US1620075A - Process of converting oils and apparatus therefor - Google Patents

Description

J. c. cLANcY PROCESS OF CONVERTING OILS AND APPARATUS THEREFOR Filed April 16,l 1924 March 8, 1927.

[NVE/WUR.

Pate-med Mar. 8,1927.'

PA-TENTIoFFlcE.

JOHN coLLnvs cLANcY, oF- AsBUnY PARK, NEW. JERSEY.

rnocnss or convnnrme ons Ann APPARATUS rnnnaron.

application mea April 1e, 1924. serial No. 706,854.

This invention relates'to an improved process for converting oils and toapparatus therefor, and more particularly to the catalytic treatment of high boiling hydrocarbon oils, such as the various high boiling coal tar distillates (solvent naphtha), gas

. oil, solar oil, fuel oil, high boiling crude oils,

chlorid sludges resulting from the distillation of higher boiling oils with aluminum l0 chlorid, petroleum reslduums and other high boiling petroleum materials-for the purpose of catalyticallyproducing low boiling oils, whether these *latter be of aromatic nature (benzol and toluol), or of petroleumcharacter, such as gasolene.

Many processes have been employed or suggested for `catalytically transforming or converting the above materials into, the desired hydrocarbon products, but all of them involved the separation'or deposition of carbon either on the surfaces of the catalytic metal employed, or accumulations oi carbon and carbon compounds of the catalyst, when hydrocarbon oils into low boiling'hydrocarbon oils have been through the intermediacy of a catalyzing/metal halid such, for ex'- ample, as aluminum chlorid. Y As is well known, aluminum chlorid has the l effect o`f`vapor outlet of the system-,take place'. This changing the character of hydrocarbon oils num chlorid is in a. measure unchanged chemand by gummy masses formed during the' when agitated therewith under -distilling conditions. 'Under such conditions the alumiically; acting, therefore, as a contact substance or catalyst. On the other hand, however, the 'activity of this catalyst becomes impaired, more or less gradually, by reason of contamination with the carbon deposited lcourse of the' operation. This decrease in eiiciency makes it necessary, Y'atquite' irequent intervals, to separate the remaining oil from the aluminum. chlorid and regenerate the' latter, or'addA fresh portions' of aluminum chlorid. The continued -addition of fresh aluminum chlorid is obviously sive increase ill-bulk of material involved,

and regeneration ofthe catalyst is, hence,

the method commonly practised. nlegenerathe catalyst used was a catalytically acting.

'from prohibitive on account of the relatively high 'cost of this substance as well as the progrestion of the aluminum chlorid, however', is both diliicult and expensive; Now, when working with dry oils the bulk of the aluminum chlorid at the completion of the distillmg operation is found in the'residue in the still, united in part with hydrocarbon in the Jform of aluminum chlorid hydrocarbon compound, e'nmeshed or buried in the cokymass of carbon separated out during Other methods of lusing aluminum chlorid, d

with or without admixture. of other anhydrous chlorlds, have been suggested, wherein the hydrocarbon material to vbei-treated 1s converted intov the vapor form and intermingled with the vapors ofaluminum chlorid for a suitable length off time; the aluminum chlorid and the hydrocarbon vapors being subsequently separated and the hydrocarbons condensed and collected for use. Here again, however, under the elevated temperature conditions necessarilyem ployed in vaporizing high boiling oils, cracking distillation occurs simultaneously with catalytic action, .and deposition of, carbon and adhesions of aluminum ehloridhydrocarbon compounds in the cracking tubes and highly objectionable deposition of carbon andgummy masses mixedfwith aluminum chlorid hydrocarbon compounds, necessitates Processes Vwhich involve the cracking of hydrocarbons in presence of catalytic metals U'j s'uch as copper and like metals, suifer similar -disadvantages in that the' vcracking tubes and surfaces of the catalytic Y metals employed become clogged or sooted up'with deposited carbon. In fact, as is well4 known, many desirable processesfor the con# version of high boiling hydrocarbons into -lower boiling hydrocarbons havevbeen rendered commercially'impractical by reason of such carbon deposition on the'surface's 'of the catalytic materials employed.

