US1322762A - A cobpobation ov new jebsey - Google Patents

Description

5.43. co.r MAKING LOW BOILING 0H. FROM HIGHER BOIlING PETROL'EUM 0R RELATED OIL. APPI.I CATION FILED DCT. 4- 19|?.

111,322,762. Patented Nov. 25, 1919.

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n wb2 ddnnyg cal E. 8.13083. MAKING LOW BOILLNG OIL FROM HIGHER BOILI'NG PETROLEUM ORRELAIED 0H..

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Y 1 ,$322,762. Patented Nov. 25, 1919.

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' UNITED sTATEs* PATENT OFFICE.

ERNEST B. COBB, 0F JERSEY CITY, NEW J ERSEY, ABSIG'NOB TO STANDARD OIL (IOMIEAIBIY, 0F BAYONNE, N EW JERSEY, A. COBFOMTION 0F NEW JERSEY.

MAKING LOW-BOILING OIL FROM HIGHER-BOILING PETROLEUM 0B RELATED OIL.

'Bpeoiiloation of Letten Patent.

Patented Nov. 25. 1919.

Continuation of application Serial No. 884,844, iiled April 85, 1914i. This application nled Dotober 4,1919. Serial Ro. $98.578.

To all whom it may concern Be it known that I, ERNEs'r B. CoB, a citizen of the United States, residing at Jersey City, in the county of Hudson and State of New Jersey, have invented certain new and useful Improvements in Making Low-Boiling Oil from Higher-BoilingPetroleum or Related Oil, of which the followinfr is a specification.

his invention relates to obtainlng oils which are composed mainly at least of hydrocarbons with boiling points normal to naphtha and the lighter end of burnin oil (kerosene) (say up to 302 F. for nap tha and 302 F. to 450 F. for the lighter end of burning oil, the boiling points re arded herein as normal to the heavier end o burning oil heilig from 450 F. to 572 F.) by operating upon petroleum in forms (distillate and undistilled) 'which contain a lar proportion at least of higher boiling hycrocarbons (say hydromn-nons with boiling points above 450 F.) inc c particularly,but not exclusively, distillate oils of this description which are mainly at least composed of hydrocarbons with viscosities too low for normal constituents of other than light grades of lubricants (say with viscosities under onehundred and seventy seconds at 100 F. with an Engler viscosimeter with which water exhibits a viscosity of fifty three seconds at E), such as the inferior redes of burn ing oi (kerosene) (either nlshed or un treated) and the oils commonly disposed of as gas oil or fuel oil on account of their being unfit on the one hand for burnlng. oil (kerosene) and on the other for medium and heavy lubricants; for which products there is usually a good demand at higher prices than those of as oil or fuel oil.

In accordance wit the present improvements, the petroleum is distilled with anhydrous aluminum chlorid (ALC/1.,) in solution in (combination with) a part of the oil operated upon (useful proportions hereinafter indicated) at temperatures sufficient to split up component hydrocarbons of the oil; and

.the said distillation, after continuance for such appropriate period as ma be preferred, is arrested While the resi ual-matcrial is in condition for its carbonaceous content and the main part at least of its aluminum chlorid content to be separated from each other by washin with water. Y

This separation wil be possible as long as the residu al material is liquid in whole or in part (or in other words, as lon as it has a substantlal content of li uid ydrocarbons) and it may be eifecte even after the residual material has attained an at least approximately dry condition; but it is liable to be defeated by carrying the distillation too. far with consequent overheating of the resldual material.

By terminating the distillation at the lowest point at which the residual material is suiiieiently liquid for substantially the whole of 1t to be pumped out or 'otherwise withd rawn from the still through a pipe connection or the like, that is to say, after the manner of a liquid, practically the vmaximum service will have been obtained from the anhydrous aluminum chlorid employed consistently with the minimum of work in cleaning out the still. By continuing the distillation beyond this point, more work must be expended in cleaning the still; but greater service will have been obtained from the anyhdrous aluminum chlorid employed. By sto ping when the residual material attains t e lowest point at which it can be freed wholly from the element aluminum (traces only exce ted) by boiling with water, practically t e maximum service will have been obtained from the aluminum chlorid employed consistently with a complete recove of the aluminum chlorid content of the residual material by washing with water; but the service obtainable from the anhydrous aluminum chlorid is not necessarily exhausted even then.

Further, in accordance with the resent improvements, when the desired distillation has been completed, the Whole, or any appropriate part, of the then existing residual material is washed with water in such manner that the Washing water is applied to niaterial which contains a large part at least of the aluminum chlorid content of the said residual material.

