# Transcript of Record — Standard Oil Co. (Indiana) v. United States > Briefs, arguments, decisions, and more. URL: https://www.frixlaw.com/law-library/documents/brief%3Amicro_IA40386008_0009%3A08 ## Record - **Collection:** Supreme Court brief - **Document type:** Transcript of Record - **Published:** January 1, 1931 - **Citation:** 283 U.S. 163 ## Text CLEF K = vor Vol. Vill "TRANSCRIPT OF RECORD PATENT sarap holt — y 3 x eet +4 pieet nine ¢ :4 * . ie fe - F af Sd e nf Hy pameegs fo ! ie Gam... .. J Tee a eT : : . % ) > ° . Pie er ys Tar ’. ‘ i « : BoA ¥ & ’ ye ees gaventar? , , agar Ciara: 4476 Foren pre eee Sage ‘{fol. 1175) w- United: States Patent Office so ee ‘Mager M. Clark, of Alton, Tlinois (Method of Distilling Petroieum . 1,119, 496. Speciation of Letters. Patent. . “Patented Dee. _ + 1914 : ak "Application ied April 20, 1914. Serial No. '939, 243 To all whom it may concern : Be it known that’ 1, Edgar. M. Clark, a ditieen. of ‘On : United States, residing at Alton, in thé county of Madison ‘and State of Illinois, have invented a new arid useful Im. provement in Methods of Distilling Petroleum, of which. the following is a specification: My invention relates to an improvement in distilling pe-. - troleum, particularly for obtaining therefrom prunes e point. hydrocarbons. Where in distilling petroleum, according. to. common tan the liquid material is contained in a reservoir- ike still, to the bottom of which the heat is «applied, the danger i is ever present. of an opening fo in‘ the boiler- bottom, due to-flaw in the metal, the bottomburning out, or other cause. When this occurs, the entire contents of ‘the . still discharge |into the fire, prodneing: a more or less dis- S : .astrous conflagration. This result is more likely to en-. | = sue where the distillation:is carried on at a temper ature sufficiently high to.crack the petroleum-contents of. the still, whereby free carbon is developed | and accumulates on the still-bottom, on which it lies in red-hot cama - and tends to burn it out. - The primary object of my. in¥enition is to. provide: a . method of distilling petroleum, whereby discharge of the contents of. the still, Ahrough an accidental. opening occur- ring therein from.any cause, shall not produce serious con- sequences but shall-avoid damage of any kind ‘other than the loss of a. small part-of the charge and pemnporery dis- - ’ abling of the still. The accompanying aucaine illustrates diagrammatically, | "as suitable for the practice of my’ improved method, an quipment of apparatus involving* a so-called pressure- or, till, in 7 the distillation is carried on under = tem- _ a perature’ ‘(of 650° to 850°. F.). and a pressure of 3 to 7 at- — ~ Tnospheres Eredaees by thé vapors aacharee from the still. At‘1 is shown an hia ‘asi or reservoir su nerad 3 mm , - elevated position and having a rounded bottom, f m above ¢ which leads a pipe 2 containing a ‘force-pump 3, of any ‘suitable construction. This pipe leads from the discharge- . .. ‘ side of the pump to one end of a pipe-coil 4 in a furnace . 5, which is preferably coal-burning. The opposite\end of the coil communicates through a pipe 6 with the reservoir _ 1 at its upper. end, from which leads a discharge-pipe 7 © _ to the upper end of a water-cooled condenser-coil 8, the _ discharge-end of which, containing a valve 9, leads'to a - receiving-drum 10 for the distillate. A pipe 1 rises from | the lowermost branch of the coil 8 through the condenser- aes above which the pipe con a valve 12. - ag apparatus is particularly designed for the een natactare of- gasolene by distilling under pressure’ the cenia of petroleum-distillation, such as fuel-oil, to pro: | duce it. It is:to be understood, however, that my invention is applicable generally. to the distillation’-of petroleum = ~ + while it has peculiar advantages in connection with. the _ pressure-distillation process referred to.. In the apparatus — \2 illustrated, the liquid material to be distilled is charged’ into the reservoir, which may ‘contain several thousand gallons. With the pump in action and the furnace going, | the valves 9 and 12 beine closed, the: contents: of the res- ervoir -are circulated, passing from the reservoir by way of the pipe’ 2 through the pump, which. forces the liquid : ae relatively-fine stream through the ¢oil 4, whence it.re- - - ~ turns in heated condition through the pipe 6 to the reser- _. voir. By continuing this circulation, the heated liquid re- .. turning fromthe coil 4 to the reservoir heats the contents . of the latter and the resultant. vapors -pass off through the upwardly-inclining pipe 7 and condenser. These vapors - build up a pressure on the contents of the reservoir of from about 3:to 7 atmospheres and-raise their tempera- ture ‘to about 650° F. and as. the. run proceeds, to about’ ,. 850° F. Gases accumulating in the condenser are allowed * ‘to escape from time. to time,,on opening the valve 12, for ~ . relieving the gas-pressure, which is liable t6 accuinulate in - _-, the coil and obstruct. the action of the apparatus. From — _. time to time. the valve'9 i is opened for Sas the dis-. . : . > j 5 : e : . ‘ : . : 4 ‘x ‘ -tillate into the drum 10. This distillate is cred gpcene ie ioe superior quality and it may be subjected to Oe set ae ‘’ " ment, well-known in the art, for refining it. , By thus subjecting to the action of heat-the material ‘on ue der treatment in a relatively fine stream, while free: ‘earbaen © __ is formed in the liquid passing through the coil 4,it courses under the’ high pressure at which the liquid is circulated _ [fol. 1176] so rapidly through the same as to pre ent ac * eumulation therein of the carbon, which it carries. back - into the reservoir in the bottom of which it may accumu- _ late without injurious effect, since there is.no fire under. ~ the reservoir. Should, however, a leak accidentally occur ~ in the coil, so little of the liquid will discharge into-the fire — | the furnace that no damage will ensue: My improved: _ method, therefore, not only greatly. decreases’ the danger. of accident, but if the latter occurs the resultant damage _is comparatively immaterial. Moreover, it enables from ~ _ 8.to 7 runs to be made of the still without. requiring the ap- paratus to be stripped and cleaned, whereas where the __ boiler 1 is fired but one run can be made without. stopping _ and cleaning the carbon depoffit out of..it. _ While.a pump is shown for circulating the liquid ma- .. terial; any other way of producing the necessary rapid circulation i is intended to be within my invention. - _ - What I claim as new and desire to secure by Letters Patent is: : 1. The method of ¢ disti | petroleum, Which consiats in circulating it forcibly andfrapidly in a. relatively-small ~ stream under confinement fd subjection to a.cracking tem-.. > perature from and back ta bulk-supply of the liquid ma- | - “terial, taking off. and condensing the resultant vapors and . Pe maintaining a pressure of said vapors on said supply. 0 ie Method of distilling liquid residue of petroleum- Bes eR geee which consists in circulating said liquid forcibly. and rapidly in a relatively-small steam and under confine- ~ ment and subjection to heat from and back to a bulk-supply __ . of the residue, taking off and condensing the resultant va-. pors and maintaining said liquid at a temperature of from about 650° F. to about 850° F. under .a pressure thereon of said vapors of about 3 to 7. atmospheres. | | _. .8.The method of. distilling liquid residue of italia: me ~somians which consists i in eee said liquid — a he ee te | 4479. and rapidly in a relatively-small stream under confinement == — gnd subjection to heat from and back to a bulk-supply of . _- the residue, taking off and condensing the resultant vapors — - and'maintaining said liquid at-a temperature of from about ~— 650° F. to about 850° F. under-a pressure thereon of said. _ * vapors of about 3 to-7 atmospheres exerted throughout — . their course to-and during condensation. eS Rae ceed Be Pe a ee vee \ io) eer ML Clark, . Tn presence of Nellie B. Dearborn, Daisy C. Thorsen. : ee -Correetion in Letters Patent No. 1/119,496 a _» It is hereby certified that Letters Patent No. .1;119,496, © _. granted December 1, 1914, upon the application of Edgar * M. Clark, of Alton, Illinois, for an improvement in “* Meth- - ods of Distilling ,Petroleum,”’ was. erroneously issued to _ the inventor, said Clark, whereas said Letters Patent should _ ® have issued to Standard Oil Company, of Whiting, Indiana, - a corporation of Indiana, as assignee of the entire interest. _ "in Said invention, as shown by: the records of assignments © © in this office; and that the said Letters Patent should. be — _. yead with this correction therein that the same may con- “. form to the record of the case in the Patent Office. — ” Signed and sealed this 15th day of December, A. D., 1914. . ‘J.T. Newton, Acting Commissiorier.of Patents. - (Seal.) ame ES % | [fol 2177} Peririoner’s Exurerr 178 R. E, HUMPSREYS. - METHOD OF DISTILLING HYDROCARBONS, ‘ “APPLICATION FILED JUBE 96, 1914 4,480,700, °°" Patented Des. 1, 1914 pe ae Wo VW WH PAWN a | a) oot {fol. 1178]: . United States Patent Office Robert. E. cai pans: of. Whiting, Indiana, Assignor ew: Standard Oil Company, of =e Er a Corpora- . tion of Indiana | Method of Distilling Hydrocarbons 1119, 700. Specification of Letters Patent. Patented Dee. Pe fe ee - Application fied June 26, 1914. Serial No. a7 412 Bx all whom it may concern: , Be it known that I, Robert E. Humphreys,- a citizen of the United States, residing- at_Whiting, in ‘the county of .— - Lake and State of Indiana, have invented a rieéw and useful — improvement in the Method of Distilling Hydrocarbons, of “which the following is a specification. 3 | My invention consists in a novel method for the distilla- tion of hydrocarbons, its object being primarily so to treat hydrocarbons of relatively high boiling-point (such, for example, as the product known in the trade as fuel-oil, a para-fixt oil, the boiling oint of which is upward of 500° F.), as to produce therefrom hydrocarbons of muck lower boiling-point, such as the commercial product known as : gasolere which is a para-fin oil of much lower boiling point. In the practice of my process, in its preferred form, I employ as measures of commercial expediency, all the de- vices, and processes which have been found useful for that -purpose.. Among these processes and devices may be men- - 7 _tioned the process of the Burton Patent No. 1,049, 667, dated January 7, 1913, and the process of my application, Serial No. 813,220,’ filed J january 20, 1914.. However desirable these features are in practice, they form no part of my present invention and are, therefore, not here illustrated, but are enumerated.in order that those skilled in the art - will understand that the highest possibly efficiency requires 3 ‘that the present invention be ‘supplemented by what is now . the most approved practice in the same general field. ‘My process is preferably carried out in an apparatus, ; “such as that herein mere hae in which—. ces ecciaas s PR ‘ Figure 1.1 is a side soctiouni elevation, and Fig. 23 is, a top plan of the ee a suitable for carrying out the pr Referring t the drawings, 3 is a still which may be ‘*f | ordinary form. Extending: obliquely upward, from the still _ is a conduit.c Cpa of two pipes, 4, side by side, each con- ‘trolled by. valve 5. The pipes 4 communicate with a header 6 which. opens into a condenser 7. The condensed . products enter a receiving drum 8, and the uncondensed gases pass out eercags a: relief pipe. 9 controlled iy the «, valve 10. | . The valve in the ‘relief. -pipe is so manipulated as to main- : ‘tain in the system a pressure of upward of 4 atmospheres; -go that the distillation takes place at the temperature re- quired by the high pressure thus produced. When’ the raw - material-is the commercial product known as fuel oil,, the ‘temperature’ will be upward of 650°: F. and the distillate entering the receiving drum 8 will be crude gasolene. The essence of the present invention is the use of the in- clined conduit, consisting of the pipes 4, and in practical ~—operation‘the u is’ commonly termed in practice, is most important. - Its : operation i is as follows: The complicated chemical processes _ going on in the still produce products of varying gravities, and consequently. of varying molecular weights and boiling- points. The fractions vary from non-condensable. gases through the light napthas down to fractions which are but - slightly lighter than the raw material. The operation of the inclined conduit, or run-back, is td condense the heavier - _ fractions of the distillate and automatically to return them eae, - to-the still 3 for further treatment therein. In other words,. this inclined conduit has the practical effect of subjecting © ; the heavier fractions repeatedly tq the action of the pres- © sure and temperature in the still, until the desired molecu- ' lar re-arrangement has occurred, while permitting those fractioris which have already been ‘sufficiently acted upén to - pass over and be condensed.. It is manifest, therefore, that the size and dimetisions of the inclined conduit, or run-back, is.of considerable importance, ard I may suggest, by way eee example that I have found thut in the use of a still 8 ft. _ in diameter and 20 ft. in length an inclined conduit, or run- — _. back, consisting of two pipes each 12 inches in diameter and — 40 ft. tong es a distillate of the proper gravity 4 a o- 4 -t ; ‘ > - ' . * > - x ¢ crude gasolene... The use of. two pipes is a vantageous be- eause, when the end of the run approaches and the flow of. , that-condensation.can be maintained of: the proper amount. the vapors is slow, one half the conduit can be closed, so While-as. heretofore stated, I prefer to Pe the vapors . under pressure throughout their course and while under- . going both the initial and final condensation, das by: control-' ling the relief pipe 9, it is manifest that the pressure control . of the final condensation, i. e., the condensation of the light - (fol. 1179] vapors which pass from the run-back is not es- - ' sential to the invention. Such fractional condensation: as ‘ _oecurs in the run back itself, however, should evidently be under pressure for the carrying out of my process, as - otherwise there:would be considerable difficulty in return- ing the condensed fractions to the still for, further treat- _ment therein. T realize that ¢ considerable variation: is ‘losaible. in the _ details of the process hereiri shown, and I do not.intend to . limit myself thereto, except as pointed out in the following claims, in-which-it-is my intention-to claim all the novelty © _itherent'in the process as broadly as is ee by ™ , state of the art. : _ What I claim as new and desire to secure ed Letters Pai. ent i is: 1, The mathiod of treating liquid spikion of the asain series of petroleum distillation having a boiling point of upward of 500° F. to produoe therefrom hycrogsroge oils i, of the same series but of- be which-con= ‘sists in distilling the high boiling point hydiveatbons under a pressure of upward of four atmospheres, cooling all the. vapors passing from the still while under such pressure to condense. the heavier fractions thereof, and simultaneously. returning the condensed heavier fractions ‘to the still to undergo therein further treatment, and leading off and con- densing the light vapors. ; 2. ‘The method of treating’ liquid residue of the paraffin | - — of petroleum distillation having a boiling point of . - wpward of 500°:F. to produce therefrom hydrocarbon. oils _/ of the same-series but of lower boiling points, which con- sists in distilling the high boiling point hydrocarbons under a api of upward of four atmospheres, vice: all the re 3 ‘ 4484 vapors passing from the still to condense the heavier frac- tions thereof and simultaneously returning the condensed © heavier fractions to the still to undergo therein further treatment.and leading off and condensing the light vapors, ' maintaining such distillation pressure of upward of four . atmospheres on said vapors throughout their course to and while undergoing condensation. _ In testimony whereof I Bes hereunto set my hand this © atth day of June, me Robert E. Humphreys. % _ In the presence of two subosttbhiie witnesses ; A.C: : Fischer, F. A. Florell. - - [fol 1180} iia a | | PETITIONER'S EXHIBIT ‘179 5 : ,) E.. M, OLARK. og ) ' ART OF PETROLEOM DISTILLATION: APPLICATION TILED APR. 20,1916. - Js - Patented Feb. 16, 1915. 