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Патент USA US2406477

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_ AUS'- 27, `1946
I
`2,406,477
E. SOLOMON ET A1.
CATALYST MANUFACTURE
Filed May 29, .1942
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Patented Aug. 27,1946
` 2,406,477
UNITED STATES Pnl'riëzrrrV oFFlcE '
CATALYST MANUFACTURE
Ernest Solomon, Nutley, and Louis C. Rubin, West
Caldwell, N. J., assignors to The M. W. Kellogg
Company, Jersey City,
N. J., a corporation of
Delaware
Application May 29, 1942, Serial No. 444,970
1 Claim.
1
This invention relates to ther preparation of
catalyst material and more particularly to an
improved method for impregnating a solid ad
sorbent supporting material with a metal halide.
Metal halides, such as the chlorides or bromides
of aluminum, iron, zinc, zirconium, tantalum and
columbium are highly active catalysts for hydro
carbon conversion reactions such as polymeriza
tion, isomerization and alkylation. Preferably,
they are employed in combination with supports
of highly adsorbent capacity such as activated
carbons, carbon black, gels of silica or alumina,
Activated Alumina and clays, to maintain their
catalytic activity longer, thereby bringing about a
(Cl. 252«-251)`
'
2r
_
Y
.
supports with metal halide which is adaptable to
continuous operation. Other objects and advan
tages of the invention Will become apparent dur
ing the course of the following description.
»
According tothe present invention, adsorbent
materials, such as activated carbons, carbon
black, silica gel, alumina gel, Activated Alumina
and natural and synthetic clays, are impregnated,
with a metal halide by being contacted with a
continuously replenished stream of inert gas or
vapor, carrying `vaporized metal halide. ' This isv
accomplished by passing heated inert gas‘through
a mixture’of metal halide and adsorbent or in
succession through a body of metal halide anda
greater production of conversion products per unit
body of solid adsorbent material to vaporize the
quantity of catalyst employed. Such supports
may be impregnated with these metal halides in
batch procedures, as for example by heating mix
metal halide into the inert gas which then serves
as a carrier for the vapors while they contact
tures thereof in closed chambers to sublime the
catalyst which is then adsorbed by, and deposit
ed on, the support. This method, however, re
quires heating the materials for extended periods
of time, particularly in those cases where it is de
sired to impregnate the support with the maxi
mum amount of metal halide. The metal halide
also may be dissolved in a solvent' and deposited
on a support by evaporative concentration in
which the support is covered by the solution and
the solvent is then evaporated from the mixture
by prolonged heating. In'preparing supported
and become adsorbed by the support.
gas, thus stripped of its metal halide
20 recirculated through the system. The
the heated metal halide-containing
The inert
content is
passage of
inert gas
through the body of adsorbent material, advan
tageously, but not necessarily, is maintainedatY a
velocity sufficiently moderate to Ainsure substan
tially complete stripping of its metal halide con-.p
tent. vThe process is carried out either in batch
>or continuous procedures. In continuous opera,
tions the adsorbent supporting material is moved
substantially continuously and either counter
currently or concurrently through a zone of con
catalysts by these batch methods, the ingredi
tact with the stream of metal halide vapor-con
ents must be proportioned properly in the initial
taining inert gas, the time of contact being regu
mixtures to produce supported catalysts which
lated to permit adsorption of the required quan
contain optimum amounts'of the metal halide
tity of catalyst. The introduction of granules of
for the subsequent conversion reactions, other 35 adsorbent support into the contact zone, and their
Wise the catalyst Will tend either to vaporize and
withdrawal therefrom, can bek accomplished by
leave the'reaction zone with the product or else
any known method for handling solid particles.
fail to produce a favorable yield of conversion
Gases employed in this invention include any
products per pound of `catalyst.
gas that substantially is not reactive either with
It is an object of the present invention to pro
the metal halide or the support under the condi
vide a method of impregnating solid adsorbent fio tions necessary for the impregnation and conver
supports With optimum amounts of metal halide
sion operations. - For this reason oxygen-contain
catalyst which does not necessitate the use of pre
ing compounds usually are to beL avoided as such
determined proportionated mixtures of catalyst
compounds exhibit a tendency to react with metal
and support. It is also :an object of this inven
halides and thereby produce inferior catalysts.