Thus if the distillation should be arrested Whiie the residual material is in condition for a separation to be eifected between its liquid hydrocarbons (some of them at least) and the remainder of said residual material by settlin and decantation (or in any other waywhic does not involve a washing with water), such a separation can be effected in any known or suitable way; and the remainder of the residual material (containing all, or neai'l all, the aluminium chlorid) can then be was led with-water' but it is not necessary in any ease toseparate liquid hydrocarbons from other matterfcompos' the residual material prior to washin wit water; since the was ii rrwatcr can applied to the undivided resi( ual material, whatever maybe itsI condition with respect to the presence therein (or absen therefrom) of liquid hydrocarbons.

One eilect of the washin with water is to separate the aluminum eh orid and the carbonaceous content of the washed material from each other, the aluminum chlord being obtained in aqueous solution. Liquid hydrocarbons if any) contained m the washed materia will also be separated from the remaining carbonaceoiisl matter (if any).

Another feature forming part of the present improvements consists in subjecting all or any desired part of the li uid hydrocarbons which may be recovered romthe aforesaid residual material to distillation with a fresh supply of anhydrous aluminum chlorid. y

By thus recovering all the liquid hydrocarbons from said residual material and distillin them with anhydrous aluminum chlorid, practical] the entire carbon content of the oil originallyV operated upon '(excluding loss) can be o tained either in the form of distillate from distilling in Athe presence of anhydrous aluminum chlorid or else inthe form of coke, without continuing the distillation with anhydrous aluminum chlorid so far in' any run as to leave the residual material without a substantial content of liquid hydrocarbons at the close' of the run.

ost advantafreously oil composed .at least in part o? recovered hydrocarbons would be distilled (say to dryness, or to a lesser extent, if preferred) and the resultiiig distillate would then be distilled with the new supply of anhydrous aluminum ehlorid; but (if preferred) the recovered hydrocarbons can be distilled with a new sup ly of anhydrous aluminum |chlorid witlibut undergoing this intermediate distillation.

The yrecovered oil can be disposed ofotherwise, in whole or in part, as ma be prefel-red, in case-it should not be desired to distil it with a new supply 4of anhydrous aluminum chlorid; and the residual material likewise can be disposed of otherwise, in whole or in art, as may -be preferred, in ease it should not be desired to wa'sli the saiiie (in whole or in part) with water. Whe'reliquid hydrocarbons are recovered' by a separation without washing' with water, they can bedistilied 4with a fresh supply of anhydrous aluminum chlorid or be otherwise disposed of (in whole or in part) without reference to what may be done with the remainder of the residual material; and conversely the remaining residual material can be disposed of-as may be' referred, without reference to what may, be done with oil recovered from the residual material with out washin with water.

The pr nets of the distillation with anhydrous aluminum chlorid are fractionated to obtain oils of such grades as may be desired and obtainable.

Fi ures 1, 2 and 3 are diagrams, which are lieved to be sclf explanatory, and which illustrate certain typical procedures; and Figs. 4, 5 and 6 are diagrams of apparatus appropriate to be used in distillinpr petroleum with anhydrous aluminum chlorid. The illustrations are not intended to be exclusive; neither is the invention restricted' to the examples hereinafter set forth, or tothe details of such examples.

For effecting the distillation with anhydrous aluminum clilorid, an ordinary still and an ordinar water cooled condenser connected with said still by a vapor pipe will answer. In Fig. 4 the still n, is shown as being of ordinary horizontal cylindrical form and as having manholes b, a valvcd charging line c for supplying petroleum to the still, and a valved discharge line d 'for withdrawing the residual material (iii whole or in rt) after the manner of a liquid, when t e same is suiliciently fluid to be -so withdrawn; and the water cooled condenser e is connected with the still ri by the vapor pipe f. The distillate flows into the receiver g; and the uncondensed vapors and the gases pass, by the pipe/i., to waste, or to such place of utilization as may be preferred.

A; still, which would hold say six hundred barrels of forty gallons each when full, may well receive a charge of about fomhundred barrels of the gas oil or fuel oil mentioned, and a limited proportion, not more than about ten per cont. by weight, of anhydrous aluminum chlorid. The temperature is gradually raised until distillate commences to flow from the condenser outlet (which may be in say six or eight hours oi thereabout from t e commencement of firing); and the ,fires are regulated to give a ood flow (say fifteen to twenty barrels an iour or thereabout) of' distillate.

Distillatioii is best conducted in this way to the end. or at least approximatelv to the end, oi the run, the ti-uiiperaturc of the oil increasin gradually with the progress oF the disti lation. The run is terminated sooner or later, as hereinabove explained.

In' practice, in order to terminate runs with practical uniformity at suoli point as may previously have beewdeterniined upon. it would -be ascertainedby test runs that the proper point had been reached when a certain percentage of distillate had been received; and distillation would be stopped in the dilerent runs when such standard percentage of distillate had been received.

