US2537999A

US2537999A - Process for obtaining valuable products from waxy hydrocarbon stocks

Info

Publication number: US2537999A
Application number: US32018A
Authority: US
Inventors: Donald A Hermanson; John L Biles
Original assignee: Socony Vacuum Oil Co Inc
Current assignee: ExxonMobil Oil Corp
Priority date: 1948-06-09
Filing date: 1948-06-09
Publication date: 1951-01-16
Anticipated expiration: 1968-01-16

Description

D. A. HERMANSON ET A1. 2,537,999 PROCESS FOR OBTAINING VALUABLE PRODUCTS an. M, i195@ FROM WAXY HYDROCARBON STOCKS 5 Sheets-Sheet l Filed June 9, 1948 INSK m. M, E951 D. A. HERMANSON ET AL 2,537,999

PROCESS FR OBTAINNG VALUABLE PRODUCTS FROM WAXY HYDROCARBON STOCKS 3 Sheets-Sheet 2 Filed June 9, 1948 INVENTOR.

Jan., "1l-1L E951 A. HERMANSON ET AL PROCESS FOR OBTAINING VALUABLE PRODUCTS FROM WAXY HYDROCARBON STOCKS 3 Sheets-Sheet 5 Filed June 9, 1948 material.

Patented Jan. 16, 1951 PROCESS FOR OBTAINING VALUABLE PRODUCTS FROM WAXY HYDROCAR- EON STOCKS Donald A. Hermanson, Plaineld, and John L.

Biles, Woodbury, N. J., assignors to Socony- Vacuum Oil Company, Incorporated, a corporation of New York Application June 9, 1948, Serial No. 32,018

16 Claims.

This invention relates to a process for preparing valuable hydrocarbon products from a wax bearing high boiling mineral oil stock. It is particularly concerned with a process for obtaining from waxy stocks a substantially deoiled wax, gasoline and other products boiling lower than the original charge stock.

The present process is broadly applicable to the problem of separating wax and/or petrolatum and the like from hydrocarbon oils in substantially oil free form. The present process is particularly directed to the deoiling of crystallizable wax present in high waxy stocks such as in Slack wax.

A process commonly employed heretofore for the deoiling of wax is the well known sweating process wherein the slack wax is chilled in pans to cause congealing of the wax after which the mass is slowly heated to effect sweating out of `is mixed with a nonviscous non-solvent while in molten state after which it is cooled to congeal the wax. 'I'hen the congealed wax is separated from the oil in non-solvent emulsion by means of a basket type centrifuge lined with a lter material. Such processes involve extensive wax recycle to obtain high yield of low oil content wax.v

It has also been customary in the prior art to employ lter aids such as diatomaceous earth in powdered form to act as an air in the dewaxing of oils by the filtration of the wax from the l liquid oil. In such a process the liquid oil from which most of the wax has been crystallized is withdrawn free of the lter aid and the waxy The process has not been found practicable as a method for deoiling waxes to obtain oil free wax. As a matter of fact, the waxy material left behind with the filter aid is generally known as Slack wax and contains substantial i amounts of oil.

In United States Patent 1,278,023", dated Sepwholly absorbed by a solid porous material such as fullers earth after which the fullers earth is chilled to eiect congealing of the sorbefd wax. The fullers earth is then treated with a suitable oil solvent whereby the liquid oil is removed leaving behind the wax within the pores of the adsorbent. The wax is subsequently separated from the solid adsorbent. This process is unsatisfactory because oi the diiiiculty in obtaining satisfactory wax yields thereby and the difficulty of removing this wax from the adsorbent pores without the use of a second solvent for the wax. All of these processes provide as products only a deoiled Wax and a foots oil fraction containing varying amounts of residual waxy material.

A major object of this invention is the provision of a process for separation of wax from oils which not only overcomes the disadvantages of the prior art processes described above but also provides a gasoline containing product instead of ioots oil.

A specific object of this invention is the provision of a novel continuous, cyclic process for the deoiling of waxy stocks and the conversion of the oil removed to gasoline containing products by means of a porous solid adsorbent material.

These and other objects of this invention Will become apparent in the course of the following discussion.

The present invention broadly comprises a process wherein the waxy stock such as slack wax is brought into intimate contact with a suitable porous particle form solid adsorbent material which is preferably catalytic in nature as to hydrocarbon cracking reactions. The temperature conditions of the contacting are controlled so that the waxy constituents of the charge stock become congealed in point of time at least substantially immediately after the initial contacting with the adsorbent whereby the waxy constituents become and remain coated on the outer surface of the adsorbent particles while the noncongealed liquid oil constituents are sorbed into the pores of the adsorbent. Thereafter the wax is removed froml the surface of the adsorbent leaving behind the adsorbent bearing in its pores the sorbed oily constituents. The adsorbent is then heated to a temperature at which the Oily constituents are cracked into lower boiling products which may be removed in the gaseous phase. The adsorbent may then be subjected to a regeneration wherein carbonaceous contaminants deposited during the cracking step are burned off by an oxygen containing gas. Thereafter rlower-.section oft tower ill.

the adsorbent may be cooled and employed again for deoiling waxy stocks.

In order to obtain the optimum yields of wax it is highly important in this process that the temperature be controlled such that the waxy constituents in the waxy stock are ina congealed or crystallized state either prior to or preferably substantially immediately after being brought into contact with the solid adsorbent particles and remain congealed at least until the step of removing the wax from the adsorbent commences. It will be readily understood by those skilled in the art that such expressions as congealed Wax constituents and non-congealed liquid'oil constituents and the like as used indescribing and claiming this invention do not necessarily mean pure oil-free wax or pure wax-free oil since theamount of wax which will congeal from a wax-oil mixture is to some extent dependent upon the temperature of the mixture. For example, if the mixture 4were vcooled to 9G F. waxy constituents Amight congeal but in the non-congea-led liquid oil there very probably will be present in non-congealed state some :material which chemically should be classified as a wax. For the purposes of describing .and claiming 'this` invention a wax which is free of voil shall be taken as meaning one in which the oil content iszero as determined by the A. S. T. M. method for determining-oil ccntentsof waxy stocks, A. lS. T. M. test number D721-43T.

The invention may be more readily Aunderstood `by reference tothe ,drawingsattached hereto in which VFigure 1 isan elevational fiow'plan, partially in section, of a` preferred form of the invention and. Figures 2 and 3 are detailed-elevational views, partially `in section, of certainportions of the system shown in ligurev 1.

