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Aug. 16, 1938. A. ENGELSTEIN CONVERSION OF HYDRO‘C‘ARBON OILS 2,126,988 Filed Oct. 8, 1934 INVENTOR 2,126388 Patented Aug. 16, 1938 iiNi'iED STATES PATENT OFFIQE 2,126,988 CONVERSION OF HYDROGARBON OILS Alvin Engelstein, Chicago, 111., assignor to Uni versal Oil Products Company, Chicago, 111., a corporation of Delaware Application October 8, 1934, Serial No. 747,272 2 Claims. (Cl. 196—58) This invention particularly refers to an im proved process for the conversion of hydrocar bon oils which is particularly well adapted to the treatment of relatively high-boiling oils or 5 oils of relatively wide boiling range. It is one of the primary objects of the present invention to provide an improved process for the conversion of relatively high-boiling oils such as fuel oil or residual oils, generally, as well as ther cool and remove from the vapors selected high-boiling components and to heat the charg ing stock whereby its low-boiling components are subjected to vaporization and fractionated together with said vaporous conversion products, 5 returning high-boiling components of the charg ing stock remaining unvaporized by said contact with the vaporous conversion products and con densate removed from the vaporous conversion 10 oils of relatively wide boiling range such as crude petroleum, topped crude and the like, which contain an appreciable quantity of relatively high-boiling components, wherein heavy compo nents of the charging stock unsuitable for con 15 version under conditions as severe as those which give the best results for the treatment of its low-7 er boiling components are removed from the charging stock and subjected to more suitable milder conversion conditions within the same sys 20 tem. In the present invention this is accom plished in a single uni?ed system of simple form, segregation of the charging stock into selected low-boiling and high-boiling fractions being ac complished by direct contact and heat exchange 25 with vaporous conversion products of the process, prior to fractionation of the latter for the forma tion of re?ux condensate, which is returned to the heating coil of the system for further conver sion, and subsequent to partial cooling of the 30 vaporous conversion products by their indirect contact and heat exchange with said re?ux con densate. In one speci?c embodiment, the invention com prises subjecting an oil to conversion conditions 35 of elevated temperature and superatmospheric pressure in a heating coil and communicating reaction chamber, withdrawing vaporous and liquid conversion products from the reaction chamber, subjecting vaporous conversion prod 40 ucts of the process, following partial condensa tion and cooling thereof, as will be later more fully described, to fractionation for the formation of re?ux condensate comprising their insufficient ly converted components suitable for further 45 conversion in said heating coil, passing a regu lated portion or all of said re?ux condensate in indirect heat exchange with said vaporous con version products, prior to said fractionation thereof, and then supplying the reflux conden sate to the heating coil for further conversion, introducing hydrocarbon oil charging stock for the process into direct contact with said vaporous. conversion products of the process subsequent to said heat exchange with the re?ux condensate 55 and prior to said fractionation,_whereby to fur-, products by said direct contact with the charg- 10 ing stock and said indirect heat exchange with the re?ux condensate to an intermediate point in the heating coil whereby said condensate and high-boiling fractions of the charging stock are subjected to less severe conversion conditions 15 than the re?ux condensate. ' It is also Within the scope of the present in vention instead of supplying a condensate, com prising the high~boi1ing components of the vapor ous conversion products, and the high-boiling 20 fractions of the charging stock to an interme diate point in the heating coil to commingle the same, all or in part, with ‘the stream of hot con version products passing from the heating coil to the reaction chamber or to introduce the same 25 into the reaction chamber at any desired point in this zone. This provision is of particular ad vantage in case it is desired to subject said condensate to somewhat milder conversion than that obtainable by passing the same through the 30 ?nal stages of the heating coil. In case still less or substantially no conversion of the condensate is desired it may be supplied to the vaporizing chamber or commingled with the stream of prod ucts passing from the reaction chamber to the 35 vaporizing chamber, in which case a major por tion of said condensate will commingle in the vaporizing chamber with the residual liquid con version products in this zone to form the ?nal residual liquid product of the process. The accompanying diagrammatic drawing and following description thereof is included for the purpose of illustrating one speci?c form of appa ratus in which the invention may be carried out. It will be understood, of course, that