A suflicient test for ascertaining when the distillation has been carried approximately atleast to the lowest point at which the resi ual material can be freed wholly from aluminum (traces only excepted) b boilin with water is to secure samples of ne resi ual material at diferent periods, to boil each sample in water for say ten minutes and to subject the undissolved remainder of the same to any known or suitable test for ascertainin the quantity of the element aluminum gif any) therein. solved remainder of any sam le is the first to exhibit more than traces 0F said element, it will be known that the residual material at the time of taking the sam le had attained (or had perhapsoverpasse somewhat) the lowest point at which it could be freed wholly from aluminum by water (traces only excepted).

At the close of the run, the heating is discontinued; and later, when the running (if any) from the condenser outlet has ceased, the residual material is removed from the still preparatory to charging the still for a new run. If the said residual material is suiciently fluid (or to the extent to which it may be suiiciently fluid) the samel is advantageously withdrawn after the manner of a liquid.

Assuming that it should not be preferred to operate upon or to dispose of the residual material in whole or in part) in some other way, the same would be washed with Waterof appropriate temperature, say at or above 150 F.; so as to separate the carbonaceous content of said residual material and the main part at least of its aluminum chlorid content from cach other, vthe aluminum chlorid being obtained as a solution in water a nd the carbonaceous matter either as liquid hydrocarbons. or partly as liquid hydrocarbons and partly as soft coke, or as soft coke, according to the extent to which distillation has been carried.

It is desirable to use as little water as will suffice to unite with the aluminum chlorid. An amount equal to twenty live er cent. by volume of the material to w ich the washing water is applied 'will suffice; and a smaller amount may do so, especially if the washing be conducted in a systematic manner by transferring the washin water from a previously partly washed bo y of residual material to residual material which has not been washed to the same extent, if at all.

Liquid hydrocarbons (if any) forming part of the washed material will fioat on the aqueous aluminum chlorid solution and can he readily separated from the latter, say by settling'and decantation for exanlile. The aqueous solution of aluminum c orid and When the undis-` dual material boiling with the iion-liruid carl'ionaceous matter (if any) of the resi ual can also be readily separated from each other. A Y Oil composed at least in art of so recovered hydrocarbons (if4 obtained in swbstantial proportions) would be distilled to dryness, o r to a lesser extent if preferred; and the distillate (separated from whatever water, ifany, may pass over) would be distilled with a fresh suppl .of `anh drous aluminum chlorid, it may by itse f, but better in admixture with other oil.

e aqueous aluminum chlorid solution and the coke (if any) derived from the resiof the distillation with Aanh drous aluminum chlorid as aforesaid would be disposed of as might be preferred as would be also the coke l(or other residual material) obtained in distillin liquid h drpcarbons (if any) recov'e from t e said residual material of the distillation with anhydrous aluminum chlorid.

By evaporation of the aluminum chlo'rid solution toqdryness, alumina can be obtained as residue; while hydrochloric acid would pass olf with the water vapor.

Alumina and hydrochloric acid (the latter in vapor form) can also be obtained by combustion of residual material -from any distillation with anhydrous aluminum chlorid (with or without prior separation of its liquid hydrocarbons, if any, therefrom); if it should be preferred thus to burn said re sidual material rather than to wash it with water as aforesaid.

From alumina and hydrochloric acid, ill whatever way they ma be obtained, anhydrous aluminum chloriiiI can be reconstituted by known methods. For example, anhydrous aluminum chlorid distils over when dry chlorin (which is obtainable by known means from hydrochloric acid) is passed over an incandescent mixture of coke and alumina.

Returning now to the distillation of petroleum with anhydrous aluminum chlorid, it suiiices to collect the distillate all in one receiver, whatever may be the form of petro leum operated upon. Any solution of anhydrous aluminum chlorid which may come over with distillate is allowed to settle out l denser c is shown as thus elevated; a liquid i separator c'. is shown between said condenser e and the distillate receiver g; a trapped pipe j connects the bottom of the separator with the still for returning thereto any solution of aluminum chlorid which may pass over; the trap being formed asshown bythe upward bend of the pipe j on leaving the separator i; and s. pipe l: connects the upper part of the said separator with the receiver g for delivering distillate to the latter.

The distillatemay be washed with water and then fractionated with partial or with com lete distillation by means of dry heat; or t ie frmtionation may be performed -b partial distillation in a steam still, in whlc 1 case vthe water of condensation serves to wash -the distillate. Washing the distillateY with water can precede the steam distilhng, if preferred; and the residual oil from partial distillation with dry heat or in the steam vstill can be fractionated by dry heat, or can be disposed of otherwise, as may be referred. In some cases at least `it may be est to agitate the washed distillate with sicient alkali (caustic sodallye) to neutralize any remaining acid (hydrochloric acid) therein before fractionating by distillation. In fractionation cuts are made to obtain oils of the desired grades, all of which may well becolnposed at least mainly of hydrocarbons with boiling points not exceeding 450 F. and also to obtain, if desired, higher boiling oils. The lowboiling oils, say various grades of naphtha, may be finished for. use or sale b giving them the customary treatment wit sulfuric acid and alkali; and the burning oil kerosene) distillate can be similarly finishe The higher boiling oils, as a whole or in such part as may be preferred, can be distilled anew with anhydrous aluminum chlorid; orthey can be disposed of otherwise as ma be preferred.