Turning now-to `Figure 1 and considering the invention from-the standpoint of its operation, a

suitable waxy charge stock such Yas slack wax entering through pipe 9 is pumped by Vpump Iii Athrough heat exchanger l l wherein it is heated to Va temperature slightly above that at which the waxy constituents begin to Vcongeal. vThe heated slack wax then passes via pipe l into the upper section. ofthe elongated `vertical vessel M. The operation within vessel I4 may be more readily :understood by' reference'together with lFigure l `to Figure v2 which `showsin more vdetail theconstruction of tower It. A column of the-molten slack wax is maintained rwithin section A of the lcoating tower it. A- column of water or other suitable cooling `liquid is maintained within a This liquid should be of greaterldensity' than the slack waxrancl a non- .solvent `as to vboth wax and oil. The water vin that-portion ofthe tower it just below the slack wax column is -maintainedsat a temperature suffi- Ciently high to `avoid congealing of wax at thevinterface between .the slack wax and water columns. This isaccomplished by circulating .water through -pipe il intoand through h-eat exchanger i8 and `back into the water column via'pipe i9 just below the interface. Cold water enters the water `column via pipeZti below .the level of warm water .outletnpipe il. Particle form porous adsorbent `material which may preferably be of spherical :formfenters the tower M from supply hopper I it viaverticalpipe 2 I- at about the same temperature -as theslack wax or at asomewhat .lower temperature. Inrgeneral, the inlettemperature of the adsorbent shouldfusually be belowabout 100 F. and

preferably below about .80 F. The rate of introof the height of the outlet end of pipe 2i from nscribed hereinafter.

' tanks 33 or 38.

,adsorbent to the desirecllevel.

conical spreader 22 and by rotation of spreader 22. The spreader is rotated by means of gears 23l shaft 24 and motor lit). Upright conical bailles 25 and 2S supported by rods 2l and 2S are properly positioned below the spreader 22 in such a manner as to distribute the particles of adsorbent uniformly over the entire cross-section of the tower lll. The adsorbent particles drop downwardly through the column of slack wax and become coated on their surface with a film of slack wax. The particles then drop into the water column and the cool water acts to congeal the wax constituents on the surface of the particles. When the difference between the particle density and vcooling liquid is small, it is desirable to add some substance such as potassium oleate to the water or .other cooling liquid to lower the interfacial tension at the water-slack-wax interface. This will prevent hold up of adsorbent particles at this interface. The particles of adsorbent bearing the congealedrmaterial on the Isurface thereofesettle tothe vbottom of tower id andare picked up by thel continuous bucket elevator 2S which connects into the lower section of tower M. The buckets Glare perforatedon their bottoms so that the water may Idrain from the adsorbent in the buckets once the buckets rise above the level ofthe liquid. column in the elevator shaft. The partiallydrainedadsorbent vis discharged from elevator v29 through duct onto a movingscreen belt drainer -32 driven by motor 3d. A drainer of this typegis shown in attached Figure at "landwill be de- The separated water is withdrawn from the drainer 32 through pipe 36 to accumulator 6 i. rifhe water may -be cooled inaccumulator-:tl byfmeans of Va cooling fiuidpassing throughcoil'. Cold make up water maybeintroduced into the accumulator 6l .through pipe The water passes from accumulator El `via pipe 35, pump and pipe 2o back to `Vthecoating tower ii. The drained adsorbent materialcoated with the waxy stock is discharged from drainer 32 into conveyorl. Theadsorbent is discharged from conveyor 3l' into one of `-the sorption These tanks are several in number although only `two are shown. 'The tanks are employed inV cycle, each tank being shut ofi from the conveyor after being lled with `The `adsorbent-is permitted to stand in the sorption tank whilethe temperature is controlled by means of heat-trans- -fer tubes (not shown) ata level at .which thewax constituents of the slack wax will remain congealed. A suitable cooling fluid may be supplied to the heat transfer'tubes within each of .the tanks A3&3 via piper-ll and withdrawn via pipe42. The adsorbent is retained within the -tankor .33 until substantially all of the non-,congealed liquid oil constituents of the slack wax are sorbed from the congealed mass on the .surface'of the particles into the pores of the particles leaving `substantially only the waxy constituents coated on the outer surface ofthe adsorbent particles. The adsorbent is then withdrawn through outlets 3@ and 39 and conveyed by Ascrew conveyors :i3 and-4d intotheuppersection of the wax melting tower Aliwhich is maintained substantially filled with a column of hot water. The operation of the wax melting tank Y12,5 may be more readily understood-by reference to Figure 3 in conjunction with Figure l. In Figure Sthere is shown in greater detail the wax melting tank 45 andthe subsequent drainer 'l0 and wax separating tank 49. The adsorbent particles drop from conveyor I throughthe column of -hot waterin azigzag path provided by baflles 46 so that the Wax deposited on the surface of the particles is melted olf from the particles and is passed from the upper section of tower 45 via pipe 40 to the wax separator 49. The molten wax is withdrawn from the upper section of separator 49 via pipe 5|] and the separated water is returned via pipe |09, pump 5| and pipe 52 to the lower section of the wax melting tower 45. The water is maintained substantially above the melting point of the Wax by means of the heating coil 53 within separator 49. The adsorbent particles which still retain the liquid oil within the pores of the particles are carried from the bottom of tower 45 in a water stream via conduit 54 and discharged onto the moving screen drainer F56. The screen 65 is a continuous screen which passes over rollers II2 and H3, the roller |I3 being driven by motor II4 through belt I I5. The screen ES is of such mesh size as to permit passage of water therethrough while retaining the adsorbent particles. A pan 61 is provided to catch the water passing through the screen. This water passes via pipe B8 into accumulator 49 from which it is returned via pipe. |09, pump 5i and pipe 52 to the melting tank 45. Additional warm make up water is added to the accumulator through pipe 'I9'. The drained adsorbent material passes from the end of moving screen 55 into duct 'II by which it is delivered into a purging apparatus It@ which may be a moving screen similar to that shown in chamber 10, which screen is driven by motor IZI'. A suitable purge gas such as steam or heated flue gas may be introduced via pipe V22 and caused to jet down on the adsorbent on the moving screen so as to purge additional water from the catalyst. The purge gas may be withdrawn from the purging apparatus via pipe |23 while the water removed from the adsorbent passes via pipe I 24, pump |25 and pipe |26 to pipe 58 leading to accumulator 4Q. The purged catalyst drops through duct |21 into conveyor |28 by which it is transferred to a cracking reactor supply hopper |29. The adsorbent bearing the oily constitulents then passes downwardly through gravity feed leg |30, seal Zone IBI and pipe |32 into the reactor |33 wherein it is mixed with hot regenerated adsorbent of similar type in such proportions as to provide a mixture temperature suitable for converting the sorbent oily constituents to lower boiling gasoline products. The hot regenerated adsorbent is obtained from hopper |32I from which it flows via gravity feed leg |33 into seal zone |40 and then via pipe |39 into reactor |33. An inert gaseous blanket, for example of ue gas or steam, is maintained in seal zones 53| and |40 to prevent escape of hydrocarbon gases through feed legs |39 and |38. The converted hydrocarbon products are withdrawn in gaseous phase from the lower section of the compact adsorbent column in reactor 53 via pipe |41, and may be fractionated in conventional equipment. The spent adsorbent now substantially free of oily constituents but bearing a carbonaceous contaminant deposit, is purged free of hydrocarbon gases by means of an inert purge gas, for example steam or iiue gas, entering at |42 and is then passed from the reactor via pipe M3 to conveyor |44. The adsorbent is transferred by conveyor |44 to regenerator i415 in which it is contacted with air introduced at Mt to burn off the contaminant deposit. The combustion products are withdrawn from regenerator I 45 via pipe I4?. The temperature of the adsorbent may be controlled below a heat damaging level during` regeneration by means of a cooling uid passed.`

