Патент USA US2132639код для вставки
„ "Oct.' 11', 1938. J. c. MORRELL. f 2,132,639v ' TREATMENT OF HYDROCARBON OI`LS Filed Aug. -l0, 1936v 272@ A n l F38 PgatentednOct. lll, 1938 » x 24325639’ y ‘ UNITED STATES PATENT oFFI'CEÍ* 7 " . ' 2,132,639 ' y TREATMENT oF ¿nynnocaanou oms Jacque C. Morrell,` Chicago; Ill., assigner to Uni-.1" l versal Oil Products'Cornpany, Chicago, lll., a > corporation oi’ Delawa Í (Applicacxdnaumc’lo, 193s,E semi No, 95,166` o s This is a -continuation*-in-part of myco-pend~ ing application> Serial #524,430, filed March 23, 1931. ; » ‘ ' (ci: 13s-4s) prior to their discharge from the lower portion' ,f Theinvention relates to animproved kprocess 5 for thecracking of hydrocarbon oils ofrelatively thereof. The secondary charging stock is heated to a substantially higher cracking- temperature K high-boiling characteristics to produce substanor,~ln part, to‘each'ot these zones. ‘Y’ ` ' . r`When highly heated products from the, sec~ ondary charging stock heating coil are supplied 15 10» the process. The process employs two charging stockì‘jmé of which comprises hydrocarbon oil oi'high-boil ing characteristics or, of relativelyv wide, crease the temperature *andrete of cracking'in 15 ` »the reaction chamben- In this method otoper'a- ` tion, ber :without encountering theexcessive formation anddeposition of `coke in the heating coil(y 'I'he vaporous. components yare _ thereby subjected, ' in the reaction chamber, ‘ the relative quantities of the two. ~ The process," is ‘preferably conducted, in a >the 1owervporuon ofthe _, , , L5 the coking chamber. Separate heating coils are employed for independently heating the primary ' and secondary charging _stocks each to the' de sired temperature'. preferably at a, V.substantial ~ substantial forma-lé` tionand deposition of coke inthis me and the communicating lines,` while the „q vtity sup ` pass downwardly through this `zone andare sub- .t .plied to the coking chamber is' suiiicient tore ;` Jected to appreciable duce .the residual products in this zone to coke continued cracking therein, . of the desired low volatility. - 2,182,639 2 line 8 and valve l preferably into the upper por Vaporous products are directed from the cok tion of reaction chamber I0. ing zone to a fractionator wherein their com Chamber I'II is also preferably maintained at a substantial superatmospheric pressure and, al ponents boiling above the range of the desired gasoline product of the process are condensed as reflux condensate. The vaporous products re 10 though not indícateà inthev drawing, this zone , is preferably insulated to conserve heat. heated products supplied to chamber I0 pass downwardly through substantially the entire and of good antiknock value, are subjected to condensation and the resulting distillate re length of this zone and, in the particular case here illustrated, both vaporous and liquid prod 10 ucts are withdrawn in commingled state Vfrom covered. y ‘ The reflux condensate formed by said frac tionation is, of course, the result of cracking the' ' two virgin charging stocks and I have found that this reflux condensate- contains a substantial amount, at least, of oils which, although of 15 higher boiling characteristics than the secondary the lower portion of the reaction chamber and are directed through line II and valve I2 into chamber I3. It is also within the scope of the invention, 15 although not illustrated in the drawing, to separately remove vaporous and liquid conversion products from the lower portion of chamber I0 charging stock, may be further cracked to vbet ter advantage under the relatively severe crack ing- conditions employed in the secondary charg ing stock heating coil than under the ymilder 20 cracking conditions employed for the higher and to introduce both of these materials into chamber vI3 at the same or at separate points 20' ’ in this zone boiling primary virgin charging stock. There» fore, in the present process, such components of ing, together with the secondary charging stock, 25 are segregated in the fractionatingstep from its .higher boiling components .and supplied for addi tional cracking to the secondary charging stock heating coil. so ~ or, when desired, to supply a regu lated portion or all of the vaporous products separately withdrawn from chamber IIs directly 4to fractionator I8 instead of to chamber I3. the reflux condensate as are suitable for crack y The sulting from such fractionation, preferably com prising gasoline of the desired end boiling point However, in accordance with the preferred 25 method of operation, the total vaporous and liquid conversion products from chamber II! are supplied to chamber I3 either as a single stream or as separate'streams. 