Goodresults have een obtained in a small way with an amount of anhydrous aluminum chlorid Vequal to about seven per cent. by weight of the oil operated u on; cent. by weight would `probab y 'give better results. Thepropprtion can be varied within wide limits. duction of the ropertion of* anhydrous aluminum chlori ytends to lower -the yield of hydrocarbons with.

boiling points below 450 F. Increase in the proportion of anhydrous aluminum chlorid tends to vincrease the proportion of such-hydrocarbons; buttit will probably not 'be worth while to exceed aboutr ten per cent. by'weight in any case. -If this percentage be added to petroleum distillate (gas oilor fuel oil' orfother distillate) the 'anhydrous aluminum chlorid dissolves at appropriately elevated temperature in a part of such distillate; a 'd .the solution form a distinct fla underneath the remainder ofthe distil ate if' not -kept in reus aluminum chlorid can '-be added to suspension therein by agitation. `The anthe oil inthe still in solidstate or inlsolunin'e Vper y forma 4free from para the still before tion; or it can bc placed' in When the still it is not believed that so large a proportion would be desirable, if racticable.

From gas oil or uel containing some paraffin wax and of a gravity of `531|? B., which comprised over ninety per cent. by volume of hydrocarbons with boiling points above 450 F. and which, if distilled in t-he usual way in a laboratory flask, would give first rumiings equal to live per cent. by volume with a Gravity of 48. B., an amount of naphtha (distilling over up to' 302 F.) of 67 B.equal to about twenty and a half per cent. by volume of said gas oil or fuel oil and water white burning` oil (kerosene) of 45.6 B. equal te twenty nine per cent. by volume of said gas oil or fuel oil have been obtained, using about 7% by weight of anhydrous aluminum chlorid and working a small way. These oils comprised the naphtha wholly and the kerosene mainly of hydrocarbons. with boiling points not exceeding 450 F. The first 5% runnings of the distillate had a gravityof 80.7 B. The naphtha hydrocarbons have been found to be mainly at least of a saturated character, exhibitin small-heating elect, as com ared with nap tha roduced in the yor mary cracking of cru e petroleum,'when shaken up with sulfuric acid of 66 B. If it should be desired to collect an oil consisting wholly of hydrocarbons having boilin points up to 350 F. (useful as fuel in gaso ene explosive engines) the yield might be between five and ten per cent. by volume more than that of the naphtha mentioned. A

From a finished burning oil (kerosene) obtained from crude ptroleum o'f Cali- `wax and having heated the aluminum chlorid dissolves a gravity of 40.3 B., which-comprised'bver Y.

y thirty per cent. of hydrocarbons with -boiling mts above 450 F., and which, if disti ed in the usual Away in a laboratory flask, would give rst runnings equalftove per cent. by volume having a gravity of 51.9 B. there has been obtained (using about 7% by weight of anhydrous aluminum chlorid andhworking in a small way) a yield of nearly twenty seven per cent. by volume of naphtha of 57.7 B. gravity, com- `posed wholly of hydrocarbons with boiling points up to 302 F. (first runnings sequal to live per cent. by -volurnehaving a vity of 71 B.) and about sixty percent. o burning oil (kerosene) distillate over ninetyfive per rent. of whose hydrocarbons had boiling points not exceeding 450 F.

From finished burning oil (kerosene) of low grade and Aabout 45.3 B. gravita'V obtained mostlyfroruPennsylvania and Lima crude petroleunLOn part from-each), using about 7% by weight ot aluminum cblorid and working in a small Way, about 24.5% by volume of naphtha of 68.7 B. distilling over up to 302 F.) first 5% runnings 81.7 B.) was obtained and over 61.5% bv volume off-,burning oil (kerosene) distillate, more than eiglhty five per cent. of whose hydrocarbons a Vboiling pointsnot exceeding 450 F. The oil operated tained some paraiiin wax.; it consisted more than fifty per cent. by volume of hydrocarbons with boiling points above 450 F.; and the first 5% runnlngs 60.3 B.