through heat transfer tubes (not shown) within the regenerator. The heat transfer medium may be supplied to the tubes via conduit I 48 and withdrawn therefrom via conduit |49. In general clay type adsorbents should be controlled below about 1200o F. and synthetic gel type adsorbents below about l400 F. during regeneration to prevent permanent loss in activity. The regenerated absorbent is passed from the lower end of the regenerator |45 via pipe I 5I). A portion of the hot regenerated adsorbent passes to conveyor I5I by which it is transferred to the reactor supply hopper I3?. The remaining portion of the regenerated adsorbent passes via pipe |53 to conveyor |58 by which it is transferred to the cooler-hopper H0. In hopper IIE the adsorbent is cooled to a temperature suitable for its reuse in the coating tower I4. In general, the adsorbent should be cooled to a level below about 100 F. and preferably below about F. The cooling may be accomplished by introducing a cold gas into the bed of adsorbent in the cooler via pipe |55 and passing the gas through the bed. The gas may be withdrawn from the cooler through pipe |56. The cooled adsorbent then passes via pipe 2| to the coating tower I4.

The conversion system shown is of the continuous type wherein the adsorbent, preferably a cracking catalyst, moves through the reactor and regenerator chambers as a compact column of particles. The operating conditions Within the reactor I 33 will vary depending upon the activity of the catalyst employed (if it is a catalyst) the particular characteristics of the oily constituents sorbed on the cool adsorbent charge, the reaction involved and the products desired. In general, it has been found desirable to maintain the pressures within a range varying from below atmospheric to about 200 pounds per square inch. Pressures of the order of 5 to 50 pounds per square inch gauge are preferred. The temperature for the conversion for cracking operations may vary from about 800 F. to 1100 F., temperatures of the order of 850 F. to 100()0 F. being preferred where gasoline is the desired product. Where non-condensible gases are the principal desired product somewhat higher temperatures may be employed. Theratio of contact material to hydrocarbon throughput for the reactor may vary from about 1.0 to 40 parts by weight of adsorbent per part of hydrocarbon charge. The ratio of fresh hot regenerated adsorbent introduced via pipe |39 to cooler adsorbent, bearing sorbed oily constituents, introduced via pipe |32 should be so controlled that the resulting temperature of the mixture is suitable for accomplishing the desired hydrocarbon conversion. The exact ratio used may be varied somewhat by control of the temperature of the hot regenerated adsorbent and by preheating the oil bearing adsorbent before its introduction into the reactor I 33. It has been found preferable to employ about 2 to l0 parts by weight of fresh hot regenerated adsorbent per part of the cooler adsorbent bearing the oily constituents.

In some operations it may be desirable to add additional liquid or vaporiaed hydrocarbon charge into the reactor |33 via conduit |60 to be cracked concurrently with the oily constituents on the adsorbent from hopper |29. The: mixed conversion products are withdrawn together` via conduit |4I.

While the above described arrangement for converting the oily constituents to lower boiling acerbes products represents a preferred form of this invention, the invention not considered to be limited thereto. The conversion reaction may be strongly catalytic or mostly pyrolytic depending on the nature of the par'icular adsorbent emn ployed. Moreover, the adsorbent may be heated to the conversion temperature by means other than that described above. For example, it may be heated by mixing with a hot inert heat carrying mate 1ia-l which may be later separated from the regenerated adsorbent. Also the adsorbent may be heated by means of a suitable heat exchange fluid passed either in direct or indirect heat transfer relationship with the adsorbent particles. The adsorbent may be heated by partial oxidation and burning of the oily constituents thereon. The adsorbent may pass through the reaction zone as a compact stream, a stream of suspended particles or as a fluidized bed. On the other hand the adsorbent may be charged to a suitable vessel wherein it remains in place during the heating, hydrocarbon conversion and adsorbent regeneration steps. In some operations wherein the reaction is more pyrolytic than catalytic and wherein the amount of carbonaceous contar ant deposited on the adsorbent is small, the adsorbent may be cooled and reused in the coating tower without regeneration after each reaction step. When after a number of cycles a substantial contaminant deposit has accumulated, it may then be removed by burning. .all of these and other modifications which will be apparent to those skilled in the art are considered to be within the broad scope of this invention.

The invention is also not to be considered as limited to the particular method or coating the adsorbent with waxy stock and for recovering the deoiled wax described hereinabove. In an alternative method instead of eirecting the congealing of the wax after Contact with the ad sorbent, the waxy constituents oi the charge stock may be caused to congeal at least partially so as to provide a soft pasty mass into which particles of adsorbent are pressed. rIhen ater the mass has been maintained in congealed state for sufiicient time for sorption oi the oily constituents into the pores of the particles, the wax may be melted to separate from adsorbent particles. This and other methods for coating the waxy stock on the adsorbent are shown and broadly claimed in copending application Serial Number 31,948, filed in the United States Patent Onice June 9, 1943, in which one ci the present applicants is applicant. Any ci the methods described in that application may be employed in the process of this invention.

It will be readily understood that apparatus and methods other than that shown in Figure 1 may be employed to accomplish the transfer ci materials between vessels, the adsorption step and the draining and wax melting and oil recovery steps. Moreover, the removal of wax from the surface of the adsorbent particles may be accomplished by methods other than by the melting of the wax. For example, the wax may be removed from the particles while in solid form by mechanical attrition. This latter method is particularly applicable when the wax is of brittle texture and where the adsorbent particles are spherical in form. One method for accomplishing the mechanical separation is to rotate the adsorbent particles in a closed drum for a period of time to crack oli the brittle wax. The particles of wax may then be separated from the adsorbent -particles by elutriation, i. e. suspension in a stream of gas the iiow rate of which is controlledto carry one the wax particles without entraining the adsorbent.