^ A search for a means` to obviatesome of the above mentioned disadvantages, involved a' line of experiments which has resulted in the discovery that if `the coky mass containing the aluminum chlorid or aluminum chlorid hydrocarbon compounds referred to is suspended in a molten mass of zinc chlorid, the aluminum chlorid can he readily separated from the coke or carbon; the latter remaining in suspension in the molternzinc chlorid while the aluminum chlorid distills off. AOn repeating this experiment, using a copper still to hold the molten zinc chlorid containing the valuminum vchlorid coky material in suspension, l added nickel turnings and bubbled a current of hydrogen therethrough; thus contacting the hydrogen with the metal and the molten material. Light saturated and readilyT condensahle hydrocarbons then distilled oli withtheA aluminum chlorid; the latter being easily separated from said hydrocarbons by simple condensation.

ll have discovered that it' is possible to make the process of convertingl higher boiling hydrocarbons into lower boilinghydrocarbons a truly continuous one, the objectionable formation of the coky and gummy masses being eliminated, and at the same time to prevent the deposition of carbon on the surfaces of the catalytic metals employed to facilitate conversion and hydrogenation ofthe hydrocarbon material beingA treated.

@neef the objects of my invention is, therefore to provide a process for quickening the action of aluminum chlorid on the oil and enhancing the extent of utilization of said chlorid, and preventing the Jformation of coky and gummykmasses resulting from the action of aluminum vchlorid on the oil undergoing conversion. rlhese and other objects of the process will hereinafter be referred to and the novel combination of steps whereby said objects may be attained will now be related in detail. l

,My process broadly comprises reacting uponhydrocarbon oils with aluminum chlorid in the presence of and in contact with a molten body containing Zinc chlorid, but preferably, with .a molten body containing a mixture of zinc chlorid and sodium chlorid; the molten body also functioning as a menstruum to hold in suspension a portion of the carbon separated during the pyrolytie and catalytic treatment of the oil. The process, more specifically, .is characterized by the fact that the molten body referred to, and the hydrocarbon material to' be treated are contacted with each other as downwardly flowing vstreams in a suitable reaction `which retain their physical forlnand posi- Y tion and serve not only as a catalyzer for the hydrogenation and cracking reaction; but .also behave to present an extended surface Lezama for contacting the flowing body of molten material with the hydrocarbon material and the vapors of metal halids; suchas, aluminum chlorid, ferrie chlorid and the like., 'lhe process is furthercharacterized bythe fact that the 'molten body vnot alone acts as a catalyst; but also functions simultaneously as a fluid heat carrier and menstruum to. automatically remove'from the reaction zone a portion at least of the carbon formed or separated out in the process; thus preventing the accumulation or vformation of gummy and coky masses referred to, even though the oil or hydrocarbon material being treated, originally contained such carbon impurities in suspension. This tendency of the molten catalyzer, or molten body, to hold considerable amounts of carbon in suspension, serves to maintain' clean surfaces and effective catalytic action of the solid metal catalysts, employed in the process, whereby to facilitate the saturation of any. unsaturated hydrocarbon and a portion of the separated carbon formed in the converting and distilling oper-A ation. rllhis further effects the hydrogenation of a portion of the carbon contained iu the'oil. Y l

Another noteworthy feature of the process is that the conversion of the higher boiling oils into lower boiling oils `is effected in a. reaction zone or chamber to which the molten material is supplied through a trappe-d inlet, while the liquid reaction products comprisingmolten material containing `carbon in suspension, and the unvaporizcd liquid hydrocarbons containing carbon in lui) suspension, are withdrawn from the lower end of the reaction chamber as streams diverse inspecific gravity, ,through liquid sealed passages. Simultaneously the vapors of aluminum chlorid and vapors of lower boiling hydrocarbons formedin the heat-inf,r zone arev allowed to pass through a cooling zone to separat-e the higher boiling hydro- -carbons and to aluminum chlorid and allow passage therefrom of lower bollng oils.