The temperatures of the oil in distillation and other things will vary considerably, according to the character of the starting material and othepcircumstanoes. In a small scale test run (which was made by way of example subsequently to the filin of my application of April 25, 1914, olicia ly numbered 834,344, of which the applicatlon for the resent patent isa continuation, in order to i lustrate a particular case in detail and in which a charge of 2,500 cubic centimeters of a gas oil of 34.4 B. gravit was distilled with anhydrous aluminum c lorid to dryness) the oil in distillation showed a temperature of 315 F. when distillate commenced to ow from the condenser outlet (about an llpon con- `hour and twenty-five minutes after -commencement of firing) and a temperature of nearly 700 F. when less than one per cent. of obtainable distillate remained in the still (about eleven hours and forty five minutes later). 'The observed temperature of the vapors passing over to be condensed as distillate was 200 F. when distillate commenced to flow from the condenser outlet and 470 F. when the oil had been distilled to the above mentioned state of approximate .1

dryness. In this test run one hundred and fifty grams of anhydrous aluminum chlorid (equal to seven per cent. by Wei ht of the original still char e) were emp oyed, the whole being intro uced at the start. The distillate was collected in sixteen fractions, each equal to live per cent. b volume of the original still charge, and a nal fraction of 72/100 of one per cent. The residue (coke and aluminum chlorid) left in the still weighed 389 grams. .Some of the aluminum chlorid passed over with the vapors which Were condensed as distillate. The first of the followin tables (Table A) shows the gravities oft e several fractions, the respective temperatures of the oil in distillation and the vapors passing over to be condensed as distillate at the close-of each collection, andthe time occu ied in each co'llection. The second table Table B) gives the results of assays of the several 5% fractions of distillate and shows the percentages of each had a gravity of -on account ot' the -'larger proportion of carfraction with boiling points up to 302. F., 350 F.. 450 F. and 572 F... respectively. This table also shows (1) the final temperature of the va ors in the ask neck in each assay in whic such final temperature was below 572 F., (2) the percentage of oll remaining 1n the flask at he close of the assai 1n each casein which the vapors 1n the flas neck attained a temperature of 572 F., and (3) the percentage of loss 1n each assay.. 75

Table A Oilin Vapor Fmatm 0105111000 5% ffafg m Time,

Dassin by volume. B .R wat. i minutes.

1 00.1 402 01a 40 50.0 404 300 a5 50.2 412 340 00 4.. 51.0 502 05s a5 5.. 50.1 sa 010 40 50.0 551 005 50 54.0 500 300 40 85 s. 54.2 510 m a5 0.. 50.5 512 420 40 1o. 55.1 551 424 40 1l. 56.6 590 43d 45 12.. 55.8 600 440 50 1s.. 5er 015 '450 55 14.. 54.2 005 415 55 15.. 50.5 550 415 50 10...... 55.0 002 `510 05 90 x1 012%). 54.5 l800 450 55 l Plus TubleB Fractions distillate 350 450 572 Final Botu) 5% by vol- "F "F. 11. F. "I". toms. 5'

Perot Petct. Peral. Perot. Peral Per cl. l... 76.0 83.0 89.0 91.0 490 9.0 2... 10.0 00.0 50.5 02.0 54s 5.0 0. 51.0 11.0 55.0 00.0 500 1.0 4. 40.0 00.5 52.0 00.5 500 0 5 5. 40.0 51.0 10.0 04.0 550 0.0 6. 42.0 55.0 73.5 93.5 558 6.5 7. 36.0 48.0 74.0 95.0 565 5.0 8. 35. 0 47. 0 67. 5 94. 5 570 5. 5 0... 50.0 40.5 54.0 04.0 2.0 4.0 10.. 35.0 45.0 03.0 05.0 50s 5 0 106 11 50.0 40.0 00.0 00.0 0.0 4.0 12 00.0 40.0 50.0 05.0 510 5.0 32. 0 4l. 0 57. 0 91.0 7. l) 2. (l 31.0 40.0 55.0 89.0 9.0 2.0 39.0 33.5 50.0 73.0 25.0 2.0 35.0 45.0 58.0 14.5 20.5 2.0

110 An assay of a speclmen of the as o1l charged (34.4 B. gravity) showed t e followmg percentages: Boiling points up to 302 F 1.5% Belang points 302 F. 50 350 F 2.0% 11.5 Bolling points 350 -F to 450 F 3.5% Bolling points 450 F. to572 F 13.5% Residual o1l 1n Hask at 572 F 86.0% LOSS Q-; 0.5 U0

Instead of operating upon distillate, use may be made of petroleum in undistilled forms, as crude etroleum, orl residues from reduction (partial distillation)` of crude petroleum with or without injection of superheated steam into the oil; but it is considered less advantageous to operate upon undistilled petroleum than upon distillates bon in the former. 1730 tillate can be operated u Gas oil yields more carbon than burning oil (kerosene). A considerable amount of gas and light vapors, which would escape condensation in the ordinary water cooled condenser, are likely to be formed in any case.

