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Патент USA US2404551

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Patented July 23, 1946
2,404,551
UNITED STATES PATENTEOFFICE ‘
John‘ D. Upham, Bartlcsville, 0kla.,'assignor to
Phillips Petroleum Company, a corporation vof
Delaware
'
No Drawing. ‘Application October 5, 1942,
j
Sverial'No. 460,853
10 Claims.
>
i
(01. zoo-‘6835) '’ ~
1
This invention relates to hydrocarbon conver
sion processes utilizing metal halide catalysts of
the Friedel-Crafts type. More, particularly it re
lates to the treatment of metal halide-hydrocar
bon sludges formed in hydrocarbon conversions
such as isomerization and alkylation reactions
catalyzed by aluminum chloride, aluminum bro
bons,‘ as well as dissolved aluminum chloride.‘ ‘In
, the'case of sludges formed primarily by. contact
of catalyst with. hydrocarbon reactants; as for
example when normal butane is passed over a bed
of solid aluminum chloride, such sludges have'a
high absorption or solution capacity for free a1u-'
minum chloride‘ and generally carry substantial
amounts of free aluminum chloride when re—'
moved‘ from the reaction‘zon‘e. Unless this alu
time are the isomerization and alkylation of low 10 minum chloride can be recovered in some way, it
is lost from- the system. In the case'wherein a
boiling hydrocarbons, particularly‘ members of
slurry of aluminum chloride is used‘in or circu
the paraffin series such as the butanes and pen—
lated through a reaction zone, a portion or all of
tanes. In these reactions a simple chemical
such slurry is withdrawn and replaced by fresh
change is effected under relatively mild condi
mide, and the like.
7
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Of great commercial interest at the present
tions.
In the case of isomerization a change in 10 aluminum chloride. ‘ Generally this must be done
carbon skeleton without change in number of car
whilev the slurry still contains relatively‘ large
amounts'of free aluminum chloride,‘ but insuffi
cient for carrying out the reaction at an uneco
nomic level. In general, reference in this appli-‘
paraffin and ole?n, occurs to'produce a, higher
molecular weight saturated hydrocarbon.‘ "The 20 cation to sludges refers to sludges formedby con
tact of hydrocarbon reactants with a catalyst,
alkylation of aromatic hydrocarbons, for example
and to suspensions or ‘slurrie's of metal halide
the alkylation of benzene ‘with ethylene, is also
catalyst in suitable liquids such as,‘ for example,
of considerable importance at the, present time,
bon atoms occurs, and in the case of alkylation
the direct union of two molecules, such as an iso
These various reactions are known to be: catalyzed
heavy-hydrocarbons, > ‘Said, sludgeszmay comprise
Friedel-Crafts type metal halide catalystaamong
to treatment‘ according to my-invention' contain
the better known of which may be mentioned
aluminum chloride, aluminum bromide, boron
free or uncombined aluminum chloride.“
to a greater or'lesser extent by the’so-c'alled 25 metal,zhalide-hydrocarbon complexes;v and prior
‘
‘ ‘
It is an ‘object of this invention to provide'for
improved‘ ‘ hydrocarbon ‘reactions wherein "a
?uoride, zinc chloride, ferric chloride, antimony
tri?uoride, and other polyvalent metal halides. 30 Friedel-Crafts typemetal halide is'used as cata
lyst, particularly when a hydrogen halide is used
as catalyst activator. ‘Another object'is.v to'pro
vide'for vthe treatment of metal halide sludge
ity, relatively low cost, and availability. Accord
formedduring such reactions. A further object
ingly, because of its importance, and for the sake
of convenience, I shall describe my invention with 35 is to provide for carrying'out such hydrocarbon
conversions as isomerization, alkylation and the
particular reference to the isomerization of nor
like with aluminum‘ halide .and similar catalysts
mal ‘butane to‘ isobutane a's-catalyzed by alumi
continuously. Yet another object is to recover
num chloride. Application of the invention to
free aluminum chloride from aluminum chloride
other similar hydrocarbon conversions, using alu
minum' chloride or other .Friedel-Crafts type 40 hydrocarbon sludges in a form suitable for re-use.
