means, not irustrated in the drawing. When coluirm 49 functions as a fractionator wherein the relatively heavy components of the vapors supplied thereto are c)ondensed, collecting as re6 flux condensate in the lower portion of this zone, said reflux condensate may be withdrawn through line 64 and valve 65 and mAy be directed, all or in pait, to storage 'or to any oi the heating elbments 6, 34 or 42 for further treatment or 11) the reflux condensa:te may be treated in any' combination of the manners described. Pressures employed within the system may range from substantiafly atmospheric to super@ atmospheric pressures as high as 2000 pounds, 7- @3 or more, per sq. in. Temperatures employed in the various heating elements may range from temperatures below th6 conversion range,'of the order to 750' F. or -less to gas-makink, temperatures of the order of 1800' F. or thereabouts. 90 Temperatures employed in the heating element to which the charging stock is supplied' may range from 7501 F. or less to 900' F. or thereabouts. Substantial super-atmospheric pressures of the order of 100 to 500 pounds per sq. in. are preferably employed in this zone. The heating element to which reflux condensiite from the fractionator of the coiiversion and coking @ystem is supplied preferably uti@lizes temperatures of the order to 900 to 10501 P. with pressures ranging i,O from 100 to 500 pounds or thereabotits per sq. in. Pressures employed in the chami@er or chambers utilized as a reaction and coking zone preferably range from 100 to 500 pounds or thereabouts per sq. in. although lower pressures down to sub25 stantially atmospheric may be employed, when desired.' Carbonization of -the coked residue is ic prefer ably effect ed at substa ntially atmos pher or relativ ely low superatmos pheric pressu re althou gh, when desire d, substa ntial superatmos - 40 pheric pressure up to 500 pounds or ihereabouts per sq. in. may be employed in the,carbonizing zone. When conversior, or reforming of the distillateformthecracking.-.,,nd coking opemtion for the production of maximum yields of high anti45 knock motor fuel is desired this material,,which serve-s as a heat carrying medium for the carbonizing' operation, is preferably subjected, in the heating plement, to temperatures of the orcier of 950 to 10501 P. under substantial super-,,I,t50 mospheric pressures ranging from 300 to 800 pounds br more per sq. in. When high yields of gas are desired the distillate may:be subjected to higher temperatures- Tan-ging, Ior example from 1000 to 1800, P. preferably under substan55. tially atmospheric or relatively low super-atmospheric pressure. As a specific example of the operation of the process of the present invention, th-e charging stock comprises a mixture of about equal parts 60 by xeight of mid-continent fuel oil of about 24' A. P. I. gravity and pulverized bituminous coal having a volatile content of approximately 38 percelit. The coal-in-oil mixture is'subjected in a heating element to a temperature of approxi.65 mately 8000 F. under a super-atmospheric pressure,of approximately 200.pounds per sq. in. Reflux condensate from the fractionator of the conversion and coking portion of the system is subjected, in a separate heating element, to a tem70 perature of about 950' F. under a super-atmospheric pressure of approximately 350 pounds per sq. in. The coking @one is operated under a pressure of approxirhately 200 pounds per sq. in., which pressure is substantially equaliz6ii in th-e 75 succeeding fractionating, condensing and corecting portions of t]@e conversioti-and ooking system. The -coke produced, during this pbxtlon of the ope ration may have a volatue- content of ap I I pro ximately 15 petcent and the distilla@te produc ed which may, foi'ex ' ample, have a@n oiad bbfl- 80 ing point of approximately 500' P., -!nay have ari anti knock value equivalent to an octane number 'of approximately 50. This portion of the operation niay yield, per barrel of -charging stock, appro ximately 170 pounds of coke, about 55 percent '85 of lig4t disiihate and approximatel 600,cubic feet of gas. When the coking zone. has become subs tantially. fllled with coke it is isolated from the cracking and coking cycle, whieh is continued.. in an alternate coking zonei bistillate produced 90 by th6 cracking and doking operation heat6d iri a separate heatind elenient to a temperature of app roximately 1000' F. Under a. super-atmosphe ric pregsure of about 800 pounds per sq. in., is thence introduced iiito the bed of coke in th-e t5 cha mber isolated from the cracking and coking cycl e. The carbonizing zone is maintained under a super-atmosphei-ic pr6ssure of'approximately 100 pounds per sq in. Vapors from this zone are subjected to fractionation and the resulting light 100 distillate, substantially corresponding in boiling range to motor fuel, is collected. By,the latter st6ps of the process the volatility of the coke may be reduced to less than 5 percent and the antiknock value bf the distillate may be increased 105 to an octane number of approximAteISr 78. The mc)tor