Distillates of higher boiling hydrocarbons than those of the gas oil or fuel oil mentioned (such as heavy paraili-n distillate or pressedparailin distillate, or even res1due from partially distilling pressed distillate) can lbe operated upon; but it is considered that to do so (would be less advantageous than to operate on gas oil or fuel oil, or low grade burning oil (kerosene) (finished oil or untreated distillate). The distillates obtained in reducing pressed parailin dison; and, in fact, the lighter port-lon of suc i distillate (when available) commonly forms part of the gas oil or'- fuel oil mentioned. So-called acid oil, obtained in known `ways from acid sludge from treating burning oil (kerosene) distillate and lubricant stock (one or other, or both) with sulfuric acid (usually acid of 66 B., sometimes stronger) can be operated upon lalone or in mixtures, Hydrocarbon oils which are not forms of .petroleum, but have a suitably close relation thereto, such as shale oils and the like, can be operated upon.

The fractionation of the distillate from the distillation with anhydrous aluminum chlorid, instead of being performed wholly in a distinct distillation, may be performed at least in art in the distillation with anhydrous a umnurn chlorid by means of a partial condensation or a series of partial condensations of the vapors. Condensate, or one or more condensates, from such partial condensation or condensations can be returned to the oil in distillation; or can be collected as distillate, as may be preferred. The partial condensers (one or more) may be air cooled or liquid cooled. ,They may receive the vapors at or near the bottom, so that these pass in o posite directions in contact with retrogra ing condensate; or they may receive the vapors at or near the top, so that the vapors, as well as the condensate, travel downward.

In Fig. 6 a artial condenser l is shown `betweenthe"st1lla and the water cooled condenser e; and the condensate, which forms therein, can either be returned to the .'.stillza through the valveel pipe m, or be delivered' through the 4valyed pipe n and .cooling` coil p to the distillate receiver q.

The distillation with anhydrous aluminum chlorid is not necessarily rformed b charging a still and then runnmg offV the c arge. It may be performedY in a more or less continuous manner. Oil might be supplied to the charge in the stillwhile the distillation is going on, with or without adusamos dition thereto of anhydrous aluminum chlorid, and with or without the withdrawal of residual material, during the run. Continuous stills of any known or suitable form can be used.A Y

Distillate from the d'stillation with anhydrous aluminum chlorid can be treated with' sulfuric acid and alkali prior to fractionation bged'tfurther distillation; but it is considered ter to apply such treatment to fully fractionated oils.

Other materials not inconsistent with the action ofthe aluminum chlorid on h rocarhons can, of course, be .used in ad ition thereto. Anhydrous tper-chlorid of iron (Fe2Cl0), if used in addition to the anhydrous' aluminum chlorid, is believed to combine with -the latter and so to form a double chlorid of iron and aluminum; which acts similarlyy to the aluminum chlorid; although a diderence in reaction has been observed; and probably a number of other substances would act similarly. In naming aluminum chlorid, therefore, in the hereinafter written claims it will understood that double chlorid of iron and aluminum and other similarly acting sbstances are intended to be included and not excluded by such recital..

Similarly, in naming petroleum in the claims, other `related o1l, such as shale oil or the like, is intended to be included and not excluded by such recital.

In stating in said claims that the petroleum is to be in any appropriate forni, it is to be understood that gas oil or fuel oil, burning oil (kerosene) or other like form is primarily, but not necessarily exclusively, intended. Y In stating therein that the petroleum is to be distillate with anhydrous aluminum chlorid in solution in a part of the oil operated upon, it is to be understood that the distillation, which is e(primarily intended is one which is continu approximately to or beyond the lowest point at which the residual material is suiliciently fluid for substantially the whole of it to be withdrawn from the still after the manner of a liquid,

but that a distillation which is earlier ar-` rested is vnot necessarily excluded, except in those claims Where a distillation approxi- 'mately to or beyondv such point is specilically required by recital to that effect.

In stating in any claim that liquid hydrocarbons and other matter composing the therein specified residual material are to be separated from each other, it is to be understood that said liquid drccarbons are primarily, but not necessarily exclusivel to be obtained in a form which is practica ly free from aluminum chlorid.

The application for the present atent is l a continuation of the application w ich was liled by me on April 25, 1914, and which has oeially' numbered :8341,84l It is 'alsoian application under section-i489?, Ito- 7crised-lwstatutesI for the inventiolrordiseuverywhich-1sV set forth in 'the' divisional .application that was filed by me `un Au st 16, 1917, and. wagsallowed October 6, 1 17,

thesame being oicially numbered* 186,542.

lication under said section 4897, Revisd ,tatutes, 'for subject-matter of my said divisional application was also filed by me on iJuly 14,-"1919, and has been officially numbered 310,875.- y

lI claim herein' as my invention or discoter A 4 '1. 'llhe process of making low boil-ing oil from :higher boiling petroleum, consistin in distilling petroleum in any ap ropriate form with anhydrous aluminum c 'lorid in solution in a part of the oil operated -u n arrestin the distillation whilethe resiiial materialias a substantial content of4 liquid hydrocarbons, separating liquid hydrocarbons and other matter composing said residual material from each other, distilling oil'which is composed at least in part of so separated hydrocarbons, and subjecting part at least ofthe resul-tino` distillate to disv'Form with anhydrous aluminul ,tillation with anhydrous aluminum chlorid,

substantially as y described.