the inven tion is not limited to the speci?c form of appa ratus illustrated. Referring to the drawing, heating coil I is lo cated in a furnace 2 of any suitable form which 50 supplies the required heat to the oil passing through the heating coil to subject the same to the desired conversion temperature in this zone preferably at a substantially superatmospheric pressure. Hot conversion products are dis- 55 2 2,126,988 charged from heating coil I through line 3 and valve 4 into reaction chamber 5. Chamber 5 is also preferably maintained at a substantial superatmospheric pressure which may be substantially the same or somewhat lower than that employed at the outlet from the heating coil and, although not indicated in the drawing, the reaction chamber is preferably in sulated to prevent the excessive loss of heat 10 therefrom by radiation so that the materials sup plied to this zone, and particularly their vaporous components, may be subjected to additional con version therein. Both vaporous and liquid conversion products 15 are withdrawn, in the case here illustrated, in commingled state from the lower portion of chamber 5 and are supplied through line 6 and valve ? to vaporizing chamber 8. It is, of course, also within the scope of the present invention 20 to separately remove all or a regulated portion of the vaporous conversion products from any desired point in chamber 5 above the point of removal of the liquid conversion products, in which case the vaporous products may be sup 25 plied, all or in part, to chamber 8 at any de sired point in this zone or to heat exchanger [3. vaporizing chamber 8 is preferably operated at a substantially reduced pressure relative to that employed in chamber 5 whereby further vapor ization of the liquid supplied to this zone is ac complished. Residual liquid remaining unvapor izedin chamber 8 may be Withdrawn from the lower portion thereof through line 9 and valve ill to cooling and storage or to any desired fur Vaporous products are removed from the upper portion of chamber 8 through line H and valve 12 and supplied to heat ex 35 ther treatment. changer l3 wherein they are subjected to partial cooling by indirect contact with re?ux conden 40 sate produced within the system, as will be later more fully described. The vaporous conversion products remaining uncondensed in heat exchanger l3 are directed therefrom through line I4 and valve 15 to col 45 umn 16 wherein they are subjected to additional cooling and condensation by direct contact with hydrocarbon oil charging stock for the process supplied thereto, as will be later more fully de scribed. Vaporous conversion products still re 50 maining uncondensed are removed from the up per portion of column I6, together with the com ponents of the charging stock which are vapor ized in this zone, and the commingled vaporous materials pass through line I‘! and valve l8 to 55 be subjected to fractionation in fractionator l 9. Components of the vapors supplied to fraction ator l9 boiling above the range of the desired ?nal light distillate product of the process are condensed in this zone as re?ux condensate. The 60 re?ux condensate is withdrawn from. the lower portion of fractionator 19 through line 20 and valve 2| to pump 22 by means of which it is fed through line 23, valve 24 and line 25 and may be directed, all or in part, through valve 26 in line 65 25, through heat exchanger l3, in indirect con tact with the vaporous conversion products sup plied to this zone, as previously described, the re ?ux condensate being directed thence through line 25’, valve 26’ and line 28 to heating coil l 70 for further conversion. When desired, a regu lated portion of the re?ux condensate may by pass heat exchanger 13 by means of valve 29 in line 28. ' Fractionated vapors of the desired end-boiling 75 point are removed, together with uncondensable gas produced within the process, from the upper portion of the fractionator through line 30 and valve 3| and are subjected to condensation and cooling in condenser 32. The resulting distillate and gas passes through line 33 and valve 34 to collection and separation in receiver 35. Uncon-. densable gas may be released from the receiver through line 36 and valve 37. Distillate may be withdrawn from receiver 35 through line 38 and valve 39 to storage or to any desired further treat 10 ment. When desired, a regulated portion of the distillate collected in receiver 35 may be recir culated, by well known means, not shown in the drawing, to the upper portion of fractionator 19 to. serve as a cooling and refluxing medium 15 in this zone to assist fractionation of the vapors and to maintain the desired vapor outlet tem~ perature from. the fractionator. Hydrocarbon oil charging stock for the proc ess is supplied through line 40 and valve 4| to pump 42 by means of which it is fed through line 20 43 and may be directed, all or in part, through line 44 and valve 45 to column l6 wherein it is preheated and subjected to vaporization by di rect contact with the ‘vaporous conversion prod ucts in this zone, serving to partially cool said 25 vaporous products and e?ect condensation