fuel of improved antiknock value thus recovered may be eqtiivalent to approximately 82 Percent of the distillate subjected to retreatment.. It will be understo6d that the foregoing ex- 110 ample illustrates only one of th6 mariy types of operation pos@ible within the concepts of the present invention and should ' therefore not be const.rued as a limitation. We-claim as our invention: 115 1. A process for producing anti-knock mot6r fuel and coke which comprises subiocting a mixture pf hydrocarbon oil and iolid carboriaceous material to cracking conditions of temperature, and, pressure, separating the mixture into vapors 120 and a mass of coke contairiink volatiles, fractionating the vapors to for#l a gasoline distillate,. heating a ' por@ion of the gasoline to a temperature adequate to vaporize-volatiles contained In the c:oke, and then passing the thus heated gaso- 125 line through sard mass of coke. 2. In a process for the 'conversion of hydrocarboii, oils and solid @ carbonaceous niaterials wherein a mixture of said materials is continuously subjected to con,@6rsion, conditions in a 130 heating coil and thence'intr(>duced into an enlarged r6action zone wherein coke containing s and froin vola tiles deposit which' vapors are with drawn to'subsequent fractiollation to conden se the products heavier than motor fuel dis- 135 tillat e and the,final vapors condensed and ihe mot or fuel like distillate recovered, the 'unprovemen t whicb comprises isolating said reaction zone froiii the system when a substantiai body of said cok e has deposited therein While continuing the 140 - discharge of sa4d mixture fiom the heating cofl into a second enlarged reaction zone, concurrently heating portions of the recovered motor fuel distil late sufficiently, tb vapgrize v6latiles contain ed in the coke and thence passing the same 145 thro ugh the bed of coke in the isolated reaction zon e for the purpose of substantially devolatwzing the coke and improving the antiknock characte r of the motor fuel, distillate, removing the vaporous liroducts from the devolatilizing zone, 150

subjecting- the same.-.to condensation and collecting the resulting products. ,3. The process as d6fined by claiin 2 further characterized in that reflux condensate formed 5 -by said.fractionation is passed through a, second .heating coil maintained at higher temperature than the first-mentioned heating coil and thenIC 20 .25 30 35 40 4.5' 50 60 65 70 75 discharged into the first-mentioned. reaction zone during the disch rge of the heated mixture from th@6 first-mentioned heating coil into this reaction zone. ALFRED FISHER. GUSTAV EGLOFF. 85 90 95 100 105 110 120 125 135 140 130-

Patented June 19,,"1934 1 . 9 9 6 3 9 2 6 5 UNITED@@,@STATES- PATENT OFFICE 1,963,265 TREATMF,NT OF EIYDROCAP.BONS Alfred Fisher and Gustav'Egloff, Chicago, M., assignors to,Universal OR Flioducts Company, Chicago, ][U., a corporation of South Dakota APPIication December 18, 1931, Serial No. 581,838 3 Claims. (Cl. 196-56) This invention relates to the treatment of liqqid from said fractionation to independently conand solid hydrocarbonaceous materials and M' particularly refers to an improved process and apparatus for the conversion axid coking of a mixture of hydrocarbon oil and @olid bituminous or hydrocarbonaceous material accompanied by substantial devolatilization of the carbonaceous residue. Suitable charging stocks for the process of the 10 present iilvention comprises any hydrocarbon o@l rangiiig from relatively light di@tillates such. Ei@@ gasoline, kerosene, na]Rhthas, etc. to heavy residual -oils, asphalts, pitches and the like--containing appreciable quantities of solid bituminous or hydrocaibonaceous material which has been added thereto or, which the oil contains in -its natiiral state. When si)hd hydrocarbonaci@ous material such as coal or coal wastes, peat, lignite, natural or synthetic asphaltic materials and the 20 like are added to the oil they are preferably added in pulverized or cohoidal iorm in such a. manner and in such quantities that no objectionable amount of 8olid material will separate from the mixture ilnd be deposited during passage there-@ 25 of through the heating element, through which .the charging stock is fed prio ',r to its introduction-iilto the coking zone. The process is preferably operated for the production of maximum yields of light distmate 30 prodticts, such as motor fuel, of high antiknock. value, together-with the production df a carbonaceous residual product of low volatale content. H@owever, when desired, the process may be operated for the production of high yields of 35 gas at the expense or even to the exclusion of lightdistillate products. The , primary princlples of the present invention,comprise subjecting charging stock, comprising liquid and solid hydrocarbonaceous ma40 terial, and intermediate liquid products of theoperation to ct)nversion and coking, periodically isolating t he coke thus produced from thd cracking E@nd coking cycle and subjecting it to devolatilization by passing therethrough distillate pro4-5 duced