US1801627A - Process and apparatus for continuous treatment of hydrocarbon oil with a. metallic halide - Google Patents

Description

April 21, 1931. R. W .HANNA 1,801,627

PROCESS AND APPARATUS FOR CONTINUOUS TREATMENT OF HYDROCARBON OIL WITH A METALLIC HALIDE Filed Nov. 27, 1926- corn-ansia caLER REsllmUM LQ 31a/vento@ @Hoz new Patented Apr. 21, 1931 UNITEDl STATES PATENT orner-z.

RICHARD W. HANNA, PIEDMONT, CALIFORNIA, A SSIGNOR TO STANDARD OIL COM- PANY Ol' CALIFORNIA, OF SAN FRANCISCO, CALIFORNIA, A CORPORATION OF DELA- WARE' PROCESS AND APPARATUS FOR CONTINUOUS .TREATMENT Ol' HYDROCARBON OIL WITH A METALLIC HALIDE Application led November 27, 1928. Serial No. 151,165.

This invention relates tothe treatment of hydrocarbon oils, such as petroleum o1l, shale oil,or oils` derived from coal or similar sources, with a metallic halide such as alumi- 5 num chloride, and refers particularly to a coptinuous process of treatlng the-hydrocarbon oil with a metallic halide.

In the conventional' process of treating hydrocarbon oils with aluminum chloride, the hydrocarbon oils are agitated together in batch lots with aluminum chloride in a reaction chamber in-which heat is supplied to the chamber walls to maintain the desired reaction temperature. In such a process, considerable diliiculty is experienced dueto the necessity of employing a mechanical agitator inthe reaction chamber. Moreover, the addition of the greater portion of the heat tothe admixture in the reaction chamber results in unnecessarily large tar or coke formations and in a poor eicienc of heat transfer. Furthermore, the con ucting of the process in batch lots results in a low yield of product from a given size apparatus.

An object of the present invention is toA provide a process of treating hydrocarbon oil with alumlnum chloride in which the hydrocarbon oil and aluminum chloride may be continuously agitated together with a con- ,30 tinuous conversion of h drocarbon oil to low boiling point oil or nap tha and the continuous removal ofl residual aluminum chloride. Another 'object of the present invention is to provide a continuous apparatus for treat- QI ing hydrocarbon oil -withaluminum chloride in which an agitation of the materials may be effected by circulation of liquid from the r action chamber back into the reaction chamber entering in the form of Ajets so that the 0 liquid undergoing treatment serves as an agitating means for the mixture. 'By this v method, the process of the. present invention eliminatestheproblems encountered 1n the v lprocesses employing a mechanical agltatlon 4I of aluminum chloride and hydrocarbon oil together or when the oil agitation is combined with mechanical agitation substantially simplifies and reduces the mechanical agitating problems.'

Another object of the present invention is to provide a process in which a part, preferably the major part, or final heating of the hydrocarbon oil is conducted in a heating zone separate from the reaction chamber by a continuous circulation of hydrocarbon oil or the liquid admixture from the reaction chamber through said heating zone and back into said agitatin-ggchamber. In this manner, excessive formation of carbon or ,coke and high heat losses are avoided. y

Another object of the invention is to pro`- vide a process in which a single stream of liquid .may be withdrawn from a source of bulk supply of hydrocarbon oil and aluminum chloride and circulated through a heating zone and back into said bulk supply entering in the form of agitating jets. The

necessary heat for the reaction is applied largely separate from the agitation chamber andl the heated stream serves as agitating means.

Another object of the present invention is to provide a continuous process of treating hydrocarbon oil with aluminum chloride vin which there may be circulated from the bulk -supply'of said materials a liquid which in its circulating path has separated therefrom Y Vany aluminum chloride compound so that only a substantially. clean stream of hydrocarbon 'oil passes through the heating zone;

Various further objects and 'advantages of the present invention will be understoodl from a description of a preferred form of process and apparatus embodying the invention. For this purpose, reference is made to the accompanyin drawing in which there is illustrated apre erred example of an apparatusembodying-the invention, in which i apparatus the preferred process embodying.A l

the invention may be carried out.

, The drawing represents a diagrammatic view mainly in elevation and partially in vertical section of thp apparatus.