45
tion to provide a, method of impregnation that
Necessarily the gas should be free from Water va
will produce supported metal halide catalysts con
por to avoid hydrolytic reactions. Nitrogen, light
taining substantially the optimum quantity of ad
parañin hydrocarbon gases which do not react
sorbed metal halides for the subsequent conver
substantially such'as-methane, ethane and pro
sion reaction. It is a further object to provide 50 pane, ñuoranes such as tetra?luoromethaner and
a method of impregnating a solid adsorbent sup
' port with a metal halide catalyst at substantially
hexafiuoroethane possess suitable characteristics
which make them acceptable carrying media for
the- temperature and pressure of the subsequent
metal halide vapors.
V
conversion reaction. Another object of this in
Solid materials which are suitable as supports
vention is to provide a method for impregnating 55 ,for metal halide catalysts because of their adsorp
2,406,477"
3 .
tive quality include , activated carbon, carbon
black, clay-like or mineral-like materials as the
' kaolinites, terrana, floridine, pyrophillite, apophy
lite, meerschaum, bentonite, bauxite, chamotte,
the permutites, the Zeolites, and similar materials
synthetically prepared, such as ,Zeolites,y alumi
num oxides, s'ilic‘a gel, alumina gel, completely
dehydrated alumina and the like. 'I'he natural or
synthetically made supports, free from adsorbed A
water, are employed in any lsuitable granular
form, prepared to desired size in operations com
prising crushing, grinding, pulverizing,. extrud
ing or pelleting.
For further explanation/of the present inven- Y
tion, reference is made to the accompanying
drawing which represents diagrammatic eleva
tional views of apparatus capable ci?v carrying out
the process of this invention. It is to be under»
¿stood that reference to the drawing is by Way
of example only as the invention is capable of
4
stance, should vessel I contain aluminum chloride
» as theA metal halidev catalyst, depending upon
the subsequent conversion conditions as shall be
explained, it is preferred in some cases to heat
the carrier gas to 400’ F. which is approximately
‘ 44° F. above the normal sublimation temperature
of this material. At other times it is desirable
to heat the carrier gas to a temperature some
what below the vaporization temperature of the
aluminum chloride and in this method vapori
zati‘on is effected solely by the evaporative eiiect
of the moving. stream of gas so that a higher
;_ gasv velocity is ordinarily desirable. This latter
method, as will be seen later, is especially desir
able> when producing supported catalysts which
have the greatest concentrations oí metal halides.
The -heated carrier gas upon entering vessel
n I from line ZI) passes upwardly therethrough and
by reason of its contained heat vaporizes the
metal halide. Metal halide vapors thus formed
other embodiments and is not restricted to: they
physical limitations of the apparatus indicated
are interemixed with the carrier gas and are
a vessel containing particles of metal halide and
heater 274 in order that its temperature can be n
borne along by it until they come in Contact with
and become adsorbed by the support. The car
in the drawing.
.
rier gas, substantially denuded oi metal halide,
Figure 1 shows an embodiment of the inventionV
in which heated inert carrier gas is passed repeat 25 then leaves vessel i by way of line 22, having
valve 23, Aand is immediately introduced into
edly in a continuous cyclic arrangement through
adsorbent supporting material, arranged either
‘in a mixture thereof or in alternate layers. '
Figure 2 illustrates an alternate processing
`arrangement whereby in a continuous cyclic
ïarrangement inert carrier gas is heated and then
is passed in succession through a body of metal
halide rand a body of adsorbent catalyst support.
raised sufficiently so that any residual metal
halide which may have lbeen carried along with
the eliluent gas from vessel I will not condense
in the lines. Reheated, the carrier gas leaves
heater 24 through line 25 where it is recirculated
by blower or compressor 26 by way of line 21,
having valve 28, to line I2 for return to Vessel
l theReferring
impregnation
now to
zone
Figure
and contains
1, vessel metalhalide
I serves as
I through heater I4 and line 2o, as described.
