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Патент USA US2406869

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72,406,869
Patented Sept. 3, 1946
UNITED I STATES‘ PATENT OFFICE
2,406,869
ca'rursrrasmmi'non
‘John D. Upham, Bartlesville, Okla" aoaignor to
Phillips Petroleum Company, a corporation of
Delaware
No Drawing. Application August- 18, 1942,
Serial No.'455,241
7 Claims. (01.25%211)
1
2
.
This invention relates to the manufacture of
catalysts, and more particularly catalysts com
prising or consisting essentially of normally solid.
or liquid,’ 1. e. non-gaseous halides of the Friedel
substantially so, with respect to the, dissolved
metal halide’ in order to reduce the expense of
preparation of the catalyst.
,
With this solution may be ‘admixed a solid
adsorbent particulate porous carrier material,
Crafts type, namely, non-gaseous halides of poly
valent metals and metalloids. Still more particu
larly it relates to the manufacture of catalysts
of the foregoing type which are supported on
such as charcoal, activated carbon, fuller’s earth,
activated clay, bauxite, Activated Alumina, silica
gel, kieselguhr, pumice, etc. Alternatively the
an inert adsorbent carrier material.
carrier material may have been admixed with
The principal object of this invention is to pro 10 the liquid hydrogen halide prior to dissolution of
vide an improved process of making a catalyst of
the metal or metalloid halide.
the Friedel-Crafts type. Another object is to
The proportions of the solution and the carrier
provide an improved process of preparing a sup
material relative to one another may vary within
ported catalyst of the Friedel-Crafts type. An
wide limits from the point where the. carrier is in
other object is to provide an improved method 15 completely saturated, that is, is in excess, to the
of making an aluminum chloride catalyst in
point where the carrier amounts to say only 25%
highly active powdered form. Still another ob
by weight of the solution. The relative propor
Ject is to make a supported aluminum chloride
tions of solution and carrier are chosen to give
catalyst in an ‘improved manner. Numerous
a finished catalyst containing any desired propor
other objects will more fully hereinafter appear. 20 tion of metal or metalloid halide on the carrier.
Catalysts prepared‘in accordance with my in
The carrier material may be either coarse or
vention may be used for catalyzing any reaction
?nely divided, and preferably of not over 100
which has heretofore been catalyzed .with nor
mesh size ranging therefrom down to 300 mesh.
mally solid or liquid halides of the Friedel-Craits
It is preferred in many reactions to use the cata
type, such as isomerization, for example, conver 25 lyst in-the form of a suspension or slurry. In
sion of normal para?lns'toisoparailins, such as
other cases the catalyst is suspended or floated
normal butane to isobutane, cracking, reforming,
in a gaseous medium. For such reactions the car
polymerization, alkylation, for example, alkyla
rier particles should be extremely iine in size.
tion of isopara?ins with ole?ns such as of isobu
In some cases the catalyst is used in the form
tane with butene to give isooctane, alkylation of 30 of lumps or large granules packed into a reac
aromatics with ole?ns such as of benzene with
tion tower, the liquid or gaseous reaction stream
ethylene to give ethylbenzene which is an inter
being passed thereto. My invention may also be
mediate in the manufacture of styrene, condensa
practiced using such large lumps of carrier.
tion, arylation, reactions of the Friedel-Crafts
The temperature at which the foregoing oper
type, etc. ,
The halides which are employed ‘as the active
‘component of’ the catalysts of my invention are
the normally non-gaseous halides of polyvalent
metals and metalloids which are of the Friedel
35 ations are conducted may be atmospheric or may
be substantially thereabove. However, the tem
perature must not be above the critical temper
ature of the pure hydrogen halide or of the solu
- tion of metal halide therein. In practice it will
Crafts type. Examples are the normally liquid 40 be desirable to stay below the critical temper
or solid ?uorides, chlorides, bromides or iodides
atures of the pure hydrogen halides which are as
of aluminum, zinc, tin, arsenic, antimony, zir
follows:
conium, beryllium, titanium, iron, molybdenum,
boron, etc. Usually the normally solidhalides of
polyvalent metals, the hydroxides of which are 45
-, ~
° C.
