scale due to the com
lyst ‘and charge material but {in the presentation
parative ease with which they degrade in the
' of mechanical di?iculties in maintaining proper
presence of metal halides of the Friedel-Crafts
type.
These di?iculties are offset to some degree _
by the use of fluid type isomerization catalysts.
The ?uid type isomerization catalysts vary con
siderably from one to another. They comprise
the metal halides of the Friedel-Crafts type, for
example aluminum halide, as a suspension or so
lution in a suitable liquid vehicle. The liquid ve
hicle may comprise a hydrocarbon or hydrocar
bon mixture which may be a part of the material
treated. Other carrying liquids may comprise a
?ow through the system. The addition of make
up aluminum halide to a heated portion of the
charge generally results in the formation of in
active sludw catalyst material even before the
mixture enters the reaction zone.
Attempts to
40 overcome this di?lculty by heating only a portion
of the charge to the reaction zone and adding
the aluminum halide to a separate unheated por
tion of the charge, although obviating the di?i
culty to some extent, still does not enable smooth
hydrogen halide such as hydrogen chloride; alkyl 45 operation, nor does it prevent undue loss of cata~
lyst and charge or unbalancing of catalyst com
halides; ‘S02, etc., or any other liquid inert at the
position Within the system.
operating conditions. Another type of ?uid isom
It has furthermore been found that the inac
erization catalyst comprises fluid organo-alu
tive sludgy catalyst thus formed in the reactor
minum halide complexes. Still another type of
?uid isomerizatio-n catalyst comprises the alu 50 decidedly represses the catalyst activity of many
of the more active ?uid isomerization catalysts,
minum halide as a solution or suspension in a
and particularly those of the ‘molten salt type,
suitable molten salt or mixture or molten salts.
with respect to the para?in isomerization reac
The ‘molten salt may simply function as a carry
tion. It has been found that it is essential to
ing medium or it may act as a catalyst modi?er
or as a separate catalyst component to form at 55 practical operation of the process with the aid
3
2,411,835
4
of certain of these catalysts that inactive sludge
Example III
thus formed be kept below a certain maximum
Pentane was contacted in a plurality of com
concentration and that substantially improved
parative operations with a fluid type catalyst
e?iciency in operation is obtained by removing
consisting of a solution of aluminum chloride in
inactive catalyst sludge from the reaction zone
substantially as rapidly as formed.
molten antimony trichloride at the. following
The highly repressive action of the inactive
sludge formed in the system in the isomerization
Temperature ___V________________ __°C__
95
of hydrocarbons having from 5 to 10 carbon- . Hydrogen pressure ______________ __lbs__
atoms to the molecule upon the fluid isomeriza; 10 Ratio of catalyst to hydrocarbon by vol__
55-60
conditions:
.
1:1
I-ICl added to feed___percent by weight__ 3.7-4.2
tion catalysts of the molten salt type is evidenced
by the following example.
Example I
7
Time of contact ____________ __minutes__
9
The aluminum chloride content of the ?uid
catalyst was maintained constant in each run and
15 the catalyst was maintained substantially free
of any spent catalyst sludge during the opera
tion. The amount of aluminum chloride main
molten SbCls at a temperature of 95° 0., catalyst . tained in the catalyst of each operation, and re
to hydrocarbon phase ratio of 1:1, and a contact
sults obtained in terms of pentane conversion to
time of 9 minutes. A conversion of normal pen 20 isopentane, and pentane degradation as deter
tane to isopentane of ‘71.1% was attained. In a
mined by isobutane production, are indicated in
parallel operation with identical feed and at sub
the following table:
7
Pentane was contacted with a. ?uidtype cata~
lyst consisting of aluminum chloride dissolved in
stantially identical conditions of operation, but
with the exception that a sludgy spent catalyst
(formed in a previous paraffin isomerization) was 25
added to the catalyst charge in the small amount
Run N o.
of 0.5% by weight of the ?uid catalyst. This
quantity of added spent sludgy catalyst was sufli
cient to lower the activity of the catalyst to such
41% compared to the above-cited value of 71%.
Example II
2-methylpentane was stirred in a rotary mixer
with 300 g. of a fluid type catalyst consisting of
aluminum chloride dissolved in SbCh at a tem
perature of 75° C. The time of contact was 30
minutes and 12 g. of HCl were added to the re
actants.
