CA1289496C - Process for upgrading tar sand bitumen - Google Patents

Abstract

PROCESS FOR UPGRADING TAR SAND BITUMEN
ABSTRACT OF THE DISCLOSURE
A method for upgrading a concentrate of tar sands bitumen containing fine mineral matter and optionally coarse mineral matter in which solvent-diluted bitumen is contacted for a short time in a riser with hot attrition-resistant substantially catalytically inert acid-resistant fluidizable particles, causing a selective vaporization of the lighter high hydrogen content components of the bitumen. The preferred particles are composed of silica-alumina, most preferably a mixture of mullite and crystalline silica or mullite, crystalline silica and an acid-resistant form of alumina. A portion of the heavier asphaltenes and most of the components which contain metals, sulfur and nitrogen remain on the attrition-resistant fluidizable particles. Fine mineral matter in the bitumen feed also deposits on the fluidized particles instead of being carried over with the vaporized hydrocarbon product. The contact material, with deposit, is contacted with a solution of acid to remove the deposit of mineral matter and deposited metals without decomposing the particles of contact material.
The heated particles of contact material are reintroduced into the riser for further contact with incoming diluted bitumen charge.

Description

PRO OESS FOR UPGRADING T~R S~ND BITUMEN

~ Back round of the Inventlon This invention relates to a method for upgrsding tar sand bitumen for the preparatlon of useful hydrocarbon products therefrom, such as a ~Q higher qualIty syncrude essentlally free of metals and asphaltenes and with a much lower molecular weight. In particular, the invention relates to a method for upgradlng bitumens deri~ed from tar sands which contain mineral matter lncludlng a flne partlcle slze fraction and a coarser slze fraction.
Extenslve deposits of tar sands, bitu~inous sands, bituminous diatomite and similar material~ are known to exist throughout the world.
These materials c~mprise a slllceous matrix of sands, sandsto~es or diato~aceous earth which 18 coated or saturated with relatively high lecular weight hydrocarbon materials. These deposits are generally located at or near the esrth's surface, although some deposits ~ay be buried by as much as two thousand feet of overburden. It ha~ been estl~ated that the reserves of petroleum products recoverable from the known deposlts of tar sand~ would be approxlmately equivalent to the world-wide reserves estlmated for conventional crude oil.
~8 mined, the tsr sands are present ln general as agglo~erates or lumps comprislng sand or d~atomlte, mineral particlea, water and vl~cous hydrocarbonac@ous materlal cslled bitumen. ~hlle there i8 no universally accepted definitlon of "bitumen", lt may be characterized as that portlon of petroleum that exists in the semi-solid or solld phase in natural deposit~.
It has been prcposed by the United Natlon~ Instltute for Tralnlng and aesearch (UNITAR) that bitumens, or natural tars, be deflned as the 7 ~

949~
the pe~roleum component which has a vlscoslty Breater than 10,000 mPa.s ~cp) ~easured at the condi~ions in the deposit and gravity greater than ltO00 kg/m3 (less than 10~ API) at ~tandard conditlons of 15.6C (60F) and a pressure of one atmosphere. The definitlon was suggeYted at the Second International Co~ference on Heavy Crude and Tar Sands, held in Caracas, Venezuela on February ~-17, 1982. At that time it was also noted that a continuously variable spectrum of properties can be found not only geographlcally between deposits but also laterally and vertically-within a given petroleum occurrence. ~ccordingly, the proposed definition employs essentially an arbitrary demarcation between bltumen and heavy crudes, when the materlals are compared on the basis of these physical properties alone.
Additional distinctions between bitumen and conventional healrg crude oil may be made on the basis of their chemica-l compositions. Relstive to most heavy crudes, bitumen has a large asphaltene component. Asphaltenes are complex, polynuclear hydrocarbons whlch are lnsoluble ln n-pentane snd/or n-heptane. Due to their sub~tantial asphaltene content, bitumens exhibit a high carbon/hydrogen ratio. For the preparatlon of transportatlon fuels, lt is generally necessary to reduce the carbon/hydrogen ratlo by addltlon of hydrogen through catalytic hydrogenatlon. Bitu~en typlcally also contalns significant amounts of sulfur, nltrogen and metals as contaminants, often substantially more than most conventional heavy crudes.
The predominatlng mlneral component of the tar sands bltumen material as mined i8 ln most cases slllca ln the form of quartz sand or diatomite of psrticle sises generally greater than about 10 microns, usually 8reater than abo~t 44 mlcrons (325 mesh) and up to about 10 mesh. The materlal as mlned 18 surrounded by bltumen ln qusntities of perlu~ps about 5 to over 20 ~elght percent of the total composltlon. In addltlon, tar sands generally also contain flner mineral matter of partlcle slze les~ than about 44 microlls and larger than 2 mlcrons, sometlmes referred to as sllt, and materlal flner than 2 microns, sometlmes referred to as clay. Reference to U. S. 3,811,614. The fine mlnera~ matter may includa one or more of calcite, silica, rutile ~T102), calclum sulfatQ and mica as well as clay ~inerals such as kaolinltes or smectite. The fine mineral matter generally has an appréciable content of alksline earth material present as calcium carbonate and/or calclum sulfate. Fine mineral matter (1. e., mlneral partlcles flner than about 10 microns~ i8 generally present in quantities of fro~ about 1 to about 50 weight percent of the total composition.
The bitumen as found in naturally occurring tar sands i~ not of great economic value ln it~ crude form. Such bitumen, however, may be upgraded to hydrocarbon~ of lower molecular weight, in particular to hrdrocarbons which are liquids at room temperature. Extensive recovery of tar sand oil has not been seriously consldered until relatively recently, primarll~ becsu~e of the expense of known recovery and upgrading method~ ln relation to the cost of preparing the same product~ from crude petroleum.
The rislng costs of crude petroleum production and the depletion of known petroleu~ reserves, however, have made an efficient and economical process for the treatment of such tar sand increas1ngly desirable. The vastness of the known deposits hss encouraged many people to look at these raw materlals as a potentlal source for filling energy and chemical feedstock needs ln a world of depleting conventlonal crude oil sources.

Seversl methods have been developed for purifying tar sand~ to provide bitu~en concentrates that can be used as feedstock for further upgrading to produce useful products. The princlpal purlflcatlon technique which has been applied to tar sands ln order to concentrate bitumen therefro~ is extractlon. In one ~ype of extraction, commonly known as the ~hot water" process, adYantage i8 taken of tbe fact that tar sands produce a bltuminous slurry when mulled wlth hot water and sodium hydroxide. Thls slurry divides into two components upon further dllution with hot water in a settling zone. A bituminous froth r1se~ to the surface of the water and is withdrawn for further concentration of bitumen, whlle essentlally bitumen-free ~snd is discarded as a downward flowing aqueous t~ilings 8 tream.
Another known beneficlation proce~s for recovery of bitumen from tar sand is known as the cold water process. This proce~ comprises the S following steps: grinding the ore in the presence of water and a dispersant; flotation with fuel oll; dllution of the bitumen concentrate with solvent; and separation of beneficiaeed bitumen from the sand/wster re~idue. This proce~s for the preparation of a bitumen concentrate avoids the requirement of large quantities of heat needed to rai~e the temperature of the water in Che process described in the preceding paragraph. In the first stage of preparation, the tar sands as mined are crushed, for example in a gyratory crusher, to form a coarse ore stock plle. Through the use of cone crushers, rod mllls andlor ball mills, the latter possibly in closed circuit with cyclones, a product which is approximately 80X below 150 microns may be prepared. Water and a ma~or portion of the cond~tioning and flotation reagents used in the process are then added to form a slurry. A
variety of materials may be added to the crushed tar sand ore prior to condit~oning and flotation. Fuel oil or other solvent, in quantities of about 5 lbs. per ton, may be added at this stage. Sodium carbonate (up to about 10 lb/ton) and/or sodium silicate (up to about 5 lb/ton) may also be employed. Th~ slurry i~ then passed to one or re conditionin8 tanks.
Some conditioning msy al80 be accomplished merely by the flow of slurry through pipes over extended distances. The sized and conditioned slurry 18 then fed to a flotation circuit, comprising onè or more flotation trains.
Each of these trains comprises a rougher/scavenger unit and a single- or ~ultlple-~tsge cleaner circuit utllizlng flotation cells. A typical retention tl~e in thæ flo~ation cells i8 on the order of 15 minute~. Tails from the scavenger cell are passed to thickener9, to which lime or another suitable flocculant, in an amount of about 5 lb/ton, is added. Overflow water from the thickener i8 recycled back into the circuit. A tailings slurry at about 50-60X by weight solids l-~ discharged into 8 tailing~ pond.
Concentrate~ from the last ~tage of the flotation proce~s, containing approxlmately 25 percent by weight birumen, are then ~ultable for further concentration, for example, by solvent upgradlng. Unfortunately, fine mineral matter floats with the bltumen concentrate and 18 not effectively re~oved by flotation.
~8 currently practiced, bitumen concentrate from the flotation process is transferred to a mixing ve~sel where it i~ combined with at lea~t one part, and generally several part~, of liquid solvent per part of bitumen. While the exact amount and compQsltlon of the solvent is not critical, it has been suggested that for maximum effectiveness the ~olvent should contain about 20% aromatics. Heretofore, the solvent has been almost entlrely recovered ln subsequent step~. It.is pos~ible to use the same fuel oil for solvent upgrading a~ is used in the flotation process.
The diluted bitumen is pumped lnto settling or holding tanks, where the remalning water and sands begin to settle out.
The flnal stage of the solvent upgrading proces~ comprises the solvent or diluent recovery stage. This may be a distillation tower or other mechanism which is used to separate solvent and flotation oils for recycllng to upstream stages of the extraction process. Depending on the nature of the charge to the solvent upgrading step and the intended use for the concentrated bitumen, additional separatlon steps, such as dehydration or centrifugation may be neces3ary.
In yet another type of extraction process, tar sand agglo~erates are contacted with a suitable solvent such as a gas-oil bolling range fraction to produce a solution of bitumen and gas-oil. This solution is separated from the sand and then passed bo a conventional hydrocarbon conversi~n unit.
Treatment of tar sands by these beneficlation techniques in order Oo separate an enriched bitumen stream from the sand is a substantial component of tha recovery C08 t~, above those minln8 the crude ore. These processe~ generally provlde products which contain residual fine mlneral r~atter even after repeated traatment~. The content~ of fine mineral matter (particles flner than 10 mlcroQs) in beneficlated bltume~ concentrates ~j typically range from 2500 ppm to 20 weight~, usually below 2 weight%, based on the weight of the bitumen. Since at least a portion of the fine mineral particles form~ a stable emulsion with water it canr~ot be readily removed ~rom the bltumen recovered from tar sands. All of the k~fown processe~ for preparing bitumen concentrates from tar sands provide products containing st least some residual fine mineral solids. Because of the viscosity of the bitumen and the chemical constitution of the componentQ
thereof, lt has not been possible to remove the very iEine mineral solids i`rom the bitumen b~ conventlonal methods, such as hydroclone Reparators or conventional filtration means. This mineral matter, particularly the mineral matter of finest particle slze, introduces addltional complications in hydrogen addition trea tments, as noted below. The water, which may be present in amount up to 15% based on the weight of the bitumen, also causes problems in downstream upgrading processes. For example, water causes foamlng to take place in cokers.
Selective minin8 has been employed here tofore to minimize the content of ~loeral solids in bitumen concentrates obtained from tar sands.
Tar sands bitumens containing high levels of flne mlneral solids are generally not exploited. On the o~her hand, it i8 technically feasible but expen~ive to remove ~igh level~ of coar~er mineral particles (sands) froro bitumen.

In additlon to mineral solids, bitumen concentrates generally contain hlgh level~ of sulfur, nitrogen, metals and other contaminants.
These contsmlnants have also heretofore presented ma~or problems in the ~ubsequent use of the recovered product.
Retort methods slmilar to those used in the pyrolysis or thermal cracklng of oil shale have been proposed for the recovery of bitumen froQ tar sands. The raw tar sand i~ contacted with spent sand and fluldized by reactor off gas at temperatures above about gQ0F. Volatlle products are flashed off while coke is deposited through thermal cracklng. The coke i~
burned off in a separate unit at 1200-1400F and the sand recirculated.
Sulb~ tantial amounts of spent sand, for example 5-10 parts per part of raw tar sand, are needed for the process. This makes nece~sary a very large retort uolume per barrel recoverable oil. Serious waste heat and handling problems also arise with this process, making it of llttle intere~t commercially.
Once the bitumen has been recovered (concentrated) from the tar sands, two primary Oitumen upgrading routes are available: carbon re~ection and hydrogen addition. Carbon re~ection upgrades bitumen by removing asphaltenes, and is examplified by conventional ~olvent deasphalting, -delayed coking asld fluid coking processes. Yarious modifications of the 1S basic coking process have also been proposed. For example, U. S. Patent No.

2,905,595 describes a proce~s in which tar sands are sub~ected to a coking process to produce coker gas, gasoline and gas oil and a coke-laden sand stream. The coke-laden sand is contacted with an oxygen-containing gas, such as alr, ~o effect combustion of coke deposited on the sand grains, thereby producing a clean hot sand stream which is recirculated into the process. According to the preferred method described in this patent, coke-laden sands are burned snd heated in a specially-designQd gas lift furnace. The coke-laden sand is suspended ln a plurallty of parallel vertlcal burlling zones and recycled through a furnace zone surrounding these vertical tubes. Thls process produces a distillate product directly. The method essentlally employs a recirculated stream of hot solids slmultaneously to vaporize, coke and crack the hydrocarbon fractlon.