2. The process of making low boiling oil from higher boiling petroleum, consistin in distilling` petroleum in any appropriate nl c lorid in solution in a part of the oil operated u on, arrestin the distillation while the resi ual materiahas a substantial content of liquid hydrocarbons, separating liquid hydrocarbons and other matter composing said residual material from each other, distilling oil which is composed at least in part of so separated hydrocarbons approximately at least to dryness, and subjecting art at least of the resulting' distillate to distl lation with anhydrous aluminum chlorid, substantially' as described.

3. The rocess of makin low boiling oil from hig er boiling petro eum, consisting in distilling petroleum in any ap ropriate form with anhydrous aluminum c lorid in solution in a part of the oiloperated u on, arresting the distillation while the resi ual material has a substantial content of liquid hydrocarbons, washing part at least of the so obtained residual material with water in such manner that the washing water is applied to material which contains a large part at least of the aluminum chlorid content of said residual material and which also has a substantial content of liquid hydrocarbons, and subjecting liquid hydrocarbons which have been separated from other matter by said washing to distillation with anhydrous aluminum chlorid, substantially as de scribed.

4. The process of making low boiling oil from higher-boiling petroleum, consisting in distilling petroleum in` any ap ropriate fornuwlth anhydrous aluminm` orid in solution in a part of the oil operated u on, arrestin thedistillation while the residual materia husa 4substantial content 'of liquid hydrocarbonafwashing part at least of the so obtained residual material with water in such manner `,that the washing water is applled to material which contains alarge part at least of the aluminum ehlorid content of said residual material and which also has a substantialcontent of liquid hydrocarbons, distilling oil which is composed at least in part of iquid hydrocarbons that have been separated from other matter by said washmg, and subjecting a art at least of the resulting distillate to istillation with anhydrous aluminum chlorid, substantially as described.

5. The recess of makin 1 low boiling oil from hio` er boiling petro eum, consisting in distiling etroleum in any ap ropriate form with anlhydrous aluminum c lorid in solution in a part of the oil operated u on, arresting the distillation while the resi ual material has a substantial content of liquid hydrocarbons, washing part at least of the so obtained residual material with water in suoli manner that the washing Water is applied to material which contains a large part at least of the aluminum chlorid content of said residual material and .which also hasa substantial content 4of liquid hydrocarbons, distilling approximately at least to dryness oil which is composed at least in part of liquid hydrocarbons that have been separated from other matter by the washing, and subjecting a part at least of the resulting distillate to distillation with anhydrous aluminum chlorid,l substantially as described.

6. The process of obtaining low boilin oil and other products in making low boi ing oil from higher boiling petroleum by the aid of anhydrous aluminum chlorid, consisting in distilling etroleum in any ap ropriate form with an ydrous aluminum c lorid in solution in a part of the oil operated upon, continuing such distillation at least until the residual material approximates the lowest point at which it is sufficiently Huid to be Withdrawn from the still after the manner of a liquid but not so far that the residual material ceases to havea substantial content of liquid hydrocarbons, arresting the distillation While the residual material has a substantial content of liquid hydrocarbons, and washing part at least of the so obtained residual material with water in such manner that the Washing water is applied to material which contains a large part at least of the aluminum chlorid content of said residual material, 'substantially as described.

7. The process of obtaining low boiling l oil land other roducts in making low boiling oil fnonihig 1er boiling petro eum by thc aid of anli drous aluminum chloiid, consisting in distilling petroleum in' any appl-lopriate form with an ydrous aluminum c o` rid in solution in apart of the oil operated upon,- con-tinuin such distillation at least until the residua material approximates the lowest point at which it is suiiiciently iiuid to` be withdrawn 'from the still after the manner of a liquid but not so far that the residual material ceases to be in condition to allow its carbonaeeouscontent and the main part at least of its aluminum chlorid content to be separated from each other by washin with water, arrestingthe distillation w iile the residual material is in condition to allow its carbonaeeous content and the 4main `part at least of its aluminum chlorid content to be separated from each other by Washing with water, and Washing part at least of the so obtained residual'material with'water in such manner that the washing water is applied to material which contains a large part at least of the aluminum chlorid coutent of said residual material, substantially as described.

