Патент USA US2132441код для вставки
Oct. 11, 1938. H_ ROSEN-[HAL 'l 2,13%441. EXTRACTION OF PETROLEUM FROM SOLID MATERIALS Filed Aug.Á 4,> 1934 l 4 ToPPlÑG UNIT v ` \ l 2,132,441 Patented Oct. 11, 1938 ~ UNITED STATES kPAT1.=;1\1'1‘ OFFICE 2,132,441 PETROLEUM FROM SOLID EXTRACTION OFMATERIALS ' Henry Rosenthal, New York, N. Y. yApplication August 4, 1934, Serial No. '738,405 8 Claims. (Cl. 19E-14) , gasoline as it is produced in the vapor recovery processpior portion of the petroleum refining process. My invention relates to ofa novel oilfrom oil shale the extractor proper, the solvent mixes with and .methods of extractionboiling hydrocarbons, theInoil shale, and during the operation the shale utilizing as solvent lo w are normally gaseous 'particularly those which peratures. It es and ¿QS at atmospheric pressur the tem of pe extraction to is particularly related , troleum oil from oil shale in a continuous man ner and in a process where solvent is removed from the extract as a part of the petroleum re ered as a ' ¿1,0 `ñrlíng, and where the solvent is recov portion of the petroleum reñningy process. f recovering My invention provides means ,o and in petroleum oil from oil shale in a simple oil is substantially removed, but some of the sol vent will remain within the pores of the shale. Where ra solventvhaving a low boiling point is used, separation of the solvent from the shale can easily be accomplished by applying heat to the shale after the oil has been removed. With U10 such low boiling solvent, substantially complete ` ' -recovery of the solvent from the shale may be eiiected. This separation of the solvent from `the spent shale is accomplished by converting expensive manner. Where oil shale is used as a the solvent into the vapor state. By my present 1 liquid product obtained invention, these vapors are recovered along with ' ¿1,5 source oi petroleum, the lfractionated into a number lcondensable vapors produced in the petroleum must be refined , and oil can refinery, in the vapor recovery section of the of separate products before the shale method refinery. v be used commercially. Thus, the usual empera 20 The objects of my invention, thus, are: is to subject the petroleum oil to high `t oil are vaporized 1. To provide novel apparatus for and meth of the ¿20 tures whereby portions and the vapors are recovered af ter fractionation ods of separating a solvent from the extract in the process of extracting oil from shale. as gasoline, kerosene, gas oil and similar prod ude ma ucts. -The temperatures to which the cr be either below the point terial is subjected may 25 or above the point at which pyrolytic reactions separation of the mate take place prior to the YAs a by-product of rials into commercial cuts. there is produced a gas the refining operation, 2l. To provide novel means for recovering the solvent vapors removed from the spent shale 25 after extraction. 3. To utilize the lighter fractions of petroleum such as containing hydrocarbon compounds d analogous mate reñning as an extraction medium in the re moval of shale oil and to circulate these frac tiòns substantially continuously between the ex- 30 tractor and the petroleum reñnery. Other ob-` jects of my invention are apparent from these 30 propane, butane, pentane, an be condensed rials of other series which lmay a number of ways; specifications. into a liquid under pressure in these hy My invention may best be described by refer the usual method being to ñrst absorb th which they ence to the accompanying drawing which is a 35 xed gas wi drocarbons from the n s of a high boiling pe part of this specification. In this drawing 35 are associated, by mean unds are then usually Figure l is a diagrammatic layout of one em troleum oil. These compo struum by means of bodiment of my invention. removed from the oil men separately from the fixed Figure 2 is an elevation of a preferred form »heat and are recovered been associated. of extractor for use in connection with my in- 4o gases with which theyof_ have “natural gasoline” and vention. 0 This material is a form in Referring to Figure 1, solvent is contained is usually further fractionated to remove small 2, through ell as of a fraction in tank l, and is delivered to extractor portions of ñxed gas as W minating compound. valve which propane is the predo is also theThe oil 3.shale is delivered to the4 Crusher 4, 45 Frequently in this operation a fraction is the predominating where it is reduced to proper size, which I prefer'v .45 obtained, in. which butane product of this “sta shall be such that the crushed material will fall , " compound. The principa “stabilized natural gaso through a one inch screen and will lform of bilizíng” is a bon liquid when main line” which is a hydrocar pressure, but on a half inch the oil shale passes to the screenl tained underA superatmospheric ospheric pressure. These properly graded and delivered to the conveyor it is transferred to the feed hopper 1 thatv is, thebutane thewhich extractor 2. From the hopper, the crushed “stabilized” natural fB,of by cut, the propane cut, ‘orsolvent the for removing the cut, I use as which it is asso shale oil from the rock with` natural ‘_ 55 elated, r~or I may use` the unstabilized oil shale is delivered through rotary valve 8 to the sealed inlet compartment 9 of the extractor,ì55 2 '2,132,441 from which it passes through rotary valve I0 to the extraction cylinder II. The operations within the extraction cylinder can best be explained by referring to Figure 2. The oil shaleV entering the cylinder from rotary valve I0 is passed into the rotating cylindrical compartment, I2a, by means ofthe deñector vane rotating cylindrical compartment meets a strong'solution about to be discharged from the extraction