During this operation use of line 29 is not re
‘catalyst and adsorbent supporting material suit
ably arranged for carrying out theY method of
quired and consequently it is shut Voli from the
circulating system by> having valve 30 closed.
When compressor 5 has delivered a sufficient
this invention, as hereafter shall be described.
`A supply of inert carrier gas, or‘ vapor, is stored 4,0 amount of carrier gas from holder 2 tomaintain
the operating requirements of the above de
in gas holder2 and is withdrawn therefrom by
scribed circulatory system valve I3 is closed, and
way of line 3, having -valve 4, for delivery to
circulation of the gas around saidv system there
‘the low pressure side‘of compressor or blower 5
after is maintained by blower or compressor 26.
`which then forces the gas through lines Ii and
'I and the then open valve 8 into drier 9. In 45 If necessary, however, compressor 5 may be used
at any time to force mal§e~up amounts of car
its passagethrough drier 9' the gas is dehydrated
rier gas into the circulatory system.
‘by contact with any of the known drying agents,
' After the support has been impregnated with
such’ as activated alumina or silica, to avoid
catalyst to the desired amount, valve 28 is closed
.any> subsequent hydrolytic reaction. The dried
`gas leaves drier 9 through lines I0 and I2, pro 50 and valve 3Q is opened. This allows the con
tained gas to flow out of the circulatory system
vided with valves II and I3 respectively, and is
through line 29 into the inlet side of the cold
then introduced into heater I4. YDrier I5 may
scraped-surface cooler 3 I. In its passage through
ïbe used alternately with drier 9 as, for instance,
cooler 3| lthe temperature of the gas is lowered
during the interval when the contact material
‘in drier 9 is undergoingk regeneration. In this 55 t0 condense any residual metal halide contained
therein upon the cold walls of said cooler which
event valves 8 and I I are closed, and valves I1
then can be recovered by a suitable scraping
`and I9 are opened to permit the flow of gas
means, not shown in the drawing. The thus de
`from line 6 to enter and leave drier I5 through
nuded gas is returned for storage to holder 2
`lines IS Vand I8 respectively. Regeneration of
`the contact material in driers 9 and I5 may be 60 through >line 32, provided with valve 33, or is
vented from the system by having valve 33 closed
`accomplished by any well known regeneration
and by opening valve 34 in vent line 35.
method, not shown on the drawing.
For carrying out batch impregnations, Vessel
The carrier gas passes through heater I4 and
I is charged through opening 36 with quantities
Íis delivered by line A20, having valve 2l, into
, the bottom of vessel I for contact therein with 65 of metal halide catalyst particles and granules
of adsorbent supporting material prior to ini
a metal halide andA a supporting material. In
tiating the circulation of the carrier gas. The
passing -through heater I4 the temperature of
catalyst and support are intimately mixed before
the gas is raised to a degree suflicient to enable
their introduction into vessel I, or are placed
‘it to vaporize the metal hande. The temper
‘ature level to which the carrier gas is raised 70 therein in a plurality of alternate layers. In an
alternate arrangement the entire body of the
`is dependent somewhat upon the vaporization
catalyst is located in the bottom section of ves
1 temperature of the particular metal halidepr'ves
sel I beneath the total mass of catalyst-free sup
, ent in vessel I although this temperature level
porting material. Whatever arrangement of
` may be higher, lower or equal to the vaporiza
catalyst and support is used, however, itis always
. tion temperature of the metal halide; For in:
2,406,477
5
preferable to have a body of the adsorbent sup#
port, free from adsorbed catalyst, positioned in
F. it did not evolve off any vapors of `free alu- '
minum chloride.
the upper section of vessel I in the immediate
'
proximity of the outlet opening into line 22, to
support, heated carrier gas passing therethrough
vaporizes and carries the metal halide through
the body of support until it is entirely adsorbed.