Many other objects and advantages of the inven
metal‘ halide catalysts will be ‘apparent to those
,tion will become apparent as the disclosure'pro
skilled in the art in view of the disclosure to fol
Aluminum chloride has to date received the
greatest commercial acceptance due to its activ
‘low.
In such conversion processes,‘ a catalyst
ceeds._
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In accordance with my invention, a sludge or
activator is generally used. This activator is fre
quently a hydrogen halide, preferably hydrogen 45 slurry from which it is desired to remove a free
Friedel-Crafts type metal halide, such as alumi
In processes utilizing anhydrous aluminum
num chloride, is contacted with a liquid substan
tially anhydrous hydrogen halide, such as hydro
chloride as a catalyst, the aluminum chloride may
be charged to the process as a solid, or as a slurry
gen chloride. Said liquid hydrogen halide acts
formed by dissolving and/or suspending a consid 50 to dissolve metal halide from the inactive mate
chloride.
_
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erable. amount of aluminum chloride in hydro
rial, which vmay comprise hydrocarbons and/or
carbons or other suitable liquids. In either case,
a liquid sludge is formed after a short period of
operation. Such slurries 0r sludges may comprise
hydrocarbon-metal halide complexes. In addi
tionrto the solvent action ofthe hydrogen halide,
itv may. also “act to set free a certain amount. of
complexes of aluminum chloride with hydrocar 55 metal halide not ordinarily recovered fromloose
2,404,551
. combination in the sludge.
solution of aluminum chloride in liquid hydro- >
In this manner, val- '
' .1 uable
sludge,free
and metal
may inhalide
turn be
is recovered
recoveredffrom
from soluthe "
' ‘ tion in the hydrogen halide and re-used as de
‘
1
sired-
k
gen chloride into the reaction zone‘. The hydro
gen chloride, which may or, may not-vaporize in
the reaction zone, acts as activator therein, and
aluminum chloride carried out by the sludge is
I
returned to the reaction zone for re-use as isom
IA convenient manner of. recovering said‘metal ‘
} halide from solution in hydrogen halide is to sub;
ject the solution to a sufficiently high tempera
erizationv catalyst.
Liquid 1 hydrogen [chloride
: ture and/or'a su?icien'tly low pressure to effect
‘ vaporization of the hydrogen halide. Since all of
the hydrogen halides are relatively low-boiling »
‘materials, this is readily accomplished. The
if convenient, in dissolving aluminum chloride
irom the sludge, with subsequent introduction of
the resulting solution into the reaction zone.
The spent sludge from which free aluminum
chloride has been removed has substantially no
other than that recycled may of course be used,
, metal halide may in some cases form a loose com
1 plex with the hydrogen halide, but such com;
v 1 catalytic activity .for the isomerization reaction,
‘ plexes are readily broken upinto their compo
15 is substantially‘ insoluble in the hydrocarbons be
ing converted, and may be disposed of or utilized
; nents.
As an example of the application of my inven-j ,1‘
‘
‘
,
‘
in which normal butane is converted to isobutane
by the action of aluminum chloride activated with
hydrogen chloridefv In such a process,-' dry normal
butane; is passed "at suitable temperatures and
for any desired purpose.
.
As another example, the invention may be ap
‘.tion, an isomerization process will be discussed
plied suitably to the continuous alkylation of ben
20
zene with normally gaseous ole?ns ‘such as eth
ylene using aluminum chloride 'slurried in the
reaction mixture.
In such -;aiprocess a slurry of
?nely divided {aluminum chloride may be ?rst
1 pressures over an aluminum ‘chloride catalyst,
, along ‘with hydrogen chloride. As the isomeri
preparedjby suspension of aluminumchloride in
,1 zation'reaction proceeds, a liquid aluminum chlo 25 a heavy oil, or aluminum chloride may be sus
pended directly in liquid reactants. In any case,
‘I ride sludge is'formed which containsv considerable
a common method of operation is to circulate
, aluminum chloride that is still catalytically active
‘ insofar ‘as theisomerization reaction is concerned.