Under these conditions 34% neohex
ane was produced. In a comparative experiment
carried out under substantially identical condi
tions-but with the exception that 25 g. of a
Per cent
A1013 in
conversion to
ation of
catalyst
isopentane
pentanes to
.
a degree that conversion to isopentane was only
1‘
Per cent
disproportion
Wt. per cent
isobutane
0. 5
60. 6
' 0. 5
1.0
2. 0
2. 9
65.1
71. 1
69. 7
1. 2
2. 2
2. S
Maintaining such small amounts of aIuminum
halide in a highly dispersed condition in the re
action zone in the treatment, at isomerizing con
ditions, of the more'readily degraded hydrocar
bons, is, however, exceedingly di?cult, and often
impossiblain processes utilized heretofore. Im
‘ mediate deactivation of at least a' substantial
40 portion of the small amounts of aluminum halide
content of the catalyst with the formation of un
desirable sludge is generally encountered. Dis
persing such small amounts of aluminum halide
through the catalystmass or reactants in the re
sludgy spent catalyst,-resulting from the action 45 action zone during operation has. generally been
of AlCls on methylpentane, was added to the sys
tem, ‘only 3% neohexane resulted.
di?'icult to attain by addition of the metal halide
together with the charge or by direct addition as
such into the reaction zone. Introduction of the
active metal halide by such means as practiced
It has also been found that substantially im
proved results as determined by conversion and
yield per pound of active metal halide constituent 50 heretofore usually results in a localized concen
in the catalyst is obtained by maintaining in the
tration of the metal halide for a period of time
catalyst mass and subsequently adding to the
which, even though exceedingly short, is sufli
charge an amount of the activemetal halide
cient to bring ‘about the difficulties referred to
component suflicient to maintain only a small
hereinbefore.
'
quantity of highly dispersed active metal halide 55 It is an object of the present invention to pro—
in, the ?uid catalyst mass. Another advantage
vide an improved process for the more eiiicient
inherent in‘ the use of only such small amounts of
isomerization of paraf?nic hydrocarbons having
active metal halide component in the catalyst mass
from 5 to 10 carbon atoms to the molecule and
resides in the ability to use higher temperatures
hydrocarbon fractions comprising them wherein
within the permissible operating range in the ab 60 the above difficulties are obviated to at least a
sence ‘of the, diinculties normally encountered
substantial degree. Further objects and advan
when using greater concentrations of the active
tages of the invention will become apparent from
halide component. With the use of ?uid salt
the following detailed description thereof.
type isomerization catalysts it has been found
It has been found that the difficulties hereto~
that a concentration of the active metal halide 65 fore encountered in the isomerization of the more
of the Friedel-Crafts type in the catalyst mass not
substantially in excess of about 3% by weight,
and preferably not substantially in excess of
about 2% by weight, is highly-desirable.
readily degraded hydrocarbons is obviated to at
least a substantial degree by introducing the active
metal halide constituent of the catalyst into the
react-‘on zone in the form of a dilute solution in
The e?‘ectof the reduced amount of aluminum 70 a suitable solvent substantially free of hydrogen
halide. In accordance with the process of the
carbons having from 5 to 10 carbon atoms tothe
invention, an isomerizable paraf?nic hydrocarbon
molecule with the aid of a ?uid type isomeriza
having from 5 to 10 carbon atoms to the molecule
tion catalyst of the molten salt type is shown by
optionally in the presence of other hydrocarbons
the following example.
'
~
75 capable or not of undergoing isomerization under
halide in the catalyst when isomerizing hydro
2,411,885"
conditions of execution of the invention and/or
in (the presence of anadded inert gas, is contacted
with a ?uid type isomerization catalyst compris
from about 0.3% to about 40% of the hydrocarbon
charge is found to be‘su?icient. Higher propor
tions of the hydrogen chloride may, however, be
used. It is to be stressed that in order to attain
the full realization of the advantages of the in
vention it is essential that the presence of hydro
ing a metal halide of the Friedel-Crafts type. The
solvent for the metal halide is preheated in a
separate stream to a temperature sui?cien'tly high
gen halide in the solvent for the active metal
to dissolvea su?icient amount of the metal halide
halide component of the catalyst, or in the dilute
therein. The resulting heated solvent stream is
passed through a vessel containing the active
solution of metal halide in the solvent, be avoided,
metal halide component of the catalyst and the 10 or kept at a minimum practical concentration,
prior to entry into the reaction zone.
resulting stream consisting of adilute solution of
The hydrocarbons or hydrocarbon mixtures
thecmetal halide in the ‘solvent is passed‘ into
treated are preferably substantially free of mate
the reaction zone. The solvent is separated from
rials, the presence of which adversely affects the
the reactor e?luence and recycled through the
vessel containing the ‘metal halide and the reac 15 activity of the catalyst. Ole?ns, diole?ns, aro
matic ‘hydrocarbons or other detrimental impuri
tion zone. .In-a preferred embodiment of the in
ties in the hydrocarbon or hydrocarbon mixture
vention only a small amount of the active metal
vto be, treated are preferably removed prior to
halidecomponent of the catalyst is maintained
isomerization by a suitable treatment which may
in a~highly dispersed condition throughout the
catalyst mass and/or reactants in the reaction 20 comprise one or more of such steps as mineral
zone.