by the cracking and coking operation reheated to a relatively high temperature. A more speciflc tmbbdiment of the irivention may- comi@rl@e sul@jecting charging stock comprising a mixture bydrGearbon 6il and coa I to 50 heating in a heating element, Introducing the heated materials into an enlarged coking zone,. subjecting vapors from the coking zone tofractionation, condens!ng and corecting a relatively light'distillate product resulting irom said frac55 tionatiozi, subjecting reflux condensate resulting trolled conversion conditions in a separate heating element and introducing the heated material into said coking zone, periodically isolating said coking zone from the operating cycle described 60 and accomplisliing conversion and coking of the cbarging stock and reflux condensate in an alternate coking zone, heating said relatively light distillate product resulting from the conversion and coking operation to a relatively high tem- 65 Perature in a separate heating element, introclueing the heated material into the bed of coke in said isolated coking zone, separately fractionating th6 vapors therefrom and separately condensing and collecting the light distillate prod- 70 ilct. The heating element through wliich the charging stock is passed, prior to its introduction into the coking zone, may employ relatively mild conversion conditions, or temperatures below the TS conversion ran . ge may be utilized in this ione. Tn any event -the conditigns employed in this zone preferably are sufflciently mild to.preclude the deposition of any.objectionable.quantity of solid materail in the.heating element. the pro- 80 When the process is operated for duction of niaximum yields of liglit distillate products, such as motor fuel -of high antiknock value, temperature and pressure conditions emliloyed in t I he hpating element through which distillatb from the ciacking and coking operation is passed are, preferably, not stifficiently severe to effect the production of undesirable quantities of g@as and in the preferred embodiment of the.'invention are of a nature which will effect go converson'of reforining@ of the dist!Hate for the production of maximum yields of material- 6f motor ftiel boiling range ho;ving high antflmock characterlitics. However, when the production of ll,gh y . ields of gas is desired m6re severe con- 95 @,ers4on condiiions may be employe d in this zone ind in all cases thq heated distmate is Introduced into the bed of coke at a temperature suf-. . ficient to effect substantial -devoiatilization thereof. 100 Reflux condensate Prodiiced by fractionatit)n of the vapors evolved in the devolatilizing operation may be retu'rned to any ot in part, to all the three heating,elements of tbe,system or-may be with&awn, an or in part, froin the systpm. joi I)istillate resulting from the devol.atilizing operation compilses ihe' flnal light distillate product of the system whi@n such -is produced but may,, when desired, and especially when the process is operated for the production of high 110

yields of gas, be returned to'the heating element to which distillate from the conversionand coking operation is supplied. The attached diagrainmatic drawin illusI 9 trates one specific form of apparatus embodying the principtes of the present invention and the following description of the drawing will serve to more clearly illustrate the process of the invention as it may be practiced in the @app4ratus io shown. Charging stocli for ihe system may be supplied it is fed through line 4 and valve 5 to heathig element 6. Heating element 6 is located in a 15' furnace 7 of any suitable form and the material supplied thereto is heated to the desired temperature under any, desired pressure conditions and passes therefrom through line 8, valve 9, lines IO and II and valve 12 into chamber 13. 20 Vapors from ebamber 13 pass through lines 14 and 15 and through valve 16 to fractionation ;n fractionator 17 wherein the relatively heavy components arecondensed as reflux condensate, oollecting in the lower portion of the fractionator 25 to be withdrawn therefrom to further, treatment as will be @ later rjrore fully described. Vapots from fractionator 17, comprising relatively light distillate and uncondensable gas, are withdrawn from the fractionator through l-ne 18 and valve 30 19 to be subjected to condensation and cooling in' condenser 20,, the resulting distillate and uncondensable gas frorw wliieh passes through line 21 and valve 22 to be collected in Teceiver 23. Gas ma@ be released from receiver 23 through line 35' 24 - and -valve 25 Y@hile distillate i@ withdrawn from this zone through line 26 to be subjected, all or in part, to further treatrnent, as will be later more fully described, or, when desired, a portioii of the distillate may be withdrawn. from the sys40 tem thfough line 27 and valve 28. Reflux condensate collecting witbin the lower portion of fractionator 17, as alteady des6ribed, is withdrawn therefrom through line 29 and valve 30 to pump 31, by means, of which it is fed 45 through line 32 and valve 33 to heating element 