'llhe separation of the heavier' vapors and aluminum chlorid vfrom the vapors of lower boiling oils-being preferably eiected by controlling the cooling of the coolfng zone by the passage therethrough of the higher boiling oils to be treated maintained at such a temperature as tocondense vapors of higher boiling hydrocarbons and aluminum lchlorid vapors in the cooling zone but-to allow passage of vapors of lower boiling oils and gases lli'i from said cooling zone', and condensing and' collecting such lower boiling oils, and returning 'the condensed higher boiling hydrocarbons mixed with condensed aluminum chlorid .-intermingled with the stream of fresh higher boiling oils passing tothe retort for treatment, the volatile aluminum chlorid is, hence,` used repeatedly inthe process. The cooling zonels preferably lled with The molten zinc chlorid materlal withdrawn from "the reaction chamber inthe foregoing manner is used repetitively until it becomes too lhighly charged with sus- -pended carbon which had escaped hydrogenation in thel process. When this carbon in suspension accumulates to its saturation point, cthe molten material is filtered to remove the bulk of carbon therefrom and the filtrate used over agan as said circulating flow of molten material. Operating in this manner the 4molten catalytic body, the aluminum chlorid and the oil to be treated are supplied to and the reaction. product withdrawn from the reaction chamber respectively without interruption or interfer- -ence with the continuity and estab-lished reacting conditions of the process. Further features of this process and apparatus will vhereinafter appear as the invention' :'s' described in detail.

In the accompanying illustration I have shown, more or less diagrammatically, an assemblage of apparatus elements adapted for use. in the performance of the described y shown). In chamber B is the reaction process.` ln the drawing, the figure is a' view vertical section certain parts being shown in elevation. i

In this illust-ration element 1, indicates as a 'Whole a furnace casing containing two fire chambers A and B heated by the torches -T and T respectively as shown.. From the top of each lire chamber the flue gases may be withdrawn at any suitable point (not chamber comprising the/liquid sealed .vertical iron retort 2 and containing nickel metal packing units 3, on top of which and' embedded therein is the trap pot 4. Resting on the oor of this trap pot and passing upwardly through the retort cover. 5 is the molten body feed pipe 6 terminating 'in the bell and cone-shaped' charging hopper 7 within chamber A. The heated charging hopper 7, serves to maintain the halid material used in the process in a state of fusion. The cone 8 of the bell and hopper may be vadjusted to' regulate the How of molten material through pipe 6 into trappot 4. The bottom of pipe 6 is serrated,.as shown, to allow the flow of molten material from the charging hopper 7 to rise up in and How over the edge of the trap pot 4 and pass downwardly through the nickelv metal packlngunits 3. Conduit 9 terminating at the bottom of the va or reflux or scrubbing ltower 10 is the 'in et to the reaction chamber'for the supply of oil'to be treated after i it has servedpreliminarily as a scrubbing process together 'with the vrefluxed hydro- .of the skimming conduit is a shield 22 4provided and adjusted to prevent the molten cai-bons Ato the reaction zone. F1anges'9" and 9 are providedfor cleaning out the pipe assemblage connected therewith.

nThe reaction chamber-2 discharges vapors through exit 1`1-`into the vapor reiiux or scrubbing tower 10 as shown. Ihis'scrubbing tower may be., asv shown, air cooled or it may be water cooledand its temperature so adjusted that not-hingbut gasolene and lower boiling hydrocarbons can get past into the condenser.y At its top it is provided with the vapor exitv 12 leading to any suitable condensing Ine-ans (not shown). The oil feed to the scrubbing tower 10 on its way to the reaction chamber or retort 2 is shown at inlet pipe 13 extendinointothe small trap pot 14. The bottom eiid trap pot and flow downwardly 'through the scrubbing tower packing units 15 countercurrent to' a flow of vapors from the vapor exit conduit 1l. The scrubbing tower packing units may bemade of any suitable material, such as coke, or ther'inert materiah but preferably, lthe packing uni-ts employed are Raschig rings of about one inch diameter `made of iron. tion chamber or retort 2 is provided Witha screen for supporting the packing units (as shown) and a flange cover 16 perforated -to accommodate the trappedoutlet conduit 17 serrated at its lower end and' resting'on the iio'or of the molten body trap `pot 18. This trapped conduit, or outlet pipe 17 is sealed from the atmosphere by thev constant' depth level of molten material maintained by the elevation of its overflow discharge 19'on the side of said trap po't.". Trap` pot 18 is also providedy with the unvaporized oil skimming or take olf conduit 2O which extends-upwardly above thelevel of the molten material within conduit 17` and downwardly through the bottom of this trap potinto the lower oil-trap pot .21. Over the upper end# The bottom of the Ieac'- material from the retort' entering this conl duit but allows free access of the unvaporized oil into same.- The lower end of the unvaporized loil skimming off pipe or cond-uit20l is serrated-as shown to allow the oilfpassing therethrough to rise up in the oil trapp ot 21 and overflow at 23 thereby maintaining a constant depth level. of unvaporized oil therein which keeps the system .closed from the atmosphere vatthis point. Receptacles 24 and 25 receive the discharged molten-ma- 'terial and unvaporized oil ispectvely. Inlet 26 is'provided for the introduction of. l1y