‘
acid re?ning, hydrogenation, alkylation, contact
-
Suitable solvents for the active metal halide
withclay or with a part of the spent catalyst,
solvent extraction, etc.
component of the catalyst comprise suitable ?uid
,In order to set forth more fully the nature of '
materials capable of introducing the metal halide
into the reaction zone indilute solution, thereby 25 the invention it will be described in detail here
in in its application to the conversion of pentane
to isopentane with the aid of a ?uid type iso
merization catalyst of the molten salt type. It
is to be understood, however, that it is in no
solvent isone that is inert or has noedeleterious
effect upon catalyst, reactants or operating con 30 Wise intended to limit the invention to the iso
merization of this particular hydrocarbon or to
ditions at the-conditions of execution of the proc»
the use-of this particular type of ?uid isomeriza
ess.. .Itis, furthermore, advantageous to use as
tion catalyst and that the invention may be ap
the solvent one that is readily separated by avail
plied broadly to the isomerization, comprising
able means from the reactor ei?uence within the
. the treatment under isomerizing conditions, of
system; A suitable solvent comprises, for ex
obviating local concentration of the metal halide
in “the catalyst or reactants and enabling its im
mediate dispersal through the reaction zone. The
ample, ethyl chloride. Advantageous solvents
comprise the less readily degraded paraffin hy
drocarbons, particularly those of lower boiling
point than the hydrocarbon being isomerized.
Such a solvent hydrocarbon may undergo isomer
ization to some degree under conditions of opera
tion of the process and may comprise a mixture of
. isomers corresponding .to an equilibrium mixture
thereof .at the conditions of operation. Particu
larly advantageous low-boiling para?inic hydro
carbons suitable as solvents for the active metal
halide components of the ?uid typeisomerization
catalyst in the isomerization oi’ para?lnic hydro
carbons having from 5 to lO'carbon atoms to the
molecule comprise the butanes.
'
Isomerizing conditions at which the para?inic
hydrocarbons are converted in the presence of
any of the .para?inic hydrocarbons having from
5 to 10 carbon atoms to the ‘molecule, mixtures
of two or more thereof, or hyocarbon fractions
comprising one or more thereof, with the aid of
any of the available ?uid type‘ isomerization
catalysts. The description of the invention Will
be madev with reference to’ the attached drawing
forming a part of this speci?cation and wherein
the single ?gure illustrates one form of appa
ratus suitable ‘for execution of the invention.
' An isomerizable para?inic hydrocarbon hav
ing from 5 to 10 carbon atoms to the molecule,
for example normal pentane, from any suitable
source is forced by means of pump I, through
valved line 2, into v‘a heating zone comprising,
for example, an externally heated coil 3 where
inthe hydrocarbon stream is heated to a tem
perature-suf?ciently‘high to maintain the desired
temperature conditions in a subsequent scrub
temperature to about 150° C. The operation may _ a bingand/or reaction zone. From the heating
zone the heated hydrocarbon-stream is passed
be carried out in the liquid, vapor or mixed phase.
into an extraction column 5. Within extrac
It is to be pointed out that operating tempera
tion column 5 the hydrocarbon stream is con
tures have been‘largely limited by the scope. of the
accompanying decomposition reaction and that , tact-ed in theliquid phase with a portion of the
the fluid ‘type catalysts comprise a temperature
in the range of, for example, from about room
consequently the‘ present invention enables ef?- ‘' kit) catalyst, emanating from the reaction zone as
cient operation at somewhat higher temperatures
than possible heretofore in the absence of hyr ro
The isomer~
ization reaction may be executed at subatmos
pheric, atmospheric or superatmospheric hres
sures.v In the case of ‘liquid phase operation a
' carbon decomposition suppressors.
described ‘more fully below. Liquid pentane
comprising extracted catalyst components is
passed from extraction column 5 through valved
line e and heat exchanger 1 into a reaction zone.
' The reaction zone may consist of a suitable
reactor 8 provided with stirring means and a
separator 9. Within the reactor 8 the pentane
sufliciently high superatmospheric pressure is, of
is
contacted with a suitable‘isomerization cata
course, maintained to keep at least a substantial
lyst of the ?uid type, for example a molten salt
part of the reactants in the liquid phase.
The isomerization is preferably executed in the . "* type catalyst comprising a metal halide of the
. FriedeLCrafts type. A suitable catalyst com
presence of a hydrogen halide promoter such as,
prises a solution of a halide of aluminum, for
for example, hydrogen chloride. The amount
example aluminum chloride, in a halide of anti- ~
of hydrogen chloride used may vary widely in
accordance with operating conditions, In gen
mony, for example antimony trichloride. Al
eral. an. amount of. hydrogen chloride equal :to
though the‘ amount of aluminum chloride 1111 the
2,41 1,8351
.