U. S. Patent No. 3,320,152 descrlbes a process in which tar sand agglomerates are lntroduced into a feed preparation zone and admixed with relatlvely hot contact materlal in order to drive off water and reduce the ~l~$9~
viscosity of hydrocarbon material~ thereby providlng a fluidizable mlxture of sas~d partlcles and hydrocarbons. A portlon of the fluidizable mixture is pa~sed through 8 pressure-developing zone and then introduced into a renction zone containing a fluidized bed of solid particulate material.
Ij This reaction zone 18 maintained under conditions to carry out thermal coking of hydrocarbon ms terial.
U. S. Patent No. 4,082,646 descr1bes a modified direct coking process in which ~he combustion stage is divided into two sequen~ial operations. In the first operation, coke sol1ds produced in a reaction are introduced into a coke burning zone where they are contacted with combu~tion alr and the minlmum amount of supplementary fuel, lf any needed to burn substantially all the coke. Part of the solids is discarded while the remainder, required for heating the coking reaction ~one, is introduced into a fuel burner zone. Here the ma~or portion of the supplemental fuel requlred to maintain heat balance is combined with air or oxygen to heat further the clean solids until their heat content i8 sufficient to meet the requirements of the coking reaction zone.
Carbon re~eetion alone cannot deal with the bitumen upgrading ~ob in a cost effectlve manner. This is because an extraordinarily high amount of either a coke byproduct or an asphalt byproduct i8 produced. These by-products necessarily contain high contents of sulfur, metals and ash, renderlng the coke or asphalt relatively valueless. Moreover, the production of unnecessary coke or asphalt markedly reduces the yleld of lighter, more valuable liquid hydrocarbons. This yield consideration is of particular importance with respect to tar sand processing, where mining represent~ roughl~ 80% of the total operating costs. Thus, an increase in usable fuel yields fran each ton of ore can result in d1sproportionately large overall cost savings.

U. S. Patent No. 4,161,442 de~cribes a process in which high temperature solids comprising sllica are combined wlth tar sands in a thermal stripping operation restricted not materially to exceed incipient cracking of the petroleum materlals. The operating temperature is limited to within the range of 600F to 850F, and preferably below 800F. An oily residue deposited on the ~and is used to generate fuel gas by heating to a ~i temperature above 1500F with addition of steam or air. Slnce the fluid distillation iB operated to minimize cracking, the concentratlon of residual oil material on the sand is relatively high? and only those.components which vaporize below the temperatures of incipient cracking are removed`. This process provides only minimal amounts of desirable liquid hydrocarbon products because of the low process temperatures employed.
An alternative route for the upgrad~ng of bitumen ~s hydrogen addition. When hydrogen additlon is used alone as the upgrsding route, the large amount of hydrogen required to prepare useful products from the l~drogen-deficlent asphaltene molecules raises the cost of the fuel produced thereby to unaccepable levels. Moreover, nickel, vanadium and asphal tenes interfere with the hydrogenation and converslon catalysts, shortening run lengths and requiring a more frequent replacement of catalyst. Any fines present in the hydrogen addition feedstock not only block the active sltes of the hydrogenation catalyst, thereby reducing it~ activity, but also lead 2D to the formation over time of obstructions in ~he flow path of the feedstock through the catalyst bed. This in turn leads to the development of large pressure gradients in the system, ultimately resultin~g in it~ shutdown.
Combinations of prior art carbon re~ection and hydrogen addition processes would onl~ serve to compound the mo~t undesirable characteristics of each.
Another method for deriving useful l~rdrocarbon productQ from heavier precursors such as bitumen i~ the method of catalytic cracking.
Durlng the 1930'~, the process constituted a ma~or advance over the earlier techniques for increasing pressure to charge catalytic cracking units with heavier crudes and product~ such as bltumen. Two very effective restraints have limited the extent to which th~s has been practical: the coke _ Q _ ~;~s~9~
precursor content and the metals, especially heavy metals, content of the ~le~d~ As thes~ values rise, the capacity and efficiency of the catalytlc cracker are adversely affected.
Polynuclear aromatics, such as asphaltenes, tend to break down during the catalytic cracking process to form coke. This coke deposits on the actlve surface of the catalyst, thereby reducing its activity level. In general, ~he coke-forming tendency or coke precursor content of a msterial can be ascertained by determining the weight percent of carbon re~aining after a sample of the ~aterial has beèn w rolysed. Th~s value is accepted in the industry as a measure of the extent to which a given feedstock tends to form coke when treated in a caealytic cracker. One method for ~aklng this evaluation 18 the Conradson Carbon Test. When a comparison of catalytlc cracking feedstocks is made, a higher Conrsdson Carbon number (CC) reflects an increase in the portion of the charge converted to "coke'`
deposited on the ca~alyst. The Conradson Carbon test has been adopted as an American Natlonal Standard and is described in ASTM Method D189. Another generally accepted method for evalusting coke precursor content is the Ramsbottom Carbon test, as described in ~STM Method 524. The Conradson Carbon test, however, is the preferred method for samples that are not mobile below 90C, such a8 bitumens.
It has been conventional to burn off the inactivating coke with air to ~regensratQ" the active surfaces, after which treatment ths catalyst 18 returned in cyclic fashion to the reaction stage for contact with and convers10n of Additionsl feedstock. The heat generated in the burning regeneration s~age i8 reco~ered and used, at least in part, to supply heat for vaporization of the feedstock and for tbe cracking reaction.
The regeneration stage generally operates under a maximum temperature limitation in order to avold heat damage to the catalyst. Uhen feedstock wth a high CC content is processed, a larger amount of the feedstock in weight pereent is depo~ited as coke on the catalyst than would be the ca~s w~th low CC feeds~ock. When this catalyst is regenerated, the additional coke leads to hi8h temperaeures in the regenerator. ~t these hlgher temparatures, a number of problems arise. The circulstion rate of the cstalyst 18 reduced, often resulting in lower conversion rates.
S Incomplete regenera~ion of the catalyst may also occur, reducing its catalytic activity. Finally, if the temperature of the regenerator is sufficiently high, an inactivation of the catalyst takes place. There is thus a practical limit to the amount of coke which can be burned~per unit time.
~8 CC of the charge stock is increased, cokeburning capacity becomes the limiting factor, often requiring a reduction in the rate of charge to the unit. Moreover, part of the charge la diverted to an undesired reaction product, ~hereby reducing the efficiency of the process.
Since bitumen comprises to a great extent hydrogen-deficient, high molecular weight hydrocarbons such as asphaltenes, a direct catalytic cracking of bitumen would clearly be a highly inefficient method for upgrading for this resson alone. This is confirmed by Bunger et al., "Catalytic Cracking of Asphalt Ridge Bitumen", Advances in Chemistry Series, No. 179, "Refining of Synthetic Crudes". p. 67 (1979). ~hese authors report an inhibited rate of catslytic cracking, low octane ~umbers for the gasoline produced and substantially higher coke make than experienced presently for commercial gas-oil cracklng.
An sdditlonal drawback to direct catalytic cracking of bitumen is the metals content of the feed. Most bitumens contain heavy metals such as nickel and vanadium. These metsls are deposited almost quantitatively on a catal~tic cracking cataly~t as the molecules ln which they occur are broken down. The deposits of these metals build up over repeated cracking cycles to levels which become troublesome. Some of these metal~ also unfavorably alter the chemical composieion of catalysts. For example, vanadium tends to form fluxes with certain components of common FCC catalysts, lowering their 1 oelting po~n~ to a degree that tinteri~g begln~ at FCC operating temperature~ with re~ultant lo-~ of catalytic ctlvity.
The hea~y metals pre~ent ln bltu~enJ recovered from tar ~and are also potent cataly~tJ for the prodùction of coke and ~drogen fro~ the cracking feed~tock. The loweJt bolling fractionJ of ~he cracked product -butane and llghter - are proce~oed through fractlonatlon equipment to recover components of value great-r th~n a~ fuel for the furnaces. ~his fractlon comprise~ prlmarily of propane, butan~ and olefin~ of like carbon number. Hydrogen, belng incondenJable ln the '`gao plant~, occupie~ space a~
a gas in the compre~aion and fractlonation traln. ~8 the metal~ level of the charge stock i~ increaJed, hydrogen production become~ the limiting factor, often requlrlng a reduction in the rate of charge to the unit.
Moreover, ~lnc~ bl~u~n 1J already hydrogen deflclent, the generation of addltlonal hydrogen therefro~ would be a ~erlou~ problem.
lS The ~odlum content of bltu~en al~o pre~entJ problems for a conventional catalytlc cracklng ~y~tem. Sodlu~ react~ vlth a z~ollte cataly~t to produce the lnactive form of zeollte. The product bitumen generall~ contalns at lea3t about lZ vat r, with ~igniilcant amountJ of Jodium compound~ dl~olved th~rein. The~e Jodlum co~pounds comprlJe primarily ~odlum carbonate and ~odlum hydroxide, which are conventlonally u~ed as condltloning g-nt- ln th- upgradlng of tar sands. TheJ~ compounds are depo~lted on the cat-ly-t a~ the bltu~en 1J ~ub~ected to cat lytlc cracking, and can lead to a Jub~tantlal deactivatlon of the catalytlc crackl~g catalyst ov~r tloe, rsquirlng ltJ replace~ent. Sodlum, llke 2S vanadlum, al~o tend~ to foro fluxes wlth certaln FCC catalyJt componento.
T~E INVENTION
Accordingly, it is an object of an aspect of the invention to provide methods for deriving a useful hydrocarbon proauct from tar sands bitumens in an economically acceptable manner.
It is an object of an aspect of the invention to provide methods for upsrading bitumen derived from tar sands which m~ximize the yield of ~. .

higher-valve middle distillate components, while avoiding the disadvantages of the known upgrading routes for tar sand bitumen.
It is an object of an aspect of the invention to provide a method for upgrading a concentrate of bitumen which is not adversely affected b~ the content of fine particle size mineral matter and water in the bitumen concentrate.
It is an object of an a~pect of the invention to provide a method for upgrading bitumen which results in a product with reduced Conradson Carbon number, sulfur and nitrogen, and a minimized content of metals and fine mineral matter.
An embodiment of the invention involves the provision of a method for upgrading a concentrate of bitumen which makes effective use of at least a portion of coarser residual mineral matter contained therein.
Variou~ aspects of this invention are as follows:
A process for upgrading a charge of a tar sand bitumen concentrate containing mineral matter including fine particles which comprises contacting said charge in a riser in the presence of a low boiling organic solvent diluent with finely divided attrition-resistant particles of a hot fluidizable substantially catalytically inert solid which is substantially chemically inert to a solution of mineral acid, the contact of said charge with said particles being at high temperature and short contact time which permits ` vaporization of the high hydrogen containing components of said bitumen, said period of time being less than that which induces substantial thermal cracking of said charge, at the end of said time separating said vaporized product from said fluidizable particles, said fluidizable particles now bearing a deposit of both combustible solid, adherent particles of fine particles of mineral matter and metals, and passing said particles of inert solid with deposit of combustibles and fine particles of mineral matter to a regenerator to oxidize the combustible portion of said deposits, removing at least a portion of deposit of mineral matter and metals by removing said inert solid from said regenerator and contacting removed inert solid with a hot mineral acid, and recirculating fluidizable solid depleted at least in part of deposited mineral matter to contact with incoming charge of tar sand bitumen concentrate and diluent.
A process for upgrading a charge of a tar said bitumen concentrate containing fine mineral particles and water which comprises contacting said charge in a riser in the presence of a low ~oiling organic solvent diluent with finely divided attrition-resistant particles of a hot fluidizable substantially catalytically inert solid consisting essentially of crystalline mullite and crystalline silica, said contact being carried out at high temperature and short contact time which permits vaporization of the high hydrogen containing components of said bitumen, said period of time being less than that which induces substantial thermal cracking of said charge, at the end of said time separating said vaporized product from said fluidizable particles, said fluidizable particles now bearing a deposit of both combustible solid, metals and adherent particles of fine mineral particles, reducing the temperature of said vaporized product to minimize thermal cracking and recovering said product for further refining to produce one or more premium products such as gasoline, passing said particlas of inert solid with deposit of combustibles, metals and fine mineral particles to a regenerator to oxidize the combustible portion of the deposits, at least periodically withdrawing an additional portion of said particles from said burning zone and contacting them in an extraction zone with a solution of mineral acid selected from the group consisting of sulfuric, nitric and hydrochloric at elevated temperature to remove deposited mineral matter and metals from the tar said bitumen without substantial 13a A

coextraction of alumina from said attrition-re~istant particles and without appreciably changing the size and hardness thereof, and reintroducing at least a part of the solid particles thus extracted from said extraction zone into said burning zone for recycle to said decarbonizing and demetallizing zone.
A process for upgrading a charge of a tar sand bitumen concentrate containing mineral matter, including particles of fine particle size, and water which comprises contacting said charge in a riser in the presence of a low boiling organic solvent with finely divided attrition-resistant particles of a hot fluidizable substantially catalytically inert acid-insoluble solid at high temperature and short contact time which permits vaporization of the high hydrogen containing components of said bitumen, said period of time being less than that which induces substantial thermal cracking of said charge, at the end of said time separating said vaporized product from said fluidizable particles, said fluidizable particles now bearing a deposit of both combustible solid metals and adherent particles of the fine particle size mineral matter, immediately reducing the temperature of said vaporized product to minimize thermal cracking and recovering said product for further refining to produce one or more premium products such as gasoline, and passing said particles of inert solid with deposit of combustibles, metals and fine particle size mineral matter to a regenerator provided with cyclones and high velocity air jets to oxidize the combustible portions of the deposit and to heat said fluidizable particles and to attrite fine particle size mineral matter containing a portion of said metals from said attrition-resistant f}uidizable particles, recirculating the heated fluidizable solid depleted at least in part of fine particle size mineral matter to contact with incoming charge, and recovering mineral matter removed by attrition from the regenerator.