Hydrogen ?uoride___; _________________ __ 230.2
amphoteric, and especially of aluminum, are pre
Hydrogen chloride _____________________ __
51.4
ferred.
Hydrogen'bromide ______ -.’ _____________ __
90.0
_
Hydrogen iodide? _______________ __‘ ____ __ 151.0
In accordance with my invention, in a typical
embodiment, a solution of the anhydrous metal
The pressure during these steps of the process
or metalloid halide in a liquid anhydrous hydro 60 will be at least sufficient to maintain the hydro
gen halide, such as lique?ed hydrogen ?uoride,
gen halide in liquid phase. .This will depend upon
chloride, bromide or iodide may ?rst be prepared
the temperature and may range from atmospheric
preferably by dissolution of the anhydrous metal
where the‘temperature is below the boiling point
or metalloid halide in the liquid hydrogen halide.
of the pure hydrogen halide or of the solution
Preferably the solution so formed is saturated or 56 obtained up to the critical pressure of the pure
9,406,869
-
4
3
hydrogen halide or of the solution or higher but
seldom above 100 atmospheres. The critical
pressures of the several hydrogen halides are:
immediately or after lapse of a suf?cient period
of time to allow soaking of the solution into the
pores of the carrier, the hydrogen halide is vola
tilized from the mixture to eifect precipitation
Atmospheres
Hydrogen ?uoride ______________________ __ 90
Hydrogen chloride ______________________ __ 81.8‘
.
of the metal or metalloid halide in solid or liquid
form, as the case may be, within the pores of
the carrier. This vaporization of hydrogen
halide and consequent deposition of the metal
halide upon the carrier may be brought about by
Ordinarily the carrier material and the solu 10 the release ,of pressure to a‘suitable ?gure or the
tion of metal or metalloid halide in the liquid or
elevation of the temperature to a suitable level,
lique?ed hydrogen halide are thoroughly mixed
or by both of these measures. The selection of
with one another as by vigorous agitation so
pressure and temperature to accomplish this re
as to effect impregnation of the carrier with the
sult will be well within the skill of the art in the
solution. Other methods of effecting contact and 15 light of this disclosure.
.
impregnation may be employed, however. For
If in the contacting step the carrier is at a
example the carrier may be sprayed with the solu
temperature above the boiling point under the
tion in any desired manner, as by exposing a
prevailing pressure, this causes vaporization of a
layer of carrier agitated to continuously expose
portion of the hydrogen halide and partial pre
Hydrogen bromide ______________________ __ 84
Hydrogen iodide
_....
82
fresh surfaces as in a rotating drum or cylinder 20 cipitation of the metal or metalloid halide. Like
while spraying the solution thereon, or by inti
mately dispersing both carrier and droplets of
wise if the pressure prevailing in this step is below
that upon the solution and the level necessary to
solution with one another in a suitable gaseous
keep thehydrogen halide in liquid form, this ef
medium. The method of impregnation may be
fects vaporization of some hydrogen halide. Or,
analogous to spray drying. Thus, a cloud or sus 25 both higher temperature and lower pressure may
pension of the carrier in a suitable gaseous me
bring about some precipitation. Usually, how
dium may be sprayed with the solution in such
ever, it will be desirable to e?ect additional vola
manner that the solution coats and impregnates
tilization and precipitation by subsequently ele
the carrier particles.
vating the temperature and/or releasing the
If desired the carrier may have been previously 30 pressure in the manner described in the preced
treated in such a manner as to promote more
ing paragraph.