Referring to the ydrawing, the reaction chamber in which the bulk supply of materials is maintained is generally indicated at 2. Said reactio'n chamber is preferably an incumbent cylindrical tank. 3 indicates a storage vessel 'or other suitable source of hydrocarbon oil. The storage vessel 3 is indicated as provided with a line 4 including a pump 5 by which the hydrocarbon oil may be withdrawn from the storage vessel 3 and passed into the reaction chamber2. The fresh hydrocarbon oil may be directly introduced into the said reaction chamber or into a vapor line 6 leading from said reaction chamber.

Preferably the hydrocarbon oil line 4 is connected with the lines 7 and 8, the line 7 leading to the upper portion of a dephlegmator or reiux tower 9 connected with the vapor line 6 and the line 8 leading to a circulating line 1( The circulating line 10 is connected with the reaction chamber at one end, as indicated at 11, and includes a ump 12 by which liquid may be withdrawn rom the reaction chamber and forcibly circulated through the heating zone and back' into the chamber. Preferably the heating zone comprises a coil 13 positioned within a furnace 14. The circulating line, 10 also preferably'includes a trap 15 between the pump 12 and coil 13 by which any aluminum chloride or tarry residue may be separated from the circulating stream of liquid, said trap being indicated as preferably provided with the central bale 16 having openings at its top and bottom and with a line 17 leading back to the reaction chamber 2 for return of separated tar or aluminum `chlo ride to the reactionv chamber. The line-8, introducing part of the feed oil int-ol the system, preferably connects with the circulatr ing line 10 between the trap 15 and heating coil 13.

The trap 15 operates as follows: The oil whichenters the trap rises upwardly through the trap and heats vthe baflie 16. This causes the tarry particles to be impounded against ,the baiiie while the liquid particles flow -around`the batlle and out through the upper outlet of the trap. The tarry particles im- .pounded against the baille collect and drip back to the bottom of the trap and are forced throughl the lower opening` of the trap`b'aclc into the chamber 2.

The circulating line 10 is indicated as, terminatingwithin the reaction chamber 2 inv a pluralty of jet pipes 18 positioned near the bottom' of the reaction chamber and spaced apart throughout the bottom of the reaction chamber so that the oil entering the reaction chamber vfrom the circulating line 10 is distributed through the reaction chamber in ,a number of high velocity jets'. The 65 end 11of the circulating line'10 is preferably connected within the still to a line 19 which leads to a position under the yvapor line 6 and is there connected with a pan 20 for catching reflux oils and feed oil lfrom the vapor line 6. The reflux tower 9 is indicated as connected with a vapor line 21 which leads to a condenser 22 from which a line 23 carries condensed oil to a receiving tank 24 for the rcduced low boiling point oil or naphtha. I aid receiver 24 is indicated as provided wlth a valved gas vent 25 by which pressure, if desired, may be imposed upon the system. The tank 24 also may be connected with a line 26 for discharge of the produced low boiling point oil or naphtha. The reaction chamber 2 is also preferably provided Iwith a charger 27 by which anhydrous aluminumv chloride may be intermittently or continuously introduced into the reaction chamber 2 while the said chamber is under pressure. For this purpose, the

charger 27 includes the two spaced apart valves 28 and 29, and the hopper 30. In certain cases, it may be desirable to introduce the. aluminum chloride continuously into the reaction chamber 2 in a liquid form, for example, by admixing the aluminum chloride with some hydrocarbon oil and for this purpose, thecharger 27 is indicated as connected with a line 31. The reaction chamber 2 is also indicated as preferably connected with a residual draw oif line 32connected with a cooler 33 and hence to a resid.- uum tank 34 having the oil withdrawal line 35 and the tar withdrawal line 36.

The process as conducted in the apparatus thus describedl is preferably as follows: In starting the apparatus, the hydrocarbon oil in proper quantity s charged into the ieaction chamber 2 an is then circulated from said reaction chamber 2 through circulatin line 10 and the heating lzone back into sai chamber until the desired reaction temperature is reached. When the desired reaction temperature is reached, aluminum chloride 1.10 or equivalent metallic halide is added to the hydrocarbon oil and the process is then con tinued in a continuous manner by continuously or intermittently adding the requisite aluminum chloride and continuously passing ,115 further fresh oil to the system.

While'the process may operate employing any desired hydrocarbon oil, an example of a suitable oil responding particularly well to the process is gas oil fractions of petro- 120 leum oil such, for example, as have a Beaum gravity of 25c and derived from California or asphaltic base crude oil.A The quantity of aluminum chloride added to the oil will vary largely with the character of oil to be r1,25 treated and the temperature of treatment, and the character of product desired. When desiring to produce U. S. motor'grade gaso line from the' particular il referred to, I generally prefer to employ between 5 and 10 per 1130 cent. by weight of aluminum chloride. The temperature of the `reaction may also be varied through considerable range but is vapor line 6 together with some higher boiling point oil and some aluminum chloride.