By way of added explanation, the present invention in one aspect provides a process for upgrading a charge of a tar sand bitumen concentrate containing fine mineral matter or fine and coarse mineral matter. The process comprises contacting the charge of tar sand bitumen concentrate in a riser contactor in the presence of a low boiling organic solvent diluent with finely divided attrition-resistant particles, preferably microspheres, of substantially catalytically inert solid which are also substantially insoluble in solution of mineral acid. The contact of the charge with the fluidizable particles is at high temperature and short contact time which permits vaporization of the high hydrogen containing components of the bitumen, the period of time being less than that which induces substantial thermal cracking of the bitumen. At the end of this time, the vaporized product is separated from the fluidizable particles now bearing a deposit of both combustible solid, metal, and, unexpectedly, adherent particles of finer mineral matter originally present in the bitumen concentrate. The particles of inert solid with deposit of combustibles, metals and adherent fine mineral matter are passed to a regenerator at a temperature below 2000F., usually below about 1800F., 2S to A 13c oxidi~e the combustible portlon of the deposit~. In one embodiment of the invention, the regenerator i8 provided wlth c~clone~ and high velocity sir ~ets, whereby a portlon of the adherent deposit i~ ~electivity attrited off of the partlcles of contact material by design of cyclones and air distribution to induce attrition and a ball milling actlon. The material removed by attrition ~ recovered in bag houses, CyClQneS or scrubbers downstream from the regenerator burner. At least a portion of the deposit of fine mineral matter i~ ~hen leached from the particles of cont`act material by removing the inert solid from the regenerator and contacting the 1~ removed inert solid with a solution of mineral acid. U~ually at least a portion of the deposited metals are also leached. Fluldizable 301~d, depleted at least ln part of flne mineral matter, i8 circulated to the regenerator and then into contact with incoming charge of tar sand bltumen concentrate and dlluent.
If the mineral matter accreted on the particles of contact msterlal were noS removed by some means, a dense shell would form on the partlcles of contact material which would grow ln slze. The resultlng material would not be useful in removing metals in a rlser contactor unless extremely high additlon rate of fresh contact material was to be practlced.
2 This 18 dsmonstrated by the following estimation of what would occur if removal of accreted mineral matter did not take place ln a commercial selectlve vapori~ation contactor operated wlth a feed containing I wt % flne material matter ~3.5# fine mineral matter/ barrel), 70 ppm Ni + V and wlth fresh contact material added to control metals level on equilibrium contact material to 3a,000 ppm. If no fine mineral matter were deposlted, 1.2 t/barrel of fresh contact material per 100 ppm N~ + V would be needed; hence 0.84 ~/barrel of contact matsrial would be nesded in the cited case of feed contalning 70 ppm Ni + V. If 1 wt. X flner mineral matter were permitted to accumulate and form a dense shell, the welght of deposited mineral matter 3~
per unlt weight of fresh contact material would be 4~16~/~ contact matsrial 49~
~3.5~ fine mineral matter deposlted/0.~4# contact matcrial). In other words, the we~ght of the contact material would be multipliéd by 8 factor of about four and the size of the particle~ of contact material would lncrease correspondingly to levels not suitable for u~e in a riser. Laboratory te~t re~ults indicste that at these levels the deposited mineral matter may impart undesirable catalytlc cracking properties to contact material originally substantially catalytically inert.
I~ a preferred embodlment of the invention, the inert 601id comprises kaolin clay which has been calcined at higb temperature, above 1800F. and preferably above 2000F., prior to use in the process. Among other things, high temperature calcination serves to render the kaolin clay substantislly inert to acid. Even if the depo~ited mineral matter includes minerals such as kaolins, such clay would not hav~e been exposed to thermal conditions which would render such clay material lnert to attack by acid.
Consequently, the ac~d soluble components of any deposited clay, such as alumina and iron, could be selectively dissolved from withdrawn (spent) contact material by action of the mineral acid without undesirable dis601ution of the inert solid.
The especially preferred inert solid contact material is composed of particles which comprises a mixture of crystalline mullite and crystalllne sillca snd substantially all of the silica is present in mullite and crystalline ~ilica and substantially all of the alumlna is prQs~nt in mulllte or mullite and acid insoluble acid alumina such as alpha alumina.
The advantage of using the especially preferred mulllte-crystalllne silica composltion is that metals, especlally vanadium and nickel, deposited on the contact material during use may be effectively removed from the system by treatment with acids without decomposing the particles of contact material.
It should be noted that an acid treatment which will result in the efficient removal of deposlted vanadlum and nlckel may requlre conditions more severe than those that will ~uffice to remove the deposit of mineral matter.

.$9`~
Consaquently, when sub~tantial amount~ of vanadium and nickel are removed by Creatment wlth mineral acid, an undesirable s~ount of alumina may be co-extracted from contact materlal (calcined clay) in splte of the fact that ~inimal alumina would be co-extracted if deposited mlneral matter were removed but vanadium and nickel were not also present.
Most preferably, the contact material is in the form of fluidizable microspheres which analyze at lea~t 95~ by welght combined SiO2 and A1203 and conslst essentially of mullite crystals and cry~talline silica, the Mlcrospheres having a mullite index of at least 45, an EAI below 1%/sec., a surace area below ~ m2/g, a total porosity in the range of 0.01 to .09 cc/g and a pore structure such that the ma~ority of the pores are larger than 1000 ~ngstrom unlt~ in diameter. Especially preferred are microspheres further characterlzed by a resistance to agglomeration below about 25 when tested by the static agglomeration test method ~5 hereinabove described st a metals loadlng of 8 weight X nickel plu8 vanadium, and a vanadlum/nickel welght ratlo of 4/1.
In one embodlment of the lnvention, the regenerstor i~ provided wlth cyclones and hlgh veloclty alr ~ets to attrlte portions of fine particle size mineral matter deposited on the attrition-resistant particles of contact materlal. Mineral matter removed by attrition from the regenerator i8 then recovered Addltlonal mineral matter may then be removed by contact wlth hot mineral acid.
In an embodlment of the lnventlon, spent fluldlzable inert contact material 18 w~thdrawn on a contlnuous or seml-continuous basl~ ln order to maintain a predetermlned average metal content in the circulatlng contact materlal and to preYent, ~ con~unctlon ~ith the re~oval of deposlted mlneral satter~ the bulldup of hi8h levels of metals a8 a deposlt on the particles of contact materlal.
In another embodiment, the tar sand bitumen concentrate ls prepared by wet processlng such as flotation or gravlty separation. The wet ~.

*~
proce~sed tar sand bitumen is further proces~ed by solvent extraction to recover a bltumen concentrate. In practice of thi~ e~odlment, the chsrge is preferably diluted with st least a portion of the solvent used in the purification to obtain the concentrate, whereby the smount of solvent that i~ removed by fractionatlon fror~ said concentrate prlor to contact with the heated fluidizable solid 18 reduced or eliminated.
In another embodlment of the invention, the charge i~ diluted with }ight gll~ oil and/or gas recovered from the vaporized product ob~ained by contact of a pre~rious charge of tar sand bitumen concentrate with hot t fluidizable inert Yolid.
In order to dlsclose more clearly the nature of the present invention, the following drawing, description and examples lllustratlng specific embodiments of the invention are given. It ~hould be understood, however, that thi~ is done solely by way of example and is intended neither to delineate the scope of the invention nor the ambit of the appended claims.
Figure 1 i8 a schema tic diagram of a tar ~and~ bi tumen upgrsding proce~s incorporating selective vaporization and utilizing solvent employed in upgrading the bitumen as dlluent for the bltumen ln the selective vaporlzatlon contactor.
Figure 2 i8 a diagramatic sketch of a selective vapor system for upgrading tar sand bitume~ concentrates ln a rlser/burner systQm.
Flgure 3 contalns dlstlllation curves of tar sand bitumen feedstock and a synthetic cr~Jde product obtained therefrom.
DESCRIPTION ~)F SPECIFIC EMBODIMENTS

1. Selective Vaporlzation Process The selective vaporlzation process of the lnvention 18 a modiflcaelon of the process dlscloQed ln U. S. Patent No. 4,263,128, whlch removes from the feedstock most of tho~e contaminant~ which would poison downstream converslon processes, whlle retalnlng those havlng à hlgh ~ lm~en ~n~emt. The selective vaporization process also shlfts the range of compound~ in the feedstock towards the middle distillate range, thereby reducing re3idual oils and molecular weight. In the process of the lnvention, the selective vaporizatlon process also remove~ fine mineral matter and thus minlmizes contàmina~ion of product~. The process of the invention can also utllize feedstocks containlng signiflcant levels of coarse mlneral ~atter ~sands).
The solld contacting agent 18 essentlally inert in the sense that ~Q it inducas mlnimal cracking of heavy hydrocarbons by the standard microactivity test conducted by measurement of amount of gas oil converted to gas, ga~ollne and coke by contact wlth the solld in a flxed bed. Charge in that test is 0.8 gram~ of mid-Continent gas oil of 27 API contacted wlth 4 grams of catalyst dur~ng 48 second oil dellvery time at 910F. This tS results ln a catalyst to oll ratlo of 5 at welght hourly space veloclty ~WHSV) of 15. By that tegt, the solid here employed exhlbits a mlcroactlvity less than 20, preferably about 5. The most preferred solid contact material composed of mullite and crystalline silica typically has a microactivity less than 1-3.
The selective vaporlzation proce~s is operated to minlmize molecular conversion of that portion of the hydrocarbon feedstock which i~
sultable for later catalytic cracking or other method~ for producing hlgh octane hydrocarbon products. The a~phaltenes present ln the bitu~en are elther converted to 104er molecular ~eight hydrocarbons or deposited on the contact material. The selective vaporization process al90 removes essentially all of the metals (over 90X9 and typically over 95~).
In order to cope wlth the contaminant concentratlon and the vl~c081ty of tar sand bitumen employed, it is generally desirable to dllute the feedstock unless sufficlent ~olvent is already present. One particularly suitable diluent whlch may be employed in the selectlve vaporl~ation proce~ i8 a clean, light 8a~ oil boiling in the 250 - 600F
range which 19 produced from tar ssnd bitumen by the selective vaporlzatlon proce~s. Thi3 light Bas oil material i~ repeatedly recycled through the selective vaporization proce~s 88 a captive diluent materlal. This dlluent 18 practically devoid of carbon resldue or metal In general, at lesst one equivalent by ~eight of dlluent 18 used per uni ~ bitumen.
Another suitable diluent for use in the ~electlve vaporl~ation process 18 the solvent employed durlng the puriflcatlon of the ~itumen fro~

water and sand. Thls solvent may be left ln large part in the bitumen, rather than being removed by fractionation as customarily done. This results ln overall energy savings in the production scheme. Solvent can be allowed to remaln, ln whole or ln part, within the bituman stream introduced into the selective vaporizatlon process. See the accompanying Figure 1.
This allows for a single fractionation of the purifled bltumen, rather than fractionation ln two steps - once during the conventional solvent "clean-up"
snd again during the selectlve vaporlzation proces~.
Referring to Figure 1, crude tar sand bitumen ore ls crushed, condltloned with alkall (e.g., sodium hydroxlde) and water and sub~ected to flotatlon to produce as a 10at product a concentrate of bltumen mlxed with water, coarse mlneral matter (sand) and flner mineral matter. The underflow from the flotation cell, a concentrate of sand and water, is charged to a fllter for recovery of water which 18 reused ln the flotatlon plant. The float product 18 then sub~ected to solvent extractlon, using, for example, fuel oil ln an amount roughly equal ln weight to the welght of the bltumen.
Wlthout recovering the so}vent ln fractionation equipment, as in conventional tar sand3 bitumen beneflciatlon, the solvent dlluted mlxture of bitumen, flne mneral matter, water and posslbly sand, is circulated through the contactor riser/regenerator system shown in detall in Figure 2. ~he regenerator (burner), dlscu~sed below ln connectlon wlth the descrlptlon of Flgure 2, may be one that operates wlth cyclone~ and high veloclty air which attrices clay deposited on the fluidizable particles of hot contact materlal circulating in the system. Uhen such cyclone~ are used, the flue gas from tha regenerator therefore contains~attrited deposit of fine mineral matter as well as fines resultlng from physical breakdown of contact material.
Unless all sand is removed by the cyclones assoclated with the riser, fine sand will also be present in the flue gas. These fines sra recovered by conventional means such as baghouses after separatioo from the flue gases which are handled in equipment suitable to remove oxides of sulfur before discharge to the atmosphere.
In the proce~ shown in Figure 1, product from the selective vaporization riser, after quench and fractionation to separate the solvent snd gas from the syncrude, is pa3sed to a hydrotreating facility to produce a synthetic crude oil. Solvent liquified and separated after the quench is recycled to the solvent extraction plant. Flue gases from the regenerator are processed to remove oxldes of sulfur in a llmestone bed boiler and steam recovered during this operation is used to operate utlllties. The gas produced in the selective vaporization riser is u~ed to provide hydrogen for the hydrotreater.
In general, an lnitial charge of f}uidizable contact materlàl 18 made to clrculate lnto the contacting zone, into the burning zone and again lnto the contacting zone prior to the introduction of feedstock. A
combustible materlal, such as what is sometimes referred to as "torch oil", i8 charged to the selective vaporization process burning ~one to initiate combustion. This materlal may be a waste product from a refinery. The heat ~5 of combustion of thls ~ater~al warms the system to the operating temperature range. Feedstock is then lntroduced and torch oil in~ection discontlnued.
As noted earller, lt is technically feasible but costly to remove coarse mineral matter from tar sands and the resldual content of fine minerals 1~ bitumen derlved from tar sand has in the past proved to be a ma~or problem in the subsequent upgrading of these tar sands. One of the sdvantages of the ina tant invention i~ these fine mlneral particles ha~re 8 ~inimal adverse impact upon the selective vaporizatlon process because the flne mineral particles are continuously removed from the system and at least that portion of the coarser mlneral particles -hich is or can be si2ed to fom~ a fluidi2able ~olld ~rass can be used as contact mineral in upgradlng cha rges of bitumen concen tra te s.
The bl tumen feed may CO~Dprise a crude bi tumen concentra te prepared by extraction or one which has been sub~ected ~o some addi~ionalrtreatment, such as solvent upgradin8-Por treatment of the initial bit~nen char~e as well as for use throu~hout the selective vap~rization rocess, calcinecl kaolin cla~J
~nicrospheres containin~ a mixture o crvstals of mullite and ~lllca. Commercial sources of mullite and crystalline silica 1~; may be used after belng ground and slzed to a particle size distribution such that the materlal can be fluldized.
The heat requirements of the syYtem are supplled essentially by the heat of combustion of the coke deposlted on the contact materlal during the vaporlzatlon process. The requlrements lnclude the heat necessary to brlng the various components of the feed (hydrocarbonaceou~ materlal, entrained water and any sand, etc.) to the contactor temperature and the heat of vaporlzatlon and reactlon of the varlous hydrocarbon feed c~mponent~. The regenerator heat requlrement~ ~ust al~o be consldered.