oi their heavy components. It is also within the scope of the present invention, when desired, to direct regulated portions of the charging stock through line 46 and valve 41 to fractionator 19 30 to serve as a re?uxing and cooling medium in this zone and be thereby heated and subjected to vaporization or regulated portion of the charg the stock may, when desired, be directed from line 44 through line 48 and valve 49 into line 25 35 to commingle therein with the re?ux condensate from fractionator l9 and be subjected to further treatment therewith, in the manner already de scribed. Condensate removed from the vaporous con 40 version products in heat exchanger l3 by their indirect contact with re?ux condensate or com mingled re?ux ‘condensate and charging stock in this zone is withdrawn from the lower portion thereof through line 50 and valve 5| passing 45 thence, in the case here illustrated, through line 52 to pump 53. Condensate comprising addi tional quantities of the high-boiling components of the vaporous conversion products formed in column I6 is removed together with high-boiling 50 components of the charging stock supplied to this zone which remain unvaporized therein through line 54 and valve 55 and, in the case here illus trated, is also directed through line 52 to pump 53. The relatively heavy oils thus supplied to pump 53 are fed therefrom through line 56 and may be supplied, all or in part, through line 51 and valve 58 to a suitable intermediate point in heating coil i wherein the relatively heavy oil commingles with the stream of lower boiling oils, or the conversion products resulting therefrom, "passing through the heating coil to be subjected therewith to conversion in the remaining portion of this zone. The temperature employed in the ?nal stages of 65 heating coil I, following the introduction of said relatively high-boiling oils, may be sub stantially the same, somewhat higher, or some what lower than the temperature to which the 70 relatively low-boiling oils are heated in the pre ceding portion of the heating coil. In any case, however, the conversion conditions to which said relatively high~boiling oils are subjected in the heating coil are less severe than those to which 75 2,126,988 the relatively low-boiling oils are subjected in. this zone, due to the shorter time factor vem ployed for the relatively high-boiling oils- and to the somewhat lower pressure necessitated in the 5 ?nal stages of the heating coil, due to the fric-v tion through this zone. Preferably, although not illustrated in the drawing, the arrangement of heating coil l within furnace 2 is such thata considerable degree of independent control is ex 10 erted over the heating conditions about the ?nal stages of the heating coil, subsequent to the intro duction of said relatively high-boiling oils, rela tive to the heating conditions in the preceding portion of the coil. Means for accomplishing 15 this are now well known in the art and, for the sake of simplicity, are not here illustrated. In case it is desired to subject the relatively high-boiling oils from heat exchanger l3 and column IE to somewhat milder conversion condi 20 tions than those obtainable by introducing the same to an intermediate point in heating coil I, provision is made in the present invention for commingling the same with the stream of heated products passing from the heating coil to the re 25 action chamber, subsequent to their discharge from the heating coil, or they may be separately supplied to the reaction chamber at any desired point in this zone. Valve 59 in line 56 is illus trative of the means which may be employed for 30 introducing the relatively high-boiling oils into transfer line 3 to commingle with the stream of heated products from heating coil ! and be di rected therewith to chamber 5 and line 60 con trolled by valve Si is illustrative of means for 35 separately supplying the relatively high-boiling oils to the reaction chamber. It is also within the scope of the present inven tion to supply all or a regulated portion of the "high-boiling oils from heat exchanger l3 and 40 column IE to vaporizing chamber 8 at any desired point in this zone. This may be accomplished by ccmmingling the same with the stream of products in line 6 passing from chamber 5 to chamber 8, for example, by means of line 62 and 45 valve 63, or the relatively high-boiling oils may be separately supplied to the vaporizing cham ber at any desired point in this zone by well known means, not illustrated. In case this meth od of operation is employed, little or substantially 50 no conversion of the relatively high-boiling oils will be accomplished and their components re maining unvaporized in chamber 8 will com mingle with the residual liquid conversion prod ucts withdrawn from this zone, as previously de 55 scribed, the commingled materials forming the ' ?nal residual liquid product of the process. The preferred range of operating conditions which may be employed to accomplish the ob jects of the present invention in an apparatus 60 such as illustrated and above described may be approximately as follows: A conversion