Aug. 7, 1923. G. R.

SEUART
1464,373
PROCESS FOR THE REGENERATION OF ANHYDROUS ALUMINUM, CHLORIDE
Filed Nov. 26, 92.

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 Patented Aug. 7, 1923. 1464,373

UNITED STATES PATENT OFFICE,

GoRDON R. STEUART, OF IDENVER, COLORADO, ASSIGNOR OF ONE-THIRD TO A. H.
EIIRSIG AND ONE-THIRD TO WILLIAM. C. HOLLISTER, BOTH OF DENVER, COLORADO.
PROCESS FOR THE REGENERATION OF ANHYDROUS ALUMINUM CHILORIDE,
Application filed November 26, 1921. Serial No. 517,966.
To all whom it may concern: proper proportions to form aluminum
Be it known that I, GoRDON R. STEUART, chloride. 50
a subject of the Kingdom of Great Britain, In spite of the fact that aluminum chlo
residing at the city and county of Denver ride volatizes at a low temperature (about
5 and State of Colorado, have invented cer 180° C), it is found to be impossible to re
tain new and useful Improvements in Proc cover more than a very small proportion by
esses for the Regeneration of Anhydrous heating the coke, even to a very high tem- 55
Aluminum Chloride; and I do declare the perature.
following to be a full, clear, and exact de If care is taken to stop the distillation
0 scription of the invention, such as will enable
before the residue has become too dry, it is
others skilled in the art to which it apper possible to separate the aluminum chloride
tains to make and use the same, reference in its entirety by washing with water at 60
being had to the accompanying drawings, ordinary atmospheric temperature, but this
and to the characters of reference marked method of recovering the aluminum chloride
thereon, which form a part of this specifica is subject to several objections, among which
tion. is that it is recovered in the hydrated form
This invention relates to a method for the which is of no value in the treatment of oil, 66
regeneration of anhydrous aluminum and before it can be so employed it must be
chloride, after it has been used as a catalyzer converted to the anhydrous form by a proc
20 mineral
in the treatment
oils.
of petroleum and similar ess which is both complicated and costly.
It is the object of this invention to provide
In the treatment of oils it is often found a method by which I can recover the alu- 70
to be desirable to convert high boiling oils minum chloride directly in the anhydrous
into lower boiling oils, and in performing form, and I will now proceed to describe my
29 this conversion anhydrous aluminum chlo process in detail.
ride has been found to be among the most In order to enable me to more clearly de
effective
employed.
of the catalyzing agents that can be scribe my process, I shall have reference to re.
the accompanying drawing, which shows
As the manner in which the anhydrous diagrammatically an apparatus by which
3 aluminum chloride is employed in the treat my process can be carried out.
ment of oil is well known, I shall not at After the treatment of the oil, the alu
tempt to describe the same, but will limit minum chloride is contained in a coky mass 80
the description to the method by which the of carbon, substantially free from hydro
anhydrous aluminum chloride is recovered carbons, and I shall hereinafter refer to
and made available for further use, after it this as aluminum chloride coke.
has been employed in the above referred to The aluminum chloride coke is fed into
treatment. a suitable retort 1, either continuously or 85
As is well known in this art, the anhy intermittently, which has a grate 2 and
drous aluminum chloride is added to the suitable air inlets 3 through which air is
8) oil to be treated in an amount up to ten supplied for the combustion that is to take
per cent by weight of the original charge of place. As the desired subsequent reactions
oil operated on, and the process of distilla all take place in the retort, but in different 90
tion carried on until the contents of the still zones thereof, it is essential that the avail
constitutes an approximately dry residue able space occupied by the coke shall be suffi.
which resembles colke and which contains cient, and the retort is therefore made of
enmeshed therein the original amount of considerable size. After the coke has been
anhydrous aluminum chloride, or at least placed in the retort, it is ignited at the bot- 05
the elements aluminum and chlorine in thetom and air admitted through pipes 3 in
 1,464,378
sufficient quantities to sustain the combus ditions is reduced to carbon monoxide and
tion. After combustion of the carbon has. leaves the retort through pipe 5. Mean
proceeded for a time, the heat evolved there while, the chlorine has combined in part with
from will bring all or a part of the coke in any alumina it may have come in contact 0
the retort to a high temperature. During with to form aluminum chloride, thus:
the combustion of the coke and the passage
of the gases formed therefrom through the
incandescent coke column, the desired re actsThewith chlorine which does not so combine re
the newly formed carbon monoxide 5
actions-which will now be described-will to form carbonyl chloride COCl, thus:
0. take place.
On first entering the retort the oxygen of CO--2Cl=COCl.
the air immediately reacts with the carbon On coming in contact with further alu
to form carbon dioxide with the liberation of minum oxide (which, as shown in a previous 80
a large amount of heat. This heat, due to paragraph, is abundantly available) and car
5 the passage of the gas through the retort,
bon (in
serves to bring the mass of coke therein to a acts as followsthe coke), the carbonyl chloride re
high temperature. At the same time, such chloride: to form anhydrous aluminum
aluminum chloride as was enmeshed in the -
carbon thus oxidized, is liberated. Due, 3COCl.--AlO-AlCla--3CO, 85
20 however, to the high temperature existing
The conditions existing in this
and to the excess of oxygen present, all or retort in which the above reactions occur for zone of the
some of the aluminum chloride is oxidized the
to alumina (Al...O.) and chlorine is liberated. thatformation of aluminum chloride, are such
Up to this point and while still in the first due tothere is no uncombined oxygen present, 90
the amount of incandescent carbon
25 or lowest zone of the retort, we have then present through which the various gases
converted the aluminum chloride coke to car
bon dioxide, chlorine and aluminum oxide. have passed.
The aluminum oxide is non-combustible and verted
The oxygen has all been con
to carbon monoxide, and under these