drogenor hydrogen rich gases to the reac- As stated, the process is applicableto the treatment of any high boiling hydrocarbon oil', such as the varioi lgh boiling coal tar distillates4 (solvent naphtha), vgas oil, *solar of this pipe is serrated to allow the feed oil to overflow this oil, fuel oil, high boiling crude oils, chlorid sludges resulting from the distillation of lhigher .boiling oils with aluminum chlorid Sac., for the purpose of catalytically producing low boiling oils, whether these latter be of aromatic nature, or of petroleum character, such as gasolene. l shall, hereinafter describe' its' use with a reduced or dried crude petroleum oil. as illustrative. Coal tar4 naphtha may betrcated exactly in the same way to produce bcuzol. Gas oil or solar o1l or other distillates may be treated similarly.

The reaction chamber heated by the 'torch' packing units to one somewhat lower at the top of same. The temperature at the top of the retort or packing units, however, must always be maintained above the freezing point of the halidmaterial employed; the freezing point of the molten mixture depending, of course, upon the relative propor-` tions of the ingredients thereof, and the temperature employed should in no case be below such freezing point. The freezing pointof the mixture is profoundly adected by the percentage of aluminum chlorid absorbed by the moltencmaterial, inl some cases, the percentage of aluminum chlorid may .build up to a point where the freezing polntot the mixture is below 300,? C. lln starting thev operation of the process, halid material com-` prising a mixture of 80 parts of Zinc chlorid and 20 parts of sodium chlorid is charged into the melting hopper 7 and brought to a state of fusion by means of the oil or gas torch 'l" inserted throughthe port in chamber A. After 'the process is in operation, this moltenmaterial is advantageously returned to said charging hopper in the molten state as hereinafter referred to. ylihe fused material Vflows downwardly through pipe 6 into the trap pot 4 and over the edge 'thereof on to the catalytic metal packing units over which --it flows in sheets or thin films and drips from unit tounit Vdownwardly through the intersticed 'catalyzermass where it is subjected to progresswel'y increasing temperatures.

Y The rate of flow of the molten material is vregulated by the adjustment of cone 8. The

height of the reaction chamber or retort is preferably about 20 .feet and the height of the layer of catalytic packing filling' is ap- 5651` proximately 2 feet below Jthe vapor exit 11.

readers The catalytic metal packing units comprising the retort filling are solid masses of nickel, preferably shaped in the form of the so called Raschig rings about 1 in diameter arranged in either a. promiscuous or symmetrical filling. When the rate of iow of the molten material has 4been e;tablished as is determined by the rate of discharge of said material at overflow 19, the oil trap pot 21 is filled with a heavy oil up to its overflow level 23 to keep the system closed to the atmosphere at this point. rlhe react-ionl chamber now being sealed at all Vpoints and the vapor exit opened to the'condensing system, the oil to be treated mixed with approximately 5 to.10% of its weigh-t with finely divided aluminum chlorid is then introduced through inlet 13 so that it feeds into the reaction chamber through conduit 9.' After the process has been in operation, the aluminum chlorid required for admixture with said oil is obtained from the returned Y reflux condensate, replenishment with additional aluminum chlorid being made to coinpensate for losses. As the oil enters at inlet 9 in the liquid state, it is converted in part at least, into `the vapor state, that is, the part which will vaporizeat the temperature maintained in the reaction chamber, ascends together with the hydrogen or hydrogen rich gases introduced at 24 countercurrent to the downward flow of molten material containing carbon in suspension percolating through the catalyzer mass while the unvaporized oil accompanies same to flow below the packing units into -the trapped discharge conduit 17 where they separate by difference of specific gravity. The molten material with the unvaporized oil floating upon the surface thereof, accumulate to their predetermined levels in said conduit and automatically discharge through their respective overflow outlets 19 and 23. The unvaporized oil which collects in receptacle 25 maybe returned to the system or worked up for lubricating stock if desired. The overflow of molten material from 19 collects in receptacle 24, and is returned to the melting hopper 7 for instance, by means of a crane not shown, this molten material is constantly circulated through the retort filling of packing units until it becomes too highly chargedv with carbon in suspension, it being then filtered to remove the excess carbon and used over again and repetitively by making such filtrations when necessary. rlhe vapors of aluminum chlorid and lower boiling hydrocarbons evolved during the pyrolytic and catalytic treatment of the oil in the reaction chamber discharge'through exit 11 into the scrubbing tower 10 where they meet the in-i flowing oil stock trickling through the packing units in such manner as to allow passage of vapors of lower boiling oils to the final cond vil systemr (as shown), the heavier hydrocarbons being thus reuxedwith 'the condensed aluminum chlorid thereby inter-- minglingwith the infiowingfoil stock delivering into the coolingy zone 10.. The