tempera ture ranging, for xarnple, from 800 to 950° F, may be employed at the outlet from the heating coil preferably with a substantial superatmo (55 spheric pressure measured at this point in the sys tem of from 100 to 500 pounds, or more, per square inch. The conversion temperature in the heating coil measured at a point just prior to the point of introduction of the relatively high 70 boiling oils, when this method of operation is employed, may range, for example, from 850 to 1000" F., or thereabouts. A substantial super atmospheric pressure which may be either sub stantially the same or somewhat lower than 75 that employed at the outlet from the heating coil 3 is utilized. in the reaction chamber and the va porizing chamber is preferably operated at a substantially reduced pressure relative to that employed in the reaction chamber ranging, for example, from 100 pounds, or thereabouts, per square inch, down to substantially atmospheric pressure. The portions of the system succeed; ing the vaporizing chamber may utilize pressures substantially the same or somewhat lower than the pressure employed in the vaporizing chamber. 10: ‘ As a speci?c example of the operation of the process of the present invention as it may be accomplished in an apparatus such as illustrated and above described, utilizing as charging stock a Kansas crude oil of about 20° A. P. I. gravity 15 containing no appreciable quantity of materials within the boiling range of gasoline, high-boiling components of the vaporous conversion products and of the charging stock, recovered, in the man ner illustrated and above no substantial quantity of low 650° F., are supplied to in the heating coil. The described, containing 20 materials boiling be an intermediate point lower boiling compo nents of the charging stock and the re?ux con densate are subjected in that portion of the heat 25 ing coil preceding the introduction of the rela tively high-boiling oils to a temperature of ap proximately 950° F. The temperature at the outlet from the heating coil is approximately 900° F. A superatmospheric pressure of approximate“ 30 ly 350 pounds per square inch is employed at the outlet from the heating coil and substantially the same pressure is utilized in the succeeding reaction chamber. The vaporizing chamber is operated at a reduced pressure of approximately 35 50 pounds per square inch which is substantially equalized in the succeeding portions of the sys tem. This operation will produce, per barrel of charging stock, approximately 48 percent of motor fuel having an antiknock value equivalent 40 to an octane number of approximately '70 and about 42 percent of premium fuel oil, the remain der being chargeable, principally, to unconden sable gas and loss. I claim as my invention: 45 1. A hydrocarbon oil conversion process which comprises heating re?ux condensate, formed as hereinafter set forth, to cracking temperature under pressure while ?owing in a restricted stream through a heating coil, subsequently sep 50 arating the resultant heated products into vapors and residue, partially condensing the vapors by indirect heat exchange with said re?ux conden sate prior to introduction of the latter to the heating coil and by direct contact with relatively 55 heavy charging oil for the process, thereby pre heating the re?ux condensate and partially dis tilling the charging oil, combining condensate formed by said indirect heat exchange with the unvaporized portion of the charging oil and in 60 troducing the resultant mixture to said coil at an intermediate point in the ?ow of the re?ux condensate therethrough, fractionating the va— pors uncondensed by said partial condensation to separate insufficiently cracked fractions there 65 of, passing such separated insu?iciently cracked fractions in indirect heat exchange with the ?rst named vapors and thence to the heating coil as said re?ux condensate, and ?nally condensing the fractionated vapors. 70 2. A hydrocarbon oil conversion process which comprises heating reflux condensate, formed as hereinafter set forth, to cracking temperature under pressure while ?owing in a restricted stream through a heating coil, subsequently sep- 75 2,126,988 arating the resultant heated products into vapors and residue, passing the vapors ?rst through an indirect heat exchange zone and then into a di rect heat exchange zone, contacting the vapors ‘ in the last-named zone with relatively heavy charging oil for the process, thereby partially distilling the charging oil and condensing heav ier portions of the vapors, fractionating the un condensed vapors from the last-named zone to 10 separate insu?iciently cracked fractions thereof, passing such separated insu?‘iciently cracked fractions in indirect heat exchange relation with the vapors in said indirect heat exchange zone and thence to the heating coil as said re?ux con densate, combining condensate and unvaporized charging oil from said heat exchange zones and introducing the resultant mixture to said coil at an intermediate point in the ?ow of the re?ux condensate therethrough, and ?nally condensing the fractionated vapors. ALVIN ENGELSTEIN.