A wide variety of adsorbent materials may be employed in the process ci this invention. For example, bauxites, fullers earth, synthetic silica, alumina or silica and alumina gel catalysts and other materials of similar porosity. Certain porous sorptive silica glasses such as are described in United States Patent 2,106,744, issued February 1, 1938, to Hood et al. may be employed. In general, the pore size oi the adsorbent mate` rial should be adapted to eiiect rapid sorption thereinto of the oily constituents of the waxy charge stock. The adsorbent particles should be of substantial size as distinguished from powdered adsorbents. When powdered adsorbents of size less than about mesh Tyler are employed the waxy constituents tend to be sorbed into the pores along with the oily material before complete congealing of the waxy constituents can be accomplished thereby preventing the desired separation. In general, it has been found that the adsorbent particles should be broadly at least about 0.01 inch and preferably at least about 0.022 inch and less than about 0.5 inch average diameter. A preferred adsorbent is a synthetic silica-alumina gel catalyst in spherical form prepared in i manner described in U. Patent 2,384,946, issued September 18, 1945, to Milton M. Marisic.

In conducting the methods described in con` nection with Figures 1, 2 and 3, the temperature of the waxy stock brought into initial contact with the adsorbent should be only several degrees above that at which the waxy constituents will commence to congeal. The temperature of the cooling iiuid employed to cause the congealing of wax constituents and to maintain them congealed during the sorption period will. of course, vary somewhat depending on the melting point of the waxy constituents involved. For many operations a cooling water temperature of about 70 F. has been found satisfactory. The operation should be conducted so as to eiiect congealing of the waxy constituents as soon as possible after the initial contacting with the adsorbent. The waxy constituents should be congealed at least within about l0 minutes of the initial contaoting and preferably within less than one minute thereof.

The ratio of adsorbent to waxy charge stock employed will depend to some extent upon the oil sorption capacity of 'the adsorbent, the percentage of oil present in the waxy stock and other operating variables. In general, for synthetic gel catalysts the ratio should be o1 the order of 0.5 to l0 pounds of adsorbent per pound of waxy stock. In any case, suiiicient adsorbent should be employed to sorb substantially all oi the oily constituents in the waxy charge.

The length of time to be devoted to the sorption period during which non-congealed liquid constituents are sorbed into the pores of the adsorbent will vary depending upon the thiclr ness of the waxy stock coating on the adsorbent particles and upon the particular adsorbent involved and the viscosity and molecular size of the oily constituents under the sorption temperature conditions required to maintain the waxy constituents in a congealed state. In general, it has been found that with adsorbent particles of about 0.09 to 0.19 inch average diameter and having a porosity similar to a synthetic silica-alumina gel catalyst the length of the sorption period should 9 be at least about 0.1 hour and preferably from 1 to 24 hours.

In general the average thickness of the waxy stock coating around each adsorbent particle should be less than about 0.1 inch and preferably less than about 0.05 inch.

As an example of the process of this invention the production of a deoiled waxy product and of a gasoline containing product from a waxy mineral oil stock by the general method shown in Figure 1 may be considered. The waxy charge stock was a paraiiinic petroleum stock having a melting point of 116.9 F. as determined by the test procedure recommended by The American Society for Testing Materials, test number A. S. T. M. D-87-42 and an oil content of 19.2 as determined by A. S. T. M. tentative test number D-721-43T. The adsorbent employed was a syn thetic silica-alumina gel bead catalyst prepared by the method described in United States Patent 2,384,946, dated September 18, 19115. The cata lyst had a bulk density of about .'74 as determined by pouring the catalyst into a measured container and weighing. The individual particle density was about 1.15. The catalyst particle size was about 0.09 to 0.19 inch average diameter. The catalyst beads were dropped through a column of molten waxy stock one inch in depth and maintained at about 126 to 183 The weight ratio of catalyst to waxy stock charge was about 3.5 to 1. The catalyst beads bearing a coating of waxy stock then dropped through a column of cooling water maintained at about 70 F. About 0.3 to 0.5% potassium oleate was added to the Water to reduce the interfacial tension at n the water wax interface. The catalyst bearing the congealed coating of waxy stock was permitted to stand for about four hours at about 80 F. after which the wax remaining on the surface of the particles was removed by mechanical attrition. The recovered wax had a melting point of .l2-5.3 F. and an oil content of 3.2% by weight and the yield of recovered wax amounted to 58% by weight based on the waxy stock charge or d 72% by weight of the wax present in the charge as determined by A. S. T. M. test method D-721-43T. By way of a comparison the yield of wax obtained by the method described above using a minimum cooling water temperature of 70 F. amounted to 83% by weight of the yield of wax obtained by solvent deoiling the same waxy stock employing benzol-methyl ethyl ketone as the solvent at a temperature of 0 F. The wax obtained by the solvent deoiling process contained 2.4% by weight oil. The adsorbent subu stantially freed of waxy constituents contains about 12% by weight of an oily paraflinic stock somewhat similar to foots oil although containing less waxy material and may be purged substantially free of water and mixed at about 100 F. with about 2.5 to 3.0 times its weight of hot regenerated catalyst entering the reaction zone at about 1100" F. whereby it is heated to a suitable hydrocarbon conversion temperature. A heated gas oil charge entering at about 850 F. may be passed through the catalyst charge in amount controlled to provide an overall catalyst to hydrocarbon oil charge ratio of about 2 parts catalyst to one part total oil charge to the reactor. The reaction pressure is about 5 pounds per square inch gauge. Gasoline containing hydrocarbon products may be withdrawn in gaseous phase from the reactor and the spent catalyst may be separately withdrawn at about 800 F. The spent catalyst is regenerated by burning the 10 contaminant and a portion of the regenerated catalyst is cooled to about F. and recycled to the coating tower.

In another experiment conducted similarly to the one just described the sorption period was increased from 4 to 20 hours and the catalyst to waxy oil charge ratio to the coating tower was decreased from 3.5 to about 1.4. The wax yield was increased to 61% by weight of the original waxy charge stock but the oil content in the recovered wax increased to about 6.7% of the wax. The catalyst after removal of wax from its surface contained about 28% by weight of oily parafnic material. This amounted to a catalyst to oil ratio of about 3.5 to one by weight which is a satisfactory ratio without addition of extraneous oil charge or catalyst in the cracking step. Thus, the catalyst may be heated alone to about 850 F. by means of a heat exchange fluid to crack off the sorbed oily constituents.