non-volatile and collects at the bottom of the conditions such aluminum chloride as may 95
30 retort. The amount of the aluminum oxide
be present is perfectly stable and thus con
thus produced is and must be proportional the tinues its passage through the remainder of
to the amount of chlorine liberated. retortunaltered, together with the carbon
This liberated aluminum now in the form monoxide. These products on issuing from
of an oxide is then extracted from the retort, is the retort are hot, and the aluminum chloride 100
either at intervals or continuously, either theinaluminum
the vapor state. On cooling sufficiently
chloride condenses to a solid
by hand or mechanically, as by screw con and may then be separated from the carbon
veyors, and added to the coke as it is fed to monoxide. The carbon monoxide may then
the opposite end of the retort. In view of be burnt for the production of heat or power 05
this step, it will be seen that the coke pres or both.
40 ent in the retort will consist, in reality, of a Since the aluminum chloride has been re
mixture of the original aluminum chloride generated for the purpose of reuse with fur
coke, together with that amount of alu
minum oxide produced during the oxida ther oil, the preferred method of condensing
tion of this carbon attended by the liberation same is by means of the oil itself, thus avoid 0
45 of chlorine, or, in other words, that there is ing considerable labor and possible loss in
and must be at all times sufficient aluminuin handling.
oxide present in the retort to combine with above It must be clearly understood from the
all of the chlorine liberated to form alu not limit description of my process that I do
minum chloride. myself to any particular form of 5
50 For reasons that will be clear from a de retort in which it may be carried out. Also
scription of the subsequent reactions to be de Iofdocondensing
not limit myself to any special method
scribed, it may be advisable to add an excess I have inventedthe a
aluminum chloride vapor.
particular operation which,
of aluminum oxide, which will be distributed
evenly throughout the coke column and through a series of clearly described chemical 20
55 which will become a floating or circulating reactions, results in the end desired, and it
load. This step is not essential to the suc isoutclear that these operations may be carried
cess of the process, but under certain condi without in any different
in several forms of apparatus
way altering the novelty and
tions may be useful in promoting a lessened value of the principles involved.
loss in chlorine.
Reverting now to the gaseous products of Having now described my invention, what 25
combustion, namely: carbon dioxide and claim is:
1. The method for the separation of an
chlorine. These gases, subsequent to their hydrous aluminum chloride from petroleum
formation and on movement through the re
tort, come in contact with incandescent car coke, which consists of oxidizing the carbon 30
85 bon. The carbon dioxide under these con to the gaseous state, thereby liberating the
 1,464,378
occluded aluminum chloride, converting the
latter to aluminum oxide and chlorine, sub
jecting the aluminum oxide and chlorine to
5
further heat in a reducing atmosphere,
whereby the aluminum oxide and chlorine
combine to form anhydrous aluminum
chloride.
2. The process of separating occluded an anhydrous aluminum chloride from the resi
hydrous aluminum chloride from petroleum due
coke which consists of burning the coke in eral oils there with, which consists of oxidiz
a closed retort, whereby the occluded alumi
num chloride is liberated in the form of
chlorine and aluminum oxide, adding alumi
num oxide to the upper part of the coke,
passing the gaseous products of combustion,
including the chlorine, upwardly from the
oxiding zone to the reducing zone of the
coke where the chlorine will combine with
the aluminum oxide to form gaseous an
20 hydrous aluminum chloride and removing
and cooling the same, whereby the anhy
drous aluminum chloride is condensed.
3. The method of recovering anhydrous
aluminum chloride from petroleum coke,
25 which consists of burning the coke in a re
tort, passing the products of combustion
upwardly through strata of progressively
smaller oxidizing properties to which alumi
num oxide has been added into strata hav
3. 9 ing reducing properties, removing the gases
from the retort and subjecting them to a
temperature sufficiently low to cause the
anhydrous aluminum chloride to condense.
4. The method of recovering anhydrous
35 aluminum chloride from petroleum coke,
which consists of placing a comparatively
deep bed of coke in a retort, igniting the
lower side of said coke bed, whereby the
aluminum chloride is converted into alumi
40 num oxide (Al...O.) and chlorine, passing
said chlorine upwardly into and through
the reducing zones of said coke to which
aluminum oxide has been added, whereby
3
the aluminum oxide is reduced to aluminum
and combines with the chlorine to form gase 45
ous aluminum chloride, removing the gases
from the retort and subjecting the same to a
temperature sufficiently low to cause the
aluminum chloride to condense.
5. The method for the regeneration of
59
remaining after the treatment of min
ing the carbon to the gaseous state, thereby
liberating the occluded aluminum chloride,
oxidizing the aluminum to aluminum oxide
(Al...O.) and liberating the chlorine, mixing
the aluminum oxide with coke, passing the
gaseous products through the heated mix
ture of coke and aluminum oxide, whereby
the aluminum and chlorine will reunite to
form anhydrous aluminum chloride, remov
ing the carbon monoxide and anhydrous
aluminum chloride from the retort and sub
jecting them to a temperature of such value 65
that the anhydrous aluminum chloride will
condense and become separated from the
carbon monoxide.
6. The recovery or regeneration of anhy
drous aluminum chloride from the residue ()
remaining after the treatment of mineral
oils there with by oxidizing the carbon to
the gaseous state, resulting in the liberation
of the occluded aluminum chloride with the
attendant oxidation of the latter to alumi 5
num oxide and chlorine, and the Sub
sequent reunion of the aluminum oxide and
chlorine to form anhydrous aluminum
chloride under the influence of heat and
carbon, and the further conversion of the 80
carbon contained in the original residue
from distillation into carbon monoxide as a
valuable by-product.
In testimony whereof I affix my signature.
GORDON R. STEUART,