8
7
catalyst melt may vary considerably within the
scope of the invention, an advantageous fea
ture of the process of the invention is the pos
sibility of maintaining lower concentrations of
aluminum chloride highly dispersed throughout
the melt with substantially improved conditions
of operation. The amount of aluminum chlo
thereof corresponding to the equilibrium mixture
prevailing at the conditions of operation, from
any suitable source through valved lines l5 and
I 6 into a heating zone. The heating zone may
comprise a heat exchanger Or an externally heat;
ed elongated coil |'!. From coil I‘! the preheated
butane stream is passed through at least one of
ride in the catalyst melt is preferably main- '
a series of vessels Ill-lea containing aluminum
tained below about 3%‘ and preferably below
chloride. Butane comprising dissolved aluminum
about'2% by weight of the catalyst melt. The 10 chloride is taken from vessel l8 and passed
ratio of the catalyst to hydrocarbon in the re
through valved lines l9 and 20 into reactor 8.
action zone is maintained in the range of, for
Solubility of the aluminum chloride in the butane
example, from about 1:5 to about 3:1, and pref
stream increases progressively vwith increase in
erably from ‘about 1:1 to about 1.521 by volume
temperature. Thus, the amount of aluminum
The hydrogen halide promoter, for example HCl, 15 chloride dissolved in normal butane varies from
is introduced into line 6 by means of line I0.
about 0.02% by weight at 40°C. to about 2.0% by
Within separator 9 a hydrocarbon layer is sepa-'
weight at 95° C. . The temperature to which the
rated from a lower catalyst layer comprising
butane solvent is heated in heater I‘! is carefully
spent catalyst produced within the system; The
controlled to dissolve the proper proportion of
catalyst layer is constantly withdrawn through 20 the aluminum chloride therein to maintain the
valved line 12 and passed to the upper part of
desired composition of the catalyst in the reac-‘
extraction column 5. A portion of the catalyst
tion zone. In this wise the ?ow rate of solvent
may be returned to the reactor through line 13.
can be maintained constant and the quantity of
' The portion of the catalyst introduced'into ex
A1Cl3 dissolved therein controlled by varying the
traction column 5‘ will‘pass ‘countercurrent to 25 heat input in heater ll. By operating in this wise
the upflow of liquid hydrocarbons. In its pas
they maintenance ‘of a low concentration of alu
sage through column 5 active components com
mium chloride in a highly dispersed state through
prising antimony chloride are dissolved in the
the reactants in the reaction zone is made possi
hydrocarbon stream and passed therewith'to re
ble in the absence of any of the di?iculties here
actor 8. Another portion of the catalyst com
,tofore experienced in the treatment of readily de
prising components which’ are spent or at least
graded hydrocarbons in the presence of the ?uid
partly spent with respect to‘ their ability to
type isomerization catalysts comprising metal
halides of the Friedel-Crafts type. The advan
tages of the process comprise not only an im
rated therein as a heavier ?uid catalyst residue. 35 proved means for introducing the aluminum hal
The hydrocarbon charge to scrubber-5 is pref
ide into the reactor but the ability to maintain
erably preheated to a temperature favorable to
the added aluminum halide in a highly dispersed
the extraction operation. This temperature will
state due to the increased volume of hydrocar
vary with the nature of the material being
bons within the reactor.
.
treated and the particular catalyst used. Tem 40
As stressed above, it is essential that the bu
peratures in the approximate range of from ‘50°
tane solvent entering drums Iii-Illa be free of
C. to 125° C. and preferably from 50° C. to 100°
any substantial amount of hydrogen halide. For,
C. are-found suitable. The pressure within col
though the butanes are relatively stable in the
umn 5 is always sufficiently high to maintain
presence of A1013, the inclusion of a hydrogen
at least a substantial portion of the hydrocarbon 45 halide in the solvent, while dissolving AlCls there
stream passing therethrough in the liquid phase.
in, or in the dilute solution passing through line
The rate at which catalyst is withdrawn from
20 into the reaction zone, still results in'rapid
separator 9 and passed to the upper part of ex
production of undesirable spent catalyst sludge
catalyze the isomerization reaction remains in
soluble in the hydrocarbon stream and is sepa
tractor 5 may vary within the scope of the in
and difficulties in maintaining the active com
vention. In a preferred embodiment of the in 50 ponent of the catalystin the properly dispersed
vention, however, not only is the amount of
state. In the process of the invention the hy
aluminum chloride maintained in the reaction
drogen halide promoter is removed to at least a
zone exceedingly small and 'in a highly dispersed
substantial degree from any butane solvent re‘
state but any spent catalyst formed in the re
cycled to vessels lB--l 8a. .
action zone is removed therefrom'substantially
When continuously scrubbing a part of the
as rapidly as formed and replaced by‘active cata
least spent catalyst in extractor 5 the pentane
lyst. At least partly spent catalyst is, there;
charge alone often does not su?‘lce to e?ect com
fore, passed substantially continuously > from
plete removal of active catalyst constituents from
separator‘ 9 to extractor 5 to eifect the removal
the catalyst introduced into the upper part there
of inactive spent catalyst from 'reactor 8 sub 60 of. To supplement the charge functioning as the
stantially'as rapidly as formed therein.
scrubbing agent, a portion of the butane stream
Maintenance of a low concentration of alumi
is diverted from line It through line 48 and in
num chloride in the catalyst melt, together with
troduced into pentane charge line 1, leading to
continuous withdrawal of spent catalyst, requires
the substantially continuous addition of fresh
aluminum chloride throughout the operation in
order to replace the catalyst‘removed and main
tain a desired substantially constant catalyst
composition. Continuous addition of the make
scrubber 5.
