US1332018A - Utilization of aluminum-chlorid residues - Google Patents

Description

L. S. ABBOTT.

UTILIZATION. OF ALUMINUM CHLORID RESIDUES.

APPLICATION FILED JULY 1. 1919.

Patented Feb. 24, 1920.

Lyle Asa/755027;

UNITED STATES PATENT OFFICE.

LYLE STOCKTON ABBOTT, 0]? PORT ARTHUR, TEXAS, ASSIGNOB TO GULF REFINING COMPANY, OF PITTSBURGH, PENNSYLVANIA, A CORPORATION OF TEXAS.

UTILIZATION OF ALUMINUM-OHLORID RESIDUES.

Application filed July 1, 1919. Serial No. 308,005.

T 0 all whom it may concern: 7

Be it known that I, LYLE STOCKTON An- BOTT, a citizen of the United States, residing at Port Arthur, in the county of J ef-" ferson and State of Texas, have invented certain new and useful Improvements in the Utilization of Aluminum-Chlorid Residues, of which the following is a specification.

This invention relates to the utilization of aluminum chlorid residues; and it comprises a process of obtaining aluminum chlorid from certain coky, tarry or oily residues formed in various processes of refining, altering and improving oils with aluminum chlorid, wherein such residues are heated and baked to free them as far as possible of hydrogen-containing oils and hydrocarbons and are then treated with superheated chlorin at a temperature sufiicient to produce and liberate aluminum chlorid, the heat of such superheated chlorin being afforded by the combustion of excess carbon contamed in such residues, the combustion of the carbon being either before or after the production of aluminum chlorid, as by treating heated and baked residues with superheated chlorin until such residues are stripped, or substantially stripped, of aluminum chlorid and bodies capa le of yieldmg aluminum chlorid, thereafter transferring the strlpped carbon to a suitable combustion chamber and blasting it to incandcscence and superheating chlorin to be used on such residues by the heat of the incandescent carbon, or as 'bv blasting up a portion of such residues in a. suitable combustion chamber to obtain an incandescent heat and passing chlorin through the incandescent material, the heated chlorin being thereafter contacted with another portion of residue; all as more fully hereinafter set forth and as claimed.

There are a number of processes of treating petroleum oils with aluminum chlorid for various purposes, such as the productlon of gasolene, the productlon of improved lubricating oil, the manufacture of medic nal oil, etc., as more fully disclosed 1n various patents to one McAfee (see Patents Nos. 1,127,465, 1,235,523, 1,277,092, 1,277,328 and 1,27 7 ,329, etc). In these processes anhydrous aluminum chlorid is heated wlth the oil under various circumstances to produce various changes in the oil. After a time the activity of the aluminum chlorid as a catalytic agent slackens and ceases; and after a certain time it is removed from the still or other apparatus and replaced by fresh material. At this time, 1 the aluminum chlorid generally occurs in a black, oily; tarry or coke-like mass. If the various operations utilizing its catalytic power have been carrled on with dry oil, substantially free of oxygen and sulfur, the aluminum chlorid'is probably contained as such, that-is, chlorin and aluminum are present in the proper proportions to form aluminum chlorid; but the aluminum chlorid is, so to speak, masked; 1t no longer displays catalytic activity. Possibly this is due to the presence of inactive compounds of aluminum chlorid with further to liberate and distil ofi' aluminum chlorid.

It is with material of this character that Iv deal in the present invention. The aluminum chlorid residues, after freeing from oil as far as possible and baking somewhat, either to break up hydrocarbons or to liberate such aluminum chlorid as can be freed thereby, contain a large amount of carbon in addition to the residual aluminum chlorid or alumina. In the treatment of some oils, and articularly where any moisture is present, t ere is, or may be, a considerable amount of aluminum oxid present. In the present invention, I utilize this carbon for its fuel value and also recover or utilize the aluminum chlorid and alumina present.

In the manufacture of aluminum chlorid from alumina, carbon and chlorin as usually carried out in the art, alumina and carbon have been placed in retorts situated in a suitably heated furnace and a current of chlorin passed over. By a well known reaction, aluminum chlorid and carbon monoxid are formed and the aluminum chlorid, which is in the vapor form, is condensed and separated. In this method of manufacture, however, it is a matter of extreme difiiculty to obtain good reults on any large manufacturing scale, for the reason that the larger the retort the more intense must be the heat of the walls and it is diflicult'to obtain matelials for making retorts which will withstand the chemical action. The production of aluminum chlorid is a heat-absorbing or endothermic reaction and, while it does not require any reat amount of heat it does require a very i h temperature. uch a temperature is di cult to obtain in the center of a pervious mass contained in a retort of any large size. In another and copendin ap lication, Serial No. 167,962, May 11, 191 I have described and claimed a method of producing aluminum chlorid from alumina, carbon and chlorin, wherein I carry the necessary heat units into the mass of carbon and alumina by superheating the chlorin, the chlorin being passed through a space or chamber which is brought to a high temperature from time to time by producing active combustion therein. he superheated chlorin carries the necessary number ofheat units and is at a suflicient temperature for effecting the reaction. This obviates the necessity for transmitting heat to the reaction mixture through the walls of 'a' retort. In the stated method, while the temperature necessary may be imparted to a heating chamber, such as a checkerwork, by occasional combustion of air and gas therein, I find it better to use as the heating chamber a structure like an ordinary as roducer filled with hot coke or charcoa he coke or charcoal from time to time is blastedup to a state of vivid incandescence by a current of air. Most advantageously the current of air used in blasting is sent throu h at such a rate of s eed as to produce 0, rather than CO, utilizing the well known principles employed in the blow stage of makmg water gas. After the blasting up is com leted, the air is cut off and the exit for b ow gases closed and a current of chlorin is sent directly through the incandescent coke and is thereafter passed into a suitable reaction chamber containing briqueted alumina and carbon. In this chamber it produces vapors of aluminum chloridwhich are sent to a suitable condenser. As will be seen, in this specific embodiment of my described method,

two chambers are employed, one serving as a heating up chamber for the chlorin and the other as. a reaction chamber.