Said vapors are cooled within the dephlegmator 9 to a discharge temperature suitable for condensing therefrom all fractions but those desirable in the finished naphtha. For this purpose, the discharge temperature is enerall held between 300 and 360 F.

he coo g of the vapors is preferably accomplished by passing a ortion ofthe feed oil through line 7 into t e uprising vapors whereby the cooling of the vapors also results in heatinglthis portion of the fresh oil. This portion of the flux or condensed heavier oils pass through the vapor line 6 into the reaction chamber 2 andare there caught in the pan 20 and part at least thereof/is circulated or recirculated from the bulk suppl `of materials within said chamber throug the heating coil 13 and back into said chamber. In the process, part of the bulksupply in the chamber 2 is circulated from the chamber to the line 10 and heating zone back into the chamber, by reason of the fact thata part of the supply in chamber 2 is continuously vaporized and entrained with vapors passing 'fout the line 6, where the dephlegmator 9 returns the same to the pan 20, from whence it passes to the' line 10. Within the trap15 any portion of the aluminum chloride or tar in the circulating line 10 is separated therefrom and preferably continuously passed again to the reaction chamber 2. There is also added to the stream of materials being circulated in line the reaction chamber 2 thoroughly agitates and commingles the hydrocarbon oil wlth the aluminum chloride, thus overcoming the agitation problems encountered in the normal" processes.

Preferably during the process, aluminum chloride residue is intimately or continuous'- ly withdrawn through line 32', passed through cooler 33, and hence into areceiver or reslduum tank 34. In said tank 34, any oil entrained in the residue is separated and eed oil together with any rewithdrawn from line 35 while the residuum is withdrawn throughline 36. V

While the particular form of the invention herein described is well adapted to carry out the objects of the invention, numerous modifications may be made and the invention is of the scope set forth in the appended claims.

I claim:

1. A process of treatin hydrocarbon oil with anhydrous metallic alide which comprises maintaining a bulk supply of hydrocarbon oil and metallic halide at a' conversion temperature and undergoin adecomposing reaction in a reaction cham r, passing the evolved vapors therefrom to a refiux tower, withdrawing reflux liquid from said reflux tower and circulating a part of said liquid through a heating zone and back into said reaction chamber, separatin metallic halide sludge from the circulatin uid and passing the metallic halide slu ge acl: into said reaction chamber without passing through said heating zone.

2. An apparatus for treating hydrocarbon 'oils with anhydrous metallic halide in order ing from said reflux tower through 'a heating zone and back into said-reaction chamber, .a separator operative for separating metallic halide sludge from the liquid circulating in said line, and a by-pass line for passinv the metallic halide sludge thus separated ack into said reaction chamber without passing through saidfheating zone. i

3. A process of 'treating hydrocarbon loils with metallic halide which comprises continuously maintaining a bulk' supply of hydrocarbonoil and metallic halide at a c onversiontemperature, continuously passlng evolved vapors from said bulk supply to a reflux zone, continuously circulating reflux liquid from said reflux ,zon-e through a cleansing and separating zone to remove halide contained therein, and then passing. the cleansedliquid through Aa heating zone into said bulk supply, the liquid thus circulated ioa and cleansed being caused to continuously agitate said bulk supply, and continuously passing fresh oil into said bulk supply while divertlnga portion of said oil to said reflux tower.-

4. An apparatus for vtreating hydrocarbon oils with anhydrous metallic alide for 'decomposing the hydrocarbon oils into lower boiling point oils, comprising a reaction chamber, a reflux tower operatively connected with said reactionchamber, a circulating'line leading from said reux tower through a heating zone and back into Isaid reaction chamber, said vline terminatingin a plurality ofjetting means within said reaction chamber whereb liquid from said line is caused to agitate t e contents of said reaction chamber, separating means for separating metallic hahde sludge from the liquid circulating.

in said line positioned in said line between -said reflux tower, a heating zone, and a bypass line for passing the metallic halide sludge thus separated back into said reaction chamber without passing through said heating zone.

Signed at San Francisco, California, this 16th day of November, 1926.

RICHARD W. HANNA.

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