.
j
l
vessel in a quantity as to occupy one-fifth of the
total volume of said vessel. 'I'he remaining four
fifths volume of the impregnating vessel was filled
with “Norit” activated carbon, prepared as de
scribed in the preceding examples. The vessel
and its contents then were heated to 400° F. and
a stream of nitrogen slowly passed upwardly
therethrough at a velocity of 6 to 7 feet per hour
To accomplish this most expeditiously, the passage
of the metal halide-carrier'gas mixture through
vessel I preferably is maintained at a velocity suf
ñciently moderate to afford ample time for 'the
gas stream to be substantially stripped of its metal
'
Y
Example III
placed in the bottom of a vertical impregnating
This also serves
as a precaution against condensation of metal
halide in any part of the system subsequent to
the adsorption zone.
After vessel I has been filled with catalyst and 10
halide content.
`
‘ A, body of granular - aluminum chloride was
adsorb residual amounts of metal halide vapors
» from the exiting carrier gas.
'
for 'T1/2 hours. Analysis of the prepared body of
supported catalyst showed that a slight alumi
num chloride concentration gradient existed from
a maximum at vthe bottom to a minimum at the
top. During the preparation procedure there was
.
For further'description of the invention, by way 20 .no _evidence of free aluminum chloride in the
exit vapors leaving the top of the impregnating
of- illustration, reference is made to the following
vessel.
„
f
examples:
The slight catalyst concentration gradient in
Example I
the supported catalyst of Example III is the re-‘
Activated carbon such as is sold under the'trade 25 sult of initially concentrating all lthe granular
- aluminum chloride in the bottom of the impreg
name “Norit” was obtained in particle sizes com
nating vessel. The absence of such a gradient
monly called 6-10 mesh. This material was sub
in the supported catalyst prepared in Example
jected to drying at 800° F. to drive 01T volatile
II shows that by having thealuminum chloride
and adsorbed matter. After cooling, it was mixed
with aluminum chloride in powdered form in the 30 distribution in the original mixture properly
equalized it is possible to eliminate sucha con
proportion of three parts of activated carbon for
centration gra dientrin the finally prepared cata
each part of aluminum chloride. The mixture
Vwas charged to an impregnating Vessel and a'
lyst.
'
pheric pressure during the adsorption period is
preferable for most eñicient operation but is not
essential to the execution of the present inven
tion.
In those cases where the carrier gas is intro
duced initially into Vessel I at a temperature
' vessel was increased gradually throughout the
period of impregnation to a final maximum tem
perature of 400° F. A supported catalyst was thus
above the equilibrium vaporization temperature of
the metal halide, the lowering of the gas tem
perature during its passage through that vessel is
prepared Which contained 25> weight percent of
aluminum chloride.
.
The maintenance'of vessel I at a super-atmos
stream of nitrogen slowly passed therethrough
at a velocity of approximately 6 to 7 feet per
hour. Beginning at 325° F. the temperature of
the nitrogen passing through the impregnating
'
Example II
to be avoided so that crystals of free metal halide
45 may not be precipitated from the gas stream.
A supported aluminum chloride catalyst was
The metal halide crystals deposited in this man
made using as support dried “Norit” activated
ner are not adsorbed by the supporting material.
carbon, obtained and prepared as described in
These free crystals of metal halide if present in
the preceding example. Powdered aluminum
the finally prepared catalyst will sublime during
chloride in the amount of 35 weight percent was 50 the'subsequent conversion reaction and will have
mixed with 65 weight percent of “Norit” carbon
a detrimental effect both on catalyst life and
and the mixture charged to a vertical impreg
nating vessel. Upon this mixture was superim
posed a body of “Norit” carbon equal to one fourth
the volume of the mixture. The contents of the 55
product yield.
The temperature within vessel
impregnating vessel were maintained at 400° F.
and a stream of nitrogen was passed upwardly
therethrough at a velocity of the order of 6 to '7
feet per hour for 21A». hours. Following this pro
heat to the carrier gas. As an alternate precau
the nitrogen was increased fifteen fold and at
the same time the temperature was reduced to
325° IF. which is approximately 31° F. below the
not shown in the drawing.