2 SEEETO-SHEST 3. ~ 4,199,084. Benen (geen Mae 9 ieaaet ‘pias wee" 4 ah Vt 1 el ae ee ee ' | ry ’ ' P 1 ee i Be ONY j ' ee 7 : Zs pee ‘ ‘ ; 4 we & “et H "a0 , J : Led _—s : f a } : : H 4 : ' 4 ° : : 2 i, : : i : ' H ‘ ' ‘ Le ) bane Hees 2 u. o/ bese i ood | j : ¥ se £ 'f- mg, a Fi EL oS Yofy, Yj ) a MEE Se “= Patenthd Feb. 16,1915, _ 2 SHESTO-OEBBT 2 4, YG ‘ 14, A process of. converting aes hydrocarbon lie into 8 1189] hydrocarbons of lowering boiling points which “eomprises passing the vapors of the hydrocarbons: to be : treated, under a pressure of several atmospheres, in the absence of steam, over a metallic substance capable of producing a catalytic action, while maintaining said .sub- _ stance ata temperature capable | of cracking the heavy oils. 15. A process of converting lamp oils or other hydro- carbons into hydréearbons of lower boiling points, which» comprises passing the vapors of the hydrocarbons to be- - : treated, under a pressure of several atmospheres, over a _ -“eatalytic metal maintained at a temperature at which said _ catalytic metal Possesses catalytic activity. . ae , 16. A process. of converting heavy . hydrocarbons into hydrocarbons of lower boiling points which comprises pass- ‘ing the vapors of said hydrocarbons, under superatmos- pheric pressure and in the absence of steam-or added hy- drogen’ over a substance capable of producing a catalytic action, while maintained ata temperature capable of erack- ing oils... hte Pe process of converting heavy hydrocarbons ine hydrocarbons of lower boiling points, which comprises passing the vapors-of said heavy hydrocarbons in the ab- sence of steam or other extrafieous hydrogen, under super. eS _- atmospheric pressure, over a ‘catalytic body ofthe nickel” ~ Py type, ’? at a temperature approximating a red heat, - -allow- ing the products. of the reaction to expand.to a lower pres- — | ‘sure, and removing the solid materials from the vaporous a products. : ° .18. In the manufacture of mikes fuel. aa nyikesear ban oils of which at least portions having boiling points ma- terially higher than those of ordinary gasolene, the step of | passing such an oil in the form of a flowing current, in the substantial absence of: extraneous. water, through-a coil . maintained at a temperature not materially below 500° C., while at a pressure sufficiently low to allow vaporiagsion, a bat materially above atmospheric.. In testimony whereof I have signed my namé to this specification i in nas _sisreeanee of two subscribing: witnesses. itl Alfred 8. Barbey, 0. J. Worth. William A. Hall. =f [fol. 1190] Pirrrionen ’s Exuusrr No. 181 é 4 3 | ¢. s. PALMEk. | PROCESS OF TREATING PETROLEUM RESIDUES. - ication: fueto wae. 2, 1907 "1,187,880. Pe ee Patented June 13,1916, . Fig/ zal feetetl stl» x \ 5 “4 aA ot Se. ‘ ; Se ee ee ae een eke @ coc ccmewon «= o+- : . ¥ rs oie 1 me 2 ees TEMPERATURES 010008 WE -t E 00 200 300 pe Witnesses Ae as M Rese aa eel cee gs oer : e. [fol 1191] United States Patent Office _ Charles s. Palmer, of Upper, Montelair, New Je ersey : Process of Treating Petroleum Residues “187300. nm segs of Letters Patent. Patented as |. | June 13, 1916. ieee Application filed March 2, 1907. Ser ial, No. 260, 975 . To all whom it may concern: Be it known that I, Charles S. Salen, a citizen of the United States, and resident of Upper Montclair, in the county of Essex and State-of New J ersey, have invented certain new and useful Improvements in Processes of | _ Treating Petroleum Residues, of which the following is’ @ specification. My invention. relates partioalariy to improvements in making volatile hydrocarbon compounds from petroleum residues, such' as ‘‘Florence,’’ ‘‘Boulder,’’ ‘“‘Wyoming,’™ “California’’ and ‘‘Louisiana’”’ residues or pitches which _ are substantially non-volatile below 300° centigrade: _ The usual process of “‘eracking”’ or decomposing petro- - Jeum residues consists in subjecting the same to a high degree of heat whereby they are partially decomposed and disintegrated into, volatile compounds. Thése are simul- taneously distilled with the result that more or less residual eoke or carbonaceous residue is produced. This carbon or ‘earbonaceous residue resulted from the decomposition of | the compounds treated, into free carbon, at the relatively” high temperature and relatively low pressure employed. - In practically ali cases. where. pressure was employed the temperature was in excess of 350° C., whereas the pres- ~ gure was at or below two atmospheres. gt an 3 The important features of my process: consist: (1.) In the complete separation of the so-called Neal a ing” from the step of distilling, the former being carried out at high pressure, usually in excess of four atmospheres, — _ while the latter is conducted ey at or a helow atmos- ' pheric pressure. — Perea (2: :) In conducting the ‘toracking”’ i in as comatzucted ae aa = of ee enormous | Pressures, i > while sesbios sufficient: heat: theréo to liquefy, to: vola- tilize, to create a predetermined pressure, i: e. autogenous pressure, to furnish latent heat of volatilization, and to. - furnish the requisite endothermic heat of formation. (3.) In, utilizing the pressure element to ‘direct and con-— : trol the reaction quite contrary to usual expectations, the — greater the pressure the gréater will be the decomposition, recomposition and polymerization into volatile products, « . which are formed in spite of the pressure and work with and intensify the pressure. -The: pressure is ‘controlled in each castbyjthe equilibrium established and. varies accord- ing to’ the materials treated, the resulting products, and the . - factors of heat and time of action but ordinarily the pres- .- gure when if reaches 130 pounds i is sufficient to effect the “nécessary conversion. - (4.) The time of action. This aang cade from the time required for the preliminary melting and heating i in the reservoir, occupies but a very few minutes. Tht carrying out the said process in accordance with my invention, the residues, ‘substantially «non-volatile, below — —- . 800°-C., such as ‘‘Florence,’’ ‘*Boulder,”’’ “Wyoming,” “California”? and “Louisiana” pitches or residues, are - first introduced into a steam jacketed reservoir’ wherein the ' game are melted, and thence are introduced: into a high pressure digester wherein they are subjected to the ‘requi- . site conditions of temperature, and pressure necessary for carrying out the process, the means for producing the __ Tequisite temperatures and pressures &. Being indicated — in the drawings accompanying this specification and form- . ing a part thereof. In the drawings, Figure 1 is an elevation chiefly i in-sec-. | tion of an apparatus adapted for this purpose. Fig. 2 represents a curve illustrating the process in operation. - _ Referring to the drawings the reference numeral 1, desig- ~ nates a tank or reservoir provided with a cover, 2, a ‘steam jacket 3, a ‘drainage pipe 4, and a steam inlet pipe 5. An _ outlet pipe 6, proyided with a valve 7, is connected by a - pipe 8; provided with a valve 9, with a digester 10. The - digester, which is constructed preferably of half-inch steel, . « 48 provided with a cap or closure 11, securely packed in. the usual manner, a manhole 12, and. pipe extensions’ 13, i @ and 21 respectively. A jacket 15 preferably as shown being. - ~ -- provided with steam coils 16, completely sur esaid - digester, openings being provided it both the digester and — the said jacket. for the insertion of a pressure-gage 17 and a thermometer 18. The pipe-extensions 14 and 21 project.. “through the jacket 15 and are provided with a check valve 19 and a stop-cock. 20 respectively.. These extensions are connected with piping 22 and 23 to a still 24, of well known “eonstruction, provided ‘with the usual steam-coils 25, inlet . and vapor outlet 27, and thermometer 28. Wea oe ~The residues treated in the above described apparatus, as actually practised, consisted in so far as could be deter- mined from the specific gravity and melting points, of mix- _ [fol. 1192] tures of hydrocarbons of the paraffin: series . - OsHyae of the range CoH, to CsHss. Said residues are — empirically known as residues or‘ pitches from, as for ~~ example ‘‘Florence,’’ ‘‘Wyoming,4’ ‘‘California’”’ and. “Louisiana” pitches, which. were ‘the ones actually tested and operated on by this process.. nay Arn 3 _ During the treatment in the digester, 10, ‘which usually’ 2 did not exceed a few minutes, the pressures gradually in- _ ereased with the temperature, according to the curve shown in Fig. 2, until a pressure of 130 pounds was reached, when there was apparently a sudden conversion of the materials "present into more volatile compaunds which caused a rapid _ increase in the pressures as shown without the indication . of any great increase in temperature. Since the heat was. - being uniformly applied thereto, it is apparent that at this = pressure there wag.a large absorption’ of heat, which pre- . vented any noticeable indication of an\increase in tempera- . - ture. Such absorption of heat being evidently due to the — formation of new compounds which as the results slow are - to a certain extent, at least, cyclic in character. -" = 5 _- In order that the pressure may be accurately controlled during the operation, I provide the check valve 19, which a may be adjusted for any degree of pressure desired, when - upon an increase of the pressure above that to which the valve is set, the vapors from the digester will pass over: Oe 8 ae eee eR The steam heating coils are utilized in the apparatus for __ - ¢arrying out my invention in preference to other common _ heating means, because of the accuracy with which the tem- — 7” ~ ‘ Res oT ie . deportes . “git 4 . - p . ee ! ; | perature ot can ne adjusted, particularly if specheniols steam > is marion therein ‘as is preferably the case. _ ‘The volatile products obtained from the above’ treatment, - as actually carried out, were drawn off through the pipe = —% 23 and collected in a still and subjected to distillation sepax § rately from the. undecomposed residues remaining” in said e digester, at atmospheric pressure and upon fractional dis- tillation gave results substantially“as follows: Up to 100° es _ C;, about 5% distillate; between 100° C. and 150° C., about | 10% to 20% distillate; between 150° OC. and 200° C., about 10% to 20% distillate; between 200° C. and 250° C. about 20% to 30% distillate ; between 250° Cc. and 800°C, about 10% distillate. | ‘While the first fraction doubtless contained some volatile paraffin C.H...., the higher distillates: were mixtures. of | some paraffins, some benzenes C.H,, &c. and considerable naphthenes or ‘‘cyclic’’ or ‘‘closed ring’’ paraffins, such - for example-as- polymethylenes, 28, CoH, 2 and their ‘homo- es logues. = + Ta wee : The materials which had been previously non-volatile—_. "below 300° C., after treatment uniformly yielded from 65% __. or treatment, and were again treated there was no a © lation of none-volatile residue. In fact a non-vola' - to 75% of volatile. matters at temperatures varying from 100°. C..to 300° C.. Moreover, when the residues of one treatment ‘were mixed with the residues of another b teh » le resi- due remaining from the last fraction of one trea teven.. if subsequently treated alone, would often be d mposed on in a manner substantially similar to that: of untreated resi-_ dues when heated alone since each treatment’ would have — its quota of undecomposed residue according to the equi- . . librium established. * Accordingly, each regidiuie when re- treated would decompose exactly as though it had not been _ previously treated, as decomposiiion. takes place at the : appropriate equilibrium and Tong before all the residue. i is: - transformed. - . en In Fig. 2 the curve - ean illukteaten: the process when. a4 fe operating up to 300° C. and the pressures ranging from 30. pounds up to 160 pounds, and in fact experiments show, . that when operating even up to 400 pounds, the decomipo-—- sition, | recomposition | and. polymerization, other a _ being equal, is directly dependent upon the increase. of _ ‘pressure, and that: the radical — a —: new ‘stimpénat having new siobacoilate arrangements, does’ — not begin muc): below five or six atmospheres independent : of the temperature. On the other hand, the said experi- ‘ments indicate that at pressures ranging from 20 to 30 . atmospheres the formation of new compounds. takes place with great rapidity. In all eases the volatile products of decomposition - increase with more pressure at -tempera- tures from 200° 300° C. This indicates it is not’ merely — the high temperature, but rather. moderate temperature - and high pressure that govern the decomposition and de- . termine the result. ‘As a specific example: When operating. with heavy, . waxy, tarry or pitchy’ materials, such as: ‘‘Florence,’’ | **Boulder,’’ ‘‘Wyoming,’’ ‘‘California’’ and ‘‘Louisiana’’. age at temperatures ranging from 200° to 325° C. and u pressures of from 60 to-90 pounds, but. a rela- ively small percentage approximating from’ 25% to 35% . of volatile products: were obtained. With temperatures from 200° up to 325° C. and