These include the heat necessary to ~rlng alr, contact materlal and the deposlted colce to the regeneratlon temperature. Finally, some allowance must be made for heat 1088 to the environment. Through evsluatlon of these heat balance requlrements of the sy~tem, it hss been determlned that raw bitumen charge contalnlng optlonally up to about 7.5% by welght of coarse mlneral matter (sand) thst doe~ not deposit on particles of contact material relative to the bltumen can be treated through the selectlve vaporization 3~

~9~
process wlth a practical m~nimum conversion to coke ~quivalent to about 80 of the Conradson Carbon value. Moreo~er, upwards of 300% by weight coarse mineral matter in the bitumen charge could be accommodated, albelt with a higher production of coke. The bitumen charge may also contain substantial amounts of water. For the llmiting case in whlch the sand content of the feed is minimal and the converslon to coke ls equivalent to 80X of the CC
value, at least 14 weight percent of the charge based on the bitumen may be water, and as much as about one-half of the charge as water can ~e accommodated with an acceptable level of coke production.
The selective vaporization process i~ characterized by short resldence times of the charge in the contactor. As used here~n, hydrocarbon residence time 18 calculated as length of the contactor from the charge introductlon point to the point of separatlng solds from vapors divided by the superficial linear velocity at the solids separation polnt, thus assuming that linear velocity 18 constant along the contactor. The assumptlon 18 not strlctly accurate but provldes a hlghly useful measurement. As 80 measured, the hydrocarbon residence time will be less than 5 seconds and preferably less than 3 seconds when applying the process to best advantage. Slnce some cracklng, partlcularly of the deposit on the inert ~olld, wlll take place at the preferred temperatures for bitumens, the extent to whlch residencQ tlme can be reduced 18 ofeen limited by characteristics of the equipment employed. If the equipment permits, readence elmes of less than Z seconds are preferred and residence tlmes of le3s than one second are most preferred.
In general, ehe selectlve vaporizatlon process is carried out under temperatures and pressures correspondlng to those currently used ln 3electlve vaporlzation of ~ea~y crudes and dlstillatlon resldua thereof.

The contact materlal is generally heated above about 1100F; the upper temperature llmlt 18 determlned by the partlcular burner employed and rarely exceeds 1800F. When lmpacted by the charge, the contact materlal has ln 9~6 most ca~es a temperature of at least 800F; temperature~ above 850F, and ~ost particularly ln the range of 900-1050F, are preferred. The operatlng pressures in the sy~tem are preferably as low a~ possible. Thi~ presgure rarely exceeds 50 psia, and i8 usually about 20-35 psia.
The instant invention is preferably conducted in a contactor very similar ln construction and operation to the riser reactors employed in modern fluid catalytic cracking (FCC) units. Bitumen charge prepared according to the cold or hot water processes described above, diluted with an equal weight of low boiling hydrocarbon diluent such as kerosene and containing about 2500 ppm to 7 wt X fine mineral matter ba~ed on the bitumen, i8 introduced at the lower end of a vertical conduit. ~nless sufficlent solvent used to refine the upgraded tar sands remains with the bltumen, additlonal volatile material, such as light hydrocarbon recyclad in the process, steam, gas and/or water, 18 added in amounts sufficlent to decrease substsntially the hydrocarbon partial pressure of the feedstock.
The pressure ln the system should be sufficient to overcome pressure drops, and is generally on the order of 20 to ~0 psia. The charge may be preheated ln a hest exchanger or a furnace before introduction to the contact~r. This preheating may be to any desired temperature below thermal cracking temperature. Typically, the charge may be heated to about 200-800F, and preferably to about 300-700F. Hlgher temperatures would induce thermal cracking oi the feed, wlth the result being increased production of low valued product.

With réference to the accompanying Figure 2, the feed, optlonally 2~
further diluted by llght hydrocarbon~, steam or the llke, rlses ln the contactor 1 at high velocity, such a~ for example 40 feet per second. Hot lnert 801~d in flnely di~ided form is lntroducet lnto the feed from a ~tandpipe 2 in a qusntity sufficient to provide a mlxture at a sultably elevated te~perature which csuses depositlon of all components of hlgh CC
number and high metal content as well as the ma~ori~y of the fine mineral ~atter onto the contact material and volatili2stion of l~ghter, hydrogenrich hydrocarbons.
The length of the contactor 1 i8 such to provide a short re~idence time for contact between the feed and the contacting agent. This is preferably on the order of 3 seconds or less, more preferably about 2 seconds, and most preferably 1 second or le~s. The re~idence time, however, should be sufficiently long to allow for good unifor~tty of contac~ between the feed and the contacting agent, i. e., at least about 0.1 secdnd. The residence tme i8 cslculated on the baslQ of the vapor residence time .
determined from outlet condltions.
At the top of the contactor, e. g., about 30 to 40 feet above the poln~ of introduction of contactlng agent from standpipe 2, vaporized hydrocarbons are separated as rapidly as possible from particulate solids bearing the high CC deposits and metals. Thls may be accomplished by direct discharge from the contactor into a large disengaging zone defined by vessel 3. It is~however, possible that the contactor discharge~ the product directly into cyclone separators 4 from which~vapors are tran4ferred to vapor line 5. Entrained solids drop into the disengaging zone by diplegs 6 to a stripper 7. Steam and/or hydrocarbons admitted to stripper 7 by line 8 evaporate traces of volatile hydrocarbons from the solids.
The mixture of steam and hydrocarbons, together with entrained solids, enters cyclone 9 by opening lO to disengage the suspended solids for return to stripper 7 by dipleg 11. As is well known in the art, a plurality of cyclones 4 and 9 ~hy be used. These cyclones may be multistage, with gas phase from a first stage cyclone discharging to a second stage cyclone.
The cycloues may be of the stripper cyclone type described in U.S.
Patent No. 4,043,899. In this case, the stripping stea~ admitted to the cyc~one may be at a relatively low temperature, such as 400-500F, and may ~erve to perform part or all of the quenching function presently to be described. Alternatively, superheated steam or ga~ may be introduced to 94~S
1 keep the products from condensing before an external quench. A system of preference in ths present invention i8 the vented rl~er described ln ~eyers et al. U.S. Patent Nos. 4,006,533 and 4~070,159.
One embodiment of the invention utilizes hiRh efficiency cyclones.
~lith such design, cyclone efficiency will increase 80 that the minus 40 or minus 2G micron sand wlll essentially stay in the unlt. ~s this material is retained in the unit, it will become part of the circulating inventory and increase the inventory. It will eventually become l002 of the inventory and will need to be wlthdrawn a~ the inventory increases. This will eliminate the need of fresh contact ~aterial and will in effect become a manufacturlng facility for producing contact material. This same phenomena will occur lf the efficlency of the extraction plant decreases ~i.e., mineral content of the bitumen concentrate feedstock lncreases.) Therefore, sands originally in the bitumen are converted into a useful contact material after proper sizing for proper fluidization in the unit used to upgrade further charges of tar sands bitumens or even for non tar-sands operations. This could be before or after acid leach to remove deposited metals. ~8 an example, if the tar sands bitumen contains 1% mineral matter as sand, it will contain about 3.0 to 3.3# of sand per barrel of feed. If the metals level of the feed i8 100 ppm, it would take about l~/bbl of retained fresh contact material as ~akeup to control the metals level on the circulating material at 30,000 ppm. Since the feed has about 3# sand/bbl and if it is assumed that all of this is retained in the unit, then fresh contact matarial add~tion would not be needed and the equilibrium metals level will be about lO,OOO ppm. This will also requlre removal of 3#8 sandJbbl from the unit wi~h about lO,OOO ppm ~etals whlch could be used for fresh contact material addition.
The v~porized hydrocarbon from cyclones 4 and 9 passlng by way of llne 5 18 then mixed with cold hydrocarbon liquid introduced by line 12 for the purpose of quenchlng thermal cracking. The quenched product i3 cooled in condenser 13 and passed through accumulator 14. Ga~es are removed for 3~9~;
fuel from sccu~ulator 14, and water, if any, is tsken from sump 15, preferably for recycle to the contactor for generation of steam to be used ~BS an aid in vaporlzing charge st bottom of the ri~er and/or for removing heat from the burner. Condenser 13 may be advantageouQly set up as a heat S lexchanger to preheat charge to the contactor or to the FCC unit employed ubsequen tly.
In one embodiment, quenching is advantageously conducted in a column equipped with vapor-liquid contact zone~ such as disc and doughnut trays and valve trays. Bottoms from such a column quencher (Syncrude~ could go directly to catalytic cracking or hydrotreating with overhead passing to condenser 13 and accumulator 14 or the overhead could be further fraction~ted to recover the solvent, recycle streams, and naphtha, gas and water from accumulator 14.
Certain advantages can be realized in the system by the use of recycled llght hydrocarbons at the bottom of contactor 1 for further vapor pressure reduction if the solvent is present in a~ount sufficient to reduce the viQcosity oi the bitumen to an acceptable level but i8 not present in amount to achieve the desired reduction ln hydrocarbon vapor pressure.
Recycle of water from accumulator 14 for thls purpose requires that the effluent of the contactor be cooled to the condensation point of water. In thi~ water vapor/hydrocarbon vapor system, that temperature would be about 150F. When hydrocarbons are used for pressure reductlon and a~ the stripping medium at llne 8 condensation becomes unnecessary when only small a~ounts of water are associated with the bitumen. In particular, the use of hydrocarbon both as dlluent and for vapor pressure reduction allows for efficient recycling of this material. The contactor effluent may be passed directly to a catalytlc cracking reactor. In thls case, the contactor also functions as the ca~alytlc cracklng preheat furnace.
The llght hydrocarbons chosen to boll below the temperature in contactor 1 for use both as diluent and as means for vapor pressure reduction are preferably recycled in the process. Uhile for purposes of vapor pressure reduction, light hydrocarbons such as n phtha, kerosene andlor gas oll fractions derlved from the proces~ may be employed, the use of the gas fraction derived from the process is preferred. In particular, the use of these liquid solvent~ during the separation of bieumen from the ~, raw tar sand and their retention in the selective vaporization feedstock leads to an especially efficient system.
The liquld hydrocarbon phase from accumulator 14 i~ a desslted, decarbonized and demetallized fraction which, after removal of an~r entrained particlulate sand not removed by cyclones 4 and 9, would be satisfactory charge for catalytic cracking or, where desired~ hydrotreating to increase the hydrogen content. This product of contact in contactor 1 may be used in part as the quench liquid at line 12. The balance is preferably transferred directly to a subsequent refining stage via line 16. This product may be optionally treated with a partlculate separation means prior to refining.
In stripper 7, the catalytically inert solid particulate materlal, beari~g a discontinuous coating of particles of deposited mineral natter, passes by a standpipe 17 to the inlet of burner regenerator 18. Most commercial regeneration unit designs operate with air distributors in the combustor as a ~et at 125 to 400 feet per second (fps). As material is charged perpendicularly into the regenerator into contact with air ~ets at 125-400 fps the effect will be a combination of a fluid energy mill and a ball milling action, the latter taking place by particle-to particle contact. Assumlng circulation of regenerated contact material at 4~/~feed~
there w111 be 400i~ contact mster~al/~ l~ineral ~tter when operatil~g with a bltumen feed contalning 1 wt ~ minersl ~oatter. This will provide an ample number of colllslons to remove protuberances of deposlted mlneral matter contalning metals before it can build up into a den~e, attrition resistance shell.
This inert contact materlal also bears a deposlt of high CC and ~etallic content material. Standpipe 17 discharges to a riser 19 where lt ~eets a ris1ng column of alr introduced into line 19. The spent particles .

are mixed with hot inert part1cles from burner recycle 20, whereby tha ~nixture i~ rapidly raised to a tempersture for combustion of the depo~its froa~ treating the bltumen, e. g., 1200-1600~. The mixture enters an enlarged zone 21 to form a small fluidized bed for thorough mixing and ~i initial burning of deposits. The flowing ~tream of air carries the burnlng mass Chrough a restriceed riser 22 to discharge at 23 in~o an enlarged disengaging zone. The hot burned particles, now lsrgely free of combu~tible deposit, and mineral protuberances containing metals, fall to the- bottom of the disengaging zone, burner 18. A portlon of the particles is introduced into recycle 20. Another part enters standpipe 2 for supply to contactor 1 after steam stripping. Because of the high tempera~ure~ which csn be obtained in this type of burner, C0 will burn to provide a flue gas containlng very little of that 8as in the presence of a stoichiometric excess of oxygen. In other types of burners, the combustion products may contain substantial amounts of C0 whlch can be burned for lts heating value in C0 bollers of the type commonly used in FCC unlts.
In the type of burner shown, the gaseous products of combustlon, containing carbon dioxide, some res1dual oxygen, nitrogen, oxides of sulfur and nltrogen, and perhaps trace CO, enter a cyclone 25 to disengage entrained solids for dlscharge by dlpleg 26. As is known in the art, a plurall ty of such cyclones may be used. The clarlfied gases pass to a plenum 27 ~rom which flue gas 18 removed by outlet 28.
Although the system ~ust de~crlbed bears a superflclal resemblance to an FCC unlt, its operatlon is very different from that of an FCC syste~n.
Of greatest s1gnificance is the fact that the contactor 1 is operated ln such a manner as to remove fro~ the charge an amount not greatly in excess of the equi~rsle~t of twice the Conradson Carbon value of the feed. This is achieved by the very low severi ty cracking due to the inert character of the solid and the very short residence eime at cracking temperature. It i~

generally recognlzed that cracklng severlty is a function of tlme and temperature. Accordingly, lncreased temperature may be compensated for by reduced reaidence time, and vic~ versa. Ideally, no more thsn 120~ of the CC equivalent iB reaoved from the charge in tha for~ of coke. The pract~cal lower limit for the select~ve vaporization o~ bitumen is about 80X of the CC
equivalent.
The selective ~aporization process affords a control aspect not a~ailable to FCC unlts ln the supply of hydrocarbons or steam to the contactor. ~hen stocks of hlgh CC number are processed, the burner temperature wlll tend to rise because of increased supply of fuel~ to the burner. This ~ay be compensatad for by increasing the amount of t hydrocarbon~ andlor steam supplied to reduce initial pressure of hydrocarbons ~n the contactor or by recycling water from the overhead recelver to be ~aporlzed ln the contactor to produce steam.
After transfer vla llne 16, the hydroca~bon product may be introduced to the feed line of an FCC reactor operated in ~he conventional manner. Because the FCC unlt plovides a product under normal operatlons contalning 80me fines Benerated through abraslon of the FCC catalyst, it has been generally necessa~y to employ some means of physlcal separation to remove these f~nes in the FCC unlt ltself. Accordlngly, the charge to the FCC unit need not be treated to remove entrained mlneral partlcles prlor to charging.