When a portion of the material from the bottom
.ability of the supports has an important rela
.tionship -to the use of the catalyst in the subse
_I can be kept above the vaporization temperature
of the metal halide by placing suitable exterior
insulation on vessel I and by adding sufficient pre
tion against decrease in temperature within vessel
I additional heat may be put into that vessel, to
compensatefor heat losses by radiationand con
cedure for two additional hours the velocity of 60 duction, by an indirect heat interchange means,
The degree of adsorption of catalyst by the
supporting material varies with temperature, the
sublimation temperature of aluminum chloride.
adsorption effect being greater at the lower tem
At no time during either of these procedures did 65 peratures, It is possible therefore at a tempera
free aluminum Ychloride appear in the exit vapors
ture even below the vaporization temperature of
from the impregnating vessel. The aluminum
the metal halides, by employing a longer time of
chloride appeared in greater concentration in the
contact, to prepare supported catalysts which
upper three quarters of the prepared catalyst,
contain greater amounts of metal `halides than
being of the order of 32-33% by weight in this 70 can be adsorbed by the same supports in contact
portion of the catalyst mass as compared to the
with metal halide vapors at higher temperature
28% by weight in the lower quarter of the bed.
levels. This temperature effect on the adsorptive
section of the thus prepared supported catalyst
was heated separately in a closed vessel to 400° 75 quent conversion reactions _as the temperature
l 2,406,477
7
this method of operation one or more of such , Y
` conditions lof the. various conyersions in Y.Whicl'i
metal halide catalystsrare employed'vary over a Y
large range.
catalyst-containing"vessels may be undergoing
Vimpregnationfand/or regeneration'while thel re-
When elevated temperatures are
hydrocarbon conversion.
'
»
'
i
The apparatus di'agrammatically shown >in Fig
ure 2 is used when it is desired to vaporize the
minor amounts of' metal halides, namely,v sup
ported catalysts prepared by adsorbing metall
metal halide in a zone separate from that'used
halide from vapors at'çthe higher temperature
levels. By thus impregnating only that amount
of metal halide on a support whichl can be re
y '
maining ‘vessels of the group are employed' in
employed for hydrocarbon conversions it is ad-Y
vantageouswto Yuse supported catalysts containing
10
for the impregnation. This process arrangement
is particularly desirable when the support is being
impregnated uniformly with metal halide in con- l
tained by that support under these more severe
centrations of less than the ’maximum or when
the support is being impregnated by a continuous
operation; In thel modified embodiment,«shown
in Figure 2, the essential apparatus differs from
conversion conditions, yunnecessary loss of cata
lyst material fromV the reaction Yzone' by vapori
nation _isavoided and Íthe accompanying effect
of loss of activity and decreasein life of the
' they apparatus of the'previous processing ñow ar
catalyst thereby is eliminated. l
- In illustration of the foregoing, Vit is wellgknown` _ rangement, shown in Figure 1, only by the addition
a vaporizingvessei 42 and the intermediate
that the isomerization> cio-flow-Hmolecularr weight.YY of
hydrocarbons with aluminum chloride ordinarilyv ' injection lines 48, 49, 5D and 5l, the remainder ofv
is accomplished attemperatures up toïabout 575°:
le".> whereas, vpolymerization and alkylation _reac
20
the »system being similar to that shown and lde
scribed in Figure 1 and hence is omitted.` In this
modiiication, elements which have substantially
tions normally are conducted with _.thercatalyst
the same structure and function to correspond
ing elements in Figure 1 are designated with simi
Aoptimum quantityof aluminum chloride adsorbed 25 lar referencenumerals with the subscript a; de
tailed description or" these elements is super
by a supportrsuch' as-activated carbon in the
at temperatures ranging downwardlyV from about
1470" F. to as low'as _58° F.
Consequently the
preparation of anv isomerization catalyst ordi
narily is substantialiy'lower than the optimum`
quantity of this catalyst to be adsorbed for either
polymerization or alkylation.> Regulation of the
ñuous.
30
`temperature employed invessel L'therefore, regu
lates the degree of metal halideV adsorption -and
this degree of adsorption is determined and regu-> ,
lated vin accordance with the temperature to’
which the prepared catalyst will be subjected in
the subsequent conversion, otherwisethere oc- '
curs an'unnecessary loss of metal halide from thek
reaction Zone.