charging oil stock thus constantly receives'a uantityof aluminum chlorid from the reux mixtureof higher boiling oils and aluminum chlorid during thegoperation of i the process. .This quantity of aluminum chloridl is however 4constantly supplemented by thea'ddition of freshy aluminum chlorid to compensate for losses and to maintain the. requisite percentage of the molten material in admixturewith said oil.

In the case. oftreating hydrocarbon material of a more viscous nature than that of fuel voil or topped crude'petroleum, such, for example, the so called-chloridsludges re- A Suuin Afrom the distillation of higher boil? ing oi s with aluminum chlorid, this class of hydrocarbon'material need notbe introduced into the said converting system through the scrubbing tower 10, but may be admitted to 4'Ihe'tr'efluztvor scrubbing tower 10 in this case is used'only as an air cooled reliux condenser to condense the' vapors ofhigher boiling hydrocarbons and 'vapors of aluminumv chlorid. rSaid condensed vapors may either be returned through conduit. 9 to the retort in the manner already.. described, or the valve V in conduit 9 may be closed and the condensate `continuously withdrawn from the bottom of said reflux chamber by replacing iiange' 9fwith a discharge valve and collecting such condensate for admixture with the higherl boiling oils or other o il stock to be treatedfby the process. e A The use of a long vertical retort'containing a relatively long body of packing units is an advantageous feature in the operation of my. process. lVhile I have spoken of the preferred length ory height of such retort as around 20 feet it may exceed this length or height to anything within practicallimits' of.' economical heating, the .diameter of the same being adjusted accordingly. The

retort or oreaction chamber, however 'need not necessarily be a straight vertical chamber. It may9 for instance, be helical or spiral and it may have' agenerally horizontal disposition. I prefer however to use a straight "vertical form` of .retort .as it is much more y easily cleaned andgeontrolled besides being v-zgheaper in itscosltifuction.. .By using a rela-Y tively long layerlof Catalytic metal packing vunits in suchaa retort, a greater range of temperature 'and greater length of time for contact with the packing units atdifferent temperatures can be established throughout its length.. The temperatures prevailing during the operatienof the-process are, or may be, that at-which the oil normally used 5 will crack so that the cracking of the oil and conversion by the catalytic agents may besimultaneous in the heatlng zone at different parts thereof as the heavier unvaporized oil and molten catalytic material f pass down- -wardly through the packing unitsadvanta geously in countercurrentto' a flow of hydrogen.- By using hydrogen the amount of carbon separated is ma rially lessened and the total products of. lower boiling oilsand hydrocarbon vapors concomitantly' increased. 1

As stated, the molten body used in the operation of the process may either be molten zinc chlorid or a molten mixture of zinc chlorid and sodium chlorid, the use of the latter however being advantageous as the i presence of sodium chlori'd therein forms with a portion at .least of the aluminum chlorid used in the process, the double comthe molten mixture has the opportunity of exercising the converting action of its contained aluminum chlorid with said oils and aluminum chlorid lin the liquid states.