It should be understood that the specic details of operation and of apparatus arrangement and the speciiic modifications of this invention given hereinabove are intended as exemplary and the invention is not to be construed as being limited thereto or otherwise limited except as limited by the following claims.

We claim:

l. The method of obtaining a deoiled waxy product and a gasoline containing product from a wax bearing high boiling mineral oil which comprises: subjecting the wax bearing oil to an intimate contacting with a suitable particle form solid adsorbent material of at least 0.01 inch average diameter, maintaining the temperature' during at least most of said contacting at a level at which wax constituents of said wax bearing oil are congealed beginning at a time falling within the period of prior to the initial contacting to substantially immediately after the initial contacting of the liquid with the adsorbent, whereby the congealed wax constituents remain deposited on the surface of said adsorbent and the noncongealed liquid constituents are sorbed into the pores of said adsorbent, thereafter removing the wax constituents from the surface of said adsorbent while leaving the non-congealed liquid constituents within the pores of said adsorbent, heating the adsorbent containing said liquid constituents in the absence of said removed wax constituents to a temperature at which said liquid constituents are converted to a lower boiling gasoline containing product and separating said product from the adsorbent.

2. A cyclic process for removing oily constitu ents from a waxy hydrocarbon stock which comprises: subjecting said waxy stock to an intimate contacting with a particle form solid adsorbent material made up of particles having an average diameter Within the range about 0.022 to 0.5 inch, maintaining the temperature of the waxy stock during at least most of said contacting at a level` at which waxy constituents of said stock are precipitated beginning at a time falling within the period of any time prior to the initial contacting to not more than 10 minutes after the initial contacting of the liquid with the adsorbent, whereby the non-precipitated liquid constituents are sorbed into the pores of said adsorbent while the precipitated waxy constituents remain deposited on the outer surface of the adsorbent particles, thereafter effecting removal of said precipitated waxy constituents from said adsorbent leaving the oily constituents sorbed in the pores of the adsorbent particles, heating the adsorbent in the absence ofc,v said removed waxy constituents to a temperature at which said oily constituentsl are converted to lower boiling hydrocarbon products, withdrawing said lower boiling products in the gaseous phase from the solid adsorbent, cooling the adsorbent particles and again contactingthem with waxy stock as aforesaid.

3; The method of preparing a gasoline containing yproduct and deoiled wax from a waxy mineral oil stock which comprises: subjecting said waxy stock to an intimate contacting with particle form solid adsorbent material having an average particle diameter of at least 0.01 inch, maintaining said waxy stock in contact with said adsorbent for a period of at least 0.1 hour, under conditions at which at least most of the waxy constituents in said waxy stock are congealed whereby the non-congealed liquid constituents of said waxy stock are sorbed into the pores of said adsorbent particles while the congealed waxy constituents are left deposited upon the surface o said adsorbent particles, effecting removal of the congealed waxy constituents from said adsorbent particles in a separate zone while leaving substantially all of said liquid constituents still sorbed in the particle pores, heating the adsorbent particles in the absence ofthe separated waxy constituents to a temperature suitable for conversion of said sorbed liquid constituents to a lower boiling gasoline containing product, separating the gasoline containing product in gaseous phase from the solid' adsorbent, cooling the adsorbent to a temperature suitable for contacting the waxy charge stock as aforesaid and again contacting it with a waxy charge stock.

4. A cyclic process for converting a high boilingl waxy mineral oil stock to deoiled wax and gasoline containing products which comprises: intimately contacting the waxy oil stock with a particle form solid adsorbent material suitable for use as a hydrocarbon cracking catalyst, said material'consisting principally or particles of at least 0.01 inch average diameter, substantially excluding the sorption of the waxy constituents in said mineral oil stock into the pores of said adsorbent particles by maintaining said waxy constituents in congealed form while permitting the non-congealed liquid constituents to be sorbed intothe pores of said adsorbent, and after substantially all of said liquid constituents are sorbed in the pores of said adsorbent eiiecting a separation of the adsorbent bearing said liquid constituents from said waxy constituents in a separate Zone, heating the catalyst in the absence of the separated waxy constituents to a temperature suitable for effecting conversion of said sorbed liquid constituents to lower boiling gasoline containing products, maintaining said catalyst at the suitable conversion temperature to effect said conversion with a resultant deposition of carbonaceous contaminant on said catalyst, separating the-gasoline containing products in the gaseous phase from said solid catalyst, subjecting the used catalyst to contact with air to effect removal of said'contaminant by burning at a controlled elevated temperature, cooling the catalyst and again employing it for contacting waxy mineral oil stock as aforesaid.

5. The method of separating oily constituents from waxy constituents present in a waxy hydrocarbon stock which comprises: coating said waxy stock onto the surface of particles of solid adsorbent material of greater than about 0.01 inch average diameter, permitting the adsorbent particles to remain coated with said waxy stock for a period within-the vrange 0:1`V to 2li hoursand* maintainingk the temperature of the waxy-'stock' during substantia'llysaid` entire period-beginning at least substantially? immediately after" initialv contact with said adsorbentA ata level at which waxy constituents in said stockv ares congealed'V whereby the non-congealedr liquidV constituents are sorbedA into the Vpores of saidadsorbent'particles while the` congealed waxy constituents remain on the surface of'said particles, thereafteru effecting removal of said waxy constituents'from the surface of said adsorbent particles while leav'- ing sorbed said non-congealedliquid constituents;` mixing the adsorbent bearingsorbed liquid oily;y constituents with a suicientamount of notadsorbent ofsimilar'type to heat it to" a temperature suitable for the conversion' of saidsorbedV liquid oily constituents to lower'boiling products',r eecting substantial separationof'said lower boiling products fromV the used adsorbent'upon which a carbonaceous contaminant has beendeposited', effectingV removal of said'` contaminant from theA used adsorbent andreusing atleast a portion of'v the adsorbent after said contaminant removal as the adsorbent on which said waxy stockzis coated as aforesaid.