cylinder il. The rotation of the compartment I 2a carries the shale forward and upward and discharges it into rotat ing compartment i221, where the solution strength is somewhat weaker than that in compartment I2a. In a similar manner the shale is carried reaches compartment 12d, into solvent is delivered through the valve 3. The shale, leaving compartment I2dv and delivered to the compartment I2e by defiector 20 vane I3e, is substantially free from shale oil, butA including propane, butane etc. are separated from the liquid components. These gases with their condensable vapors are shown as leaving the cracking unit through the valve 35. The solution passing through Valve 26 is de livered to the tube-still 36 by the pump 31. In the tube-still 36 the solution is heated and delivered to the fractionating column 38 from which as shown a number of side cuts are re moved. As shown, a gasoline cut is removed from the top of the column, passed through the condenser 39 and delivered to the separator 40, the gasoline being withdrawn from the bottom of the separator through valve 4I and the vapors and non-condensable gases including propane and butane are Withdrawn from the separator through valve 42. ' The vapors and gases removed from the crack ing unit through the valve 35 and/or removed 4from the topping unit through the valve 42, are will be wet with solvent besides carrying amounts delivered to- theA vapor recovery unit 43. This 20 of solvent by absorption and similar means. therotary cylinder I2e the spent shale is drained may be of any well known type and therefore of its solvent and is passed by means of deflecto-r vane I3f to the compartment I 4. The spent shale with its absorbed solvent is passed4 from the com partment I4 to the conveyor I5. The conveyor I5 is provided withY a heating jacket I6, into which 30 suitable heating medium is admitted through the valve I1, and discharged through While in the conveyor I5 the spent shale is heated to the rotary valve I9, which discharges the spent 35 shale into the sealedV outlet compartment 20 45 to the stabilizer or column 46. The fixed gases', dissolved in the liquid which is delivered through 30 pipe 45, are removed through pipe 41. The stabi lized gasoline is removed from the bottom of the column and delivered to the tank 48. Pro butane vapors through valve 50, and delivered to 35 the condenser 5I, in which they are liquefied and fromrwhich the liquid is delivered to tank 52. 40 " The solvent entering through the valve 3 into I through with the necessary absorbers, compressors, stills, 25 tanks, condensers, etc.V The liquid product com prising propane, butane and pentane is With drawn from the absorption unit through the pipe pane vapors may be removed through valve 49 or where it is subjected to a vacuum applied through pipe 2l. This vacuum acts to eliminate the sol the rotary compartment I2d, passes in contact with the shale about to be discharged from the extraction cylinder. It is then delivered consecu 45 tively to rotating cylinders I2C, I2b, and I 2a in counterñow to the movement of the shale, and is then discharged from the extraction cylinder by outlet pipe 23. Again referring to Figure 1, the spent shale is 50 ' discharged from rotary valve 22, to conveyor 24, whichV delivers it to any convenient location. The solution discharged from the extractor only sufficient detail is shown to explain the op-eration in connection with this invention. The rectangle 44 represents the usual-absorption unit The propane or butane may be delivered to the solvent storage tank I by opening valve 53, or the natural gasoline may be delivered to tank I by 40 opening valve 54. » The exhauster 55 is connected on its suction side to the sealed inlet compartment 9 and re moves therefrom solvent vapors Which enter the compartment 9 through the rotary valve I0 and 45 the air which enters the compartment 9 through the rotary valve 8. I prefer that exhauster 55 be so adjusted that the pressure maintained withinY the sealed inlet compartment 9 be slight ly above the pressure of the atmosphere. The 50 'exhauster 55 compresses the gases and vapors 55 recovery unit 43. Exhauster 51 is connected on its suction side 55 with the sealed'outlet compartment 20. I prefer `the ñgure, only sufficient detail being shown to 60 fully explain my invention. The solution passing through valve 25 enters the pump 29 which delivers it to the cracking still 30 where it is subjected to conditions favor able to cause pyrolytic reaction. After passing exhauster 51 be so adjusted that it main tains Within the outlet compartment a pressure of less than half a' normal atmosphere. gases and vapors removed by exhauster 51 from the sealed outlet compartment 20 are compressed through the cracking still, the solution is delivered to the reaction chamber 3l and the dephlegmator 32, where a portion is condensed and is recircu lated through the cracking still 30 by the pump 34. The vapors from the dephlegmator 32 pass 70 into the rectification portion of the cracking unit as represented by the rectangle 33. This rectangle here represents the various fractionating col umns, condensers, storage tanks paratus making up the balance of the cracking ‘is unit, including the separator in which the gases the cracking unit and/or the topping unit. 65 Many changes may be made in the details of my invention Without departing from thespirit of my invention, and I do not limit myself to the particular forms shown. Having described my'invention so that it may 70 be readily understood by one skilled in the art, I claim: ' 1. The method of extracting oil-shale which comprises dissolving'shale-oil in a hydrocarbonî‘n; 3 2,132,441 liquid that is gaseous at normal temperatures and pressure by contacting the