Y
'
In preparing sup-ported metal halide catalyst ’
Y
by batch operations in Vvessel la, when it is de
sired to impregnate the granular support to'its
full adsorptive capacity in accordance with the
present modiñcation, the‘heated carrier gas from
heater ida is delivered by line.4 2Go, having valve
into 'the bottom of vessel d2 for contact with
the body of granular ‘metal halide contained
therein. Vessel» ¿l2 usually is charged initially
through opening 53 with a suñiciency of granu
' lar metal halide particles for the complete im
pregnating operation, but additional >make-up
YThe finished Ycatalyst may beremoved from
>vessel I through opening 31 for use elsewhere in 40, amounts of `metal halide maybe added thereto
either continuously or intermittently during the
hydrocarbon conversion operations. However,
operation by any well known chargingrmeans,
the preparation of the catalyst may beeffected
in the Ysame vessel which is rto. be'employed ,for
carrying out the hydrocarbon conversion treat
ment.
For example, after theV impregnation «ï
treatment has been accomplishedvalves 2l and
23 are. closed. VThis isolates vessel l from said>
carrier gas circulatory system. The hydrocar
bons to b_e reacted then are introduced through
line 353,Í provided with valve Y33 and subjected to l
conditions of pressure and temperature suitable
for accomplishing the `desired conversion treat
ment. The inert carrier gas remaining in ves
>sel l may have :been removed either by evacua
tion or by displacement by the hydrocarbon I
not shown on the drawing. The effluent from ves
sel
consisting oi a mixture of carrier gas and
vaporized metal halide, ñovvs through line 44, pro
vided with valves 45 and 2id respectively, and is
introduced into the bottom of vessel la for contact
therein with a body of granular supporting ma
terial. Ordinarily to avoid depositing metal
halide in the transfer line eil the-eiiluent from
vessel d2 should be heated toa temperature not
substantially higher than the temperature to be
>maintained in vessel la. The contact conditions
imposed on the bodies of catalyst arid support in
vessels 42 and la and on the circulatory ilovv of
reactant. YThe hydrocarbons pass upwardly
carrier gas therethrough, are the same as those
through the chamber in‘contact with the cata->
which have been described in the embodiment for
lyst and the reaction products are withdrawn
Figure l, and hence will not be reiterated.
_
may be introduced through line 40 and with- '
supporting material adjacent to the entrance
limoen’ preparing supported catalysts by batch
through Yline 4E, provided with valve 4l. The
direction of iiow of the reactants `through vessel 60 operations, particularly a catalyst which con
tains lessthan the maximum concentration, the
i is not essential, however, since if desired, they
drawn through line 38. For the purpose of main
taining catalyst activity while carrying out the
point of the stream of catalyst-carrying medium
Jrends to become impregnated excessively with
conversion treatment additional amounts of the '
catalyst whereas, supporting material adjacent to
metal halide may be incorporated in the hydro
the exit is impregnatedinsufficiently.
carbon feed either in solution therein or `as a
condition of non-uniformity in concentration isA
Such a
or as a vapor mixture with the feed in the event »
undesirable for, during hydrocarbon conversions
promotedV by these non-uniformly impregnated
the conversion isconducted in the vapor phase.
It is within the scope Yof the invention to ar
catalysts, part of the catalystmass will have a
low'activity and yet metalrhalide will sublime
slurry, if the feed is charged in the liquid phase'Y
from Vthose portions containing excessive quan
tities thereby further impairing catalytic activity.
To avoid making preparations which contain un
tem, >and the hydrocarbon conversion system. By 75 ‘even distribution of adsorbed metal halide,V al
range a plurality lof vessels similar` to Vessel l
whichmay be arranged for alternate connection
with the metal halide-inert gas circulation sys
2,406,477
9
ternative methods of preparation are resorted to.