'
continuously the aluminum chloride through the
reaction zone. A small‘side stream of aluminum
‘ Ordinarily this sludge ‘is withdrawn from the re
‘ action‘ chamber‘ and discarded, or subjectedlto 30 chloride-containing sludge is 'COHtiIlllOllSly drawn
off, and fresh make-up aluminum chloride added
‘ use involving .loss or destruction of the active
to the reaction mixture. [My invention may be
alu-rriinum chloride; However, in the practice'oi
used to recover free aluminum chloride'from said
‘ the present invention, this‘ sludge may be with
sludge, and to reintroduce ‘the, thus-recovered
drawn from" the reaction chamber, 1 and is inti
, mately'oontacted with liquid hydrogen ‘chloride. 35 aluminum chloride into the reaction zone. Unde
sired material is thus removed from the system
as an inactive sludge, while unoombined alumi
j This'may be'done conveniently by counter-cur
, rent ?ow through a small tower packed with
‘ stones; Raschig ‘rings, or the like, or the two liq
‘ uids may be‘ mixed mechanically as by stirrers,
1
pumping, etc. ' '
num chloride is returned to use.’
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While the invention has been described with
40
particular reference to analuminum halide, espe
‘The temperature chosen for this contacting is
cially aluminum chloride, as the . Friedelj-Crafts
of coursebelow the critical temperature ofhy- 1
type halide, and to hydrogen chloride asthe hy
drogen halide,.other metal halides and hydrogen
‘halides may be used by following the ‘general
principles set forth herein, suitably modi?ed with
regard to the particular application.
drogen chloride, and is generally chosen as a mat
‘ ter'of convenience, depending upon the tempera;
‘ ture'at 'which' the sludge and ‘hydrogen chloride ~
‘ are'obtained. "Heating or cooling either ‘or both
: to the desired‘temperature ‘is readily accom
Iclaim:
The hydrogen‘chlorideis’ maintained
l. A process for the isomerization of normal
under sufficient pressure in the contacting-step to
butane to produce isobutane which, comprises
‘ plished;
‘ ensure-the presence or liquid'hydrogen chloride. 50 contacting normal butane admixed with catalyst
" 'In the isomerization process described, the hy
activating amounts of hydrogen chloride, with an
‘ drogen chloride, which may comprise, for exam- ‘
aluminum chloride isomerization catalyst in a. re
action zone at conditions effecting the forma
tion of isobutane and a liquid aluminum
j ple, from ‘about 3 to about 15 per cent or more
of’ the butane feed, is ‘ordinarily separated .from
f the 'isobutane, unconverted normal butane and 55 chloride-hydrocarbon sludge _ containing substan;
other-"constituents of ‘the e?‘luent, and recycled
tial amounts of uncombined aluminum chloride,
withdrawing said sludge from said reaction zone,
‘ to ‘the reaction‘zone. 'One of the most suitable
. methods" of effecting this separation is'b'y frac- .
fracti'onally‘ distilling e?luents of said‘reaction
‘ tionaldistillation, in which ordinarily the over
zone comprising hydrogen chloride, 'isobutane,
and unconverted normal butane to produce an
, head comprises hydrogen chloride, and sometimes
propane'or other light hydrocarbon gases. ' This
. overhead is at least partially condensed," and a
overhead product'comprising said hydrogen chlo.