pressures ranging from 100 © to 150 pounds to the square inch, a large percentage ° of the originally non-volatile material treated was trans- - _ formed into volatile’ compounds, the percéntage rang- _ . ing from 50% ‘to 75% of the original. At pressures ranging from. 150 pounds' up to 300 and 400 pounds per ‘square inch, and at temperatures of from 200° to 325° C., from 75% to 90% of the materials were converted into volatile products.” These products were in all cases _ subjected to distillation, - at, or below atmospheric pres- [fol. 1193] stire, separately from the digesting operation. Thus if one starts. with a mixture consisting, for example, B. of paraffin of the C.Hm,, series itis obvious that if it is . - attempted to split up the said mixture into lighter mdle- cules of the same series that there will be enough hydrogen © _ to satisfy but a part of the possible’ new molecules that — i _ may be formed. The result will be the formation of com- | pounds as CH, or even CrHn-- “2y CrHin-- -4 “CaHas- Horace P. Chamberiain, of Buffalo; New York, Assignor to ‘Standard Oil Company of Hew York, of New sats N. Yo a Corporation of New York - - ‘Ontisining, Products from Petroleum by Decomposition of Pa . Component Hydrocarbons Thereof , ; th 790. — of Letters Patent. Patented Apr. ; : 3, 1917 : : | Application filed October 20, 1913. ‘Serial No. 796 B10 - To all whom it may concern: . Be it known that I, Horace P. Chamberlain, a citizen of the United States, residing at Buffalo, in the county of Erie and: State of New York, have invented certain’ new ‘and useful. Improvements in Obtaining Products from Pe-_. _ troleam by Decomposition of Component - Hydrocarbons — Thereof, of which the following is a specification. s This invention relates more particularly to obtaining naphtha, burning oil (kerosene), an asphaltic material and another hereinafter mentioned product from petroleum - which is of a character to yield paraffin wax; but each of the improvements composing the invention is intended to . § be secured for all the uses to which it can be applied with % _ or without modification. | | Heretofore.in my experience petroleain (of the char- . acter mentioned) dras most*commonly' been subjected im the - verude form in which it is produced at the wells, after sepa- ration therefrom. of water and earthy matter by settling, to distillation under atmospheric pressure at gradually in- | creasing temperatures in one or more stills: (with. interme- __ - diate transfer of the residual oil when more than one still- ~ js used, with cooling or cooling and storage of the so trans- ferred oil when necessary Or desired and with .condensa- _ tien of the Ny ut in a series of condensers ‘at different | rosaries wes uring part at least. ‘of the distillation) ; such distillation has been continued until only a dry coke re mains as undistilled residue; and distillates have been ob- tained principally, if not exclusively, in,the several forms — ; (0), of eceaee se. in: one or more grades, (b) watel oe meer * . tillat ve. 2 PS ent \ 7 ..qwhite burning oil (kerosene) disti te, (c) mixed distil-. late which consists in part of hydrocarbons ‘with boiling - points normal for naphtha, in part of higher ‘boiling hy- . drocarbons with viscosities normal for burning.oil (kero- | sene), and in part of hydrocarbons with viscositieS too’great . fot normal constituents of burning oil (kerosene) and not "great enough to be normal in other than light grades of - jubricating oils, (d) heavy: paraffin distillate, : paraffin slop, and (f) crude still wax, also bag slop, as wax tailings or as gum. From’ thy ') heavy pwn as wax 4 om’ the’ heavy paraffin _* glop and the erude still wax, an additional amount of ont Raha e distillate has been obtained by further dis- ion of them.. The points at which the different cuts © _ (divisions or collections in different receivers) have been made have differed somewhat in different establishments . _- and also at different times in the same establishments, ow- ing to different views of thé manufacturers as to the best — methods of working, and so on, or to different ‘market con- - ditions. The normal boiling points of burning oil (kero- — sene) hydrocarbons have been recognized as between 302° F. and 572° F., or 518° F. (Allen, Commercial ‘Organic | ' Analysis, vol. 2, London, 1886, pages. 397 and 398); as so: defined, boiling points normal for naphtha would extend — up to 302° F.; but for some years naphtha has included less volatile hydrocarbons; and for the purposes of the pregent _ ‘specification volatility normal for naphtha should be taken - to include boiling points up to 338°-F. For the same-pur- | . poses viscosities normal for burning oil (kerosene) hydro- -earbons may be taken to extend up to seventy seconds at 100°. F. by an Engler viscosimettr, on which water would — exhibit a viscosity of fifty-three seconds at the same tem- ~~ perature; and the intermiediate viscostties mentioned may be taken as from seventy to one hundred and seventy sec- _ onds by. the same Engler instrument ; which is also referred - ‘to whenever viscosity figures are given hereinafter, _ . With a view to increasing the ‘yields of naphtha and — burning oil (kerosene) hydrocarbons, it was long ago pro- posed to distil under superatmospheric pressure oils which are composed of, or. contain higher boiling hydrocarbons, 4 as crude petroleum, for example, or undistilled residues - -° of.erude petroleum after removal therefrom of crude naph- _ tha and water white burning oil (kerosene) distillate (with ~ ades of it is believed that advantage over the prior state of the art 5 ‘ean be obtained without the aid of either of said features. oa * Heavy paraffin distillate in each of four forms, that is to "gay, either pressed or unpressed and either treated or un- . treated with sulfurie acid: and alkali, can be ‘distilled un- : - der pressure in accordance with the invention, although not for all of said forms with the same advantage. ‘ _* Such heavy paraffin distillate in each of said forms con- tains liquid hydrocarbons with viscosities normal to heavy ‘ ' and. medium grades of lubricating oils and also hydro- ‘carbons with the intermediate viscosities mentioned in such relative proportions that in the distillation under pressure - the decomposition of the-hydrocarbons of each of said kinds ~ is modified. by the presence of the two other kinds. -For exerting such modifying effect the hydrocarbons of any of said kinds should not be less than about ten-per cent. by volume of ‘the’ sum total-of the three kinds; and in the _ distillate mentioned the kind present in least proportion i is in excess of such ten per cent. Said distillate is also co far free from still wax and like heavy matters_of sticky character and from elements. yielding the same or coke that charges of the said distillate of practical size can be: distilled under a superatmospheric pressure of: seventy five pounds tothe square inch to the extent of fifty. per x. tent. or more by volume without heating the-still bottom - to redness. I have‘also discovered that certain advantages _ over the prior state’of the art can be obtained by distilling as aforesaid oils related. to heavy ese: distillate as here- inafter explained. _ In yielding naphtha and burning oil: ‘(harosesia’ the ‘i composed hydrocarbons may yield also a residual -product of an asphaltic character which is useful and I believe new i __. and-which is included inthe invention as a new article of Ae manufacture or composition of matter. * we. ape : IT have also discovered I believe a new process of dis- _ tilling hydrocarbon ‘oils under superatmospheric pressure; which I have applied to heavy paraffin distillate in each of ue ' the forms mentioned; but which I believe can be applied - ' advantageously (as compared with the prior state of the - art) te other forms of petroleum (including crude oil and undistilled residues i in case it should be found expedient to - distil-the same under superatmospheric pressure, as well . as the herein above mentioned gas oils or fuel oils and other distilled or:partly distilled products), and also to hydro- carbon oils from other sources than petoleum I have also devised a distilling apparatus which is useful. for performing said process and which I believe to be new and consequently mgere as forming pant of the present in- vention. The accompanying drawings represent by way of example an apparatus within the invention, Figure 1 being a longi- tudinal vertical section, partly in elevation, of the still and ~ accessories, without the condenser, Fig. 2 a view in cross section, partly. in elevation, showing still and condenser, and Fig. 3 a detail view in séction on an enlarged scale of: an expansion valve appropriate to. be employed as a va- por throttling device in said apparatus. -- ~. “4 ‘{fol. 1197] The still-a-is advantageously of. box-like form ° and of a large enough capacity to be of practical value in industrial use, say a horizontally disposed cylinder eight feet in diameter and eighteen to thirty feet in length, or - of other appropriate dimensions. It is supported above ~ a fireplace b for heating and has its upper portion exposed* *. to the atmosphere with little or no protection. against cool-- ing. It is best provided with a dome c also exposed to the atmosphere. The heating means may be of any appro-.~ priate description. .A burner d is shown by way. of ex- | ample, the same having a gas supply pipe e connected - therewith and provided with a controlling valve f. Any _ desired number of bhirners can be used; also one or more fires burning solid ¢r liquid fuel can be used i im connection | .with supplementary gas burners; or other heating arrange- | ‘ments can be adopted. The still, when its bottom beeomes_ heated to incipient redness (the ordinary. indication of — danger toa still bottom from overheating should distilla- tion be contmued) Ought-then' to be able to withstand an. ‘guternal —— in such. + eacat oF eighty pounds age pieg ar Be 4517 square | tachi’ above atmospheric pressure as to) afford ae proper margin of safety. . The intermediate section of the still (see Fig. 2) is 19 x 27 best protected both from the atmosphere and - ‘from the’ _ fire gases, the cubic contents of the so protected portion be- . ing not less than about half the capacity of the still. As shown, about a third of the exterior surface of the still is exposed to the atmosphere, | approximately another third is exposed to the fire gases, and the remaining portion, ap- : proximately one-sixth on each side, is inclosed by and in. - contact with the walls of the still ‘setting and'is so pro- tected thereby both from the’ ener and from the fire gases. The vapor pipe g leads drsiala acai ctoa condauet of any known or suitable form; shown as a coil h immersed in a fank j. Water of a temperature to condense naphtha _and heavier vapors is. supplied to. tank j by water. inlet — _. pipe k and withdrawn therefrom in a warmer state by water outlet pipe l. At m within tank 7 is a gas separating box with a gas escape pipe » leading from its top and a distil- late outlet. pipe p leading from the bottom to a receiver (not shown). At-q is a gas main for carrying away the gas to. be burned. - Additional fuel would; of. course, be needed for heating the still ain case gas from the same-should be © burned under it. The vapor pipe g is pecvidied with an ‘iconalion valve r intermediate the dome c of still a and the condenser. As the best conduct. of the pressure distillation requires a close regulation of the volume of escaping vapors, the valve port s (Fig. 3) is best of small size as compared with the bore © of vapor pipe g; which bore ‘should not be less than about - three inches in diameter: in order to’avoid difficulty from choking. As shown, the. valve is closed by a screw ¢ and -has a stuffing box u for its stem. Stuffing boxes are also . shown at w and z for the pipe connections. . : : - Phe valye shown is a form known on the market as of needle type and employed (for one. purpose at least)! as *. an expansion valve in ice machines using liquefied ammo-- “nia as the, refrigérating agent. ,A valve of more pro- nounced needle form (more acute taper and further pro- " jection into the port) might have advantages; but the form shown has been found useful. A valve of other than needle type is net necessarily excluded. Heretofore in plans for : 4518 | ae distilling petroleum and other hydrocarbons oils under su. pératmospheric pressure it has been proposed to employ _a relief valve which rises automativally when the pressure ‘reaches a certain degree and closes when the pressure falls below the same degree. The use of such automatic valve is- not necessarily excluded; but its use. is attended with - no advantage, in my opinion; while, on the other hand, it - adds complication to the apparatus and is liable to cause ‘danger or inconvenience by sticking. If used, it would be advantageous to provide means for manually regulating the extent of the valve’s opening and for forcing it posi- - tively to.and from its seat, should occasion arise. The still is shown provided. with a pressure gage y for — - exhibiting the pressure ‘inside the still, a safety valve zfor . relieving said pressure should it. accidentally becomé ex- 3 cessive, a pyrometer 2 for exhibiting the temperature of | ' the oil in distillation, a second pyrometer 3 for exhibiting the temperature of the vapars.in the vapor space at the front of the still, a third pyrometer 4 for exhibiting the temperature of the vapors as they leave the dome c and pass over to: ‘bescondensed as distillate, a valved oil supply pipe 5, a valved discharge pipe 6 for the residual product, a. ‘steam pipe 7 for introducing steam at the.close of each run in order to expel hydrocarbon vapors and to cool the still . ‘off more rapidly, and a manhole 8 for cleaning. out the still at the end of each run. Each pyrometer is inclosed:- in a _ protecting sheath or pipe 9 closed at the inner end. ,Elec- — trie pyrometers with wires 10 are indicated. —. : For obtaining the oil to be supplied to still a crude pe- - troleum may. well be distilled to dryness under atmospheric » ' pressure in one or more externally heated stills (not shown) with gradual rise of temperature’ and with fractional con- ‘densation of the vapors in the latter part.at least of the - Tun, customary apparatus. being used for the purpose. [fol. 1198] After the collection of the water white burning oil (kerosene) distillate and of.such amourit of the mixed distillate coming over subsequently as may be desired, the distillate which is subsequently | received in such disfilla- ' tion may well be collected in the receiver 3 ‘heavy par- affin distillate as long as it is sufficiently free from still wax tobe readily pressed for paraffin wax. Assuming that the a _ erude oil operated upon is from the Kansas oil fields and has itealt z ecsiers gravity of 0. 