.
‘I
'
Thoughappreciable separation of catalyst from
hydrocarbon is effected by strati?cation in sepa~
rator 9, a certain amount of active catalyst com
ponents will generally be contained inthe upper
hydrocarbon layer. ‘The upper hydrocarbon layer
up aluminum chloride is carried out in the proc 70 is passed from separator 0 through 1ine'22 into a
ess of the invention. in the absence of any of the"
catalyst separating column 23. Within column
difficulties experienced in processes used hereto
23 hydrocarbons comprising isopentane, pentane,
fore, by forcing a'suitable solvent for the alumi
num chloride, for example a low-boiling hydro
butanes and 1101 are separated as a vapor frac
tion from a liquid fraction comprising entrained
ccarbon. such- as a butaney isobutane,- or a mixture Y5 catalyst. The-liquid fraction-is returned~ to reac
2,411,835
torv 8*‘through line 24. The vapor fraction is
passed through line 25 containing cooler 26 into
an accumulator 21.‘ In-‘passing through ‘cooler
the combination of steps which comprise using
as the isomerization catalyst a ?uid melt consist
ing' ofmolten antimony trichloride containing up
toabout 2%‘ by weight of, aluminum chloride,
26 the stream is cooled to effect the condensation
of pentanes.
10
in a reaction zone, and e?iuence from the reac
tion- zone is passed into a product separating zone,
‘
U‘ncondensed material comprising hydrogen
maintaining a ratio of ?uid melt to hydrocarbons
to lie‘isomerized in the reaction zone in the range
chloride, butanes' and some inert gas-formed in
the system is continuously or intermittently with
drawn from accumulator Zl through line 28 "and
introduced into'the lower part of an absorber 29.
ofifroin-‘about 1:1 to about ‘1:5, separately with
drawing? spent catalyst from the reaction‘zone
substantially as rapidly as formed therein, pass
solvent comprising para?inic hydrocarbons
ring four carbon atoms to the molecule through
aluminum chloride-containing vessel in the
substantial absence of hydrogen halide promoter,
Within absorber 29 the Ivapors are contacted with
a suitable scrubbing medium introduced into the
upper part of absorber 29 by means of line 29a.
H01 is-absorbed ‘by the scrubbing medium and
overhead, comprising vapors and gas substan
tially free of any H01, is passed through valved
line 3| into line 32 to be recycled to line It. To
prevent building up of gas within the system, a
thereby‘ dissolving aluminum chloride in said sol
vent, passing solvent comprising dissolved alu
minum chloride from said aluminum chloride
containing vessel to the reaction zone in con
valvedilinedlf is provided through which a part
of the uncondensed material‘may be veliminated 20 trolled amount .to introduce aluminum chloride
into the reaction ‘zone at a rate substantially
equal to the rate at which aluminum chloride
Liquid comprising pent-apes, some butanes and '
is removed therefrom in said spent catalyst, sep
, dissolved HCl is iorced'through line 35 into strip
arating said solvent from reaction products and
ping column 33. Within column 33 a vapor frac
tion comprising HCl is separated from a liquid 25 hydrogen ‘halide in the product separating zone, '
and passing solvent free of any substantial
fraction comprising butanes and pentanes. The '
amount or hydrogen halide‘ from the product
vapor fraction is passed from column 33 through
separating zone to said‘ aluminum chloride-cone
lines 34 ‘and . iii to line 6. ' Make-up HCl is intro
taining vessel.‘ '
'
~
duced as required into line id by ‘means of valved
‘2;. In‘. a ‘process for isomerizing paraffin hydro‘
line 31. ‘Liquid is taken from the lower part of ,
carbons having from ?ve to ten carbon atoms to
column- 3.3 and passed through valved line 38 into
the molecule wherein said hydrocarbons are con
a fractionator' 3%. Within ‘fractionator 39 bu
tacted in admixture with a hydrogen halide pro
taneslare separated from the pentanes. The bu
tanes‘ are passed through'linesé? and 32 to line .
iii. A liquid fraction comprising pentanes is re- ;_
moved from-fractionator 39-and forced through
line 112 into fractionator t3. Vv'ithin fraction
at‘or 43' separation of a vapor fraction comprising
moter with an isomerization catalyst compris
ing. aluminum chloride in a reaction zone, and
e?luence from the reaction zone is passed into a
product‘ separatingzone, the combination of steps
isopentanes from a liquid fraction comprising un
which comprise using as the isomerization cat
alyst a fluid melt consisting of molten antimony
converted normal pentane is effected. The vapor
trichl'orid'e containing up to about 2% by weight
fraction is removed through line‘ iil as a ?nal
of aluminum chloride, maintaining‘ a ratio of
?ui'd melt to hydrocarbons to be is'omerized in the
product.