I have found this process may be advantion chamber suc as described and pass in superheated chlorin. Under the influence of the chlorin, aluminum chlorid is liberated and formed and passes to a suitable condensing chamber as just described. Such the residues into .a reac-i .In so doing, the excess of carbon existing in the residues is utilized, efi'ecting an important economy in fuel. The process as just described may readily be made continuous, the baked residues being passed through a reaction chamber against a countercurrent 0 of superheated chlorin and thence passing continuously or discontinuously to a suitable combustion chamber wherein the carbon forms a mass which is alternately blasted with air and utilized in heating chlorin as previously described.

' In an alternative embodiment of the present invention, baked residue may be charged into the reaction chamber as above and another portion of residue charged into the fuel chamber. In the fuel chamber, the residue burns as before to furnish heat which is imparted to chlorin. In the blowing up stage of this residue some of the aluminum chlorid containedgoes off with the blow gases, usually decomposin therein with de osition of alumina an formation of H 1. Some portion, however, furnishes an incidental amount of aluminum chlorid when the chlorin is passed through the incandescent mass on its way to the reaction chamber.

In blowing up ignited baked residues with air in order to raise the temperature of the material, some of the contained aluminum chlorid is decomposed with loss of chlorin as HCl, a corresponding amount of alumina being formed. This alumina forms chlorid in the following treatment with chlorin. It is therefore advantageous to precede blowing up with a chlorin treatment. In an advantageous embodiment of my invention I provide a pair of chambers each serving alternately as a reaction cham- 7 her and as a heating chamber. In the one temporarily acting as a reaction chamber, fresh baked residue is subjected to the action of preheated chlorin coming from the other chamber, temporarily acting as a heating chamber. After a.time, the supply of- In the accompanying illustration I have shown, more or less diagrammatically, certain types of apparatus useful in the performance of the described process. In this showing Figure 1 is a central vertical section of one type of apparatus;

Fig. 2 is a central horizontal section on lines 2-2 of Fig. 1; and

Fig. 3 is a central vertical section of a modified form of apparatus.

In the showing of Figs. 1 and 2, two chambers, marked A and B, respectively intended as a fuel chamber and a reaction chamber, are provided within a common casing. As shown, steel jacket 1 is lined with firebrick or the like 2. Another lining 3 is spaced away to some extent and between is'a layer t of heat-insulating material, such as kieselguhr. The two chambers communicate at 5 and are separated by partition 6 which does not extend the full height of the casing. Two inlets, 8 and 9', for air and for chlorin are provided for the one chamber and two, marked 10 and- 10, for the other. These also serve as outlets for aluminum chlorid vapors. At the top of the sub-chambers are removable lids, 11 and at the base removable dumping plates 12.

The structure of Fig. 3 is like that of Fig. 1 (like reference characters indicating like elements) differing mainly in that two structurally separate chambers ar nrovided instead of subdividing one chamber into two sub-chambers. Chamber A has a special outlet 13 and chamber B has a special side door 11.

In the use of these structures, in Fig. 1 chamber B may be filled with baked residue and air blown into A through 8 until the contents (previously treated residue or coke) are incandescent, products of combustion escaping at the top. Top door 11 is removed during this phase. When the charge in A is sufiiciently heated, the door is replaced and chlorin is introduced through 9. This chlorin passes up through the hot fuel, is heated and passes into B through 5. In B it forms and releases aluminum chlorid as vapors which pass through 10 to a suitable condenser (not shown). After a time when the charge B is exhausted, it may be transferred to A and used for its fuel value.

In another way of using this apparatus, A being supposed to be full of fuel and B with baked residues, after the charge in B is substantially exhausted, the charge in A may be replaced by fresh residue and the draft currents reversed, air being first blown in at 10 and then chlorin at 10 while aluminum chlorid passes away to a condenser at 8.

In Fig. 3, after a charge in B has been chlorinated (vapors of aluminum chlorid being removed at 10), it may be transferred to A, side door 11 being provided to facilitate this transfer.

What I claim is 1. In the utilization of exhausted aluminum chlorid residues, the process which comprises treating such a residue with a current of superheated chlorin, burning a portion of the carbon contained in such a residue to heat the remaining carbon to incandescence and passing the heated chlorin through the incandescent mass to afford the stated preheating.

2. In the utilization of exhausted aluminum chlorid residues, the process which comprises treating such a residue in a suitable reaction chamber with preheated chlorin at a temperature sufiicient for the formation of aluminum chlorid in the vapor form until the residue is stripped of aluminum compounds, removing the stripped material from the reaction chamber, blowing it up with air to an incandescent heat and passing chlorin through the incandescent mass on its way to reaction chamber.

3. The process of recovering aluminum chlorid from oil residues'which comprises exposing such residues to a current of preheated chlorin to form aluminum chlorid, thereafter blasting up with air and once more passing through chlorin to preheat such chlorin.

In testimony whereof I aflix my signature hereto.

LYLE STOCKTON ABBOTT.

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