When the products o selective vaporlzation of bitumen are to be sub~ected to a hydrogen addition treatment, removal of most of the enerained solids should be carried out in order to mlnimize pore blockage of the hydrogenation catalyst and blockages in the hydrogen addltlon unit. It is particularly adva~tageous bo collect the selective vaporization product~

with any entrained fine mineral partlcles in a settllng tank prior to hydrotreating. The bottoms from this settling tank could be fed directly lnto a catalytic cracker, burned in the regenerator or simply removed from the syste~. The llgher fractlon, referred to as ~clarified oil", is sub~tantially free of entrained solids, any remalnlng partlcles are then removad by conventional menns, such as centrifuging or electronic separatlon. These known methods for removal of solids provide hydrotreating charge containin~ a little as 500 ppm fines or less.
In some cases, it may be desirable to sub~ect the hydrocarbon product to a hydrocracking treatment. This form of high severity hydrotreating simultaneously induces molecular conversion, desulfurization and denitrification. I~ is carried out ae much higher pre~sures than a standard hydrotreatlng process as used to saturate double bonds in the hydrocarbon product, and generally requires a significantly greater hydrogen lnput a~ ~ell. Material which is to be hydrocracked should also be sub~ected to a preliminary treatmene to remove substantially all of the flnes.
Yet another method for production of useful hydrocarbon products from the selectlve vaporization product is vacuum distillation ~n a so-called "vacuum tower." The bottoms from the tower, generally comprislng materials boiling above 1000F, may be used to prepare heavy fuel oil, ~uch as Bunker C and No. 6 oils. The fraction boiling at 600-1000F can be sub~ected to conventional hydrotreating for further upgrading, or catalytic cracking to prepare hlgh octane products.
2. The Contact Materlal Kaolin clays are naturally-occuring hydrated alumlnum sllicate~ of the approximate formula A1203-2SiO2 XH20, whereln X 18 usually 2. Kaolinite, nacrlte, dicklte and halloysite are specles of minerals in the kaolln clay group. It i~ well known that when kaolln clay 18 heated ln air that a flrst tra~sition occurs at about 500C. associated with an endothermic dehydroxyla~ion reactlon. The resultlng materlal 18 generally referred tD as metakaol~n. Metakaolln perslsts until the material i~ heated to about 975C. and begins to undergo an exothermlc reaction. This material is frequently descrlbed as kaolin whlch has undergone the characteristic exothermic reaction. Some authori~les refer to this material as defect aluminum-silicon spinel or as a gamma alum~na phase. See Donald U. Breck, ~EOLITE ?K)LECULAR SIEVES, publlshed by John Wlley ~ Sons, 1974, pages 314-315. On further heating to about 1050~C., mulllte begins to form. The mullitization reaction that takes place when kaolin clay 18 utilized a~ the sole source of silica snd slumina ~Day be represented by the followlng ~i equation where the approximate chemlcal formula for l~olin (without the water of l~ydration) is given as A1203-2SiO2, and the formula for mullite is 3Al2o3~2sio2~:
3(A1203 2siO2) > 3A1203~2SiO2 ~ 4 Si2- 7-The ter~D represented by 4S102 is the free silica generated as a result of the conversion to mullite. The extent of conversion to mullite is dependent on a tlme-temperature relatlonship and the presence of mlneralizers, a~ ls well known ln the art. The free silica can be amorphous or crystalline and this will also depend on calc~ na tion tempera ture and time and the presence of mineralizers. A high purity kaolin clay can theoretically be converted into about 64Z mullite on a weight basis. The free silica formed when high purity kaolln clay is thermally converted into mullite is amorphous when calcination takes place at about 1100C. Upon heating to temperatures in excess of about 1260C. silica crystallizes and the amount of silica detectable by X-ray increase3 with temperature and time. The crystalline silica may be tridymite or crls tobalite or both.
It i8 al80 well known that the reactivlty of kaolin clay change~
as lt undergoe~ these thermal trsn9itions. See ths Breck publication supra at page 315. ~lumina in metakaolin i9 quite soluble in mineral acids.
Solublllty decreases when the clay undergoes the exotherm and the material is ~ubs tantislly insoluble when the clay passes through the exothern~ unless the calci~ed clay underg~es chem~cal reaction with wetals such as tho~e found in bl~nten.
The particles of scid-resistallt contact material are composed of an acid-insoluble fom of alumina such as alpha-alumina, crystalline silica such a~ sand, silica-alumina, or mixtures thereof. Mlxtures of acid-re~i~tant contact material may be employe~ such mixtures including those ln which particles of cry~tallin~ slllca derived from tar sand bitumen are pre~ent. Preferred contact material is composed of kaolln clay prevlously calcined at a temperature and for a time at least such that the clay passes through the characteristic exothen~Ic reaction. ~n especlally preferred lnvention embodiment of this util~zes particulate contact materlal characterized by the presence of both mullite and free silica (silica ln addltion to the silica content of the mullite component), an appreciable amount of the free silica being present in crystalline form (tridymite, cristobalite or both). Such material may be obtained by calcining kaolin clay or kyanite at a temperature above that required to cause the clay to undergo the exotherm. The contact particles may also contain small amounts of alumina not present ln mulllte, such alumlna belng a crystalline form resistant to acid such as slpha alumina.
Most preferably the contact materlal containing both mullite and free crystalllne silica ls in the form of spray dried microspheres, as contrasted to particles obtained by calcining ores such as kaolin or kyanite to form aggregates of mullite and crystalline silica which are then ground and slzed to a partlcle size distribution suitable for $1uldization.
- 20 Use of the mullite-crystalline sllica mlcrospheres is also advantageous because ash can be selectlvely removed from the contact materlal wlthout consuming extra acld ln the undesirablQ leaching of components of the contact materlal (especlally alumlna) which would have the addltlonal dra~ back of ~mparting cracking activlty to the contact material.
~hile it i~ techni~lly feasible t~ reduce surface area and cracking actlvity to acceptable le~els by calclnlng particles of contact materlal after acld treatment, such treatment wlll add to processing costs.
Consequently, these mlcrospheres can be treated wlth a strong mineral acld for effective dissolution of deposited mlneral mater as well as deposited ~etals without changlng the compo~ition and properties of the contact partlcles.

1 The especially preferred embodiment of the instsnt invention which utilises as contact material consistlng of mullite and crystalline s11ica had its genesis ln part in attempts to provide cogt-effective technology to remove deposited metals, notably nickel and vanadium, from spent contact ~material that i8 withdrawn periodically from selective vaporizations units operatin~ with resid feedstocks or highly metal contaminated petroleum crudes and is replaced by~ fresh ~aterial. Early attempt~ tQ remove large amounts of both vanadium and nickel using acid extraction were plàgued by co-extraction of significant amounts of alumina from contact material formed by calcining microsphQres of kaolin clay through the exotherm. Removal of alumina in more tban minimsl amounts re~ulted in an undesirable increase in surface area. Tho~e knowledgeable in the art of catalytic cracking are aware that increases in surface area are generally associated with increased catalytic cracking activity which is undesirable in a selective vaporization process. ~180, ~hen removal of appreciable amounts of alumina took place, the attrition-resistance of the microspheres decreased or, in some cases, the microsphere-form was actually destroyed. In either case, the metal-depleted (extracted) microsphere~ would be of limited, if any, use as a sub~titute in whole or in part for fresh charge of sontact material. In addition to the aforementioned problems, the presence of alumina in the acid leachate resulted in difficulties in bringing about the subsequent separate recovery of nickel and vanadium from the leachate.
Contemporaneously with investigations directed to provide contact materials which responded satisfactorlly to simple acid extraction for 2~ metals removal, attempts were al80 made to develop contact material that would be ~ore resis~ant to agglomeration when used in a selective vaporization process. The efforts were thwarted by the unexpected finding that increases in poros~ty did not necessarily re~ult in decreases in tendency to agglomerate. To the contrary, it was found that some material meeting the criterlon for resistance to agglomeratlon were very low in total 9~

porosity. Some material~ exhibited promising performance wlth regard to agglomeration reslstance after one or two acid rageneration treatments but disintegrated physcally when they were sub~ected to additional cycle~ of metal loading and regeneration by acid extraction.
The resolution of these seemingly unrelated problems merged with the unexpected discovery that by prov1ding alumina-sil~ca contact material co~posed predominantly of mullite and crystalline silica, bo.th problems were fortuitously solved. This was unexpected becauae the materials that formed the basi~ for these discoveries had very low porosity, less than 0.1 cc/g.
Substantially all of the porosity was contributed by macro-sized pores, l.e., pores having diameters larger than 1000 Angstrom u~its. We do not wish to be bound to any theory or hypothesis regarding the multiple benefits achievable by provlding contact particles composed predominantly of cryQtslline mullite and crystalline silica. It is believed that such tS contact particles minimize agglomeration because they contain little if any silica that i8 not contained in crystalllne form, i.e., mullite and crystalline silica. Consequently, less silica is available in chemlcally reactive form. Since the predomlnating components of the binding agent in agglomerates iB believed to be mainly silica, sodium and vanadium rich 2 crystalline phases, less binding material will be formed under the hydrothermal condition prevailing in a selective vaporization burner. We also believe that by reducing the content of reactive silica, le~s vanadium and nickel occur as silicate compounds or complexes which are difficult to dissolve with strong mi~eral acids. Consequently, a greater fraction of both metals can be removed by acid extraction.
To prepare the especially preferred novel contact material in the form of microspheres, clay the m ally convertible to mullite and free silica 8uch as high purity kaolin clay (or kyanite, whlch is also convertible to mullite and silica~ i8 f~rst mixed with a fugitive binder, preferably water, and formed into particles of deslred si~e and shape, preferably mlcrospheres formed by spray drying. The resultlng preforms are then fired (calcined) under conditlons of time and temperature conducive to substantial conversion to mullite and also sufficient to convert sillca resultlng from the S decomposition of clay or kyanite into an appreciable level of crystalline silica.
Clay or kyanite to be proces_ed into mullite/cry~talllne sllica should be hiBh ln purity. Generally these mineralQ should be low ln Iron, titania, alkalies, and free alumina. Typically, the materlal should contain at least 95X by weight (volatile free basis) of silica plus alumina.
Presently preferred are high purity, wate~washed kaollnitic clays from deposits of the type found in Georgia, such clays typically having a SiO2/A1203 molar ratio of about 2/1, and containing, on a volatile-free weight basis, less than 2Z iron (measured as Fe203) and less than lZ total alkall and alkallne earth oxides. Many clays, for example, the smectltes (e.g., bentonltes), attapulgltes, and lllltes are hlgh in alkaline earth and alkali and some clays and kyanites contain high levels of lron e.g., more than 3X expressed as Fe203 on a volatlle-free weight basis. Georgia kaolins of both the hard and sof t types have been used successfully.
The term hard clay as used ln this speciflca tion and ln the claims, mean~ kaolin clays such as the sedlmentary clays mined ln the middle and east Georgia kaolin d$stricts. These clay~ are distinguished from the more commonly known and used soft kaolin clays in a number of ways as 2~ summarl~ed, for exa~ple~ ln table form at page 29 of "Field Conference, Kaolin, Bauxlte, Fuller's Earth, Annual Meeting of the Clay Minerals Society, 1979".
Hard and soft kaolin clays are also distinguished from each other ln Grim's "Applied Clay Mineralogy", 1962, McGraw-Hill Book Company, Inc., at pages 394 to 398 thereof A

A8 mentloned in the ~rim publication, hard kaolins are generally darker than soft kaolins. The Grlm text also point~ out that the ultimate ~ize of particles~ i.e., the ~ize of the particles ln a well-disper~ed clay pulp, of hard kaolin clays i8 signiflcantly finer than those of soft kaolln clays. ~8 described in the Grim text, a representatlve sample of hard kaolin clay had about 90X by weight of the ultimate size particles finer than 2 ~icrons and about 60% by weight finer than 1l2 micron, the average particle slze of typical hard clays being below 1/2 micron. Soft kaolin crude clays in contrast, contain a substantial amount of particles coarser than 2 microns, with the average particle size of a representative papermaking soft kaolin clay being about 1 micron, with only a minor amount finer than 1/2 micron. Such particles generally differ from - the finer particles in that the former are composed of a substantial proportlon of stacks or booklets of hexagonal clay crystals. Still other lS stated differences in the Grim text between hard and soft clays are that hard kaolin clays tend to be le~s ordered (less well cry~talllzed) than soft kaolin clays which therefore produce more sharply defined X-ray diffraction peaks, and the hard kaolin clays ab~orb less water than do soft kaolin clays .
The particle size distribution of the clay and its degree of agglomera tion in the 8reen bodies (i. e., the bodies obtained af ter for1ning into particle~ and prior to calcination) 1nfluence the hardness and structure of the calcined bodies. However, too much macroporosity may reduce the strength and attrition res1stance of mullièe/crystalline bodies.
Therefore, the partlcle size and degree of agglomeration of clay used to produce crystallineJ~ilic~ mullite partlcles 18 a compromise between maximum strength ~i.e., minimum poroslty) and some macroporosity. Clays with broad particle size dlstributions generally produce minimum porosity. An example of such a clay I~ ASP'19 900 hydrous kaolin, which contains particles up to 20 microns in diameter, an average particle size (welght basis) of ca. 1.5 A~