30 In chamber I3 the heavy residual liquid com . I have further found that „the relatively high boiling fractions yof’ the .reflux condensate, com ponents separate from the‘vaporous components prising' its components remaining after the separation therefrom of the fractions supplied reduced to substantially dry coke, the coking operation being vaccomplished either with or without the assistance of other highly heated conversion products supplied to this zone, as will to the rseco'ndarycharging stock- heating coil, are ordinarily suitable for- further cracking under A"mi the conditions employed for the primary charg ing stock, even though they are of higher boil ing characteristics or contain a substantial quantity -of‘materi'als of higher boiling charac than the primary charging stock. Such 'V40 teristics materials are, therefore, in the present process, returned to the primary charging stock heating coil for further cracking. ¿ of the materials supplied to this zone and are be later described, and in either case being as sisted by the reduced pressure employed in cham ber I3 relative to that utilized in chamber I0. It is, of course, also wit-hin the scope of the .40 invention, when desired, to employ- two or more' coking' chambers, although only one is illustrated in the drawing, and when a plurality of coking ` It will be ‘apparent from the foregoing descrip tion of the operation, that it provides a~unifiedI process for the selective simultaneous cracking .45l ' of both light and heavy oils and the Areforming of gasoline to produce high yields of gasoline of good antiknock value and minor yields of gas 50 and good quality coke. ' I am fully aware that various steps and fea chambers is employed they preferably are a1 ternately operated, cleaned and prepared for fur 45 ther operation in ¿'order‘that the coking stage, in common with the _rest of the system, may be operated continuously. Coke produced is allowed to accumulatein the coking chamber or chambers in operation and may be removed therefrom in 50 any well known manner, not illustrated, after the coking zone is substantially filled or after its tures of the process such as the reforming of gasoline, the use of a high-pressure reaction operationv has been completed for any other chamber and reduced pressure vaporizing cham reason. ber connected in series and the production of 55 product of the process are - coke as_the residual not in themselves new in the art but the improved process of this invention depends upon the co operative relation of the various steps and fea tures of the process which cooperate in a new 60 and advantageous manner to >produce the de sired final results. The accompanying diagrammatic drawing illustrates one specific form of apparatus in which the process of the invention may be con ducted. `Referring to the drawing. primary charging stock of the n_ature previously indicated issup plied through line I and valve 2 to pump 3 by means of which it is fed through line 4 and valve 70 5 to heating coil 6. The oil is heated in this zone to the desired cracking temperature, preferably at a superatrnos’pheric pressure, by means of heat supplied from furnace 1. The heated prod ucts are discharged from heating coil 5 through 75 = . f Chamber I3 is provided with a drain-line Il 55 and valve I5 and this line may ralso serve, when desired, as a means of introducing steam, water or other suitable cooling material into the cham ber, after its operation has been completed and preferably after it has been isolated from the 60 rest of the system, ln order to hasten cooling and facilitate removal of the coke therefrom. ' Vaporous products are withdrawn from the upper portion of the coking chamber and directed through line I6 and valve I1into fractionator 65 I8, wherein their components boiling above the range of the desired final light distillate product of the process are condensed as reflux condensate. Fractionated vapors of the desired end-boiling point, consisting preferably of good antiknock gasoline and gaseous‘produ'cts of the process, are directed from the upper portion of the fraction ator through line I9 and valve 20 to cooling and condensation in condenser 2l. The resulting dis tillate and- uncondensed gases are directed 2,182,689 through line 22 and‘valve 23 to collection and 3 ing stock, ordinarily require theuse of` more se separation inreceiver 24. Dlstillate may be `with drawn from the-` receiver through line 2T and-valve vere'cracking condltionslto >produce the .maxif 28 to storage or to ‘any desired further’ treatment. _ mum yields of good quality gasoline than `a virgin Uncon 'iensed gases ‘may be released from receiver oilof similar‘boiling characteristics. k_The low 24 through line 25 yand valve 26o. When desired, boiling fractions of the reflux‘condensate sup regulated quantities of the distillate collected in plied to heating coil 484preferably are substan receiver 24 maybe recirculated by Well known tially'devoid of‘ materials 'boilingL within the means, not illustrated in` the drawing, kto the range ofthe distillate recoveredffrom receiver 24 `and. are ypreferably of higher. boiling charac-v upper‘portion of fractionator I8 to serve 'asare teristics ‘than’ the"secondary charging stock or sisting fractionation -ofthe’vaporsfand to main-v _contain ra, substantial quantity of materialsmboil tain the desired vaporjoutlet temperature there ing above the range `of the 'secondary .chargingv fluxing and cooling \ edium in'k this zone for >as-> from. c I o ,. . v , 10 stock. Y The components of the mixture of `pre-'` . Simultaneous with the operation above 'de-_' y.viously cracked and virgin _oils thus suilbliedto ' scribed, secondary- charging stock of the errar;v » nearing coil' «i` are, therefore,I “suitable for treatf 15 acter previously mentioned' is