863, such collection may se well include all the distillate which at the condense Fy > Jet is between 0.855 and 0.904.in specific gravity at 60°. Distillate which is.received afterward in’said -distillatior of the crude oil may well be itself distilled to dryness, and the so obtained distillate, so long as it. is free from still eo be added to the heavy paraffin distillate of the crude © _ oil rin. . ~ The thus. obtained material ‘would ‘Best be treated ‘with sulfuric acid and alkali in the manner customary for treat- ing heavy parafin distillate therewith preparatory to chill- . ing and pressing, to wit, -by agitation with them in suc- cession and by separation of the resulting sludge after - ‘each agitation. So treated, and with its content of paraffin wax intact, it would constitute heavy paraffin distillate in: the form in which it is considered best to: employ the same for decomposition in the still a. It would ‘consist: principally of hydroearbons, whigh (if separate) would be liquid at 60° F.; but it would also con- tain over four per cent. by volume of paraffin wax (in so- lution). Its liquid portion would-comprise hydrocarbons with viscosities normal to medium grades of lubricants (to wit, from one hundred and seventy seconds to two hundred and ninety seven seconds) and also hydrocarbons with vis- _ cosities normal to heavy grades of lubricants (to wit, from two hundred and ninety seven seconds upward) as well as hydrocarbons whose viscosities lie between those normal — to burning oil-(kerosene) and those normal to medium lubri- - eants (to wit, between seventy seconds and one hundred and | seventy seconds). Each of these species of’ liquid hydro- : _ carbons would be present in above 10 per cent. by volume. ' A sample from a particular lot of treated and unpressed heavy paraffin distillate which had as a whole a specific gravity of 0.881 at 60° F. and whose distillation under . pressure gave results hereinafter set forth was chilled and - sed for paraffin wax and ‘yielded the latter at the rate “of sixteen and a half pounds to each 42-gallon barrel: of the _ unpressed distillate (equivalent to six per cent. by volume). ” The so-pressed sample was then reduced with super-- _ heated steam introduced into the oil and with fractional con- — densation of vapors in a series of condensers at different. temperatures in the manner customary .in obtaining lubri- — oils itight and median a as diatiates and / Oe | 4520 | heavy grades as residues) from pressed paraffin aan and in such reduction yielded (1) distillate with viscosities — / at the condenser outlet up to seventy. seconds equal to one per cent. by volume of the unpressed distillate, (2) distil- late with viscosities at the condenser outlet between seventy ‘seconds and one hundred and seventy seconds equal to fifty. a - six 44/100 per cent. thereof, and (3) distillate with viscosi- : ties at the condenser outlet between*one hundred and. sev- —. enty seconds and two hundred and ninety seven seconds - equal to thirteen 89/100 per cent. thereof, leaving (4) resid- nal oil equal to twenty 38/100 per cent. thereof. There was thus an estimated loss of two 90/190 per cent, by vol- ume in the assay. | The treated and. unpressed heavy paraffin distillate is introduced through pipe 5 into the still a until the latter is ‘ say six-tenths full: The contents of the still are then grad- ually raised in temperature, with valve r open, until the © -air has been expelled from the:still and oil appears as con- densate at the condenser outlet. Next the valve ris closed 4° and the pressure: in the still.a is allowed to accumulate until the gage y shows say 75 pounds per square inch above - atmospheric pressure. Thereupon the valve r is cautiously - - opened; and the heating is carefully regulated to maintain said pressure of 75 pounds without greatly exceeding it. - The extent. to which the valve r is opened is an important matter. It may well be opened to such extent that distil-' late is received from the condenser.& at the rate of about two per cent. by volume of the original charge‘per hour of running. It may be opene¢ to a lesser extent, as much less as may be desired; since the only objection to the resultant _ slower, ranning would. be the increased expense due to the longer time to make the run. It may be opened to.a greater _ extent; but with too large an opening excessive firing would be necessary to maintain. a proper pressure in the still a; and, in consequence of such firing, the hydrocarbons pass- ing over might average too high in specific gravity for profitable working...A general increase of'as much as twen- _ ty four one thousands (0.024) in the specific gravity of the high pressure distillate (as compared with that obtained . in a distillation of oil from the same lot: at the said two ~ per cent. _ per hour rate) would probably indicate a fatal . troslenest in the _— of nig preeare distillate. Such ae e235 ; ‘eomparison should be made ebaeel wastiphts to be collected - at corresponding periods of the runs,.to wit, when the dis- tillate received in each run shall be the same percentage ‘ef the original charge. F [fol..1199] The valvé r can be adjusted inion a ‘run, if considered necessary or expedient, but in normal running the valve opening may be constantly established, so as to ~ allow a continuous escape of the vapors through it; and . mately uniform escape of vapors: with. an “approximately ' gniform pressure in the still. : As distillation proceeds, .the oil-in distillation heouine: a gradually hotter. Its temperatures will be higher than - ~ those of the oil in a parallel run under atmospheric pres- - gure; but they may be (and in distilling heavy.paraffin dis- ‘ _ found to be) below those at which the vapor tension of the -. undecomposed oil is estimated to equal the still pressure on . the basis of considering the rise in vapor tension of the. - -wndecomposed oil for a given number of degrees F. above . its boiling point to be equal (or sufficiently near equal) to . the rise in vapor tension of benzene (coal tar naphtha, - O,H.) for. an Real number of. degrees F’. above its boiling : . point and the temperatures of the oil in distillation in a — parallel run under atmospheric pressures to represent (with . - ‘gufficient accuracy) the boiling points of the undecomposed — il... Hereinafter a.table is given which. shows the tempera- . -, tures of the oil in parallel runs on heavy paraffin distillate _ under atmospheric pressure and under seventy five pounds superatmospheric respectively; and it will be observed by * reference thereto that at corresponding periods ‘of the runs. ~ - the difference is less than 131° F.; which. is the difference -. in temperature between benzene at its boiling point (where . its vapor tension equals. the pressure of the atmosphere) and at the point. where its vapor tension:is seventy five pounds to the square inch above atmospheric pressure. See _ .. ‘The evolved vapors are cooled in the exposed upper part. _ of still @ and in dome c fo considerable extent (say between . about 150° F. and about.350° F. below the contemporaneous — temperatures of the oil in distillation) before they pass |; over to be condensed as distillate. ‘Such cooling results in Ae partial condensation of said: vapors and the formation it need not be altered in size, thus allowing an approxi-' : , fillates under a pressure of seventy five pounds have been — 4822 / - of condensate which returns to the oil in distillation. Itis — conceived that some hydrocarbon components. of the oil in. still a will vaporize without decomposition, owing to the . _ presence in the still a of the vapors of lighter (more vola- - tile) hydrocarbons formed by decomposition, notwithstand- — ing the fact that the temperature of the oil in distillation is _ below the estimated boiling point of the latter under the © ‘pressure in the still a. The following table gives, figures. which were. obtained 4 -in - runs performed at the rates indicated in the table with a _- small still (a horizontal cylinder 20 inches in. diameter by 42 inches long with.a dome four inches in diameter and six inches high) on batches from the same lot of oil, one under atmospheric pressure arid the other under a super-atmos- pheric pressure as near 75 pounds to the square inch as: — practicable without falling below. the same... The total « hours’ and minutés of performing the respective runs, in - connection with the total percentages received therein, show- / ‘average: yields of distillate | equal to. about seven and a half 2 per cent’ by volume of the original. charge per hour in one hi run and about eight per cent. per hour in the other; but in _ industrial operations a lesser. rate’ is considered better as hereinabove indicated. The specific gravities i in the table are those of the sseeardl fractions of distillate of 5% each by weight; and the times in minutes are thosecin which. said fractions were severally . : received. : . o | iis pressure. \ _ 5 pounds gage pressure, : . . \ \ - ceca ee EN Cie We g oe yrecthios Qu” 8 Bs a \ 38 sg E - : mom oe Bk Ug . Nght, S244 aes | 1 7 tu i are .1.:.... 663 588 8236 40 .766\ 512 .7669 48 A Breen - 679 582 8473 43 756 620 .7673 43 g...... 691 624 8529 45 766 525 .7682 46 Avct.. TOL. 635 8536 «+38, 769 530 .7762 35. NS 710 635 8581 40 775 . 529\..7770 - 37. - B..J0 TE 658. 8540 «43 «778 «530. 41. Ho i he 922 656 8571 41: 777 536. _ 88 | 8...... 734 676 .8560. 40 782 540 421 \9....... 740 680 .8555 44 793 545 46 \100.... 741. 635. 8473 43 804 550 ° .7945 \ 37° it... 752 655 8519 (40 811 554 . .7967 es | ae | Ree 760, 688 .8514 38 815 546 .8053 36 (A3..... 765 691 8524 39 834° 550 : 8170 40\ a I ts. bean to mney those skilled 3 in the art to practios ‘the. . ‘invention. | ee 770 =696 .. 8534 45 / 842 546 ~.8299 90 Total distillate 70% ; time . h 39 m. ; ; total distillate 70% 5 time9h. 36m... Percentages in table by: Salant: not volume; total distil- late 72% by volume in run under atmospheric pressure, and | 718.2% by volume in run under 75: pounds gage pressure. . In giving these and other figures in detail, it will be un- . “derstood. that they are by way of example. only, in order . fol. 1200] It is oonsidered. best in distilling under pres- a ~ gure that the evolved vapors should not be heated above the wa _-tontempotaneous. temperatures of- the oil in distillation. _As shown, therefore, only the bottom.third or thereabout of . the exterior surface of the still is exposed to the fire gases; ~ go that the walls-of the vapor space, even when this space . is enlarged by progress of the distillation, will not.be ex- : posed thereto. The cooling of the vapors is effected as shown by the exposure of the still top and dome to the cool- _ ing influence of the: atmosphere. The work dle igi 4524 the vapors in expanding as they pass the valve r in distilla- tion under high pressure, with said valve within a short distance from dome c, also exerts a cooling effect on the vapors in said dome c. The condensate as formed drops (or else runs down the sides ‘of the still): into the oil in dis- tillation. A partial condenser exteriorly located and con- nected with the still by a vapor pipe and a run. back for. returning condensate could be used instead of or in addi. tion to cooling in the vapor space: (instading dome Since . when a dome is used). . By having the middle section of the still inclosed by and in contact with the walls of the stilt: ‘setting, +the-vapors are . ¥ protected not only against overheating, . as just mentioned, - but.also against the undie cooling which might result from enlargement of the vapor space during the run, were said . middle-section exposed to the atmosphere. The distillation would best be continued as long as it is _ safe to do so, in view of the superatmospheric pressure in __ the still. The limit: of safety would probably be about reached when the appearance of the still bottom indicates Se : ineipient redness, . The run being thereupon dovinhidaited, ‘the asphaltic: ma- "- terial in the still a is withdrawn through pipe6andacooler — . (not shown) into an appropriate receiver (not shown) } the - _ still is subsequently cooled (after introduction of free. steam through pipe 7. to expel the vapors, the manhole 8 operied as the steam first enters) ; the still is cleaned; - d it is then ready to receive a new charge of the treated unpressed heavy paraffin distillate. . The high pressure distillate from condenser coil hi may - well be collected in a single receiver (none shown) and be eS then fractionated into naphtha, burning oil (kerosene) and a heavier oil useful as. gas or fuel oil. Said heavier oil, also any residue obtained in rerunning the’ burning oil ie (keresene) portion of the high pressure distillate, could be . - added in whole or in'part to a new charge of the heavy par- affin distillate, if so preferred. Other. oils could also be '. added, if so desired such as résidues (bottoms) from Tre- _ ' ‘punning the water white distillate and the mixed distillate. - (of the crude oil run.’ Instead of a single condenser h as shown, a series of condensers maintained at we tem- - a i peratures — be — to the er war | a0) oi . .The asphaltic residual material withdrawn from the still ga at the close of the high pressure run in which the figures. of the table were obtained had as a whole a specific gravity of 1.0772, and was.as a whole ninety eight 65/100 per cent.. soluble in carbon-bisulfid and eighty two 95/100 per cent. \e soluble in naphtha obtained frem Kansas crude oil and con- sisting of hydrocarbons : with specific gravities ranging from 0.7526 to 0.7692. - If so desired, the pressure distillation can be arrested — . before the material in the still attains the specific gravity mentioned. Also, if,so desired, further distillation can be carried on under atmospheric or other reduced ‘pressure, — with or without introduction of free ‘superheated steam or | _ other aeriform fluid (including atmospheric air, — = be desired to modify the composition by oxidation). obtained fromthe high pressure still the asphaltic ner ' will ordinarily be soft and sticky even at zero F., on account. _ of the conduct of the distillation only while it can be carried on with safety ; but by. reduction (partial evaporation) under atmospheric presgure at appropriately high temper- . ature and with introduction of superheated steam: inte-the .. melted material, it can be brought to such condition that _ \. when cool a lump of the samé can be molded and drawn out - _ into threads. Distillate obtained from such reduction can ~. be.added to heavy paraffin distillate to. be distilled under ° the high pressure mentioned ; it ¢ould be used as gas oil or — fuel oil; or it could be otherwise disposed of, as preferred. as a solution of the asphaltic material as: obtained ; from. - =. the high pressure. still in the naphtha mentioned (in. such _. proportions as to give the desired fluidity for application) constitutes an excellént varnish or protective coating. ‘The - material can be.so dissolved and used after reduction (par-. tial evaporation) and oxidation (either or both). It: can | be: used also (alone or in connection with asphaltum and.” with or without reduction: and oxidation, either_or both, as © -. May be,.necessary or expedient) ‘for paving and. roofing _. purposes and for other purposes i which asphaltam, has Z __ been applied. - ; While it is considered best. to vt the pressure “gtill: _ . with an oil whi¢gh represents an entire range of hydrocar- *. ~ bons from and |ineluding some with. the intermediate. vis- neities men ionie¢ t te end onee® nese nications from SoA * 4526 | | ~ heavy paraffin slop, dander" less of sai Se iipdtcchctens aa 7 . be-collected separately, if so prefe ‘and only the re- mainder of them charged i wh 7 - [fel. 1201] It is also permissible within the limits-of-the— ee invention as expressed in one or more claims be thake arti- ficial mixtures of hydrocarbons with the inte rifediate vis- cosities and those with viscosities a: al to lubricating oils — of (either or both) medium. and -heavy grades, the words ‘‘artificial mixtures’’ being used in‘oppgsition to a natural - ‘mixture of said kinds of hydrocarbons such as exist, for example, in heavy paraffin distillate obtained as aforesaid. _ Also oil composed of or containing hydrocarbons with the _ _ intermediate viscosities‘ mentioned can bé ‘enriched with paraffin wax or an appropriate substitute artificially, or pie ' eollecting a distillate containing paraffin wax. , . Net further within the limits of the invention, oil contain- . ing liquid hydrocarbons with viscosities normal\ to medium and heavy lubricating oils (either or both) and ail contain- ing hydrocarbons with the -intermediate viscosities men- tioned | be distilled separately under pressure and. the resulting products can then be mixed. In this -way burning ~ oil (kerdsene) from distilling oil of the latter kind under “pressure can. be impraved by the better quality of that from : distilling oil of the former kind. I have obtained larger _._ yields, however, both of naphtha. and of burning ‘oil; (ker- -osene) from distilling mixtures of (1). hydrocarbons -with. . viscosities normal to heavy lubricating oils arid:(2) liydro- ‘earbons with the intermediate viseosities-mentionéd than ~ from distilling like volumes of said two kinds of liquid hydrocarbons separately ; ; and,I believe that the same prin-- . ciple would hold true in respect to mixtures containing 3 “hydrocarbons with viscosities normal to medium lubricat- _ ing oils. It is also my belief’ that better results are attain- able*by distilling oil in which two or more of said three _ kinds of liquid hydrocarbons are naturally present than by - -separating such hydrocarbons and then forming a mixture | ‘artificially of them in their original proportions. he In making heavy paraffin distillate a certain amount of ; _ decomposition is considered necessary in order to form _ erystallizable paraffin wax. .It is provoked by introducing little or no inert. orm finid (like superheated steam) “ into = still and = ecoling: the evelved a ——— . x : wt PEAS r : . - > : ae? Sj form-a co condensate which i is returned to the oil in distil. lation. The cracking customary in making heavy paraffin e distillate is considered advantageous where sych distillate is to be subjected to pressure distillation, for one reason be- | : - eause it removes from the distillate certain coke forming elements ; and, if preferred, it can be carried furth«r in pre- — paring distillate for subsequent pressure distillation than is customary in preparing heavy paraffin distillate. On the other hand, it néed not necessarily be carriéd to this extent or to any avoidable extent within the limits of the invention as essed in some at least of the claims. Aeriform " fluid,/such as superheated steam, could, for example, be introduced into crude petroleum in preparing a distillate ~ to be itself distilled i superatmospheric pressure. : ‘In the pressure distillation it is considered best, as men- _ ~ ‘tioned herein above, to\use about 75 pounds to the square - inch above atmospheric pressure. Above this pressure the yields of naphtha and burning oil have not been found by me to increase (rather ‘the reverse) ¥ while, of course, the danger increases with the \pressure. Below 75 ‘pounds pressure I have found the yields to fall off gradually with ‘the diminution of pressure; sy that under 30 pounds the yield of naphtha has’ been about three-fifths and under 20 pounds less than half of the yield under 75 ra while . the. yield of burning oil (kérosené) under has - been about four-fifths and under 20 pounds less thas three- - fourths of the yield under 75 pounds. In order that, in a _ run under 30 pounds, the temperatuags of the oil in distilla- ~* tion may not be as high as those at which the vapor tension of the undecomposed oil is estimated to-equal the still pres- sure, said temperatures should not be so much as about 73° F. above the temperatures attained at corresponding pe- . Tiods in a parallel run under’ ‘atmospheric pressure. In runs under a pressure other than 30 pounds and 75 pounds, -. the temperatures of the oil. in distillation should be within a corresponding maximum above the so attained temper- atures in order that they may be less than those at which. the vapor tension of the undecomposed il is estimated to - equal the still pressure. ‘The vapor tensions of benzene | -(C.H.) are known for a wide range of temperatures. Such . tension amounts to 30 pounds superatmospheric at about . 73° F, above the boiling point, to wit, at abont 250° F., the ‘boiling: ‘point = being.about 177° F. | oe we ies The ciatiction of the invention, or of. L appliaabie por- a tions thereof, to petroleum not of a characer to yield par- affin wax and to hydrocarbon oils.other than petroleum will s : be sufficiently evident from the preceding - description, . There may well be petroleum which does not yield parafin = wax, but which does yield distillate. composed of liquid ae hydrocarbons divisible by their respective viscosities into: ~ the three kinds mentionéd; and there msy well be petro- -. leum. which does not: yield distillate having hydrocarbons . .80 divisible; but all crude petroleum can - be. distilled to dryness under a suitably low pressure and ‘with or without. — designedly provoked cracking in order to obtain’ distillate [fol. 1202] to be decomposed by distillation under high pressure, which distillate may contain at least the higher © boiling hydrocarbons yielded by such petroleum down to buat excluding last-runnings that would be objectionable by - _ * reason of the presence therein of still wax or like heavy matters of sticky character, but not necessarily excluding ae . desirable hydrocarbons recoverable ,by the rerunning of slops. — ~ Instead of relieving the vapors (to wit, at valve r) from the high pressure under which they are evolved i in a still:-a prior to their condensation (to wit, in condenser h), they ean be held under said pressure (to wit, by appropriate provisions, not shown, such as valves, for example, in pipes m and p) until condensed as distillate without thereby nec- © * essarily discarding all the new, useful and original features of the present invention. “Hither way the contents of the ~\ still would ‘be confined in order ‘to develop. therein the _ superatmospheric pressure. mentioned. - Working on the continuous. system (in which a more or less continuous stream of oil is supplied to.a high pressure still and a like stream of residuum withdrawn therefrom . during the progress of the distillation) is not necessarily excluded from the scope-of the present invention; although - it is considered more advantageous to work by 'the batch - system, as herein above described (in which a charge of oy | is supplied to still a and then run off to the desired extent, the still being. merenpen emptied preparatory to receiving a new charge). - The mention of wiithoades «modifications i is not intended to — others not mcptioned | in which the substance of 9h ee ene x ? . = or more of the siskaliiatian veritten claims may Be eatheaied.” : In reciting in claims following that the oil is ‘‘free from. - still wax and like heavy matters of: sticky character and ‘from elements yielding the-same or coke,”” a. practical . rather than a theoretically perfect freedom is to be under- - stood. It suffices, for example, for the oil operated upon to : be distillable in an externally heated: still of the dimensions -hereinbefore mentioned for still @ fohagead six-tenths full) - under a super-atmospheric pressure of ‘seventy five pounds _ . to the square inch at the’ aforesaid rate of two per cent..per. hour to the extent of fifty per cent. or more by volume of its — component hydrocarbons which have viscosities. above seventy seconds at 100° F. without, heating the aul bottom to redness. I claim as. my invention or. discovery: 1. The process of obtaining tvthonatbo products by de- composition “of hydrocarbons, which process consists in operating upon an oil that contains hydrocarbons with vis- cosities intermediate seventy seconds and one hundred and’ seventy seconds at 100° F.’and also liquid hydrocarbons - with higher viscosities in the relative proportions of not less than ten per cent. by volume of hydrocarbons of either kind to not exceeding ninety per cent. of hydrocarbons of the other kind and that is free from still wax and like heavy matters of sticky character and from elements yielding the” same or coke by distilling such oil at decomposing temper-— atures under.a superatmospheric pressure of not less than thirty, pounds per square inch, substantially as described. .2. The‘ process of. obtaining hydrocarbon. products. by . . decomposition of hydrocarbons, which process‘ consists in . operating upon an oil that contains paraffin wax and also ' liquid hydrocarbons with viscosities @vo great for normal constituents of burning oil (kerosene) in the relative pro- ' portions of not less than. four nor more than ninety per cent _ of paraffin wax to not more than-ninety-six per cent. nor _ less than ten per cent. of said liquid hydrocarbons and that is free from still wax and like heavy matters of sticky char- . acter and from elements yielding the same or coke by soe . tilling ‘such oil at eter sao fomperstanes under a su 284-378. ° - 4530 ‘atmospheric. nveestre of aot less than thirty pounds per ee square inch, substantially as described. - 3. The process of obtaining hydrocarbon products by de- composition of hydrocarbons, which process consists in. sub- jecting to distillation at decomposing temperatures under a superatmospheric pressure of not less than thirty pounds per square inch the heavy .paraffin distillate which is col- lectable-in an appropriate distillation of crude petroleum of a character to yield paraffin wax, which is free from ~still wax and like heavy matters of sticky character and. from elements yielding the same or coke, and which consists of hydrocarbons with vistosities ranging from. below: one hundred and seventy seconds at.100° F., to above two hun- dred and ninety-seven seconds at 100° F., upward of ten per cent. by volume of said hydrocarbons having viscosities intermediate seventy seconds ‘and one hundred and seventy seconds at 100° F., substantially as described. | 4, The process of obtaining hydrocarbon products by - decomposition of hydrocarbons, which’ process consists in distilling crude petroleum approximately to the point . ce which the distillate would no longer be free from still or like heavy matters of sticky character, collecting distil. - late up to this point from a-point so early in the run that | ‘ hydrocarbons with viscosities intermediate seventy seconds and one hundred and seventy seconds at 100° F. represent Biogen of ten per cent. by volume of the so collected distil- Jate, and subjecting the so, collected distillate to distillation ~ at decomposing temperatures under a superatmospheric ~ ~ [fol.1203], pressure. of not’ less than thirty. pounds ~ - square inch, substantially as. described. + 5. The process of obtaining hydrosarboa “products by decomposition of hydrocarbons, which process consists in | distilling crude petroleum approximately at least to dry- aw ~~ ness, collecting distillate in such complete distillation in distinct portions, one of them containing the runnings to approximately the point at which the ‘so cdllected distillate would be no longer free from still wax and like heavy mat- . ters of sticky character from a point so-early in the run. that’ hydrocarbons with viscosities intermediate seventy - seconds ands one hundred a seventy seconds at 100° P-: couroesat upward of ten per cent. by volume of the 80 col oe ected distillate, and the other of them comprising the sub- - ~ sequent runnings, distilling these subsequent runnings A approximately. at least to dryness with collection by itself . of distillate free from still wax and like heavy matters of - sticky character, mixing this latter distillate with said first — portion of distillate from the crude oil run, and subjecting - the mixed distillates ‘to. distillation at decomposing tem- _ ‘peratures under a superatmospheric pressure of not less _. than thirty fijuinss per grass inch, parte as de- scribed.. . . 6. The process of abiaising sisenschonk: produets “ de- — composition of ' hydrocarbons, which process consists in ob- taining oil that consists of a natural mixture of hydrocar- bons with viscosities intermediate seventy seconds and one. ee and seventy seconds at 100° F. and hydrocarbons with ‘higher viscosities including those above two hundred _ and ninety seven seconds at 100° F. in the relative propor- - - tions of not less than ten per cent. by volume of. hydrocar- 7 _ bons. of either kind to not exceeding ninety per cént. of hydrocarbons of the other kind and that is free from still : “wax and like heavy matters of sticky character and from elements yielding the same or coke, and distilling’ such oil - at decomposing temperatures under a superatmospheric pressure of not. less than thirty = per 2 ind inch, substantially as described. 7. The process of obtaining hydrocarbon ~--—— by “decomposition of hydrocarbons, which process consists in - _ distilling. at decomposing temperatures. under a super- ‘atmospheric pressure of not. less than thirty pounds to the square inch, hydrocarbons that have viscosities interme- J diate seventy seconds and one hundred and seventy seconds at 100° -F. and that are free from still-wax and like heavy © matters of sticky character and from elements yielding the. same or coke and in also distilling at. decomposing tempera- tures under said superatmospheric pressure liquid hydro- carbons that have viscosities above one hundred and seventy © seconds at 100° F. and that are similarly free from said mhatters and elements, and uniting hydrocarbons given off ' a8 vapors in such distillation from said two kinds of parent _ pene: in the relative: — of not less a the other ‘kind, exceeding ninety per cent. of product fro ‘substantially as described. 