~icrons, and about 25~ by weight ~iner than 0~5 micron. Clays with a narrower psrticle si~e distribution do not pack as efficiently as clays having a broader particle size distribution, resulting in a greater quantity of mscroporosLty. An example of such a clay is ASP~ 400 hydrous kaolin, which contains particles up to 20 microng i~ diameter, an average particle size of ca. 5 micronQ and nothing <0.5 micron. A good compromise between these extremes, whlch results in less than about 0.1 cc/g of macroporosity in microspheres after calcination, is ASPD 600 hydrous kaolin which contains nothing coarser than about 8 microns, has an average particle size of 0.9 micron and contains 35% <0.5 micron. (As u~ed herein, all particle si~es of hydrous clays in the micron-size range are those determined by sedimentation and are eherefore expressed as "equivalent spherical diameter" or "e.s.d."
in conventional manner.) A preferred source of hard clay is the coarse size fraction of a hard kaolin crude that is produced a~ a waste by-product stream in the commercial production of calcined low abrasion clay pigments from hard clay as described in U. S. 3,586,523 to Fanselow et al. This by-product stream arises when degritted hard clay crude i8 processed in centrifuges to recover a fine size fraction, typically 90% by weight finer than 1 micron, for subsequent charge to a calciner. Use of this by-product stream results in the utllization of virtually all of the degrltted hard clay crude. Thus, the fina particle size fraction is employed to manufacture a high value càlcined clay pigment having low abrasion. The pigment is substantially ` free of mullite. The remainder is employed to manufacture mullite/
crystalline silica contact msterial.
~hile tbe es~eclal7y preferred bodies contain mullite and crystalline silica as essential components, lt is possible to produce bodies in which other substantially acid insoluble ingredients are also present.
Examples of materials which are acid insoluble are certsin crystalline forms of alumina, zirconia and silica. The ;ource of added acid insoluble ~l~$~`~g~
alumina, zirconla or sllica can be a material which ls normally scld 601uble but is converted to a substantially acid insoluble form when the bodies are calcined~ For example, alumina may be added as hydrous (soluble) alumins but will be converted to acld-insoluble form dur~ng calcination. Acid solubllity 18 determined by refluxing the solid bodies with 35Z H2S04 solution for 1 hour uslng a weight ratlo of 3 part~ by weight acld solutlon to 1 part by weight of the solld bodie~. When used as an ~ngredient in making the contact particles, alumlna should be employed in a mlnor amount relative to the amount of clay. When alumlna was mixed with kaolln clay in amount in excess of 15 parts by weight to 85 parts by weight clay to form mlcrospheres, which were then calcined at 1115C to 1370C, the resulting contact material agglomerated excessively~ Microspheres which contained higher levels of added alumina (i.e., alumina added to clay in amounts of 45 to 75 parts by weight alumina to 55 eo 25 parts by weight clay) had acceptable agglomeratlon performance when they were calcined at 1260C.
However, attrition resistance was lmpalred and progresslvely decreased when the level of alumlna additlon increased. Consequently, contact materials containing hlgh levels of added alumina may be too ôOft or they may dlslntegrate durlng acld leachlng. However, whether or not small amounts of alumina or other acid insolubles are also present, the bodie~ should contain no more than about 3Z-SX by weight of comblned oxldes of alkali, alkaline earth and iron which may lmpalr agglomeratlon reslstance when present ln excessive amount.
Forming can be conducted by conventional processes known in the art. Microspheres can be fo m ed by spray drying a slurry of clay ln water.
In addltlon, a fugitlve binder, such as polyvlnyl alcohol, may be added to the slurry prior to apray drying to impart additional strength to the 8reen microspheres prlor to calclnation. The preferred method to form microspheres is to prepare a slurry contalning about 65 wt X of finely-divided, high purity hydrous kaolin clay (e.g., ASP9 600 clay), 0.3 s 1 wt X tetrasodlum pyrophosphate, based on ~he weight of the clay, snd water;
and to spray dry the slurry uslng a spray dryer operating with a ga9 inlet temperature of about 540C and an outlet temperature of about 120C. This results in microspheres which, prlor to calcination, are typlcally characterized by 0.25 cc/g of macroporo~it~ and essentially no meso- or microporosity. Particle ~ize of the microspheres i~ in the range of about 20 to 150 microns. Average size is typically 60 to 90 microns.
Control of calclnation condltions (time and temperature) influences several properties, lncluding:
1. the degree of clay conversion to mull~te and free ~lica;

2. the conversion of free sllica into required crystalllne form;
3. the pore size, bulk density and surface area of the mullite/crystalline silica product.

Useful calcining temperatures are those which give conversion of clays to mullite plu9 free crystalline silica ln practically useful ti~es.

Calcination temperature, u~ing a specific piece of calcination equipment operatlng wlth a given residence time, will vary with the nature of the clay In the particles. This is demon~trated by data in illustrative examples which indicate that lower temperatures may be used with hard clay than with soft clay. Impurities in hard clay which act a~ fluxe~ may be responsible.

Suitable calcination temperatures and times in conventional la~oratory scale muffle furnaces are shown in illustrative examples. The temperature-timQ
relationshlp has been found to vary using different muffle furnaces.

Results have been found to vary w1th the furnace used to calcine the partlcles. We believe that rotary calc1ners of the type described in U. S.

3,383~438 (Puskar et al) are suitable. However, such rotary calciners should be operated at temperatures above those mentloned ln the '438 patent since the process descrlbed therein is intended to produce low abra~ion calcined clay pIgments which should be substantlally free from mullite.
Multlple hearth furnace~ are also suitable. We bel~eve that it ls fea~lble 3~

1 to employ calciner~ in which the flame i9 noe shielded from the p~rtlcles undergoing calcinatlon. Suitable conditions are readlly determined for any given calciner. A suitable procedure is as follows. The theoretically achlevable mullite content i8 calculated from the chemlcsl compo~ltlon of S the green preformed partlcles. For example, using preformed m1crospheres consisting of high purity soft kaol~n having a S102/A1203 of 2.0, the ~axlmum mullite content will be 64%. Uslng hlgh purlty kyanite, maxlmum mullite will be about 88%. The balance, in both cases will be free slllca.
X-ray patterns are obtalned for samples calclned at varlous temperatures and lQ tlmes untll the observed mulllte content is close to the maxlmum theoretical mulllte content. Generally, a mullite index above 50 should be obtaned when calclnlng kaolln clay and sn lndex above ~5 when calclnlng kyanlte.
The progress of the development of crystalllne silica can be followed by observ1ng the helght of the peak at d - 4.11 Angstrom unlts. A6 mullite and crystall1ne sll1ca phases develop, pore volume and surface area decrease and bulk density 1ncrease 8 .
Representat1ve mlcrospherical contact material used in practlce of the lnvention has a partlcle size dl~tribution sultable for fluidization.

Typically, average particle slze is 60-90 microns. The ~artlcles should be substantlally catalytically lnert, i.e. the activity (conversion) should be belo~ 20 and ~ost preferably below 10 when tested by the MAT procedure.
F~ulk ~lensitv is in the ran~e o~r 1.1 to 1.~ ~Jcc. ~ is belc~ 2~sec~, ~re~era~lv belcw l~/sec., and most nrei~erably ~el~ 0.5%/sec.

~gglomeration of the metals and ~aden mlcrospheres should be below 4S, most preferably below 25, when determined by the test descrlbed hereinafter and expres~ed as ~mean particle slze or change ln mean partlcle slze. Uhen refluxed with 35~ H2S04 for I hours at a liquid/solids ratio of 3ll, ehe alumlna content should be reduced by no ~ore than 5~ weight, preferably less than 3% by weight; the EAI of the mlcrosphere3 should be 9~
substsntislly unchanged and the surface ares should not increase above about 20 m2Jg. Surface area of fresh microspheres is 20 m2/g or less, preferably lower and may be significantly less than 5 m2/g, e.g., 1-3m~/g. Preferably, more than 80X deposited vanadium and nickel should be amenable to removal by extraction. Most preferably, removal of Ni and V
is greater than 90~. Also, after the microspheres are u~ed and contain deposits of nickel and vanadium, more than 80% and, most preferably, more than 902 of the nickel and vanadium should be amenable to removal by the acid reflux treatment whlle resulting in reactivated mlcrospheres having physical and performance properties substantially the same as tho~e of the fresh microspheres. A posslble exception i9 that the resulting reactlvatèd microspheres can increase slightly in surface area, preferably not to value~
over 20 m2/g. In the most preferred embodiment, the microspheres should be capable of undergoing repeated cycles, for example 3 or more cycles, of metal deposition, and reactivation by acid extraction of deposited me~als to provide microspheres having physical and performance properties similar to those of the fresh microspheres.
3. The Acid Leach A variety of acid leach procedures may be used to remove the ashed deposited mineral matter from the withdrawn contact material samples. The preferred acid leach procedures will remove at least about 40X by w~ight of the calcium oxide present of the surface of the materials. Typically~ CaO
and TiO2 contents of up to about 3Z can be tolerated. Iron oxide is ~asily removed, 80 most processes capable of reducing CaO and TiO2 to the des~red levels will also reduce iron to levels below about 1.52, which is usually satisfactory.
The acid leach reactivation process shown in Fi~ure 2 is used to remove colloidal clay and, preferably, simultaneously to remove metals (nickel and vanadium) from spent contact materlal withdrawn from the burner ~0 of a selective vaporization unit and to produce reactivated contact ~aterial 9~
which 19 acceptable for reuse in the same or a different selective vaporizat~on unlt. The presently preferred process u~es a high temperature mineral acid leach to remove deposited mineral matter and metals from the substrate material followed by filtration to separate the me~als-containing solution from the contact materlal. The metals ~ay be separated from the leachate and purified in separate processing steps and can be sold as by-products. Hydrochloric acid, nitric and sulfuric acid extraction at temperatures in excess of about 88C have been used with success.
Fresh makeup of substantially inert contact materlal in a selective vaporizatlon unit is dependent on the quantity of contaminant metals in the feed as well as the desired metals loading on the contact material. As an example, a 350 ton inventory unit processin~ 50,000 barrels ~ per day of a feedstock containlng 150 ppm of Ni + V would require a withdrawal and 1088 rate of 42 tons per day ln order to maintain a 3wtX
loadlng of Ni + V on the clrculating contact material. Dally withdrawal and 1088 of contact material approxlmates the addltlon of fresh contact materlal. Metal laden mlcrospheres wlthdrawn from the burner of a selective vaporlzation unit typically contain about 0.5 to 0.01 wt.X carbon. Vanadium may be V+5 or V+4 oxidatlon states or both. The oxidatlon state of vsnad~um wlll vary wlth the level of excess oxygen ln the burner.
4. Definition and Detalls of Te~t Procedures Used Herein Identification of Nullite Crystal Phase Using X-ray Powder Diffraction X-ray Powder Diffraction File, Card No. 15-77C, Leonard G. Berry (Ed.), Jolnt Committee on Powder Dlffract~on Standards*, 1972 was used as ~;
the reference for the mullite X-ray powder diffractlon pattern.
*lfiOl Park Lane, Swarthmore, Pa. 19081 Mulllte index ls measured by standard quant~tative X-ray diffraction technlques relatlve to a nominally IOOX mulllte reference and uslng copper K-alpha radiatlon. A mulllte lndex of 100 means that the mullite X-ra~ ~eak intansity for the peaks at 16, 33, 40, and 60~erhave lntensltles equal to the 100% mullite reference.
Identlflcation of Tridymlte and Cristobalite Crystal Phases using X-ray Diffraction It is well known that quantitative analyses of cristobalite or tridymite phases by X-ray diffraction are difficult because of the influences of crystal strain and lack of a suitable standard. Qualitative phase identification can be obtained for cristobalite (Card No.~ 11-695) and for ~ridymlte (Card No. 18-1169 and Card No. 18-1170.) Surface Area and volume of pores in ran~e of 20-lOOA:
The surface area and the volume of pores having diameters in the range of 20-lOOA were determined by convention~l nitrogen adsorption and desorptlon techniques, respectively, u~ing a Micromeritics~ ~igisorb 2500 Automatic Multl-Gas Surface Area and Pore Volume Analyzer. Before being lS te~ted for surface area and volume of pores havlng diameters in the range of 20-lOOA, the materlal belng tested was flrst pretreated by heatlng under vacuum at about 250C for 16 hours.
Volume of pores in range of 100-20,000A

The volume of pores havlng diameters in the range of 100-20,000A
was determlned by a conventlonal mercury intrusion porosimetry technique using a scannlng mercury porosimeter manufactured by Quantachrome Corp. The relationship between pore diameter and intrusion pressure was calculated uslng the Washburn equation and assuming a contact angle of 140 and a surface tension of 484 ergs/cm2. 8efore being tested for volume of pores having diameter~ in the range of 100-20,000A, the materials being tested were pretreated by heating them in air to about 350C for one hour and then cooling them in a dessicator. The term total pore volume as used in the spec~fication and clai~s refers to pore volume contained in pores with diameters in the range of 100-20,000 Angstrom units.

1 ~9~
Micropores:
Pores having diametQrs below 100A as dater~ined by nitrogen porosimetry.
Hesopores:
Pore~ having dia~eters in the range of l00 to 600A by mercury porosimetry.
Macropores:
Pores having diameters in the range of 600 to 20,000k by mercury porosimetry.
Engelhard Attrition (EAI) Te~t:
Preferably, the mlcrospheres used in the ART process are hard enough 80 that they do not attrit at an exce~sively high rate in the selective vaporization unit. For example, the Engelhard Attrition Index (the "EAI") of the microsphere~ used in the process preferably should be less than 2%/sec. preferably less than lX/sec. and ~ost preferably les~ than 0.5Z/sec. The EAI is determined by ~he procedure described in the publication entitled "Engelhard Attrition Index." A copy of this publicatlon has been deposited at the Library of the Technical Infor~ation Center, Engelhard Corporation, Edison, New Jersey 08818 (Dewey Decimal No.
665.533 EC/EAI). Access to this Library, including thls publication, can be obtained by writing to or telephoning the Manager of the Technical ~nfor~atlon Center. In additlon, a copy of this publication can be obtalnad by wrltlng to: Dlrector of Patent~, Engelhard Corporation, Edison, New Jersey 08818.
2E Bulk Density Determination:
The apparent packing density or apparent bulk density of thefor~ed partlcle~ was determlned by a procedure essentlally the sa~e a~ that descrlbed in ASTM Method D-4164-82 except that 100 ml of ssmple was used and l~OO taps were employed.