oil-shale with said hydrocarbon delivered and applied to» said is in the liquid ' oil shale while said hydrocarbon phase, maintaining said hydrocarbon in the liq uid phase while in contact with said oil-shale; withdrawing the solution; subjecting the solu tion,while said solution still contains- substantial amounts of the solvent, to the action of heat at such temperature that pyrolytic reactions take while said hydrocarbon is in the liquid phase, maintaining said hydrocarbon in the liquid phase while in contact with said petroleum bearing solid material; withdrawing the solution; subjecting the solution, while said solution still contains substantial amounts of the solvent, to the action of heat at such temperature that pyrolytic re actions takey place; then separating the solution into fractions, including one fraction of the char acter of the solvent used; and returning a por tion of said fraction to the dissolving step. 6. The method of extracting petroleum bear ing solid material which comprises, dissolvinga portion of the petroleum in “natural gasoline” 15 by contacting the petroleum bearing solid ma 2. The method of extracting oil-shale which terial with "natural gasoline” delivered and ap plied to said petroleum bearing solid material comprises, dissolving shale-oil in “natural gaso line” by contacting the cil-shale with “natural while maintained in the liquid phase, maintain gasoline” delivered and applied to said oil shale ing said-“natural gasoline” in the liquid phase, 20 while maintained in liquid phase, maintaining while in contact with said petroleum bearing solid said “natural gasoline” in the liquidphase while material; withdrawing the solution, then sub in contact with said oil-shale; withdrawing the jecting the solution, while it still contains a sub 10 place; then separating the solution into fractions, including one fraction of the character of the solvent used; and returning a portion of said fraction to the dissolving step. stantial amount of said solvent, to the action of heat at such temperature that pyrolytic re actions take place; then separating the solution into' fractions including one fraction analogous and returning a por-y to said “natural gasoline”; tion of said “latter” fraction to the dissolving step. '7. The method of extracting petroleum bearing 30 solid material which comprises dissolving a por 30 comprises dissolving Vshale-oil by contacting said tion of the petroleum by contacting said petro oil-shale with “butane” delivered and applied to leum bearing solid material with “butane” de said oil shale while maintained in the liquid livered and applied to said petroleum bearing 35 phase, maintaining said “butane” in the liquid solid material while maintained in the liquid phase, maintaining said “butane” in the liquid phase while in contact with said oil-shale; with phase while in contact with said petroleum bear drawing the solution; then subjecting the solu tion, while it still contains a substantial amount ing 'solid material; withdrawing the solution; then subjecting the solution, while it still con of butane, to the action of heat at such tempera tains a substantial amount of butane, to the ac 40 ture that pyrolytic reactions take place; then sep arating the solution into fractions, including one tion of heat at s-uch temperature that pyrolytic 40 fraction of "butane”; and returning a portion reactions take place; then separating the solu of said “butane” fraction to the dissolving step. tion into fractions, including one fraction of 4. The method of extracting oil-shale which “butane”; and returning a portion of said “bu 45 comprises dissolving shale-oil by contacting said tane” fraction to the dissolving step. 8. The method of extracting petroleum bearing oil-shale with “propane” delivered and applied to said oil shale while maintained in the liquid solid material which comprises dissolving a por phase, maintaining said “propane” in the liquid tion of the petroleum by contacting said petro leum bearing solid material with “propane” de phase while in contact with said oil-shale; with livered and applied to said petroleum bearing 50 drawing the solution; then subjecting the solu tion, while it still contains a substantial amount solid material While maintained in the liquid of said “propane”, to the action of heat at such phase, maintaining said “propane” in the liquid temperature that pyrolytic reactions take place; phase while in contact with said petroleum bear ing solid material; withdrawing the solution; then separating the solution into fractions in then subjecting the solution, While it still con 55 cluding one fraction of “propane”; and return ing a portion of said “propane” fraction to the tains a substantial amount of said “propane”, to the action of heat at such temperature that pyro dissolving step. 5. The mtehod of extracting petroleum bearing lytic reactions take place; then separating the solution into fractions including one fraction of solid material which comprises dissolving a por tion of the petroleum in a hydrocarbon liquid “propane”; and returning a portion of said “pro 60 that is gaseous at normal temperatures and pres pane” fraction to the dissolving step. (Si) sure by contacting the petroleum bearing solid solution, then subjecting the solution, while it still contains a substantial amount of said sol vent, to the action of heat at such temperature that pyrolytic reactions take place; then sep arating the solution into fractions including one fraction analogous to said “natural gasoline”; and returning a portion of said “latter" fraction to the dissolving step. 3. The method of extracting oil-shale which material with said hydrocarbon delivered and applied to said petroleum bearing solid material HENRY ROSENTHAL.