8. The process of obtaining hydrocarbon. products by ds: composition of hydrocarbons, which process consists in dis- tilling at decomposing temperatures under a superatmos- - _ pheric pressure of not less than thirty peunds to the square _jnchy paraffin wax in a form that is free from still wax and ’ like heavy matters of a sticky character and from elements yielding the same or coke and in also distilling at decom: posing temperatures under said superatmospheric pressure liquid hydrocarbons that have. Yiseosities too great for _ _ burning oil (kerosene) and that are free from still wax and. - ' like heavy matters of a sticky character and from elements ° _ yielding the same or coke, and uniting hydrocarbons given — off as vapors in such distillation from said paraffin wax and ~ said liquid hydrocarbons in the relative proportions of not . _ les’ than four nor more than ninety per cent. by volume of — product from said paraffin wax to not‘ more t doin ninety- . Six per cent. nor less than ten per cent. of product from _ said liquid hydrocarbons, substantially as described. | ten per cent. by woken of geoduct tisen as kind to not oe 2. an asphaltic material for: varnish making and other ' uses, the same being as a whole more than ninety per cent. by volume soluble. in bisulfid of carbon &nd more. than-sev-. enty five per cent. soluble in petroleum naphtha, and con- - _ sisting over fifty per cent. of hydrocarbons that are heavier than water and are of.a coherent and ductile character and that ‘are residues of -the decomposition of hydrocarbons ~~~ with viscosities intermediate seventy seconds and.one hun- - dred and seventy seconds at 100° F. and.also of liquid - hydrocarbons with higher viscosities in the relative propor- — tions of not less than ten per cent. by volume of product . — from hydrocarbons of either. kind to not exceeding ninety . percent. of product from hydrocarbons’ o the other kind, substantially as described. - - 10. An asphaltic material for varnish making and ‘other * ses, the same being as a whole more than-ninety per cent. - by volume soluble in bisulfid of ¢arbon and more than sev- enty five per cent. soluble in petroleum naphtha, and con- -— 4 ping over fifty per cent. of = that are heavier 5 than water and are of a coherent and ductile character . "and that are residues of the decomposition of paraffin’ ‘wax and also of liquid hydrocarbons with viscosities too great for normal constituents of burning oil (kerosene) in the — [fol. 1204] relative proportions of not less than four nor —§. _-; +more than ninety per cent. of product from paraffin wax to . -. not more than ninety six nor less than ten per cent. of product from said haw Lnieitericete substantially. as "described. ‘ 11. The process of distilling eksolbni or wliiek vai: carbon oil under superatmospheric pressure for obtaining ? products. by decomposition, which proces§ consists in (1) heating said petroleum or other oil in an appropriate form to temperatures sufficient to effect decomposition of the oil under a superatmospheric pressure of not less that thirty ‘pounds per square inch, when the still. contents are suitably confined, (2) candueting the evolved vapors to condensing . - means through an opening that is constantly established in ~ - normal running and is of appropriate size to keep the spe- / - gifie gravities of distillate leaving said condensing mean _ within twenty four éne thousandths of those obtained i corresponding periods in a test run in which such passing — _ vapors have formed condensate at the rate of two per cent. - oO. volumé of an original charge per hour, and (3) ontrel _ ing said heating and confining the liquid contents of the still in such manner as to maintain the oil is distillation at a de- composing temperature and under a pressure of evolved vapors which is above a minimum within the preasurp: .men- _ tioned, substantially as described. | cites “The process of distilling petrolenm 4538". Oo | __top to the atmosphere as to effect a partial condensation of — the vapors in said space, (3) protecting said vapors against «— .- excessive cooling due to enlargement of said space by‘dim- _. inution in volume of the oil in distillation as well as against superheating above’ the contemporaneous temperatures ‘of: _ said oil, (4) returning condensate formed by said cooling to the oil in distillation, and (5) conducting residrfal vapors - away through a throttling device for condensation under reduced pressure as distillate, substantially as described. 20. The process of distilling petroleum: or other hydro- - carbon oil under superatmospheric pressure for. obtaining ; products by decomposition, which process consists ‘in. (1). ‘Poatine said petroleum or other oil in an appropriate form .' under a ‘superatmospheric pressure of not less: than. thirty ~ pounds per square inch sufficiently to. induce decomposi- tion. of component hydrocarbons, . (2) effecting, said de- composition at gradually increasing temperatures under . an at least approximately uniform pressure, (3) preserv- - “ “ing the evolved vapors. from heating above the contempo- raneous temperatures of the oil in distillation, (4) allow- ing the vapors to escape continuously through a throttling device at a sufficiently small rate to produce: distillate - whose specific gravity. will.not be moré than twenty four ee ‘one-thdisandths (0,024), if any, greater than’ that of’ the - obtained in’a parallel distillation distillate which would b performed at. a two pe cent per hour rate; ,and:(5) con- _densing the so escaping ‘V pors as piers ‘substantially Ls as described. i 21. ‘The process. of disti ling Pires poe oy ee hydro-. | - carbon oil under superatmpspheric pressure for obtaining products by decompositigh, which. process consists in (1) lieating said petroleunf or other oil in an appropriate from under a ‘superatmospheric pressure of not less than thirty pounds per square inch sufficiently to induce decomposi-. tion of component hydrocarbons, (2). effecting said. de- composition at gradually increasing temperatures under a .. an_at least approximately uniform pressure, (3) cooling. — _ the evolved vapors under superatmospheric pressure to: below 550° >and not so low as to prevent the passage -over of hydrocarbons with boiling points intermediate 338° - F to “ae Ee (4). ieee the: 80 formed condensate to . Stor ase ‘ . ~>-under a superatmospheric pressure of not less than thirty ~_ o é 4539 | ? the oil in distillation, ( 5) allowing the uncondensed vapors to escape continuously through a throttling device at a - sufficiently small rate to. produce ‘distillate whose specific _ - gravity will not be more than. twenty four one-thousandths | (0.024), if-any, greater than that of the distillate which would be obtained in a parallel distillation performed at a _ two per-cent. per hour rate, and (6) condensing: the so es- , ecaping vapors as: distillate, substantially as desertbed. 992. The process of ‘distilling petroleum or ‘other. hydro- — carbdn oil under superatmospheric pressure for obtaining products by decomposition, which process ‘consists in (1) _ heating said petroleum or other. oil in an appropriate form pounds pér square inch ‘sufficiently to-induce-decomposi- — tion of component -hydrocarbons, .(2) effecting said'de- . . composition at gradually increasing temperatures under an at least approximately uniform pressure, (3) preserving the evolved vapors from heating above the contemporane- ous temperatures of the oil in distillation, (4) cooling the - evolved vapors under superatmospheric pressure to below — 550° F. and not so low as to prevent the passage over of hydrocarbons with boiling points intermediate 338° F. to 518° ¥., (5) returning the so formed condensate to the oil in distillation, (6) allowing the uncondensed vapors to es- - eape continuously through a throttling’-device at a suffi- ciently. small rate to produce distillate whose specific gravity will not be more than twenty four one-thousandths —— _ (0.024), if-any, greater than that of the distillate which ‘would be obtained in a -parallel distillation performed at | a two per cent. per hour rate, and (7) condensing the so. escaping vapors as distillate, substantially as described. 23, Apparatus for distilling petroleum or other hydro- carbon oil under superatmospheric pressure for obtaining _ products by decomposition; which apparatus comprises (1) a horizontal cylinder still having its upper part exposed to — _ the atmosphere for cooling and its lower part to fire gases for heating, and an intermediate portion, equal. in cubic ‘convents. to not less than half the capacity of the still, that . 18 protected both from the atmosphere and from the fire gases, said still being of practical size, strong enough to — resist all internal superatmospheric pressure of more than , 4540" thirty pounds to the square inch; adapted for hate run- ning in which the volume of oil in ‘the still diminishes\dur- ing the run, a and so constructed interiorly. that condensate formed’ in thé vaper space is returned to the oil in dis- ‘ tillation, (2)/an outside condensér provided. with a distil- ‘late draw off, (3) a vapor. pipe leading from said stil} to said outside condenser, and (4) means ‘for maintaining a [fol. 1207] superatmospheric pressure in excess of thirfy pounds per square inch in said still during septa sub: ° stantially as described, 24. Apparatus for. distilling nebroleany:: or other Keine: ey carbon oil under. superatmospheric pressure for obtaining products by decomposition, which apparatus comprises (1) a horizontal cylinder still having its upper part exposed to .. the atmosphere for cooling and its lower part to. fire gases for heating, and an intermediate portion, equal in cubic contents to not less. than half the capacity of the still, that is protected both from the atmosphere and from the fire _ gases, said still being of practical size, strong enough to resist an interna ore than, 3 thirty pounds to the square inch, adapted. for batch: run- ; ning in which the volume of oil in the still diminishes dur- . ing the run, and so constructed interiorly that condensate _ formed in the vapor space is returned to the oil in distilla- -tion, (2) an ‘outside condenser provided with a distillate raw off, (3) a vapor pipe leading. from said still to said outside condenser, and (4) a vapor throttling device located Sobciehedtone said still and said ottside condenser and ‘- adapted:to hold the vapors in said still under: supefat-° _ -.mospherie pressure in excess of thirty pounds per square ° i / a inch, while allowing said vapors to escape through said | . throttling device to said outside condenser, see, _ as described. 25. The process of. sbteining soiieentben. rboduets by decomposition of hydrocarbons which process consists in distilling crude petroleum to beyond the point: at which the stream at the condenser outlet exhibits a viscosity of one hundred and seventy seconds at 100° F., collecting in this ‘ distillation a cut of distillate, free from ‘still wax and like a _ heavy matters of sticky character, which cut begins so far. — -. below and ends so far above the point just mentioned that —~ . | oe _ neither the liydrocarbons therein with viscosities inter- c mediate seventy seconds and one hundred and seventy sec-. . onds at 100° F. nor the more viscous hydrocarbone con- stitute less than.10 per cent. by volume bof all the com- ‘ potent hydrocarbons thereof with viscositids above seventy - geconds at 100° F., and subjécting so. obtained and so con- .. ‘stituted distillate to distillation at decomposing tempéra- tures, under a superatmospheric pressure of not less than thirty pounds. per square inchy substantially ‘as described. ae testimony wheréof I affix my. signatu: re. in “presence. of two witnesses. aap -Morace-P. Chamberlain,- . Witnesses: G: W. Armstrong BE. A. Cotten. nd a 4542 | ? if ee [folk 1208] Perrrioner’s,Exureir 183 - W. A. HALL. PROCESS For THE PRODUCTION OF MOTOR SPIRIT FROM HEAVY HYDROCARBONS, ¥ APPLICATION FILED MAR, 12, 1914. 1,242,705.” 1" "Patented Oot. 9, 1917 ~ ffol. 1209] United ‘States Patent Office . ‘William Augustus Hall, 6f New York, My Process for the Production of’ Motor: ‘Spirit from Heavy ‘ Hydrocarbons ° 1,242,795. _ Specification of Letters Patent. Patented Oct. an \ ome tS ae | Applidation filed March 12, 1914. Serial No. 824, 194 oe __.Po'all whom if may concern: Le . Be it known that I, “William Augustus Hall, a citizen OF ca }. -the’ United States of America, and residing at New York ” City; New-York, United States of America, quanta: cee “a certain new and useful Improvement in Processes for the Production of: Motor-Spirit from ‘Heavy Hydrocarbons, of which the following is a, specification. This invention relates to an improved process for the ‘ production of a liquid motor: fuel’ suitable for use. in the. * usual carburetors of i ternal combustion engines, from heavier and less volatile hydrocarbons. The said improved process contemplates the channel affixation of a hydrocarbon gas to vaporized, normally. liquid, chemically unsaturated hydrocarbon, the said gas and liquid having the properties hereinafter egpevtl there : being produced a fourfold effect : . First, a greatly increased volume of fuel pciduaal over ‘the volume obtained by any of the processes depending en- ° tirely upon cracking, with-which I am familiar; Second, a materially lower boiling. point than that of said unsaturated hydrocarbon, or of ordinary gasolene ob- | tained by cracking heavier oils; © — ie Third, ‘a lower. epecific. gravity than that of said un- saturated hydrocarbon, or of. ordinary gasolene obtained * by cracking heavier oils, and *. Fourth, greatly increased. fractions volatile at compara- - tively low temperatures, as compared with said. unsatu-_ “rated hydrocarbon, or with ordinary gasolene. | ; ae I process forming the subject matter of my present application is not a ‘process of hydrogenation, in the ordi- . . oo . we \ . - . . a — _nary7 meaning of that: tral, for very little free hydrogen: «=> |] “is present (either from the. cracking or from any other ° ‘souree) and, as far'as I have beén ablé to ascertain, nove" ‘is utilized in any pari of the process, and no ‘nickel or other metallic catalyst i is present in any part of the appa- ° ratus. \ My present process is, on the contrary, a process of -pro- ducing gases containing considerable amounts of con- ‘densable hydrocarbons, such as propane, butane,. pentane, - ‘and hexane and the subsequent affixation of these gases to the vapors of an. ‘unsaturated sists ies herein referred ’ to'as ‘‘liquid. base.’’ | In order to produce satisfactory results in accordarice with the present process, it is necessary that the “liquid ‘base’? and the gases should both be of the proper char- acter. The ‘‘liquid base’’ should best contain considefable quantities of unsaturated hydrocarbons, in order to make — ‘the chemical affixation of the gases take place readily. Un- der certain conditions, however, it appears that some of the gases are chemically affixed to saturated, as well as td. unsaturated bodies. The gas must. contain considerable ~ amount of hydrocarbons containing at ecid pio three. - carbon atoms and can not consist entirely, or even prin- cipally. of hydrogen and methane, if good results are to be secured. It is preferable that the gases. also contain some unsaturated hydrocarbons. _ The preferable ‘‘liquid base’? .is that volatile liquid of which the vapors exist (mixed with gases) in ‘the vaporous _ product produced by cracking a ‘relatively heavy hydrocar- bon. oil under a. pressure of (e\ g.) about 70 pounds per ‘4 “square inch and at about 600° or 650° OC. This tempera- ture-is méasured by.a pyrometer placed between the verti- , eal pipe coils in the furnace-A. ereafter I cool ‘the gases" : and vapors to a temperature of about 200° C., with or with- -' out more or less lowering of pressure. Such’ a ‘liquid _» “pase’’ can be produced i in other ways} and it is particularly . ‘characterized in that it consists essentially of normally - _ liquid hydrocarbons, whose vapors, if cooled under ‘a pres- - sure of about 70 pounds per squaré inch, with a wet gas — (having the composition above referred to), will nite .. chemically with constituents of said gas, to produce a motor — : _ fuel.. The said vaporized ‘‘liquid base’’ and gas must be - 4545 | present togethér at a temperature materially above atmos- _ pheric, for example 100 to 200° C., and under pressure, . to produce this union. ' _ ‘The motor fuel does not anpeat to consist of the ‘Viquid -base’’ with the gases dissolved therein, since the product -* can be. distilled without the loss of more than small amounts of the gaseous : ‘portions which have been affixed to. the : “liquid base.’’ If the product were solely a solution of _ the gases in the ‘‘liquid base’’, the gases would be lost if - the product were distilled. Of this ‘‘hquid base’’, the more volatile portions, especially, usually contain large amounts ‘(say 30 to 50%) of hydrocarbons of the’ ethlene series, un- - saturated hydrocarbons. - This ‘‘liquid, base’’, in the preferred ode: of execution -_ [fol. 1210] of ‘the process, is ‘made by cracking a cheap hy- | ' drocarbon, for instance, a distillate such as gas oil. A’suit- able gas oil is one having a specific gravity, of from about — 34 to, about 40° Bé. and an initial boiling’ point of from © about 80 to about.180° C. - A construction of appatatus suitable for the performance oe A of the improved process is illustrated diagrammatically i in the figure of the accompanying drawing. : Referring to the drawing, A denotes a converter in whiak the gas oil is subjected to a temperature of. about 650° C., under a ‘pressure of ‘about 70 pountis per square inch, whereby the oil is cracked and a considerable portion gasified. From the converter A the mixture of. oil vapor / .and gas is passed through siitable coolers B, B’ (cooled by a suitable fluid introduced: through pipes P) whereby the temperature of ‘the mixture is lowered to about 200° C. C, C’ denote separators in which the major part of ‘all frac- tions non-volatile at about 200° C: is removed, in the liquid state, from the remaining gases and vapors. The vapors of liquid, which aré volatile at a temperature of approxi- ~ mately 200° C., together with any mist of condensed liquid particles which may be carried along, together with the gases present, may then be conducted directly through a cooler or. condenser -D, under approximately the pressure. - of the converter, and ‘the condensate-collected in the re- ee E. or.may bé still further compressed by means of a mechaniéal compressor indicated conventionally at -F. The liquid, the rene of which sasid with: the gas to it 285—378- | be > ‘ ‘ f , Chi ate lel Yr, nae ; \ ‘ » , * ‘ 3 "the compressor is that herein relérved. to as the- ‘liquid ‘base’, Stich a liguid } is itself not a satisfactory fuel for motor: .cars., It is this liquid which unites with the gases, during the compression and. subsequent. cooling, to produce the motor fuel. ~ od In some respects this ‘‘liquid base’’ is similar. to the well known cracked hydyocarbon spirits at present pro- ‘ diced by cracking oils of higher boiling’ paints than ordi- nary gasolene, such as crude oil or solar oil which | have little or no value as‘a motor car fuel unless redistilled and . cut at a low temperature, e.g. about 150° C., at which [point “the yield is ‘very small. In a converter, I produce the vapors of such a ‘‘liquid ' base”’, but in the final condensation I obtain a product hav- _ ing a low boiling point, and a large fractign volatile at low temperatures, the\product being different from the ‘‘liquid base’’, on'account of the affixation of gases thereto. ‘The ‘liquid base” may, for example. be made by héat- ing to.a temperature of above 500° C., an oil known as ‘‘Crown Diamond paraffin oil’’, a low grade burning oil “of about .815 specific gravity. The “liquid base’’ so pro- duced is a product having a gravity of about .769 (at 15°. C.), and which has the 1,242,796.. _ C., under a pressure of about.70 pounds per square inch in. - 4552 | {fol 1214] _ United States Patent Office William Augustus Hall, of New York, N. Y. Producing Motor- Fuel 1,242, 796. Specification of Letters Patent. | Patented Oct. 9, 1917". ae Agielioction filed April 4, 1914. Serial No. 829, 634. To all whom it may concern: a “Be it known that ¥ William Augustus Hall, a citizen of the United States of America, and resident of New York, United” States of America, have invented a certain new and useful Improvement in Processes of ‘Producing Motor-Fuel, of: which the following is a specification. Sei ; This invéntion relatesto-an improved process for the pro- duction from heavy hydrocarbons of liquid fuels in the form of motor spirit suitable for use in.the usual carburetors of internal combustion engines and to the apparatus employed - in said process. ys ' T take. any. cheap Atencaen: for instance, a distillate - such as a gas oil of 40 to 44° Bé., and a boiling point of about pb gb Agee ? I subject this hydrocarbon to a témperature of about 650° a suitable coil of pipe, whereby the oil is cracked and 4 cop- ‘ siderable ‘portion gasified.. From this coil of pipe which I. _ term the ‘‘converter’’ the mixture ‘of oil vapor and gas thus - produced is passed through suitable: coolers whereby the temperature of the mixture is lowered to about 200° C. and the mixture thus codled is fractionally condensed in a suit- able separator or separators, preferably with a material reduction of pressure. The amount of pressure maintained in the separator or separators may vary considerably, a _ pressure of 20 to 25 pounds per square inch (above atmos- pheric) being suitable. The object of this step is to remove from the gases and vapors, the major portion of those frac- . tioris, of which the boiling points are too high for use in the production of: a motor fuel, for the purpose specified. . r, -’ major portion of those fractions of the mixture whigh ire ¥ | non-volatile at about 200° C., are thus: separated i in, “a — ae ch Wier sree ane storia - state, from the remaining gases and vapors, which gases and vapors, are then recompressed, at a temperature of ° p approximately 200° C., to a pressure of about 70 pounds | per square inch, by means of any suitable mechanical com- pressor, and then condensed under pressure in. the cooler. ‘I have found that if the gases and vapors produced.by cracking heavy hydrocarbons under the ‘conditions above ‘indicated and from which those fractions condensable at about 200° C. have here been separated by fractional con- densation, are maintained in contact with one another at a ' temperature say about 200° ©., and under a pressure of about 70 pounds per square inch or more and are then cooled '.- together ‘hot only are the vapors of the liquid hydrécarbons condensed but that a considerable quantity of the-easily - liquefiable gaseous hydrocarbons~aré-also. condensed and « that from the final condensed liquid these condensed gases _ - . (whatever may be the reason whether chemical or other- - wise) do not escape at ordinary temperatures. _ | Apparatus suitable for the performance of the improved process -is illustrated diagrammatically in the figure.of the =. accompanying drawing. = 22 hk RY ae Referring to said drawings, 1 denotes a cracking appa- — ' - ratus or converter, containing a coil of. pipe 2, in which the - hydrocarbon oil is subjected to a temperature of about 650° - C., and under a pressure of 70 pounds per square inch, more or-less. This temperature is meastired by a pyrometer.21, placed between the coils of pipe, st shown. © ene ta ~The heat-is supplied by means Of a burner 3, by which .. operation the oil is cracked and/4 considerable proportion . thereof is gasified.: From this converter a connection 4 leads’ + to cooling coils 5 and 6; which may: bé cooled by air or by other suitable cooling fluid blown in through the tubes 7 and , Serving as coolers whereby the temperature of the mixture - ~ . of gil vapor and gas is lowered to about 200°.C.. The mix- _ture of gases and vapors, thus cooled, and also preferably _ Teduced in pressure, and by suitably disposed valvés, -in- ~ . eluding the-valve 8, in the piping, is then fractionally con- . densed and separated in. suitable separators 10 and 11, . '* whereby those portjons of the mixture, liquid at about 200° _.C. are extracted from the vapors and gases,.in the form - of aliquid. This liquid may be drawn off through the'pipes — _ .1%and:20, provided with suitable valves and with suitable __ cooling means as illustrated. The gas and vapors pass by we. . 4554. - iy ee _ 3. ‘ " pipes 12 to a compressor 13 and are then forced through the . pipe 14, which is surrounded by a cooling fluid, such as water, thence into the recéptable 15, which is likewise water- -jacketed; and in the parts 14 and 19, a pressure forexample. - _ [fol, 1215] 70 pounds per square inch is majntained by. > means of the:compressor 13. Upon the amount of pressure - smployed in this step,,will depend, to a certain extent, the. properties of the*product. ; | In the preferred form of execution of the process, I lower the ‘pressure. considerably, so that during the first cooling _ operation, in the eoolers‘5 and 6, and in the traps 10 and 11,°- 3 . .a pressure materially below that employed in the cracking operation prevails, that is to say, the cracking: operation is _ effected at a pressure of, say about 70 Ibs. per square inch. - The pressure is then released and the gases .and .vapors cooled to about 200° G.; (or say to-about 160 or 200° C.), while at a low pressure, which may be ‘atmospheric or * slightly more, under which conditions the solid carbon, tarry © matters, any uncracked oil present, and substantially all ” products not volatile at the temperature of the cooling are condensed and séparated, after which the pressure is again raised to 70 Ibs. per square inch, or more, ‘before the final cooling and condensation. Sar ee NG ey . This;drop in pressure in the preliminary condehsation is —~. of especial value in the process, and constitutes a material improventent over the modification of the process in which °. _.. thie: pressure is held up to (or near) the pressure of tlie eracking coil. By this lowering of pressure, the operation | of removing the tarry matters.and especially the solid mat- “ter (free carbdn, etc.) is greatly accelerated, and moreover . the entire apparatus is very much simplified, and the main- tenance of a uniform temperature at the outlet of the trap. 11, and a uniform composition of ‘this material, is made | - mucheasier. & ; : i * By thus lowering the’pressure and cooling to the desired * temperature, substantially all of the free carbon and very. ifficultly volatile material separates in the first trap 10, and the material which separates in the second cooler and trap is - free from solid carbon and free from coke-like material, and © ' this second condensate (termed ‘‘light residue’) can be —— - directly employed for making a second ‘‘run”’ through the — apparatus, without filtration or other preliminary treat- gp Cie 4555 Another reason why I prefer to lower the pressure dur- ing the preliminary condensation is the following: It is well-known that the boiling point of a given liquid (and likewise the temperature at which the vapor of such liquid _ gondenses to the liquid state) is dependent upon the exist- ing pressure. Lowering the pressure lowers the boiling -, point. Moreover, by lowering the pressure during the conden- sation operation, it is possible to secure a much more accur- ate conde tion, while ¥ removing the undesirable fractions, and while leaving in some of the desirable constifuents which would be removed if the preliminary eondensation were ef- fected at or near the converter pressure. A pipe 17 Serves to lead from the upper end of thé con- denser the non-condensable portion of the gases. The cracking of oil under: pressure by heat lower than _. indicated and the ‘separation during distillation #f. the heavier fractions by fractional condensation are not in themselves.new but it is the-combination of these processes so carried out as to. produce both vapors and gases together — with the subsequent condensation under pressure of the mixed vapors of liquid hydrocarbons and theeasily lique- fiable gaseous | hydrocarbons which soumaitnten ra egsence 5 of my invention. pir ae The modification of the process in “which the pressure of mer - the gases and vapors is not lowered in the preliminary cool- ‘ ing step (separation of tarry matters) is included in. the _ claims of my copending writin # Serial No. 824,194; filed ° _ Mar. 12,1914. | | What I claim i is: 1. A process of making’ a ‘motor’ fuel which. _ compri cracking hydrocarbon. oils at. a temperature of about 600 to 650° C., under a pressure of about 70 pounds per square: -- inch, thereafter cooling the resulting gases and vapors to about 200° C., while said gases and vapors are-at a lower préssure to separate the most readily condensable portions therefrom, increasing the pressure of the remaining gases -and vapors, to a pressure of at least about 70 pounds per. , Square inch, and thereafter cooling the mixture of } gases and vapors ‘to condense the product. 