~$~

Static ~gglomeratlon Test:
~ procedure wa8 developed for testlng the agglomerstlon tendency of materials under conditlons that s1mulate conditions experienced by contact material~ in a selectIve vaporization process of the type di3closed herein. In general, thls procedure involves examining the change in the particle ~ize distrlbution of a ~ample after it is exposed to steam at high temperature.
More partlcularly, the procedure that was de~eloped ~omprlse~ the followl U steps:
~ ~a) a sample 18 screened by ~lbratlng lt wlth a Rotap apparatus on a 70 mesh screen for 20 minutes;
(b) 2S grams of the -70 mesh fractlon of the sample 18 weighed;
(c) the particle sl2e distribution of the 25 gram sample is determined by vlbrating it wlth a Rotap apparatus for one mlnute on a screen assembly compri~ing 70,100, 140, 200 and 270 mesh screens;
(t) the 25 gram sample is then placed lnto a porous, Inconel basket (or another porous basket, e.g., a porous, alumina ba~ket) and the basket, containlng the sa~ple, ls put lnto a furnace where 100~ steam ls pas~ed through lt for 48 hours and at a temperature of 871C;
2Q (e) the 25 gra~ sample 18 removed from the basket and its partlcle size dlstributlon 1B determined using the procedure dQscribed ln ~c) above;
(f) the mean and median partlcle slz~ distr1butlons of the 25 ~ram sample? before and after the steam treatment, are calculated, uslng ~he followlng formulas:
dmean - ~w-d~
w - .
dmedian ~ antllog [ (w log d)l where dmean-mean partlcle size (In micron~), dmedlan-medlan partlcle slze (ln mlcrons~ w elght of a partlcle slze fractlon, d-partlcle slze, which 18 detsrmlned as shown below:

~g~9~
Par~icle Size Particle Size Fractlon tMesh) (~lcrons) ~o 250 -701+100 1~
-100/+140 l~S
-140/+200 88 -200~+270 63 (g) the difference between the mean and medlan partlcle sizes, before and after the steam treatment descrlbed ln (d) above, are calculated by the following formulas: ~-~ ~ean - dmean after stea~lng - dmean before ~teamlng ~ ~edlan ~ dmedian after steamlng - dmedlan before steamlng ~e belleve th~t the values of A mean and ~ median for a materlal, whlch are obtalned by the above procedure, provlde a measure of the amount of agglomeratlon that wlll occur when that materlal ls used in a selectlve vsporlzation process of the type descr~bed hereln. In partlcular, we belleve that ~ater~als havlng high ~ mean and a medlan vslues wlll exhib~t a greater tendenc~ to agglomerate ln select~ve vaporlzatlon proce~ses than will materlals havlng lower ~ mean and ~ medlan values.
To determlne the effect that the presence of vanadlum hss on the tendency of partlcles of contact materlsl to agglomerate, dlfferent amounts of vanadlum ~ere deposited on sa~ples. Then, those samples were te~ted to determine thelr a mea~ and ~ medlan values. Because nlckel typlCAlly 18 a1BO deposlted on the particulatQ contact materlal usod in selective vaporIzation procQ~ses of the type descrlbed hereln, nlckel wa~ alao deposleed Gn the partlcles. Typlcall~, ~a~ples are loaded with 8 wtZ metals 26 at a V/Ni we~ght rat~o of 4Jl~

etal I~pregnstlon Procedure:
The metals-impregnation procedure used in some of the illustrati~e examples i6 carrled out by contsctlng the clean mlcrospheres wlth dllute aqueous solutlons containIng nickel nltrate (Nl~N03)2 -6H20) and ammonlum metàvanadate. Metals are applled to the mlcrospheres 9~
ln a V/Ni weight ratio of 4/1. ~n applicatlon of 9.16 gra~ of nlckel nitrate in 35 ~1 of water And ten applications of 1.70 8ra~s of am~onlum metavanadate ln 35 ml of hot water are u~ed to impregnate 100 grams of clean mlcrospheres with 6.4~ V and l.~Z Ni. ~ ch of the clean S microspheres are placed Into a ~hallow pan; small portlons of the aqueous solutions are added snd mixed with the mlcrospheres to form a paste. This pa~te i8 then dried in~a convection oven at a temperature of llOC. The resultlng eake i8 broken-up into small chunks and more of the aqueous solution can then be applied. Becaù~e of the high solublll ty of nlckel nltrate, the requlred amount of nlckel can be loaded onto the mlcrosphere with only one appllcatlon of the solution; since the ammonium metavanadate has a very low solubilltr, many appllcatlons of thls solutlon are needed to load vanadlum at levels ln excess of 0.76X.
The metal~ are dispersed among the microsphere~ in a series of conditioning steps. The metals-laden sample is flrst calclned at 593C ln a muffle furnace for l hour and then ~teamed at 760C ln a fluidized tube reactor for 4 hours. The steamlng proceture for ~mpregnated partlcles treated with 100~ steam at 760C for 4 hour~ is descrlbed in ~ppendix A of the publlcatlon en~itled UEngelhard Procedure for the HydrothenDal Deact~vation of Fluid Catalytlc Crack~g Catalyst~". This publlcation has been deposlted at the Library of the Technical ~nforr~atlon Centar, Engelhard Corporation, Edlson, New Jersey 08818 (Dewey Declmal Number 665.533 EC/H).
Access to thl8 Llbrary, lncludln~ this publ~catlon can be obtained by wrlting or telephoning to ~he Mana~er cf the Tech~lcal Information Center.
2~ In add~tion, a cop~r of thls publicatlon can be obtained by wrltlng to:
Director of Patents, Engelhsrd Co~ ratlon, Edlson, Ne~ Jersey 08818. The samp~e i8 t~en passed through a 70 mesh ~creen during 20 minute~ on a Ro-tap sifter apparatus; this screenlng not only breaks apart ~oft agglomerates, but also removes extraneou8 material such as clumps of metal salts. The sample i8 then ready for tes ting.
~ 4~ --The ter~s and expressions which have been employed are used as tarm~ of description and not of li~itatlon, and there i8 no Intentlon ln the use of ~uch ter~ and expressions of excluding any equlvalent~ of the features shown and described or portions thereof, but lt 18 recognlzed that various modifications sre possible within ~he ~cope of the invention claimed.
The following example~, not to be con~trued as limiting, are glven to further illustrate the lnvention.

Thl~ example demonQtrates the de~irability of removlng flne mineral ~atter deposited on contact material from tar sands bitumen in a selective vsporization proce~s prior to circulatlng the contact material to renewed contact wlth lncoming charge of tar sand bltumen ~eedstock.
The eontact material was prepared as follows:
ASP~ 600 kaolin clay (soft kaolin clay) was slurried at 60X solids in water containing 0.3Z, based on the dry clay welght, of added tetrssodlum pyrophosphate dispersant. The slurry was spray drled in a Bowen noszle spray drier. Condltlons were: Inlet temperature of 300-350~C; outlet temperaeure of 120-150C; rear pre~sure 80 p~ig; front pre~sure 25 psig;
feed settlng 0.2 relative. The microsphere~ were calcined in a rotary calciner to undergo the exotherm. ~ullite lndex was 5. The average particle size of the microspheres wa~ 75-85 mlcron~ in diameter.
Solvent-diluted tar sands bitumen were used ln a selectlve vaporlzation proces~ carrled ouS in a conventlonal pllot plant FCC
26 rlser-regenerator sy~tem. The regeneratlon air ~aB lntroduced through a frltt¢d a1r distributlon systeR; con~eguently~ there was no provi~ion to - induce ~ttrltlon ~nd a ball ~illing action to remove colloids deposited on the contact naterial (microspheres of calcined kaolin clay) prior to recirculatlng contact materlal to the contactor. Thus, ln the pllot plant test~, the deposited colloids were able to build up a3 a den~e shell on the particles of contact material.

3~ 3S

The properties of the bitumen pr~or to dilution ~ith 601vent are set forth in Tsble ~ The chemical co~position and partlcle size distribution of the mineral mattar ln the bitumen are detailed in Table I~.
The chemical, physical and catalytic propert~es of the equilibriu~
bitumen contact ~aterial sample used to heat the bitumen are presented ln Table III. For comparison purposes, representative value~ for fresh contact material are also ~nclu~ded ln the tables, along with representative values for equilibrium contact materials used in selective vaporlzation of heavy crude oll fractions havlng high levèls of metal~ and Conradson Carbon.
Comparison of the chemical analyses (Table II and Table III) o~

the bitumen trested equllibrium contsct maCerlal sample and the mlneral matter ln the bltumen concentrate clearly indicates that a large fraction of the mineral matter in the bi~umen, especially iron, titanium, calcium and ~ulfur, has been incorporated into the microsphere sample. In addition, the surface area and micropore volume of the sample of contact material used to treat tbe bltumen were significantly higher than either fresh or aquilibriu~
contact material which had been used for selective vaporization of residual fractions of petroleu~ (resid contact material sample). These changes in the physical and chemical nature of the sample are presumed to be responsible for it~ higher catalytlc actlvity in M~T te~t results ~Table IY). The high MAT conversion values for the bitumen treated contact material sample are from high yields of C3 and C4 (primarlly olefins), snt gasoli~e. The lov yields of Cl and C2 Jnd coke product~ suggest3 that the hydrocarbon products result fron scid cracking rather than ther~sl cracklng or ~etal dehydrogenation reactions. The hlgh sulfur content on the regenerated bitu~en contact ~ater~al sa~ple is also quite unusual. The sulfur i~ probabl~ present as thenmally stable sulfate compounds. The particle size distribution i~ typlcal of equilibrium ~electlve vaporizatlon contact msterisl~ ~low levels of -40 micron material).
Several representatlve SEM photograph~ were taken, and E~X (energy disperslve x-ray) aDaly~es of the bituman sample contact material are ~ 3~

presented ln Table V. Only clay-based microspheres were pre~ent.
~pparently the deposlted mineral ~sterlal wa~ ~o flne that no large (50-70 ~icron) particles were formed. The surface roughness, protruslon~ and lrregularly-shaped particles which were observed on the microspheres 6 ~urfaces are very unusual for an equlllbrium contact material and have not been observed in samples used to treat r~sidual 0118. The close match of the chemical properties of the surface particles on the micrPspheres and the fine mineral Eatter in the bitumen clesrly indicates that the fin~ miDeral ~atter in the bitumen had deposited on the exterior surfaces of the contact material during the selective vaporlzation process operation.

From particle size data in TABLE II, it can be seen that the average particle slze of the mineral matter in the bltumen concentrate was 9 micron~ and about 10-20% by weight was larger than 80 microns. Thus, in the sample of tar sands bitumen used in this test a portlon of coarser mlneral lS matter ~3ands) had been removed during processing the raw tar sands. TABLE

IX shows chemical an~lyses of what 18 understood to be typical of coarse sand removed during beneficiation of a raw tar sands. The data lndicate that the coarse material was predominaDtly silica wlth a mean particle size of about 180 mlcron.

This example demonstrates the use of various acid leach treatments to remove tepositod mlneral matter from calcined clay contact material.
Table VI ~ummarizes the re~ult~ of several ac~d leach procedures on portions of the equll1briu bitumen contact m~terial ~a~ple obtained by calcining ksolin clay to u~der~o the exothenm without sub6tantlal mullite formation (Example 1~. The acid treated samples show slgniflcant retuctions in the levels of the varlous contaminants (iron oxlde, titanlum dloxide, calcium oxlde, nickel snd v~nadium) that accumulated on the equilibrium contact ~sterlal durlng the tar sands bltumen proces~ing. The extents of extraction of the varlous contamlnsnts are functions of the type and concentration of the various mineral ~cids used ln these experiment~.
. - 50 -Chemical anal~ses of the alumina content of the leach 801U tlons and cslculatlon~ ba~ed on data ~n Table VI show that all acid leach treatment~ decreased the Al2o3Jslo2 ratio of the remaining solid, thus indicating removal of sQme alumina from the contact material and/or the deposited solid.
Table VII summari2es the catalytic activity of these samples after the acid leach, but before calcination. Table VIII summarlze~ the reduction ln surface area observed wlth these samples after calcina~ion. These results indicate that lt ~ay be necessary to cslclne or steam contact material produced by calcining clay to undergo the exotherm without sub~tantial mulllte fo~matlon after acid leach to remove deposited mineral matter ln order t~ generate material reusable ln selecti~e vapor~ations.
Temperature~ of 1200F. or higher are lndicated.
EXA~IPt,E 3 The test work described ln this example suggests that selective-attrltion will be effective for removal of mlneral contaminants deposited on contact material during the upgrading of mineral contaminated tar sand bitumen by selective vaporization.