Of course, it is to be understood that the drawing accompanying this application ismerely indicative of la type of apparatus I may use. Many other types are applicable. I mayemploy' a battery of retorts and arrange to operate some ofthem in series. For example, the liquid reaction products discharging from one. retort may be passed through a second or third retort, the numberin series being governed by limits of economical heating, such .retorts being lilled. with packing unit-s maintained at about 400 C. and'operated in similar manner to the first retort, except that, no further freshoil or aluminum chlorid is supplied to such vfollowing retorts. The hydrocarbon vapors together with any volatilized aluminum chlorid formed in said retorts is passed through the same reiiux condensing system vas is connected to said first retort in said series. In this embodiment of my invention. a longer time v"for contact between the materials maybe obtained. This method allows of intensive catalysis of the unvaporized oil together with carbon and carbon compoundscarried in suspension in the mol- -ten material or molten catalyzer menstruum;

This catalyzer menstruum with said carbon drogenation reaction with the' hydrogen or hydrogen rich gases which may be employed in the process. The molten menstruum, as was pointed out, acts to maintain clean and the-effective surfaces of the catalytic metals employed for the hydrogenation of the oil vapors as well as of the carbon'carried inl suspension in said molten menstruum. 'Ihe hydrogenation of the carbon carried in suspension is an important feature of the process, by meansl of such hydrogenation the necessity of more frequent filtrations to remove carbon from the molten material being materially lessened.

That the hydrogenation of the carbon absorbed or carried in suspension by the aforesaid molten catalyzer is an important step in the process is shown by the fact that, when nely divided carbon resulting from the separation of the latter from the molten cat-alyzer is purified, and then immersed in a molten mixture comprising sodium chlorid, aluminum chlorid and zinc chlorid and hydrogen bubbled through this mixture while the latter is contained in a. suitably heated nickel crucible; hydrocarbons are evolved and carbon disappears ou continued bubbling of the hydrogen through the molten .mixture; a temperature of between 40G-600 30 C. being adequate to produce such results. Operating by bubbling the hydrogen under pressure through such carbon bearing niolten material, materially accelerates the. hydrogenation of the carbon.

What I claim is 1. In a process of converting higher boiling oils into lower boiling oils, the comblnation of steps which comprise introducing a stream of a mixture of such higher boiling oils and aluminumvchlorid into the upper end of a sealed retort having a portion thereof maintained at a temperature to effect an oil cracking reaction therein, delivering into contact with the said oil mixture a stream of a metal chlorid which is capable of holdingin suspension a portion at least of the carbon separated out in said reaction, the said metal chlorid being in molten condition, preventing the accumulation of carbon deposits in the retort by allowing said molten chlorid containing such suspended carbon and the unvaporized oil, carrying its quota of separated carbon insus ension, to discharge from the retort, and co -lecting the evolved vapors of lower boiling oils and aluminum chlorid from the'retort.

2. In a process of converting higher boiling oils into lower boiling oils, the combination of steps which comprise introducing a stream ot a mixture of such higher boiling -oils and aluminum chlorid into the upper end of a sealed retort having a portion thereof maintained at a temperature to eiect an oil cracking reaction therein, delivering into contact Withthe said oil mixture a stream of a mixture of metal chloride which is capable of holding in suspension aportion at least of the carbon separated out in the said reaction, the said metal chlorid'mixture being in a molten condition, preventing the accumulation of carbon deposits in the retort by allowing said molten mixture containing such suspended carbon and the unvaporized oil, carrying its quota of separated carbon in suspension, to discharge from the retort,- and collecting the evolved vapors of lower boiling oils and aluminum chlorid trom the retort.

In a process of converting higher boiling oils into lower boiling oils, thecombination of steps which comprise introducing a stream of a mixture of such higher boiling oils and aluminum chlorid into the upper end of a sealed retort having a portion thereof maintained at a temperature to effect an oil4 cracking reaction therein, delivering into contact with the said oil mixture a stream of a metal chlorid which is capable ot' holding in suspension a portion at least of the carbon separated out in the reaction', the said metal chlorid being in a molten condition and comprising zinc chlorid and an ,alkali metal chlorid, preventing the accumulation of carbon deposits in the retort by allowing said molten chlorid containing such suspended carbon andthe unvaporized oil, carrying its quota of separated carbon in suspension` to discharge from the retort, and collecting the evolved vapors of lower boiltort.