Normal pentane is recycled from col
umn 113 through lines 45 and 136 to line 2.
A portion of the bottoms from stripping-col
umn 33 may be taken from line .38 and passed
into the upper part of absorber 29 to serve as.
the absorbing medium for the H01. The result
ing rich absorbent is taken fromthe bottom of
absorber 2e and passed through valved line 30
into line 35.
'
At times it may be desirable topartly or com
pletely bypass scrubber, 5. A valvedv line 49 pass
ing directly from line: d to line ii is therefore‘
reaction zone in the range of from about 1:1 to
about ' ‘115", separately withdrawing spent‘ cata
' lyst from the reaction zone substantially as rapid
ly as formed therein, passing a solvent compris- .
ing paraf?nic hydrocarbons having four‘ carbon
atoms to the molecule through an aluminum
chloride~containing vessel in the substantial ab
50 sence‘ of hydrogen halide promoter, thereby dis
solving aluminum chloride in said solvent, pass
ing solvent comprising dissolved aluminum chlo
ride from said aluminum chloride-containing ves
sel' to" the reaction Zone in controlled amount to
Although: the invention is applied with par 55 introduce aluminum chloride into the reaction
ticular advantage to the treatment of hydrocar
zone at a rate substantially equal to the rate
bons having from 5~t0 10 carbon 'atoms‘to the
at which aluminum chloride is removed there
from in said spent catalyst, separating said sol
molecule‘ or‘ fractions comprising them for, the
provided;
‘
‘
'
purpose of converting suchv hydrocarbons to iso
vent from reaction products and hydrogen halide
mers thereof of branched and more‘ highly 60 in the product separating zone, and passing sol
vent‘free' of- any substantial amount of hydrogen
branched structure, the invention may be ap
halide from the product separating zone to‘ said
plied to the treatment, with the aid of ?uid type
aluminum chloride-containing vessel.
isomerization catalysts, of. hydrocarbon mixtures‘
boilingwithin the motor, fuel boiling range, such.
3. Ina process-for isomerizing paraffin hydro
as straight-run gasoline, light naphthas, etc, for‘ 65 carbons having from ?ve toten‘ carbon atoms'to
the molecule wherein said hydrocarbons are con
the purpose of increasing the‘over-all content of
tacted' in admixture with a hydrogen halide pro
branched chain hy rocarbons‘in such mixtures
moter with an isomerization catalystcomprising
and thereby increasing octane rating and general
aluminum‘halide in areaction'zone, and e?iuence
performance characteristics of these materials.
701 from the, reaction zone is passed‘ into a product
We claim as our invention:
>
r ‘
separating zone, the combination of- stepswhich
1. In a process for converting normal pentane
to .isopentane wherein normalpentane is ‘con
tacted in admixture with a hydrogen halide pro-‘
meter at isomerizing conditions with. an isomer~
ization catalyst comprising aluminum" chloride.
comprise using as the isomerization catalyst a
?uid melt consisting of molten antimony halide
containing: up to about 2% by weight of aluminum
halide, maintaining a ratio of fluid melt to'hydm
2,411,835.
11
12
carbons to be isomerized in the reaction zone in
the range of from about 1:1 to about 1:5 sepa
vent for said metal halide comprising para?inic
arating zone to said aluminum halide-contain
tacted in admixture with a hydrogen halide pro
moter with an isomerization catalyst comprising
hydrocarbons having four carbon atoms to the
rately withdrawing spent catalyst from the re
molecule through a, supply-vessel containing a
action zone substantially as rapidly as formed
supply of ‘said metal halide in the substantial
therein, passing ‘a solvent comprising parai?nic
absence of hydrogen halide promoter, thereby
hydrocarbons having four carbon atoms to the
dissolving metal halide in said solvent, passing
molecule through an aluminum halide-contain
solvent comprising dissolved metal halide ‘from
ing vessel in the substantial absence of hydrogen
said supply-vessel to the reaction zone in con
halide promoter, thereby dissolving aluminum
trolled amount to introduce metal halide into
halide in said solvent, passing solvent compris 10 the reaction zone at a rate substantially equal
ing dissolved aluminum halide from said alu
to the rate at which metal halide is removed
minum halide-containing vessel to the reaction
therefrom in said spent catalyst, separating said
zone in controlled amount to introduce aluminum
solvent from reaction products and hydrogen
halide into the reaction zone at a rate substan
halide in the product separating zone, and pass
tially equal-to the rate at which aluminum halide 15 ing solvent free of any substantial amount of
is removed therefrom in said spent catalyst, sep
hydrogen halide from the product separating zone
arating said solvent from reaction products and
to said supply-vessel.