2, A process of making a motor fuel ries an ‘ olf of high , “boiling points, which comprises | SEES. — oil under | a Soe pressure exceeding four atmospheres, at a temperature of not less than‘about 600° C., thereby.producing a mixture ° comprising gases and vapors of ‘both high and low boiling ‘points, thereafter lowering both the temperature and pres- -sure sufficiently to remove the fractions of higher boiling ~ points,/thereafter increasing the pressure to over four at- ..° res eres and then further lowering the temperature suffi- y to condense the: product. . A process of producing a motor fuel f rom oil distillates = aving boiling points higher than gasolene, said process ' comprising, first, cracking’ said oil, under a pressure of / ‘about 70 pow Ee | square inch, and at a temperature ma- terially above 500° ©.; second, lowering’ the temperature of _ the gases and vapers to about 200° C., while allowing the pressure to drop somewhat; third, compressing the gases - and vapors to a pressure of at least 70 pounds.per square. inch, and fourth, cooling the same. under said upsehir to. condense the motor fuel.’ _ [fol. 1216] 4.-A process of: producing. a motor fuel which : comprises cracking a hydrocarbon oil under a pressure ma-: ‘ terially above atmospheric at a temperature sufficient to form gases, and vapors of materials having. high boiling points, and unsaturated hydrocarbon vapors, then cooling _ the gases and vapors, at a pressure materially lower than. _ that used in the cracking operation, to a temperature of. 83 above 100° C., but not above about 200° C., to remove ma- - ~ terials having higher boiling points, thereafter subjecting. the — gases and vapors, at.a temperature of 100 to 200° C.,.to a pressure of-not less than about 70 pounds per . square’ Sieh and thereafter cooling the gages and vapors - to condense ‘the tor fuel. - 5. A process. of producing a ‘ote fuel hie comprises . eracking a. hydrocarbon oil under a pressuré materially — above atmospheric at a a temperature sufficiently high to con- . vert a portion of the oil\into fixed gases, and to produce _ vapors containing considerable percentages of unsaturated hydrocarbons, cooling the vapors and gases, whileunder a — pressure materially below that employed in the cracking : operation, sufficiently to pees the portions having boil- ing points above about 200° C., theregfter subjecting the re- - maining gases arid vapors, ‘ata a temperature of 100 to 200° ._ ©, to a pressure materially above that used in the said cool- . 4557 ing step, ‘and then cooling the gases sand vapors ; sufficiently to cause condensation of the motor fuel. 6. A process of making a ‘motor fuel, which comprises cracking ‘a mineral oil under high pressure, at a tempera- ture above 500° C., cooling the gases and vapors,. while at a pressure materially beléw that used in the cracking opera- tion, to a-temperature of not over about 200° C., to separate out materials having high boiling points, further compress- ‘ing the gases and vapors remaining from said cooling step, - and cooling the gases and vapors derail in said compressed ide state, to condense out the motor. fuel. | - 7. A process of making’ a’ motor fuel which comprises . eracking hydrocarbon oils at a temperature above 500° C., under a pressure of about 70 pounds per square inch, lower. ing the pressure of the resulting gases and vapors, down to a pressure not ‘greatly exceeding atmdéspheric, cooling the . gases and vapors to a temperature. below 200° C., but not materially below 100° C., to separate the most readily con- oe _ densable portions therefrom, recompressing the gases to a pressure of at least 70 pounds per square inch, and evoling the remaining gases and vapors, under said pressure. 8. A process of producing a motor fuel which comprises — - passing a current of hydrocarbon oil‘at a pressure of about ah . 70 pounds per square inch through a pressure-resisting tor-- . tuous..pipe, located in.a furnace heated ‘to approximately - 600° C.; reducing the pressure of. the, gases and vapors, : _ while cooling the same to a temperature of about.200° C., and removing the condensed materials; recompressing - the -gases and vapors while materially above ordinary atmos- pheric temperature, to a pressure of approximately. 70 ' pounds per square inch, and thereafter cooling the ganes and : vapors to condense the motor fuel. , 9.:A process of producing, from. mineral él, a liquid fuel ; suitable for ,use in internal combustion engines, consisting | _in cracking the oil under a pressure materially above atmos-.- - pherie to produce gases and vapors, expanding such gases ~ and vapors, and:cooling the same to a temperature suffici- ently low to condense out material not sufficiently volatile for use.as motor: fuel,. removing such condensed ‘material and thereafter subjecting the remaining gases and vapors, to an increase in pressure, while the gases are in a anne .: ce —iiage and vaueagaod the prodnct 80 formed. ''10, A process of producing a motor fuel which comprises cracking oil under a pressure of several atmospheres at a ‘high temperature to produce gases and vapors, releasing - the pressure of the gases and vapors produced within a short time after their production, cooling said gases and vaporé to separate such material as is-not readily volatile, mechanically compressing the. partially cooled, but still warm ‘vapors. and gases from which the fractions of high ‘ boiling points have. been separated,,cooling and condensing : ' the products resulting from said compression, while under =“ a pressure of several atmospheres. .- ) : 11. A process of producing a liquid motor fuel, which ~ - eémprises cracking an oil at a High temperature under a pressure, materially above atmospheric, to produce gases, - ~~ and vapors, réleasing the pressure of the gases and vapors ‘shortly after their production, passing the gases and vapors through a dephlegmator to remove materials of relatively: high boiling points from those of relatively low boiling | points, mechanically compressing the vapors and gases re-- - maining, and- further cooling and condensing the products. 12.-A process of producing a motor fuel which comprises — (a) passing hydrocarbon oil containing fractions having: higher boiling points than ordinary gasolene, in the form -— éf.a flowing current through a tubular retort under a pres- gure of approximately 70 pounds per square inch main- tained at a temperature of about 650° C., whereby the oil is — * . epacked and a-considerable portion is gasified, (b) there. > after lowering the pressure to approximately atmospheric, - _° jowering the temperature to approximately 200° C.,in order _ ’ [fol. 1217] to condense and separite at least a portion of the products of high boiling points, (c) recompressing the gases and vapors to a pressure of approximately 70 pounds per — square inch, while at a. temperature of approximately 200°... * ' ©,, and thereafter (d) cooling the remaining gases and va- ' pors together, to condense out the motor fuel. i - 43.-A. progess of making a motor fuel which comprises — cra a flowing current of hydrocarbon oil at par sete ae ture of about 600 to 650° C., under a pressur¢ of about 70 \ - pounds per square inch, thereafter cooling the fesulting ' gases and vapors to about 200° C., while said gases and pors are at-a lower pressure than that used in the erack- ~ >‘ peration, to separate at least a portion of the most F hype 5 tats Si . ae shy : : ; a ha i “ duct. ° ‘“ suuperatmospheric pressure, to con 45. A process of making |’. boiling points which. comp) readily condensable fractions, increasing the pressure of the remaining gases and- vapors, while still at a: temperature above normal atmospheric temperature, to a pressure of at ‘least about 70 pounds per square inch, and sa cpol- ing the mixture of gdseg and vapors to condense the pro- -. 14. A process of producing a motor fuel which comprises heating a- flowing current of hydrocarbon oil containing fractions having higher boiling points,than ordimary gaso-. lene, under ‘pressure materially aboye atmospheric, to a temperature capable of cracking the said oil with the pro- © duction.of permanent gases, lowering both the pressure and temperature of the gases and vapors thereby- produced,, ‘sufficiently to separate out fractions having boiling points too high for use in the production of a gasolene substitute, i recompressing ‘the remaining mixture of gases and vapors, ~ _ while at a temperature materially above atmospheric¢,.and ~ thereafter cooling the remaining gases and vapors under .- ontdense out the motor fuel. i) | : a motor fuel from an oil of high of said oil under a pressuré ‘exceeding four atmospherés, + ata temperature of. not less than about 600°.C., thereby — _ producing a mixture comprising gases and vapors of both high and low boiling points; thereafter lowering both the . temperature and pressure sufficiently to remove at least a © portion of the fractions of high boiling points, thereafter | . increasing the pressure in the remaining gases and vapors, . while the‘temperature of the same js shove normal atmos- _ . pheric ‘temperature, and thereafter further lowering the _— temperature sufficiently to eondense the-product. 16. A process of pronaathg a motor fuel which comprises cracking a hydrocarbon oil under pressure materially-above © _. atmospheric, at a temperature of about -500 to 650° C., to, | form permanent gases and vapors of materials having high _ boiling points, and unsaturated hydrocarbon vapors, there- - after cooling such gases and vapors while at a pressure ma- . _ terially lower than that employed in the cracking operation, °° toa temperature of not above approximately 200° C., to re- — _ move materials having high boiling points,-thereafter sub- _ jJecting the remaining gases-and vapors, while at a tempera- © _ -ture of 100°to 200° C., to a pressure of not less than about rises cracking a flowing-current. ... 4560 Oe ei a 70 side per square teoh, - thaveatier setting the gases: “and vapors to condense the motor fuel. : - from, recompressing the gases to a pres ._ pounds per square inch, and cooling the oe gene and” é ana 17. A process of producing a motor fuel suitable for use ‘ * in carbureters of internal‘combustion engines, from oil dis- tillates having boiling points higher than ordinary gasolene, ~ . said. process comprising first cracking said oil under a pres. _ sure of about 70 pounds per square inch, in the form of a ‘flowing current, at a temperature materially above 500% 6., second lowering the temperature of the gases and vapors to about 200° C:, while’ allowing the pressure to drop some-_ ‘what, third recompressing the gases and vapors to a pres-— sure of at least 70 pounds per square inch while said gases - and vapors are at a temperature materially above ordinary .. atmospheric temperature, and fourth, cooling the remaining" _ gases and vapors. under said pressure, to E sssecouued the motor .fuel. ° : (18. A process. of producing a inintot fuel which comprises - _ eracking a hydrocarbon oil-under a pressure materially: . above atmospheric, at a temperature of about 500 to 600° C.,.to convert a portion of the oil into fixed gases, and to ~ ar produes vapors containing considerable percentages of un- _ saturated hydrocarbons, cooling the vapors and gases, while | under a pressure materially below that employed in the - é cracking operation, sufficiently to separate the portions hav-. : ing boiling. points above about 200° C., thereafter subject-’. - ing the remaining warm gases and vapors, to-a pressure | 3 ~~ materialy above that used in the said cooling step, and then cooling the gases and vapors sisonaed to cause -conden- sation of the motor fuel. . 19. A process of siti a motor fuel which comprises cracking hydrocarbon oils at a temperature of 600 to 650° _-C., under‘a pressure of about 70 pounds per square inch, lowering the pressure of the resulting gases and vapors, down to a pressure not greatly exceeding atmospheric cool- ing the gases and vapors to a paver own below -200°. €. to separate the most. ‘readily condensable portions there- | vn ure of at least 70. vapors, under said pressure. 20. A process of producing a inotor fuel, which comprises - (fol. pe ~crmsen a 5 doa: oil under a pressure ma- - ~~ ee 4 6 terially above atmospheric: to pao gas anil vapor, dieeh: met ing ‘the gas. and vapor while at a pressure materially below. - '. that used in the cracking operation, sufficiently to separate the materials of high boiling points; thereafter subjecting the resulting gases and vapors while at a temperature above = atmospheric, to a pressure materially greater than that used — in said first) cooling operation, and thereafter further cool- ing the gases and vepors, under a pean of several atmos- ~ pheres. 2 ZL, A process of producing a motor fuel, whish comprises -.eracking a hydrocarbon oil under pressure materially above * atmospheric, to produce’gas and vapor, cooling the gas and’ vapor while at a pressure materially below that used in the © cracking .operation, sufficiently to separate the materials of - 2 high boiling points; thereafter subjecting the resulting. "> gases and vapors while at a temperature above ordinary at- ~mospheric temperature, to a pressure of not less than 70 ‘ pounds per square inch, and thereafter cooling the gases _ and vapors under. a pressure, of several atmospheres. 22." A process of making a motor fuel, which comprises cracking a mineral oil under high pressure, at a temperature above 500° €., cooling the gases and vapors, while at.a pres: - - sure materially below that used in the cracking operation, to a temperature of not over 200° C., to separate-out ma- ee _ terials having high boiling points, further compressing the gases and vapors remaining from said cooling step while still in a heated condition, and cooling. the gases and Vapors .~ - while in said ‘compressed state, to condense out the motor | fuel. . 23. ‘A process of prodecing’ a re fuel — hydrocar- bon oil consisting in cracking. said’oil under superatmos- - pherie pressure at a temperature upward of 600° C., thereby. _ - forming gases and vapor, reducing the pressure of the gases and vapor and separating by fractional condensation that — . portion of the liquid which. is non-volatile at a temperature ~ ’ of approximately 200° C., ‘recompressing the remaining hot - sure to produce a liquid substantially’ as described. 3 _ gases and vapors, and condensing them together under pres- We ~ 24, A process of. producing a motor fuel which jocntoas. : “passing a current of hydrocarbon: oil at a pressure of about 286378 hs 70 pounds per square inch eae a pressure-resisting tor- tuous pipe, l [Text truncated at 120,000 characters. The full text is on the page linked above.] --- Source: Frix Law Library, https://www.frixlaw.com/law-library/documents/brief%3Amicro_IA40386008_0009%3A08. Public record. Not legal advice.