6; The method for converting a waxymineral cil stock into gasoline and wax products which comprises: coating the waxy mineral oil stock onto the surface of particlcsof solid adsorbent material of greater thaniabout G;01 inch average particle diameter and suitable as a hydrocarbon cracking catalyst,` substantially'immediately chilling the coated adsorbent to eiectcongealingof wax constituents in said waxy stock' coated'on said adsorbent particles, permitting the adsorbentparticles to remain coated4 with said'waxy stock while maintainingY saidVv waxy'constituents in congealed form until substantially allof the non;- congealed liquidconstituents of saidwaxystock arel sorbed into the pores of saidiparticles leavingithe congealed waxy constituents onV the surfacezof' said particles, thereaftereiectin'g removal ofsa'idA wax constituents from the surface oi said adlsorbent particles while leaving the non-congealed` liquid oily constituents still sorbed intheporesi of said adsorbent particles, `heating saidadsorbent bearing` sorbed liquid'oily constituents toa temperature at which said liquid oilyv constituentsare catalytically converted to vlower boiling gasoline containing products,l effecting substantial separation of said lower boilingvproducts from' the used adsorbent upon which a, carbonaceous" contaminant has been .deposited as a result of` the conversion ofr said liquid oily constituents, effecting removal ofv said `contaminant from. the used adsorbent, cooling the adsorbent and reusing,v it as the adsorbent upon which said waxyA mineral oil stock is coated as aforesaid.

7. The method of deoiling slack' wax stockswhich comprises I, coating saidslack wax stock in liquid form onto the surfaceof particles of'adsorbent material in an adsorbentccating zone, said adsorbent particles being of 'at least 0.01' inch average diameter, chilling., the coated adsorbent particles to eiTect precipitationcf.wax'constituL ents inr said slack `wax stock'coatedthereonV at least within about 10 minutesof the beginning` of the adsorbent coating,` maintainingv the wax constituents inprecipitated-form on-said adsorbent particles for a period-of at least'fkl hour. until substantially all of the non-precipitated 1iq uidA constituents of said slack wax aie sorbed into the pores of said adsorbent par-ticlesv leaving thel precipitated waxen the surfaceJ or-said particles.

`effecting removal of the precipitated wax from the surface of said adsorbent particles while leaving the liquid constituents still sorbed in the pores of said adsorbent particles, separately passing the adsorbent bearing the sorbed liquid constituents through a confined conversion Zone in admixture with a sufficient quantity of hot regenerated particle form adsorbent of similar type to heat it to a temperature suitable for conversion of said sorbed liquid constituents to lower boiling hydrocarbon products, separating the lower boiling products in the gaseous phase from the used adsorbent, passing the used adsorbent through a confined regeneration none while contacting it therein with a combustion supporting gas at a controlled elevated temperature to remove contaminant deposits from the adsorbent, cooling a portion of the hot regenerated adsorbent and recycling it to said coating zone and utilizing the remainder of the hot regenerated adsorbent as the hot regenerated adsorbent which is mixed with the adsorbent bearing sorbed liquid constituents as aforesaid.

8. The cyclic process for providing deoiled wax `and gasoline containing products from a wax-oil charge stock by means of a particle form catalytic adsorbent material which comprises: subjecting said wax-oil stoel; to an intimate contacting with the particle form adsorbent catalyst made up of particles of average diameter within the range about 0.022 inch to 0.5 inch and having a substantial catalytic activity for hydrocarbon cracking reactions under conditions of temperature wherein the waxy constituents of said stock become congealed at the latest within about minutes of the beginning of said contacting, continuing said contacting until substantially all of the non-congealed liquid constituents of said stock are sorbed into the pores of said adsorbent particles while leaving the congealed wax on the surface of said particles, effecting the removal of the wax from the surface of said particles, and collecting the same as deoiled wax product, mixing the catalyst bearing sorbed oily constituents `with hot catalyst of similar type to heat it to a suitable temperature for the conversion of said oily constituents to a lower boiling gasoline containing hydrocarbon product, passing the mixture through a confined conversion zone to effect the conversion of said oily constituents, effecting a separation of the lower boiling hydrocarbon products from the used catalyst bearing a contaminant deposit, passing the separated used catalyst through a coni-ined regeneration zone while contacting it therein with a combustion supporting gas at a controlled elevated temperature to remove contaminant deposits from said catalyst, utilizing a portion of the regenerated catalyst for contacting cool catalyst bearing sorbed liquid constituents from said wax-oil stock as aforesaid and cooling the remainder of said regenerated catalyst and utilizing it for contacting said wax-oil stock as aforesaid. I

9. The method for producing deoiled wax and a gasoline containing hydrocarbon product from a wax-oil petroleum charge stock which comprises: encasing particles of adsorbent catalyst having an activity for hydrocarbon cracking and having an average diameter of at least 0.01 inch in said wax-oil petroleum stock under conditions of temperature such that at least most of the wax constituents of said stock are in congealed state substantially from the beginning of the contact of the stock with the catalyst particles, maintaining said catalyst particles encased in saidw wax-oil "stock until substantially all the non-congealed `oily constituents of said stock are sorbed into the pores of the catalyst particles leaving the wax constituents of said stock in congealed state on the surface of the catalyst particles, eiecting a separation of the wax constituents of said stock from the surface of said particles and cooling the same as deoiled wax products, passing the particle form catalyst after separation from the wax constituents but still bearing the sorbed oily constituents downwardly through a confined conversion zone maintained under a temperature suit- -able for the cracking conversion of said oily constituents to lower boiling gasoline containing hydrocarbon products, moving said catalyst through said zone as a downwardly gravitating substantially compact column withdrawing gaseous conversion products from said conversion zone, separately withdrawing the particle form catalyst bearing a contaminant deposited during the hydrocarbon conversion from the lower section of said conversion zone, passing the used. catalyst through a conned regeneration Zone in contact with a combustion supporting gas to effect removal of said contaminant by burning while controlling the temperature of said catalyst above that minimum required for practical contaminant burning rates and below a temperature at which said catalyst would suffer permanent loss in catalytic activity, withdrawing the hot regenerated catalyst from the regeneration zone cooling at least a portion of said regenerated catalyst to a temperature below about F. and again encasing said catalyst in said wax-oil stock as aforesaid.

10. The method for removing oily constituents from a waxy hydrocarbon stock which comprises: subjecting said waxy stock to an intimate contacting with a particle form solid adsorbent material comprising particles of at least 0.01 inch average diameter, effecting sorption of the liquid oily constituents of said waxy stock into the pores of said adsorbent particles while substantially preventing sorption of the wax constituents by maintaining the temperature during said contacting at a level at which the wax constituents become congealed, effecting the separation of the wax constituents from the surface of said adsorbent particles, passing said adsorbent particles bearing the liquid oily constituents of said waxy stock in the pores thereof during a confined conversion zone in admixture with a substantial quantity of hot particle form heat carrying mate- `rial to heat it to a temperature suitable for the conversion of said sorbed cily constituents to lower boiling products, eiiecting the separation of said lower boiling products from the used adsorbent material, reconditioning at least a portion of said adsorbent material to put it in condition for reuse in contacting said waxy stock and then 'again `using the reconditioned adsorbent material for contacting said waxy stock as aforesaid..