34. He@ating element 34 is located in a fifrnace 35 of any suitable form and the oil supplied thereto is subjected to conversion under independently, controlled - temperature and pres@ure cond-itions, r,o which are preferably more severe than the conditions employed in heating element Heated products from heating element 34 pass through line 36 and valve 37 into line 10, co ' mmingliiig 55 therein with the heated charging @tock'from heat-, ing element 6 and passing therewith through line '-11 and valve .12 into chambek 13. Chanibers 13 and 13' comprise alternately, operated coking and carbonizing zones, two or more of which may be utilized in the operation of the 6D process. For -example@, when chamber 13 has beconie fuled to the desired extent with coke., resulting ti7om the conversion and coking operation, it is, isolated from the conversion and coking porscribed. It will be understood that any number, of a @plurality of coking and carbonizing zones inay be utilized, for exampi6, one or more such zones may Pe utilized.for the cracking and coking operation while the coke deposited in one 8 or more previously 6perated zones i8 being dev6latilized and, another or other such zones are being cleaned and prep6,red for the coking operation. Thu's, after one or more chambers has . beerl filled to the desired extent with coke, crack8 ing, coking and carbonizing operations may be riod. After a sub@tantial deposit of coke has be6h accumulated in chamber 13,. for example, and this 9 zone has been isolated from the cracking, and cokir@g cycle, distillate withdrawn from receiver 23 through line 26, as previously described, is supplied through valve 38 to pump 39 from which it is fed through line 40 and valve 41 to heating 9@ element 42., Heating element 42 is located in a furnace 43 of ahy suitable forirl aiid the distillate supplied thereto is.heated to a relatively high temperature under any desired pressure conditions and is thence discharied, preferably with- loi out siibstantial loss of heat, throu line 44, line ,gh 45'and ialve 46 into the bed of coke in chamber 13 prefeiably being introduced into the lower portion of this zone in such a manndr as to pass upward through substantially.the entire mass of .10@ (,,oke therein, whereby substantial devolatilization of the coke is accomplished. Vapors re@ulting from the devolatilizing or carboniz'mg operation pa@ss 'from chamber 13. tbro'ugb line 14, line 47 a.nd valve - 48 t,o'fractionatioh in frac- II( tionator '49. It will be understood that when chainber 13' is being utilized as the carbonizing zone the heated distillate frohi heating element 42 passes frbm'line 44 through line 45' and valve 46, into coking chaiaer 131.and 11, vapors from this zone pass. tfiroiigh line 141, line 47' a d valve 48' into line 47 and thence to fractiona r 49. The function of fractioiiator 49 Will deppnd primarily upon the desired products. for which 12( the process is operated. When maxirnum quantities of light distillate such as motor fuel. of high antiknock value are desired, fractionator 49 may function in much the same matiner as fractionator 17, distillate and uncondensable gas 12'r being withdrawn - through line .50 and valve 51, subjected to condensation a@nd cooling in condenser 52 thereafter passing t@rough-line 53 and valve 54 to be collected in receiver 55, from whi . ch uncondensable gas may be released through line 13C 56 and valve 57 while distillate is withdrawn through line 58 and valve 59. However, when the process is opfrated for the production of high Yields of gas to the exclus@on. of light distillate products, fractionation may be sb controlled in 13B column 49 that'substanti@ Lily oni u condensable gas is withdrawn from the per@.porp ion thercof, l@a.,3sing thr I ough line 60 ard g v 6 ' through line I and valve 2 to pump 3 from which carried on siriiultaneously for an indefinite petion of the system by closing valves 12 and,16, "holder or elgewhere, as de@sire,'.Veln th@e laattaesr 65 in lines 11 and 15 reppectively" the heated mateca:se 'column 49, ma3i if desi@@,, function @as an'140 rials from he@Lt'mg ele@ments 6 and 34 being thence passed through line 1 1 1 and valve . 12' into cokilng chamber 13'. Vapors from chamber 13' thence pass through line'14' and valve 16' into line 15 70 to be subjected thereafter to the treatment already described, to which vapors from chamber 13 have been subjected. Thus the continuity of the cracking and coking operation is rnaintained while the coke -previously deposited in chamber 75 13 is subjected to devolatilization, as will be deabsorber, ab'sorber oil being i Tr6duced through fine 62 and valve 63 while the enriched absorber oiliswithdrawnfroiii t-iie lower @ortion of column 49 through line 64 and valve 65. When the liquid portion of' the ch@rging stock supplied to the 14,e, process is of such a lyature that itwill function as a suitable absorber oil, all or a portion of it maybe i.ntroduced into column 49, as deser-ibed, in which case 'the enriched absorber oil is preferably directed to heating element 6 by Well known ii5o