supplied through' L. ment under the samelcracking cQnditions to proj duce high yields of gasoline of good antiknock line 4I' and valve`42 to pump 43 by means of which" _' . A _’ it isfed through'line 44, Vvalve 45 and line 33> value. The higháboiling fractions ofthe reflux con to` heating coil 40. ‘ n ‘ 'o ¿ The oil passing through heating coil 40 is main# densate supplied to heating coil '6 preferablyl are 20 tained at the desired cracking temperature and substantially devoid of` any components Aboiling preferablyV at a substantial vsuperatm«.)spheric below the range of the primary charging stock pressure lfor a predetermined time,v the tempera» supplied> to heatingV coil B or within the range` ture, pressure and time Yconditions employed in this zone being regulated to materially` improve of the low-boiling reiiuxwcondensate> fractions supplied to heating coil 40 and contain yany`coin-. ponents ofthe reflux Icondensate', of higherboiling characteristics than'the' primary charging stock.^ It‘will, of course, bey understood that Withthe vert the higher boiling oils supplied to -this. 4zone " into substantial yields of'good quality gasoline._ ` fractionating methods and apparatus necessitated Heated‘products arey discharged from heating by economic considerations therer will ordinarily the antiknock value of the poor quality gasoline or gasoline fractions supplied thereto and tocon be some overlapping of the various fractions sep-h coil 4U through line i 41 and may be directed, all ' or in part, into coking‘chamber I3, -entering either " arated ‘in fractionator I8 but preferably, in the the upper portion of this zone through valve 48 present processthe components of the low~boi1ing fractions of the 'reflux condensate, which boil'r inline 41 or entering the lowerportion of thiskr within the range of the gasoline product collecting vzone through linef49 and valve `SII or being dif rected, in part, into both the upper and lower in receiver 24, do `noty exceed approximately 5 to 6' percent andthe "components 'of the high-boiling.. portions of the coking chamber. ‘ ` of they reflux‘condensate which boil' All>` or a regulated’portio'n of the highly heated y»fractions products from heating coil 48 may, when desired, within _the _range of the lower boiling fractions . be directed' from 'line 4‘I` through line 5I and supplied to heating coil V4I) are also kept' ata mini- o. mum consistent wi„hr o economic fractionating valve 52', preferably into the upper portion of re» ,action `chamber I0 and in the preferred method of methods` and means. A The preferred operatingconditions which ’mayA operation a regulated portion of the heated prod ‘ucts from coil 40 ' is thus supplied `_to ‘reaction be employed to produce the desired results in an apparatus such as illustratedand above described chamber'lû, `while the remaining portion is in troducedinto the coking,chamber."=` A `The reflux . are approximately asf follows: The 4temperature y ‘ employed at the outlet from- the nrst mentioned condensate formed in fractionator . heating coil is preferablyA of `the Order of À800 Yto f `I8 is` preferably separated, as here> illustrated, . 50 into selected relatively low-j-boiling fractions best . suited for further cracking' in heating coil 48 and the’higher boiling fractions which may be cracked to better advantage in heating coil 6. 'I'he 4high-boiling fractions of the reflux con densateare directed fromi the lower portion of fractionator I8 through line 29 and valve 30 to pump 3 I, by means of which they are fed through line 32 and valve 33 into l‘ine 4 and thence to heating coil 6. The relatively low-boiling fractions of the `re flux condensate,which preferably constitute a major portion of the total reflux formed in the fractionating step, are withdrawn from one or a plurality of suitable’intermediate points in the i5 fractionator and directed through line 34 and valve 35 to pump'36 wherefrom they are fed 950° F. and the pressure employed at this I point in . the'system may range: for example, fromMlOO to 500 pounds, or o thereabouts, per sq. in.l , Thetcmn ‘.50 perature employed at the outlet from the second « mentioned heating coil may range, for example, from 950 to 1050° F., preferably with a superat mospheric pressure at this point in the system of from 200 to 1000 pounds, or thereabouts, per-sq. in. and, as previously mentioned, the temperature and cracking conditions employed in the second mentioned heating coil `are more severe than those utilizedin the ñrst mentioned heating coil. The pressure employed in the reaction chamber pref 60 erably is substantially the same as thatemployed'> in the'vcommunicating heating coil utilizing the lowest pressure, which is usually the first men-I tioned heating coil, and the average temperature through line 31 and valve 38 into line _38 and thence to heating coil 40, together with the sec in the reaction chamber preferably is substan-v , - ondary charging stock. ` ployed at the outlet from the firstmentioned heat» It will be noted, in connection with the draw «ing and the above description thereof, that the `reflux condensate formed in fractionator I8 con tains no oil which has not been previously sub jected tocracking. Such oils, and particularly 5 those resulting from