According to one preferred method, metal halide
10
-l wardly and continuously through vessel Ia in
countercurrent relationship to> the 4flow of the
metal vhalide vapors. In this procedurafresh
supplies of the adsorbent support are fed con
enriched carrier gas is passed, as described here
tofore, through Vessel la for a predetermined
period of time. Then, by closing valves 43 and 5 tinuously into» vessel `la through opening 36a by
45 and opening valve 51 in jump-over line 56 ves
sel 42 is by-passed, and the heated but metal
halide-denuded carrier gas from heater I4a is
passed directly through Vessel I a. This removes
the metal halide from the zones-of excessive con 10
centrations in vessel l and builds up the concen
traticns thereof in those zones containing in
sufficient amounts, and results in a substantially
a suitable continuous feeding arrangement, not
shown in the drawing, and passed downwardly
therethrough at a rate regulated to provide for
a sufficient time of contact with the rising metal
halide vapors such as is necessary for the produc
tion of a supported catalyst of desired concentra
tion, The upward velocity of the metal halide
carrier gas mixture through vessel la is main
uniformly supported catalyst. During this pro
tained sufiiciently moderate to accomplish the
cedure the inert gas usually is passed through 15 substantial stripping of metal halide vapors from
vessel la at a somewhat lower temperature as, for
the carrying medium. Quantities of the finally
instance, in the manner described in Example II.
impregnated material, comparable to those
The granular adsorbent support also may be
amounts of the unimpregnated support charged
impregnated uniformly with controlled amounts
to vessel la, are removed continuously from the`
of metal halide in accordance with a modified 20 bottom thereof through opening 31a by a suita
batch procedure. _In this case heated carrier gas
ble mechanical handling arrangement, again
bearing the catalyst vapors from vessel 42
not shown in the drawing.
through line 44, is passed upwardly through the
We claim:
granular adsorbent mass within vessel la until
A method for uniformly impregnating adsorb
the lower section thereof has adsorbed the de 25 ent catalyst support with aluminum chloride cat
sired quantity of the metal halide. Valve 2|a
alyst in the absence of hydrolytic orv other reac
then is closed and at the same time Valve 41 in
tions which comprises passing a carrier gas, which
line 45 is opened, The catalyst-bearing gas
of itself does not undergo conversion and which is
thereby is turned aside from line 44 and intro
substantially
unreactive with either aluminum
duced into Vessel I a through line 46 at the level 30
chloride catalyst or the catalyst support at the
of injection line 48. The adsorbent material in
conditions of impregnation, over a solid adsorp
vessel I a below said injection line 48, no longer
tive
agent to dehydrate said carrier gas, passing
receiving a replenishment of metal halide, will
the dehydrated gas over granular aluminum
-remain substantially at the desired catalyst con
centration during the time that the remaining 35 chloride at a temperature between 100° F. and
400° F. and at a velocity sufficient to vaporize
upper sections of the body of support are being
substantial quantities of aluminum chloride into
impregnated. By manipulating valves 52, »53, 54
said gas, contacting a body of adsorbent catalyst
and 55 in injection lines 48, 49, 50 and v5| in suc
support free from adsorbed water with the alumi
cession, the whole body of adsorbent material in
vessel la ñnally is. impregnated uniformly with 40 num chloride-enriched carrier gas with essen
tially no change in the temperature and velocity
a predetermined concentration of metal halide.
of the gas for a period of time suiiicient to sub
Valve 55 is then closed, the impregnating proce
stantially saturate said body of catalyst support
dure terminated and the carrier gas exhausted
from the circulatory system, as previously de
with aluminum chloride, discontinuing said con
scribed. The finished catalyst is removed from 45 tact of granular aluminum chloride with the car
vessel I a through opening 31a for use elsewhere
rier gas and thereafter further contacting the
or, if again desired, it may be employed in situ
aluminum chloride-contaning adsorbent support
in vessel la for a hydrocarbon conversion reac
tion.
As has been explained, the impregnation pro
cedure in Vessel la is regulated to attain any de
sired degree of catalyst concentration on the ad
sorbent support. A controlled and yet a uni
at a lower temperature with the carrier gas at a
substantially increased velocity for a period of
time suflicient to transfer aluminum chloride
from portions of the impregnated body of ad
‘ sorbent support containing higher amounts to
portions thereof containing lesser amounts until
a substantially uniformly impregnated supported
tained expeditiously in a continuous operation. 55 catalyst'l is produced.
According to this modification, particles of the
ERNEST SOLOMON.
granular adsorbent support; are passed down
LOUIS C. RUBIN.
formly impregnated supported catalyst is ob
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