4
rapid and more thorough contact, wetting, and
Generally, all or substantially all of the hydro
impregnation with the hydrogen halide solution.
gen halide solvent is volatilized so that all or sub
For example it may have been evacuated to re
stantially all of the dissolved solid or liquid halide
move the air, and kept under vacuum until, the 35 is precipitated upon the carrier. However, a
time of contact with the solution. Alternatively
small amount of residual hydrogen halide may be
the air may have been displaced with a gas which
' is soluble in or wetted by the solution, preferably
left in the product to act as promoter in the re
action catalyzed therewith; usually such residual
a hydrogen halide, as by sweeping with such a
hydrogen halide will not exceed 5% by weight
gas, evacuating the carrier and then contacting 40 based on the weight of the metal or metalloid
with the gas, or in any other way. For example,
halide. Such hydrogen halide will be very inti
in an especially suitable mode of operation, the
mately distributed throughout the precipitated
carrier may be heated to an elevated temperature
metal or metalloid halide.
and then cooled in an atmosphere of hydrogen
Occasionally use of a carrier described above
halide gas whereby the pores of the carrier are 45 may be dispensed with and the solution of nor
substantially ?lled with said gas. The carrier
mally solid metal halide in the hydrogen halide
may be treated or impregnated with any other
simply treated in such manner, for example, by
material which facilitates the wetting of the car
spray drying, as to volatilize the hydrogen halide
rier by the solution. Certain solids or liquids
solvent in substantial entirety and precipitate the
may have this wetting power.
50 solid halide in ?nely divided form. Such pul
Another mode of effecting rapid impregnation
verulent solid metal halide has an unusually high
is to heat the carrier to drive 03 the air and to
activity, much greater than that of conventional
contact while hot with the solution and allow the
powdered metal halide.
carrier to cool while thus in contact with the so
The product of the foregoing process should be
lution, thereby forcibly drawing the solution into 55 stored in an inert atmosphere until use,for ex
ample, in moistureprcof receptacles in which a
the pores.
dry inert gaseous atmosphere such as nitrogen,
Since the solution is maintained and the con
tacting step is ordinarily carried out under ele
vated pressure su?icient to hold the'hydrogen
hydrogen halide, etc. is maintained over the cat
alyst. The catalysts so prepared may be used by
halide under pressure, this pressure aids in forc 60 transfer to the reaction zone for example a sta
tionary catalyst case.
ing the solution into the pores of the carrier. If
desired this action may be accentuated by vary
If desired, the catalysts of the present inven
ing the pressure or effecting alternate increase
tion may be prepared in situ in the reaction zone
and decrease in the extraneous pressure applied
through which the reactants are subsequently
throughout the impregnation step as by intermit 65 passed. In some cases an initial portion of the
tent application of additional pressure, or by al
reactants may be employed to aid in the volatili
ternate release and application of high pressure,
zation and sweeping out of the hydrogen halide
or by alternate evacuation and application of
from the solution and consequently in the precip
high pressure. For example, a, piston and cylin
itation of the metal or metalloid halide.
der may be arranged with the space above the
The catalysts of my invention may be used as
piston connected to the contacting zone and the
suspensions in ?uid reactants, that is, in the so
piston alternately retracted and advanced to ef
called “?uid catalyst" processes now being intro~
fect the desired periodic ?uctuations in pressure.
duced commercially.
During or following impregnation of the car
The product is a highly satisfactory catalyst
rier with the solution, and in the latter case either 76 for reactions of the type enumerated in detail
2,406,869
above. It is particularly useful in those reactions
substantially all of the hydrogen halide from the
resulting solution by spray drying under condi
tions to effect precipitation of solid metal halide
tion, acylationy isomerization, etc., in that small
in the form of ‘finely divided solid particles hav
amounts of such hydrogen chloride or other 5 ing intimately associated therewith less than
halide may be left in intimate contact with the
about 5 weight per cent residual hydrogen halide
metal halide in the manner described in the fore
in substantial and effective catalyst-activating
going.
where hydrogen chloride or other halide is em
ployed as an activator or promoter such as alkyla
amount.