4. In the lmanufacture otlower boiling oils from chlorid sludges resulting from the distillation of high boiling oils with aluminum chlorid, the process which comprises establishing and maintaining a flow of a molten body containing a mixture of zinc chlorid andsodium chlorid through a re- Atort containing nickel packing units a portion ofthe latter being maintained at cracking temperature, and delivering a flow of such chlorid sludges into contact with said liowing molten body and said nickel packing vunits While passing hydrogen in countercurrent thereto, withdrawing the vapors of aluminum chlorid and vapors of lower boiling hydrocarbons generated in theretort and passing them through a cooling znone, so as to condense vapors of higher boiling oils and vaporsof aluminum chlorid in said cooling zone but to allow passage of vapors oflower boiling oils and lgases from .said cooling zone, condensing and collecting such lower boiling oils and removing the condensed higher boilingoils and aluminum chlorid from the cooling zone, supplying said chlorid sludges through an inlet in the upper part of the retort, and withdrawing the fluid react-ion products comprising molten material containing carbon in suspension nig oils and aluminum chlorid Jfrom the re- HND . retort through trapped outlets.

mixture, and al owing and unvaporized hydrocarbons from the lower end of said retort.

5. The process as claimed in claim7 in which. the molten chlorids are supplied to the retort through a trapped inlet and the liquid reaction products containing carbon in suspension are withdrawn from the -said 6. In a process of converting higher boiling oils into lower boiling oils, the vcombination of steps which comprise introducing a streamof higher boiling oils and aluminum chlorid into a sealed retort having a portion thereof maintained at a temperature to effect an oil cracking reaction therein, delivering intocontact with the said oil mixture a stream of a mixture of molten zinc chlorid andan alkali metal chlorid, said molten mixture holdin in suspension a portion at least of the car on separated out in the reaction, hydrogenating a portion of said separated carbon,'by passlng through the retortl a current of. hydrogen to contact with the carbon bearin stream of molten chlorid the said molten stream containing unhy ogenated carbon in suspension and unvaporized oil, carrying its quota of unhydrogenated carbon in `suspension to discharge .from the retort.

7 In a processorA converting higher boil'- ing oils into lower boiling oilsthe steps coniprising, maintaining a flow ot' a molten .body

containing zinc chlorid and an alkali metal chlorid through and into contact with heated surfaces within a suitably heated and sealed retort having Ka cooling zone in connection therewith, flowing such higher boiling oils as constitute the charging oils stock, mixed with anhydrous aluminum chlorid, into said retort; allowing this mixture to commingle with the aforesaid molten body while the latter is contacting with the said heated surfaces, a portion at least of said surfaces being maintained at a cracking temperature; permitting the said flowing molten body and the oil which remains unvapor- Vized under such treatment to continuously discharge from said retort; cooling the cooling zone in part at least by flowing there- 4through the incoming charging oil stock;

allowing the vapors ot' lower boiling hydrocarbons and aluminum chlorid vapors re' sulting from said treatment ofthe oil 'mixture, to pass into said'cooling zone and commingle therein .with the said incoming oil stock; utilizing the aforesaid flow of incoming` oil stock as a carr Ying medium to return to the retort the insu ciently cracked hydrocarbons and the aluminum chlorid condensed in-the 'cooling zone and to allow 'vapors'of1 lower 'boiling oils passage through said me' dium, thereby continuously recovering said aluminum chlorid and`automat1cally effect'- ing adinixture `of the same withl the flow 'of' the incoming charging oil stock .while withdrawing from the cooling zone vthe vaporsu of lower boiling oils which pass vin counter"4 -the latter being maintained at cracking temperature. p

9, 'In a continuous process of producing lower boiling oils from higher boiling oils the step comprising, delivering a mixture of higher boiling oils and aluminum chlorid into contact with materialA comprising a molten mixture ot zinc chlorid and sodium chlorid circulating through an intersticed mass of nickel packing units a portion of the latter .being maintained at cracking temperature.. A

10. 1n the conversion of higher boiling oils into lower boiling oils with catalytic agents, the process which comprises establishing and naintaining :aflow ot a molten body contain'ng zinc chlorid through a sealed retort containing metal packing units a portion at least of the latter being maintained at cracking temperature, and delivering a mixture of higher boiling oils and aluminum chloridinto contact 'with said flowing molten body, removing the vapors of lower boiling hydrocarbons formed inthe retort together with the vaporsv of aluminum ch'lorid and passing them through a cooling zone connected with said retort, cooling the said cooling zone in part at least by the passage therethrough of the oil to be treated' maintained at such a temperature as to condense the aluminum chlorid and higher boiling-hydrocarbons in said cooling zone but to allow passage of vapors of lower boiling oils, c ondensing and collecting such lower boiling oils, and returning tothe retort the condensed aluminum chlorid intermingled with vthe condensed higher boiling hydro' carbons and with the fresh higher boiling o ils passing to' said retort forv treatment,

and withdrawing the fluid reaction roducts ess .which comprisesestablishin'g a sealed heating zone `contalig nickel packing' units maintained 'atpr gressivel increasing temperature ranging from 300 to .600 C.