11. The method of deoiling waxy hydrocarbon stocks which comprises: coating the surface of porous solid adsorbent particles of at least 0.01 inch average diameter with said waxy stock at a temperature just slightly above that at which the waxy constituents begin to crystallize substanfonthesurface of the particles, thereafterimelting 'the 'waxfrom the surface of the sorbentparticles Aand collecting themelted wax separately of the radsorbent particles and sorbed oily constituents, :passing the adsorbent particles bearing the sorbed .oily constituents through a conned conversion zone under temperature conditions suitable for eiecting the conversion of said oily constituents to lower boiling gasoline containing hydrocarbon products, separating the gasoline containing hydrocarbon products from the used sorbent particles,"reconditioning at least a portion of the used adsorbent particles and returning the reconditioned particles as the adsorbent charge to said coating zone.

v12. A method for preparing deoiled wax and gasoline hydrocarbon products from wax-oil vlpetroerufn stocks which comprises: maintaining -`-a liquid column of said wax-oil stock at a temperature slightly above that at which the waxy constituents begin to congeal, maintaining below .and contiguous with the bottom of said column or" wax-oil stock a column of water, maintaining a short length of the column of water immediately below the column of wax-oil stock at a temperature near that of the wax-oil stock and maintainving 4the remainder of said column of water at a temperature at which the waxy constituents of said stock will congeal, dropping particles of solid adsorbent having an average diameter of @at -least 0.01 inch and having a substantial catalyst `activity for the cracking conversion of hydrocarbons downwardly through said column of wax-oil stock to cause said particles to become coated with wax-oil stock, causing the coated particles to drop downwardly .into and through said 'column of water to `cause the waxy constituentsin the stock coating said particles to Vbecome congealed, removing the particles bearing thecoating of wax-oil stock fr m said water Acolumn and permitting the particles to stand r at a temperature below the congealing temperature of said waxy constituents until substantialyly all the non-'congealed constituents oi the wax- -oil stock coating said particles are sorbed into the pores of said adsorbent particles while leav- .fin'g the Iwaxy constituents on the surface of said particles, then Vcontacting the adsorbent particles with heated water to melt and to remove the :waxy Aconstituents from the surface of said particles while leaving the non-congealed constituents of the wax-oil stock sorbed in the pores of said particles, purging said adsorbent particles substantially free of water by means of a suitable purge gas, mixing said purged particles of adsorbent bearingnon-congealed constituents of said wax-oil stock with a substantial quantity of hot regenerated adsorbent particles of similar type to provide a heated mixture of adsorbent Lat .a temperature suitable for eiiecting the conversion of said sorbed oily constituents to lower boiling gasoline containing products, passing the mixed adsorbent with a substantial quantity of contact particles downwardly through a coniined conversion zone wherein the oily constituents are converted, withdrawing the gasoline containing oily constituents in the gaseous phase from said conversion zone, separately withdrawing sorbent V'material bearing a oarbonaceous contaminant .deposited during the hydrocarbon conversion fromthe lower section of said conversion zone, 4passing the used adsorbent through a conned -regeneration zone in contact with a combustion supporting gas to effect burning of the contaminant deposit,f controlling the temperature of said adsorbent during the regeneration belowxa tempera-ture at which it would 'suffer permanent heat damage to its porosity and catalytic activity, returning a portion of the hot adsorbent to said conversion zone, cooling another portion of said hot regenerated adsorbent to a temperature below about returning the cooled adsorbent to said liquid column of wax-oil stock.

i3. A method for deoiling wax-oil petroleum stocks which comprises: maintaining a rliquid column of said wax-oil stock at a temperature slightly above that at which the waxy constituents begin to congeal, dropping particles vof solid adsorbent catalyst material oi at least 0..'01 inch average diameter which are suitable foreffecting hydrocarbon cracking conversions and suitable for sorbing liquid oil in its pores through column to deposit a ilm of said waxy stock on the surface of said catalyst particles, `immediately dropping said catalyst particles into a bath of a suitable cooling liquid maintained at a temperature suitable for congealing the waxy constituents of said wax-oil stock, permitting the adsorbent particles to remain coated with said wax-oil stock While maintaining the waxy constituents in a congealed state `until substantially all the non-congealed constituents are sorbedinto the pores of said particles, thereafter eiecting removal of the waxy constituents from the surface of said catalyst particles while leaving said non-congea'ed liquid constituents sorbed in-the pores of said particles, passing said catalystl particles bearing sorbed liquid constituents of said wax-oil stock through a confined conversiorrzone while heating it to a temperature suitable for effecting conversion of said liquid constituents to lower boiling gasoline containing hydrocarbon products, separating said lower boiling products from the used catalyst, effecting the regeneration of said used catalyst at an elevated temperature by means of a combustion supporting gas, cooling -at least a portion of the regeneration catalyst and returning it to said liquid column of wax-oil stock as the catalyst charge thereto.

14. The method for removing oily constituents nm a itx-xy petroleum stock which comprises:

eeting waxy stoel; to an intimate cong with an inorganic oxide gel. adsorbent 'ng of particles of generally spheroidal shape and of an average `diameter of at least about 0.01 inch, wher .3y the waxy stock is coated onto the surface of said adsorbent particles, controlling the temperature of said waxy stock so that the wax constituents become congealed -at the latest substantially immediately after the waxy stock is coated upon said particles, causing the adsorbent coated with the waxy stocklto stand at a temperature at which said wax constituents remain congealed until substantially all the non-congealed liquid constituents of said stock are sorbed into the pores of said particles leaving the wax on the surface thereof, then removing the wax from the surface of said adsorbent particles and collecting the removed wax separately of the adsorbent particles, mixing the adsorbent particles ybearing sorbed non-congealed liquid constituents of said waxy stock: with a-substantial amount of hot regenerated adsorbent of similar type to heat it to atemperature suitable for eiecting the conversion of said liquid constituents to lower boiling gasoline containing hydrocarbon products, passing the mixed adsorbent as a substantial compact gravitating column of particles downwardly through a confined conversion zone to effect the conversion of said liquid constituents withdrawing the lower boiling hydrocarbon products from said conversion zone, separately withdrawing the used adsorbent bearing a carbonaceous contaminant from the lower section of said conversion zone, passing the used adsorbent through a conned regeneration zone as a substantially compact column in contact with a combustion supporting gas to burn 01T said contaminant while controlling the temperature of said adsorbent below a heat damaging level, withdrawing the regenerated adsorbent from the lower section of the regeneration zone, utilizing a portion of the hot regenerated adsorbent for mixing with the cooler liquid constituent bearing adsorbent as aforesaid, cooling the remainder of said hot regenerated adsorbent and again contacting it with said waxy stock as aforesaid.