An especially preferred combination employed -
2. The process of claim 1 wherein said metal
in carrying out the present invention is alumi
num chloride and hydrogen chloride. Following
halide is aluminum chloride and said hydrogen
halide is hydrogen chloride.
is a typical example of such an embodiment of my
3. The process of claim 1 in which said solu
tion is spray dried in contact with a ?nely divided
solid adsorbent carrier material having a particle
size within the range of about 100 to about 300
invention.
Example ,
By way of example, the preparation of a cata
mesh,"said carrier thereby being impregnated
lyst comprising anhydrous aluminum chloride
on bauxite will be described.
with said metal halide forming a ?nely divided
A solution of alu
supported catalyst having residual hydrogen hal
minum chloride in liquid anhydrous hydrogen
chloride is prepared by dissolving anhydrous alu
ide associated therewith in substantial and e?ec
" tive catalyst-activating amount.
minum chloride in a slight excess of anhydrous
4. The process of preparing a catalyst which
comprises ?lling the pores of a solid adsorbent
lique?ed hydrogen chloride whichis held under
sui?cient pressure to maintain liquid phase.
This may conveniently be done at ordinary at
particulate carrier material with gaseous anhy
drous hydrogen halide, contacting the resulting
mospheric temperatures, although other temper
carrier with a solution of a normally non-gase
atures may be used if desired. The solution thus
formed is then thoroughly mixed with bauxite of
ous anhydrous halide of the Friedel-Crafts type
in a liquid anhydrous hydrogen halide and there
by impregnating said carrier with at least part of
a desired particle size, so as to impregnate the
bauxite with the solution. The pressure is then
said solution, the presence of said gas in said
released and/or the temperature increased to
pores facilitating said impregnation, and volatiliz
vaporize the hydrogen chloride, which results in 30 ing hydrogen halide from the mixture to e?'ect
the deposition of aluminum chloride within the
precipitation of-said non-gaseous halide in and
pores of the bauxite. The relative proportions
of solution and bauxite are chosen to give a cata
lyst containing any preferred amount of alu
minum chloride on the bauxite.
'
It will be understood that both the hydrogen
halide and the metal or metalloid halide should
be anhydrous and harmful water should be ex
cluded throughout the process. However, use of
a solid adsorbent carrier‘ containing chemically
combined water, that is only partially dehy
35
upon said carrier.
5. The process of preparing a catalyst which
comprises filling the pores of a solid adsorbent
particulate carrier material with a gaseous an
hydrous hydrogen halide, contacting the result
ing carrier with a solution of a normally non
gaseous anhydrous halide of the Friedel-Crafts
type in a liquid anhydrous hydrogen halide and
thereby impregnating said carrier with at least
part of said solution, the presence of said gas
in said pores facilitating said impregnation, and
volatilizing hydrogen halide from the mixture
drated, is not precluded in the practice of my in
vention.
Reference is made to my copending applica 45 substantially completely by spray drying to ef
tion Serial No. 454,310, ?led August 10, 1942, now
fect precipitation of said non-gaseous halide in
U. S. Patent 2,356,487 which discloses certain
and upon said carrier.
subject matter disclosed and claimed herein and
' 6. The process of claim 4 wherein said non
of which this application is therefore a continu
gaseous halide is aluminum chloride and said hy
ation-in-part as to such common subject matter.
drogen halide is hydrogen chloride.
I claim:
"1. The process of claim 5 wherein said non
1. The process of preparing a catalyst which
gaseous halide is aluminum chloride and said hy
comprises dissolving a normally solid anhydrous
drogen halide is hydrogen chloride.
metal halide of the Friedel-Crafts type in a lid
uid anhydrous hydrogen halide, and volatilizing
JOHN D. UPHAM.
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