)agents in the presencfeio' hydrogen, the proc- `and a cooling zone in connection therewith, percolatmg a molten mixture of zinc chloridr and vapors of aluminum chlorid inthe cooling Zone but to allow passage of vapors ot lower boiling oils from the cooling zone, condensing the vapors ot such lower boiling oils, and returning condensed vapors of higher boiling oils and condensed vapors ot aluminum chloridl intern'iingled with the stream ot fresh higher boiling oils flowingl to the retort t'or treatment, allowing the liquid `reactioniproducts percolating through the packing units to flow below the same and continuously discharging from the retort.

12. In the conversion ot higher boiling oils into lower boiling oils with catalytic agents in the presence of hydrogen, the process which comprises establishing a sealed retort filling of nickel packing units a portion of the latter being maintained at crackr ing temperatures and a cooling zone in connection therewith` flowing a stream oli a molten mixture of.e zinc chlorid and sodium chlorid containing carbon in suspension into the upper end ot' the retort and so through the packing units, flowing a stream of higher boiling oils admixed with aluminum chlorid into contact with said flowing streamof molten material whereby substantial amounts of lower boiling hydrocarbons are formed in said retort together with vapors of aluminum chlorid, admitting hydrogen into the lower end of the retort to pass in countercurrent to the liquid` reaction products which carry in suspension through the packing units the separated carbon formed by such pyrolytic and catalytic treatment of .said oil, withdrawing from `the upper part of theretort the vapors of aluminum chlorid and vapors of lower boiling hydrocarbons and gasesf'and passing them through said cooling zone, cooling the cooling zone in part at least` by the passage therethrough of the higher boiling oils to be treated maintained at such a temperature as to condense vapors of higher boiling hydrocarbons and aluminum chlorid vapors in the, cooling.

zone but to allow passage of vapors of lower boiling' oils and gases from the cooling zone, condensing and collecting such lower boiling oils, and returning the condensed 'higher carbon in suspension and unvaporized oil from the retort.

13. In the conversion of higher boiling oils into lower boiling oils with catalytic agents, the process which comprises establishing and maintaining a flow of a molten mixture of zinc chlorid and sodium chlorid through `a sealed retort /containing packing units a portion at `least of the said units being maintained at cracking temperature, and delivering a mixture of higher boiling oils and aluminum chlorid into contact with said flowing molten mixture of4 chlorids, removing the Vaporsof lowerboiling hydrocarbons formed in the retort together with the vapors of aluminum chlorid and passing them' through a cooling zone connected with said retort, cooling the cooling zone in part at least by the passage therethrough of the oil to be treated maintained at such a temperature as to condense vapors of aluminum chlorid a nd"higher boiling hydrocarbons in said cooling zone but to allow passage ot' vapors of lower boiling oils, condensing and collecting such lower boiling oils, and returning to the retort the condensed aluminum chlorid intermingled with 'the condensed higher boiling hydrocarbons and with the fresh higher boiling oils flowing to said retort for treatment in the' process, and withdrawing the liquid'reaction products comprising unvaporized oil and molten material containing carbon in suspensionl from the lower end of said retort.

14. The process as claimed in claim 7 in which the molten chlorids are supplied to the retort through a seal of the said molten chlorid and the liquid reaction products con'- taining carbon in suspension are withdrawn from the said retort through outlets respectively sealed with the liquids to beremoved.

15. A process of extracting carbon from higher boiling'oilsto produce lower boiling oils, which consists in subjecting a stream of such higher boiling oils'to the action of aluminum chlorid andy to contact, in the presence of hydrogen, with a stream of mol ten metal chlorids capable of carrying in suspension a portion at least of the carbon separated out in the reaction, allowing the said molten chlorids, and the oil which re- .mains unvaporized under 4such treatment,

\ Signed at Asbury Park in the county ofv Monmouth and State of New Jersey this 14th day of April, A. D. 1924.

JOHN COLLINS CLANCY.l

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