8. The process of obtaining low boiling oil and residual material of the hereinafter speciiied character in making lowboiling oil from higher boiling petroleum by the aid of anhydrous aluminum chlorid consisting-in distilling petroleum in any appropriate form with anhydrous aluminum chlorid in solution in a part of the oil operated upon, continuing such distillation at least until the residual material approximates the lowest vpoint at which it can be :treed from aluminum by boiling with water but not so far that the residual material ceases to be in condition to allow its carbonaceous con tent and the main part at least of its 4aluminum chlorid content to be separated from each other by washing with water, and arrestin the distillation while the residual materia is in condition to allow its carbonaceous contentand the main part at least of its aluminum chlorid content to be separated from each other by washing with water, substantially as described.

9. The rocess of obtaining low boiling oil and other productsin making low boiling-oil from higher boilingpetroleum by the aid of anhydrous aluminum chlorid, consisting in distilling petroleum in any appropriate form with anhydrous aluminum chlorid in solution in a part of the oil operated upon, continuing ,such distillation at least until the residual material approximates the lowest point at which itcan be freed from aluminum by boiling with water, but not so far that the residual material ceases to be in condition to allow its carbonaceous content and the main part at least of its aluminum chlorid content to be separated from each other by washing withlwater,. arrest' the distillation while themesidual mater" is in condition to allow its carbonaceous content and the main part Aat least of its aluu minum chlorid content to be separated from,

i oil and other products in making. ldW blin oilfrom higher boiling petroleum by the ai of anhydrous` chlorid, consisting in distilling petroleum in an ap ropriate form with anhydrous chlori in so utionin a part ofthe oil operated upon, continuing such distillation at least until the residual materialap roximates the lowest point at which itcan e freed from aluminum byboilin with water but not'so far that the residua material ceases to be in condition to allow its carbonaous content and the main part atleast of its aluminum chlorid content to be separated from each other by washing withA water, arresting the distillation while the residual material is in condition to allow its carbonaceous content and the main part at least of its aluminum chlorid content to beA separated from each other by washing withwater, and washing part at least of the so obtained residual material with waterA 1n such manner that the Washing water is appliedto material .which contains a large part at least of the aluminumchlorid content of said residual material, substantially as lcscribed.V y g 11. The process of obtaining low boiling oil and other products in making low boiling oil from higher boiling petroleum by the aid of anhydrous aluminum chlorid, consisting in distilling petroleum in any appropriate form with a limitedfpro ortion, not more than about ten per cent. y weifrht, of anhydrous aluminum chlorid in solution in a part of the oil operated upon, conducting the distillation with'such regulation of the fires as to maintain a good low of distillate from the condenserl outlet by reason o/the rising tem erature of the oil operated u on, arresti t e distillation whilethe resi ual materia is in condition 4to allow its .carbonaceous content and the main part atleast of the aluminum chlorid content to be separated from each other by washing with water, and washing part at least of theso obtained residual materialfwith water in such manner that the washing water is applied to material which contains a lar part at least of the aluminum'chlorid c ntent of said residual' material, substantially as described.

12. The process of obtaining low boiling oil and other roducts in makin lowboiling oil from higher boiling petro eum by the as v OEI

aid of anhydrous aluminum -chlorid, consisting in dxstilling petroleum in any appropriate form with a limited proportion, not more than about ten per cent. by weight, of anhydrous aluminum chlorid in solution. 1n a part of the oil operated upon, conducting 4 the distillation with such regulation of the fires as to maintain a good iiow of distillate from the condenser outlet by reason of the rising temperature of the oil cerated upon, continuing the distillation wi rising temperature 1n said oil at least until the residual material approximates the lowest point at which it can be freed from aluminum by boiling with water but not so far that the residual material ceases to be in condition to allow its carbonaceous content and the main part at least of its aluminum chlorid content to be separated from each other by washin with water, arresting the distillation while the residual material is in condition to allow its carbonaceous content and the main part at least of the aluminum chlorid content to be separated from each other by Washing with water, and washing part at least of the so obtained residual material with water in such manner that the washing water is applied to material which contains a large part at least of the 'aluminum chlorid content of said residual material, substantially as described.

In testimony whereof I aix my signature to the foregoing specification, at Bayonne, N. J., this seventeenth day of September,

ERNEST B. COBB.

It is hereby certified that in Letters Patent No. 1,322,762, granted November 25, 1919, upon the application of Ernest B. Cobb, of Jersey City, New Jersey, for an improvement in Makingl Low-Boiling 9i1 f rom Higher-Boiling `Petroleum or Related Oil, errors appear in the printed specification remiin'g correction as follows: Pego 6, line 106, foi; the word distillate read distilled; page 8, lines 79 and 81, claim 10, after the word "anhydrous insert the word 4almm'mzm; and that the said Letters Patent should be read with these oorrectionstherein that the same nipy coliform to the record of the case in the Patent Qce.

.rsigpgid und this 30th day af Dwmbr, 4. D., m19.

@mi M. H. CoULsToN, Acting Commieaioner fPatcnla. 01.196426.

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