V
1
hydrogen halide in the product separating zone,
6. In a process for isomerizing para?in hydro
and passing solvent free of any substantial
carbons having from ?ve to ten carbon atoms to
amount of hydrogen halide from the product sep
the molecule wherein said hydrocarbons are con
ing vessel.
,4. In a process for isomerizing paraf?n hydro
carbons having from ?ve to ten carbon atoms to
aluminum chloride in a reaction zone, and efflu
ence from the reaction zone is passed into a prod
uct separating zone, the combination of steps
which, comprise using as the isomerization cat
the molecule wherein said hydrocarbons are con
tacted in admixture with a hydrogen halide pro
moter at isomerizing conditions with an isomer
ization catalyst comprising a metal halide of the
alyst a ?uid melt consisting of molten antimony
trichloride containing upto about 2% by weight
Friedel-Crafts type in a reaction zone, and e?iu
of aluminum chloride, maintaining a ratio of ?uid
melt to hydrocarbons'to be isomerized in the
reaction zone in the range of. from about 1:1 to
ence from the reaction zone is passed into a prod
uct separating zone, the combination of steps
which comprise using as the isomerization cata
about 1:5, separately withdrawing spent cata
lyst a ?uid melt consisting of a dilute solution of a
metal halide of the Friedel-Crafts type in a mol
ten metal halide salt other than a metal halide of
lyst from the reaction zone substantially as rapid
ly as formed therein, passing a solvent compris
ing para?inic hydrocarbons having four carbon
the Friedel-Crafts type, maintaining the ratio of
atoms to the molecule through analuminum chlo
ride-containing vessel in the substantial absence
?uid melt to hydrocarbons to be isomerized in
the reaction zone in the range of from about 1:5
of hydrogen halide promoter, thereby dissolving
aluminum chloride in said solvent, maintaining
to about 3:1, separately withdrawing spent cat
alyst from the reaction zone substantially as
a substantially constant flow of said solvent
fast as formed therein, passing a solvent com
through the aluminum chloride-containing‘ves
prising para?inic hydrocarbons having four car
bonv atoms to the molecule through a supply-ves
sel, passing ‘solvent comprising dissolved alu
minum chloride from said aluminum chloride
containing vessel to the reaction zone, controlling
the concentration of the aluminum chloride in
the solvent passed from the aluminum chloride
sel containing a supply of said metal halide in the
substantial absence of hydrogen halide promoter,
thereby dissolving metal halide in said solvent,
passing solvent comprising dissolved metal halide
containing vessel to the reaction zone by con
from saidsupply-vessel to the reaction zone in
controlled amount to introduce metal halide into
the reaction zone at a rate substantially equal
to the rate at which metal halide is removed
trolling the temperature of said solvent entering
the aluminum chloride containing vessel to re
sult in the introduction of the aluminum chloride
into the reaction zone at a rate substantially equal
to the rate at which aluminum chloride is re
moved from the reaction zone in the spent cat
therefrom in said spentcatalyst, separating said
solvent from reaction products and hydrogen
halide in the product separating zone, and pass
alyst, separating said solvent from reaction prod
ing solvent free of any substantial amount of 55 ucts and hydrogen halide in the product sepa
hydrogen halide from the product separating
rating zone, and passing solvent free of any sub
zone to said supply-vessel.
stantial amount of hydrogen halide from the
5. In a process for isomerizing paraffin hydro
carbons having from ?ve to ten carbon atoms to
the molecule wherein said hydrocarbons are con
tacted in admixture with a hydrogen halide pro
moter at isomerizing conditions with an isom
erization catalyst comprising a metal halide of
the Friedel-Crafts type in a, reaction zone,‘ and
e?luence from the reaction zone is passed into a
product separating zone to said aluminum chlo
ride-containing vessel.
60
‘
'7. In a process for isomerizing para?in hydro
carbons having from ?ve to ten carbon atoms to
the molecule wherein said hydrocarbons are con
tacted in admixture with a hydrogen halide pro
moter with an isomerization catalyst comprising
aluminum halide in a reaction zone, and e?iu
product separating zone, the combination of steps 65 ence from the reaction zone is passed into a prod
which comprise using as the isomerization cat
alyst a ?uid melt consisting of a dilute solution
of a metal halide of the Friedel-Crafts type in,
uct separating zone, the combination of steps
which comprise using as the isomerization cat
alyst a ?uid melt consisting of molten antimony
a molten halide of antimony, maintaining the
halide containing up to about 2% by weight of
ratio of fluid melt to hydrocarbons to be isom 70
aluminum halide, maintaining a ratio of ?uid
erized in the reaction zone in the range of from
melt to hydrocarbons to be isomerized in the
about 1:5 to about 3:1, separately withdrawing
reaction zone in the‘ range of'from about 1:1
spent catalyst from the reaction zone substan
to about 1:5 separately withdrawing spent cat
tially'as fast as formed therein, passing a sol 75 alyst ‘from the reaction zone substantially as
2,411,885
14
trolling the temperature of said solvent enter
ing the supply-vessel to result in the introduc
rapidly
\
as formed
.