ride, at least partially condensing'said ‘overhead
portion of the condensate returned to the frac
product to form a liquid hydrogen chloride
; tionating column as re?ux. The portion of this ' containing condensate, intimately contacting said‘
condensate ‘not used as re?ux, and which it is de 65 sludge with’ at least a portion of said condensate
sired to‘return to the vreaction zone, is a verycon- . at a temperature below the‘ critical temperature
of hydrogen chloride and at suf?cient pressure
venlentsource, of ‘liquid hydrogen chloridev'for
1 Washing ‘the sludge. ‘Accordingly, a'p'referred ‘
to maintain said condensate in the liquid phase ’
I manner of , carrying out my invention involves
thereby dissolving said uncombined aluminum
‘ passing at least a portion of the recycle hydrogen
j chloride stream, which is lique?ed as described
‘ or ptherwisafinto contact with the sludge, con- 1
tain-ingfree aluminum chloride withdrawn from
‘ the reaction chambenthus dissolving out said
. free aluminum chloride, and ‘passing the resultant
chloride from said sludge, discharging‘"frorrl'the
process a resulting insoluble inactive liquidsludge,
and returning the resulting solution of aluminum
chloride in said hydrogen. chloride-containing
condensate to said reaction zone for vfurther‘utilif
zation of said aluminum chloride as catalyst and
2,404,551
5
for further utilization of said hydrogen chloride
free aluminum chloride, and recovering said free
as catalyst activator.
2. In a process for the isomerization of satur
hydrogen chloride.
ated hydrocarbons which comprises admixing
catalyst-activating amounts of hydrogen halide
with a saturated hydrocarbon material to be
isomerized, contacting the resulting mixture with
aluminum chloride from solution in said liquid '
4. A process for the recovery of a metal halide
of the Friedel-Crafts type from a. liquid metal
halide-hydrocarbon sludge containing the same
in uncombined form, which comprises contacting
such a sludge with a liquid anhydrous hydrogen "
a Friedel-Craits type metal halide isomerization
halide to effect solution of said uncombined metal
catalyst in a reaction zoneat conditions suitable
for eifectingisomerization, a formation of a liquid 10 halide in said liquid hydrogen halide, and sepa-.
metal halide-hydrocarbon sludge containing sub
stantial amounts of uncombined metal halide also
rating the resultant solution from the remaining
insoluble liquid metal halide-hydrocarbon sludge
which is substantially free from uncombined
being effected, withdrawing said sludge from said
reaction zone, separating reaction products and
metal halide.
_
5. The process of claim 2 in which said metal
hydrogen halide from eiiluents of said reaction 15
halide is aluminum chloride and said hydrogen
zone, and returning a hydrogen halide recycle
stream comprising so-separatedhydrogen halide
halide, is hydrogen chloride.
to said reaction zone for re-use of said hydrogen
6. The process of claim 2 in which said metal
halide and said hydrogen halide are compounds
halide as catalyst activator, the improvement
which comprises: intimately contacting said 20 of the same halogen.
hydrogen halide'recycle stream in the liquid phase
'7. The process of claim 4 in which said meta
with said sludge to dissolve said uncombined metal
halide is an aluminum halide.
,
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8. The process of claim 4 in which said metal
halide and said hydrogen halide are compounds
solution in said hydrogen halide recycle stream 25 of the same halogen.
I halide from said sludge, whereby said uncombined
metal halide is returned to said reaction zone in
for re-use as catalyst therein.
3. A process for the recovery of the free alumi
num chloride content of a liquid sludge compris
9. In the recovery of aluminum halide from a
hydrocarbon-aluminum halide complex, the steps
of extracting the hydrocarbon-aluminum halide
complex with a lique?ed hydrogen halide and re
ing free aluminum chloride‘ dissolved in liquid
aluminum chloride-hydrocarbon complexes, which 30 covering hydrogen halide‘, and aluminum halide
comprises selectively extracting such a sludge
from the resulting solution.
I
10. In the recovery of aluminum halide from a
with liquid anhydrous hydrogen chloride at tem
hydrocarbon-aluminum halide complex, the
peratures below the critical temperature of hydro
gen chloride and pressures sui?cient to maintain 35 steps of extracting the hydrocarbon-aluminum
halide complex with a lique?ed-hydrogen halide
said hydrogen chloride in liquid phase to form a
and separating the resulting solution from the
solution of said free aluminum chloride in said
remaining complex.
liquid hydrogen chloride, and an insoluble liquid
JOHN D. UPHAM.
comprising said complexes substantially devoid of
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