15. The method for preparing gasoline containing hydrocarbon products and a deoiled wax product from a wax-oil petroleum stock which comprises: intimately contacting the wax-oil stock with a particle form solid adsorbent in which the average particle diameter is at least 0.01 inch and which has a substantial catalyst activity for hydrocarbon cracking reaction, substantially excluding the adsorption of the waxy constituents of said wax-oil stock into the pores of said adsorbent particles by maintaining said waxy constituents in congealed form while permitting the non-congealed liquid oily constituents to be adsorbed into the pores of said adsorbent, after substantially all of said liquid constituents are sorbed in the pores of said adsorbent effecting a separation of the adsorbent bearing said liquid oily constituents from said waxy constituents in a separate Zone, mixing the adsorbent bearing the liquid oily constituents with a suicient amount of hot regenerated adsorbent of similar type to heat it to a temperature suitable for effecting the catalytic cracking of said liquid oily constituents to lower boiling gasoline containing hydrocarbon products, passing the mixed adsorbent through a confined conversion zone to effect the conversion of said sorbed liquid oily constituents, separately introducing a vaporized hydrocarbon fraction into contact with said adsorbent within said conversion zone to effect the catalytic cracking conversion of said hydrocarbon fraction to gasoline containing products, effecting the separation of the mixed hydrocarbon products in the gaseous phase from the used solid adsorbent, passing the used adsorbent through a confined regeneration zone in contact with a combustion supporting gas to burn o contaminant deposited thereon during the hydrocarbon conversion, controlling the temperature of the adsorbent during the regeneration below a heat damaging level, withdrawing the regenerated adsorbent from said hot regenerating zone, utilizing the portion of hot adsorbent with the cooler liquid oily constituent bearing adsorbent as aforesaid, cooling the remainder of said hot regenerated adsorbent and again utilizing it for contacting said wax-oil stock as aforesaid.

16. The method for separating oily constituents from waxy constituents present in a waxy hydrocarbon stock which comprises: coating said waxy stock onto the surface of particles of solid adsorbent hydrocarbon cracking catalyst of greater than about 0.01 inch average particle diameter, limiting the average thickness or" the wax coating on said catalyst particles to less than about 0.1 inch, permitting the catalyst particles to remain coated with said waxy stock within the range 1 to 24 hours and maintaining the temperature of the waxy stock during said period beginning at least substantially immediately after initial contact with said catalyst at a level at which waxy constituents in said stock are congealed whereby non-congealed liquid constituents are sorbed into the pores of said catalyst particles while the congealed waxy constituents remain on the surface of said particles, thereby effecting the removal of said waxy constituents from thelsurface of said catalyst particles while leaving sorbed non-congealed liquid oily constituents within the pores of said particles, passing the separated catalyst particles bearing the sorbed oily constituents as a substantially compact column downwardly through a confined conversion zone in admixture with a suiiicie-nt quantity of hot regenerated catalysts of similar type to heat it to a temperature at which said liquid oily constituents are converted to a lower boiling gasoline containing hydrocarbon product, withdrawing the gasoline containing product in the gaseous phase from said conversion zone, separately withdrawing spent catalyst bearing carbonaceous contaminant deposit from the lower section of said conversion zone, passing said spent catalyst through a confined regeneration, zone in contact with air to burn the carbcnaceous contaminant while controlling the temperature of said catalyst below a heat damaging level, withdrawing the hot regenerated catalyst from said regeneration zone, utilizing portion of the hot regenerated catalyst for mixing with the coolel` catalyst bearing said liquid oily constituents as aforesaid, cooling another portion of said hot regenerated catalyst to a temperature below about F. and again coating the cooled catalyst with said waxy stock as aforesaid.

DONALD A. HERMANSON. JOHN L. BILES.

REFERENCES CITED The following references are of record in the ille of this patent:

UNITED STATES PATENTS Number Name Date 115,622 Lucas et al June 6, 1871 226,001 Riebeck Mar. 30, 1820 1,278,023 Rosenbaum Sept. 3 1918 1,447,297 i Day Mar. 6, 1923 1,509,326 Weir Sept. 23 1924 1,568,018 Forrest et al Dec. 29, 1925 2,351,793 Voorhees June 20, 1944 2,382,755 Tyson Aug. 14, 1945 2,437,222 Crowley Mar. 2, 1948 OTHER REFERENCES Allibone, Journal of the Institute of Petroleum, vol. 27, pages 94-108 (1941).

Claims

1. THE METHOD OF OBTAINING A DEOILED WAXY PRODUCT AND A GASOLINE CONTAINING PRODUCT FROM A WAX BEARING HIGH BOILING MINERAL OIL WHICH COMPRISES: SUBJECTING THE WAX BEARING OIL TO AN INTIMATE CONTACTING WITH A SUITABLE PARTICLE FORM SOLID ADSORBENT MATERIAL OF AT LEAST 0.01 INCH AVERAGE DIAMETER, MAINTAINING THE TEMPERATURE DURING AT LEAST MOST OF SAID CONTACTING AT A LEVEL AT WHICH WAX CONSTITUENTS OF SAID WAX BEARING OIL ARE CONGEALED BEGINNING AT A TIME FALLING WITHIN THE PERIOD OF PRIOR TO THE INITIAL CONTACTING TO SUBSTANTIALLY IMMEDIATELY AFTER THE INITIAL CONTACTING OF THE LIQUID WITH THE ADSORBENT, WHEREBY THE CONGEALED WAX CONSTITUENTS REMAIN DEPOSITED ON THE SURFACE OF SAID ADSORBENT AND THE NONCONGEALED LIQUID CONSTITUTENTS ARE SORBED INTO THE PORES OF SAID ADSORBENT, THEREAFTER REMOVING THE WAX CONSTITUENTS FROM THE SURFACE OF SAID ADSORBENT WHILE LEAVING THE NON-CONGEALED LIQUID CONSTITUENTS WITHIN THE PORES OF SAID ADSORBENT, HEATING THE ADSORBENT CONTAINING SAID LIQUID CONSTITUENTS IN THE ABSENCE OF SAID REMOVED WAX CONSTITUENTS TO A TEMPERATURE AT WHICH SAID LIQUID CONSTITUENTS ARE CONVERTED TO A LOWER BOILING GASOLINE CONTAINING PRODUCT AND SEPARATING SAID PRODUCT FROM THE ADSROBENT.