the cracking of virgin charg tially thesame or somewhat higher than that em- j ing coil. The coking chamber is preferably oper ated at a substantially reduced pressure relative to that employed in the reaction chamber and 70, may range, for example, from 150 pounds, or thereabouts, per sq..in. down to substantially at,- t mospheric pressure. The fracti0nating„condensing and collecting portions of the System prefer 2,132,689 4 ably employ superatmospheric pressures substan tially the same or somewhat lower than that em chamber and introducing the same into a reduced pressure vaporizing zone wherein .vapors are sep ployed in the cokingrzone. arated fromresidue, subjecting vaporous prod ` i "As a specific example of the operation of the Ul process of the invention as it may be lconducted in an apparatus such as illustrated and above de il) chamber, withdrawing said products from the ucts from the vaporizingzone to fractionation, whereby their components boiling above the range of the desired gasoline product of the process are scribed, the primary charging stock comprises a condensed as reflux condensate, subjecting vapors mid-continent gas oil of about 36° A. P. I. gravity, remaining unconden‘sed by said fractionation to havingan end-boiling point of approximately r120" -cooling and condensation, recovering as the re F. and this material is subjected, together with the components of the reflux condensate boiling taneously subjecting a secondary virgin charging , above appœximately 600° F., to a cracking tem oil, of lower boiling characteristics than the first mentioned charging oil and containing atleast a substantial quantity of vcomponents of poor anti perature of ‘approximately’ 930° F. at a superat mospheric pressure of ‘approximately 400 pounds per sq. in., as measured atthe outlet from the knock value boiling within the range of gasoline, to a higher cracking temperature than the first mentioned charging oil and to substantial super heating coil to which these materials are supplied. The secondary charging stock comprises . a straight-run gasoline from paraiîinic crude and is at'mospherìc pressure in a separate heating coil, whereby to materially improve the antiknock 20 value of its gasoline components, commingling highly heated products discharged from said sep-v arate heating coil with the heated products from the first mentioned heating coil and `causing the commingled materials to pass through substan-v 25 tially the entire length of the reaction chamber, subjectedin a separate heating coil, together with 20 the fractions of the reflux condensate boiling be, tween approximately 400 to 620° F., to an outlet conversion temperature of approximately 1000° F.` at a superatmospheric pressure, measured at the outlet from the heating coil, of approximately 650 pounds per sq. in. _Approximately 60 per cent of the total products from the last mentioned heating coil are supplied to the reaction chamber and the remaining 40 percent, or thereabouts, are introduced into the coking chamber, which latter 30 zone is operated at a superatmospheric pressure of approximately 50 pounds per sq. in. Substan-> tially the same pressure is employed in the frac whereby to increase the temperature and rate of cracking of the total products from the first men tioned heating coil in therreaction chamber,- sup plying to said separate heating coil components of v30 said reflux condensate which are of higher boiling - characteristics than Asaid secondary charging oil and are substantially devoid of components boil ing within the range of said gasoline product, whereby to subject the same to further cracking tionating, »condensing and collecting portionsof the system. This operation will yield, per barrel of total charging stock, approximately 75 percent of 400° F. end-point gasoline‘having an antiknock with said secondary charging oil. 2. A process such as defined in claim' 1 wherein valueïof approximately 70, by the motor method, and approximately 17 pounds of low volatile coke, the remainder being chargeable, principally, to 40 uncondensable gas. p I claim as my invention: ' ' 1 a portion of said reflux condensate is returned to the ñrst mentioned heating coil for further crack . ing. 3. A process such as ydefined in claim 1 wherein , . l 10 sulting distillate a good quality gasoline, simul , 1. A process for the pyrolytic conversion of hy drocarbonvoils which comprises heating a virgin charging oil heavier than ‘gasoline to cracking temperature at substantial superatmospheric pressure in a heating coil, introducing the result ant heated products into an enlarged reaction chamber also maintained at substantial 'superat mospheric pressure, causing both vaporous and liquid components of saidheated products to pass 50 through substantially the entire length of _said a regulated portion of said highly heated products discharged from said separate heating coil is in troduced into the vaporizing zone. f l 4. A process such as defined in claim 1 wherein 45 a portion of said reflux condensate is-returned to the first mentioned heating coil for further crack ing and wherein a regulated portion of said highly heated products discharged from said separate heating coil is introduced into the vaporizing zone. .JACQUE C. MQRRELL.