therein, passing a solvent com
prising para?inic hydrocarbons having four car
tion of metal halide into'the reaction zone at a
bon atoms to the molecule through an aluminum
halide-containing vessel in the substantial ab
sence of hydrogen halide promoter, thereby dis
solving aluminum halide in said solvent, main
rate substantially equal to the rate at Which metal
halide is removed from the reaction zone in the
vent through the aluminum halide-containing
spent catalyst, separating said solvent from the
reaction products and hydrogen halide in the
product separating zone, and passing solvent free
vessel, passing solvent comprising dissolved alu~ '
of any substantial amount of hydrogen halide
taining a substantially constant ?ow of said sol- '
minum halide from said aluminum halide-con ll) from the product separating zone to said supply
vessel.
taining vessel to the reaction zone, controlling
9. In a process for isomerizing paraf?n hydro
the concentration of the aluminum halide in the
carbons having from ?ve to ten carbon atoms
solvent passed from the aluminum halide-con
to the molecule wherein said hydrocarbons are
taining vessel to the reaction zone by controlling
contacted in admixture with a hydrogen halide
the temperature of said solvent entering the alu
promoter with an isomerization catalyst com—
minum halide containing vessel to result in the
prising a metal halide of the Friedel-Crafts type
introduction of the aluminum halide into the re
in a reaction zone, and e?iuence from the reac
action zone at a rate substantially equal to the
tion zone is passed into a product separating
rate at which aluminum halide is removed from
zone, the combination of steps which comprise
the reaction zone in the spent catalyst, separat
using as the iscmerization catalyst a fluid melt
ing said solvent from reaction products and hy
consisting of a dilute solution of a metal halide
drogen halide in the product separating zone, and
of the Friedel-Crafts type in a molten halide of
passing solvent free of any substantial amount
antimony, maintaining the ratio of ?uid melt to
of hydrogen halide from the product separating
hydrocarbons to be isomerized in the reaction
zone to said aluminum halide-containing vessel.
zone in the range of from about 1:5 to about
8. In a process for isomerizing paraf?n hydro
3:1, separately withdrawing spent catalyst from
carbons having from ?ve to ten carbon atoms to
the reaction zone substantially as rapidly as
the molecule wherein said hydrocarbons are con
formed therein, ‘passing a solvent for said metal
tacted in admixture with a hydrogen halide pro
' moter with an isomerization catalyst compris
ing a metal halide of the Fried-el-Craits type in
a reaction zone, and e?luence from the reaction
zone is passed into a product separating zone, the
combination of steps which comprise using as the
isomerization catalyst at ?uid melt consisting of
a dilute solution of a metal halide of the Friedel—
' Crafts type in a molten metal halide salt other
30
halide comprising paraf?nic hydrocarbons hav
ing four carbon atoms to the molecule through a
supply-vessel containing a supply of said metal
halide in the substantial absence of any hydro
gen halide promoter, thereby dissolving metal
halide in said solvent, maintaining a substan
tially constant ?ow of said solvent through said
supply-vessel, passing solvent comprising dis
solved metal halide from said supply-vessel to
the reaction zone, controlling the concentration
bons to be isomerized in the reaction zone in the 40 of said metal halide in the solvent passed from
the supply-vessel to the reaction zone by control
range of from about 1:5 to about 3:1, separately
withdrawing spent catalyst from the reaction .7 ling the temperature of said solvent entering the
supply-vessel to result in the introduction of
zone substantially as rapidly as formed therein,
metal halide into the reaction zone at a rate
passing a solvent comprising paraf?nic hydrocar
substantially equal to the rate at ‘which metal
bons having four carbon atoms to the molecule
halide is removed from the reaction zone in the
through a supply-vessel containing a supply of
spent catalyst, separating said solvent from the
said metal halide in the substantial absence of
reaction products and hydrogen halide in the
any hydrogen halide promoter, thereby dissolv
product separating zone, and passing solvent free
ing metal halide in said solvent, maintaining a
substantially constant ?ow of said solvent through ; of any substantial amount of hydrogen halide
from the product separating zone to said supply
said supply-vessel, passing solvent comprising dis
vessel.
solved metal halide from said supply-vessel to
WILLIAM E. ROSS.
the reaction zone, controlling the concentration
GEORGE J. CARLSON.
of said metal halide in the solvent passed from
the supply-vessel to the reaction zone by con 65
than a metal halide of the Friedel-Crafts type,
maintaining the ratio of ?uid melt to hydrocar
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