A sample of the equilibrium calcined kaolin clay contact material used ln the pilot plant te~t run of Example 1 wa~ sub~ected to attrition to determine whether deposited mineral matter could be ~electively attrited from the mlcrospheres of calcined kaolln clay. AB shown in Table III, the fresh contact mstQrlal (~lcro~pheres of calclned kaolin clay) analyzed approxlmately 45 wt% U 203, 52 wt~ SiO2, 2 wt% T102, less than lZ
lron oxlde and negliglble calclum. The analysis of the equillbrium contact material l~cluding dep w lt of Aineral mstter also appear~ in Table III under the lege~d ~Bitu-en Contart *sterial Sample and shows appreciably higher leYel~ of ~ron, tltsnium and calcium than were present in the contact msterial.
Since the run in whlch the mineral matter was deposited on contact ~aterisl was csrriet out in a pilot unit not equlpped with mean~ to attempt ~s~

to contlnuously attrite the Qineral depo~it during regeneratlon of the contact ~aterial, the effort to determlne the response of the equilibrlum ~terial to a high velocity air ~et was carried out in a Roller ~ttritlon test unit. This Roller attrltion test is well known in the FCC industry w'here it is used to determine the attrltion resistance of samples of fluid crackln~ cataly~t. The Roller test applles a hlgh ~elocity air ~et to a ~ample located in a U-tube below a cyclone. After the appllcation of the high velocity air, the attrited material which passed through the-cyclone is collected ln a filter. In thls exa~plè, the attrlted material wa8 recovered and analyzed by SEM/EDX techniques, insu~flcient materlal belng avallable for complete chemlcal analysis or to make a material balance.
The attrited material was found to con~ist of two general types of particles, 1.e., ~hell pieces of the order of about 10 mlcrons or less in ~ize and fine dust. SEM analysis of the mlcro3pheres remainlng after removal of attrlted material ln the Roller unit showed evidence of cracking and partial removal of the shell. The chemical compoYltions of the attrited components, expressed as oxides, are set forth below:
wt.X Shell Pieces Fine Dust Na20 ~ 0.44 Mg~ 4.95 __ 23 13.83 ~7.93 S102 23.87 51.36 P205 5.09 1.16 ~3 4 35 0.76 2~ Cl 0.14 ~
K2O 0.63 0.57 CaO 20.27 2.94 TiO2 11.16 2.79 Fe203 15.70 2.05 3~

3~3S

~ Utah, US~ tar sand bitumen ha8 been treated in a selectlve vaporization process unlt pilot plant to produce an upgraded synthetic erude. The contact ~aterial was composed of calcined kaolin clay and was slmilar to the ~aterlal descrlbed in Example 1.
The extremely heavy bisumen material had an API of 9.3 and contained 1.2 wtX ~lneraL matter.
The Table presented below ~ummarizes expected commercla`l unit yields b~sed on calculations from re~ults of pilot plant te~ts ad~usted for heat balance and providlng for continual removal by acld treatment and/or attritlon of deposlted mineral matter.
TAR SAND BITUMEN YIELDS

C2- ~ 3.2 LPG 2.7 Cs-205C. 14.1 (Cs-400F.) 205C.-345C. 10.8 (400-650~F.) 345C.+ 56.4 (650F 1) COKE 12.8 To illustrate the dramatlc change in boiling range which took place ln processin~ of thls tar ~and bltumen we ha~e illustrated in Figure 3 the distlllation curvcs of the synthetlc crude product and the bltumen feedstocL Pigure 3 shows e~tinated true boiling point distlllation and API

gravit~ curve~ of the products aod feedstoc~ ~di~t~llatlon only). Most intere~tlngly the bitu~en feedstock had an inltlal bolling polnt of about 482C. ~9OQ~F.). The synthet1c crude was substantially llghter, 70 Vol.
of which bolled below the initial boiling point of the bitumen feedstock.
Very ~mportant was the fact that the 565C.+ (1050F.+) portion of the synthetic crude amounted to only 12 Vol X of tbe synthetic crude oll. This fraction, corresponding to ~acuum residum9 comprised about 92 Vol. % of the bltumen feed~toc~. In fact, comparing the synthetic crude oll whlch would ~- produced fro~ the bltumen ~lth hea~y Arablsn crude oil indlcates that the synthetic c N de, being of much lower conta~inant content and havin~ much ~re distlllate range materlal, could be of a slgnlflcantly hlgher value.

This example illustrates the preparation of low pore volume, ~croporous fluldizable microspheres of mulllte/crystalline slllcs from hard and soft kaolln clays and suggests that both types of c18y8 can provlde contact material~ capable of belng reactlvated with bolllng sulfuric acld for removal of depo~lted nickel and vanadium at levels of about 80% wlt~out substantial coextractlon of alumina. For practical reasons the metals were deposited from aqueou~ solution~ and not during test runs (88 in Example 1) in which metal~ and colloidal clay were deposlted during contact with bitumen. The example further illu8 trates how calcinatlon conditlons alter the pbyslcal properties and response to extractlon of nlckel and vanadlum.

ASP9 600 kaolin clay (soft kaolin clay) wa~ ~lurrled at 60Z solids in water containing 0.3X, based on the dry clay weight, of added tetrasodium pyrophosphate dlspersant. The slurry was spray drled ln a 80wen nozzle spray drier. Conditions ~ere: inlet temperature of 300-350C; outlet temperature of 120-150C; rear pressure 80 psig; front pressure 25 psig;

feed settlng 0.2 r~lative.
Portlon~ of the mlcrospberes were calcined at temperatures between 1149C and 1371C for 2 hours in a muffle (~arrop) furnace. During calcination, the mlcrospheres were cont~ined in cordlerlte trays whlch were left uncovered during ~alcinatlon.
The procedure was repeated with a composlte of coar~e re~ect fractlons of hard Georgla clay kno~n as Dlxle clay. The coarse fractlons were obtalned fro3 a plant as follows. Crude Dlxle clay was blunged in water, degrltted to remove plus 325 mesh overslze, and fractlonated ln a ~0 commercial Birt centrlfuge, ln conventlonal manner, to recover a flne ~$~ 6 particle sl~e fractlon, Approxlmately 90% flner than I micron a9 centrifuge overflo~ products~ The underflow products containing the so-called coar~e re~ects" were comblned, screened to remove 325 mesh particles; portions of the screened suspenslons were centrifuged in a pilot scale Blrd centrlfuge S to recover a fine si2e fraction which was about 78% by ile~ght finer than 2 oicrons and had an average partlcle size of about 0.4 microns. The suspensloDs were flocced wlth sulfuric acld, flltered snd redispersed at about 60~ ~olids ~ith tetsasodlum pyrophosphate prlor to sprsy dr~ng as described above. Portions of the spray dried mlcrospheres were calcined as descr~bed above.

Propertles of the calcined mlcrospheres from ASP 600 clay and Dixie clay are reported in Table X.
The resulting calcined mlcrospheres were then impregnated with 3%
(wt.) metals (2.4~ V and 0.6X Nl) and then treated with mlneral aclds to remove metals. Sl~ce metals were depo6ited from aqueous llquids colloldal ash was not co-deposited.
The typical laboratory reactivation procedure consisted of weighing 50 gms of metal laden micro~pheres lnto a 100 ml round bottom flask which contained 85 8ms of 35~ (wt.~ H2S04 (llquid/solid ratlo of 1.7) and a magnetic stirrlng bar (2.5 cm length). The flask was connected to a reflux condensor and heated by means of a heatlng mantle to boillng. The tlme of leaching was measured from the onset of refluxing and typically was onè hour. The alurry was ~tlrred at th- mlnlmum speed necessary to prevent ~ettlln~ of the ~Dlcrosphere~. After oDe hour the slurry was flltered on a ~Dedlum poroslty sintere~ 2~1ass funnel ~nd the sollds were rinsed twice with about twenty mllllliters of deionized water. The reactivated microspheres were oven drled (110C.) and sub~ected to analysis of the varlous phvsical propertles and thelr resldual nickel and vanadlum levels.
For purposes of compari30n, commercial contact material was lmpregnated wlth metals and then reacti-rated. This m~terial was prepared by 3~
TABLE I
TAR SANOS BITU~EN FEED PROPERTIES
`~ API 10 Sulfur 0.4 wt. 2 Ramsbotto~ Csrbon 16 wt.
Nlckel 60 ~ppm.
Vanadlum 10 wppm. .
Ash ca. 1 wt. X

TABLE II
CHEMIC~L AND P~YSICAL PROPERTIES OF MINERAL MATTER IN TAR SANDS BITUMEN
Welght Percent L. O. I. 25.8 2 (as i8) 22.3 SO4 (as i8) 5 . 68 Volatile ~ree ba~i~
Na2O 1.12 g2 1.31 CaO 6.75 Fe2O3 16.7 TlO2 14.1 SiO2 16.3 ~l23 5.~0 NiO ---V25 0.13 SO3 6.5 TOTAL 99.8 Partlcle Size Di~trlbutlon (*~) % 0-20 ~ 61 77 ~ 0-40 m 69 86 % 0-60 ~ 76 91 0~0 ~ 84 91 Average ~artile Size m 9 9 *Sample slmllar to but not identlcal to the one for which the chemical analysls wa~ provlded.
**Dupllcate snalyses.

. .

.

TABLE III
CHEMICAL AND PHYSICAL PROPERTIES
EQUILIBRIUM SELECTIVE VAPORIZATION CONTACT MATERIALS
`
Ij ,~ Bltumen Equilibrium ChemicalContact Fresh Resid Contact ~nalyse~Material Contact Material 5wt.X)Ssmple Material Sample LOI3;541.0 0.15 ~12O344.03 45.10 '~ 44.59 SiO247.10 51.72 51.95 Ns2O0.510.45 0.91 ~e23 1.82 0.40 1.10 ```
TiO2 2.71 1.90 1.87 K2O 0.17 0.10 --CaO 2.19 0.05 MgO 0.52 0.03 --P2O5 0.63 0.45 Ni (ppm) 62S 1300 - V (ppm) 1620 2400 Leco C wt.Z ~as i8) 0.02 - .02 Leco S wt.Z (as i8) 1.32 Mullite Index 7 4 --BET S. A. (m2/g) 16.0 8.6 7.8 N2 Pore Size Dist..02 .004 --100-600 ~ (cc/g) .04 .05 --Hg Pore Volume 0.20 0.25 0.17 (cc/g) (100-20,000 A dia) Particle Size Distribution Bitumen Fresh Crude Micron Size:

0-~0 3 14 6 Avg. Part. Size 86 71 82 ` (miCrOQ) Il ~

'3~9~
TABI.E IV
il ilMAT RESULTS
`'SELEC~IVE VAPORI~ATION CON5ACT M~TERIALS
Bitumen Equilibrium HAT Contact ~re~h Contact ' Yields Haterial Contact Material (wt.~) Sample Materlal Sample C:o~ersion 23.19 7.0 6.1 H2 0.13 0.06 0.12 C2 0.56 0.50 0.69 c3+c4 2 20 0.70 : 1.1 Cs-421F 18.38 5.0 ~ 3.0 421-602~ 23.95 22.41 25.1 602+ 52.86 70.54 68.90 Coke 2~05 0.85 1~30 (Average of 2 runs) (Average of 2 runs) (Average of 2 runs) TABLE Y
EDX ANALYSIS
BITUMEN SAMPLE CONTACT MATERIAL
. Overall Micro~phere Compo~ition:
Oxide Compooent Wt. %
MgO 3.24 A1203 10 .79 SiO2 30.31 P2O5 3.41 SS)3 9.13 C80 14.60 TlO2 7.76 V25 0.46 Fe23 9 97 CuO 0.31 B. Protuberance Compo~itlon:
Oxlde t~ onent l~t. %
!!
gO 2.41 Al2O3 30.42 SiO2 39.~1 P2O5 1.63 SO3 2.61 ! K2O 0.12 CaO 3.69 T1~2 1.66 V25 0.37 Cr2O3 0.38 MnO 0.19 Fe203 16.79 g 1 _ ~ ~ O ~ ~ ~ o C
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i T~BLE IX
CHEMIC~L AND PHYSIC~L PROPERTIES OF DISCARDED
i~SAND" FRON BITUMEN TAR SAND CONCENTRATION

! L. 0. I. (wt. ~) ~.69 I! Leco C~ (wt%) 0.69 Leco S, ~wtZ) 0 . 34 Volatlle Free Ba~is (wt . X ) Ns20 2 . 29 K20 3.45 CaO 1.13 MgO 0.43 Fe203 0.89 TiO2 <0. 13 S~2 81.7 ` ~l23 8.92 Total 98. 8 Mean Particle Slze (microns) (dry screen analys1s) 181.8 .~

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calcining micro~pheres of soft Georgia kaol~n clay to undergo the exotherm and had 8 mullite index of 5 tSample A). For further purposes of c:omparison, commercial contact material also made from soft clay but calcined to mulll~e index of 39 ~Sample B) was also tested for reactivation.
E'hysical propertles of microspheres before snd after ~ulfurlc acid teactivation are ~hown in Table XI (Dixie clay) and Table XII (~SP 600 clay).
~ e~als analyses and physical properties of reactivated ~
microspheres were measured after acid extraction ln order to determine both ~ the effectiveness of nickel and vanadium removal and posslble changes In properties of the resul`tinB reactlvated microspheres thnt miBht make them unsultable for reuse ln aD ~RT unlt. The nickel and vanadium extraction results for microspheres ob~ained from Dlxie clay and ~SP 600 clay are shown ln Tables XIII and X N.
lS It ~as found that nickel was poorly extracted (20%) from commerclal contact material (control ~) by refluxlng 35Z sulfurlc acld uhlle vanadlum extraction was falrly good (63X). Extraction of vanadlu~ and nickel from the other commerclal ~ample (control B) was better (75X Nl and 80X V). See Table XV. The data for experlmental samples obtalned by calclnlng microspheres of ASP 600 clay and hard clay show that nlckel extractlon increases rapldly wlth calcination temperature over the range of 1093-1260~C. snd then more ~lowly between 1260C. and 1371C. Vanadiu~
extraction from ~oft clay microspheres showed virtu~lly a llnaar increase ~lth ri~lng calclnatlon temperature whereas the hard clay mlcrospheres exhlblted 8 ~uch grea~er extractlon ~ncre~ae betweeD 1204C. and 1260C.
calcinatlon tenperatures.
The mlcrospheres haviDg 39 mullite index (control B) exhlblted metal axtractlon performance corresponding to calcination temperatures between 1204C. and 1260C. Furthermore, the phys1cal properties of thls contact materlal are comparable to those of ASP 600 c}ay mlcrospheres prepared by laboratory calclnatlon at 1204C.

. - 56 -~;~s~
The data indicate that calcination temperatures in exce~ of 1260C. and 1316C. ~re requlred for hard clay and soft clay microspheres, respectiv~l~, to attain >BOX metals extraction.

Samples of ~SP 600 kaolin that had been spray dried and calcined in a ~uffle furnace at bed temperatures of 1149C to 1371C were used in test3 to determine whlch calcined mlcrosphere~ met the following deslred performsnce criterla related to use ln a selective vaporization unit EAI

0.5%/sec., leschability of impregnated Ni + V > 80% (Ni + V) with 35%
H~S04 under reflux contitions snd resistance to agglomeration by the static agglomeration test below 25. The result~ sre summarized in Table XY
along with 80me properties. In the aRglomeration testing, metals were loaded to total metals level of 8~ in order to provide a means to descriminate betweeu samples~ In the leaching tests, metals were loaded at 3X total. Calc~ned microspheres with superior agglomeration performance, e.g., less than 25, al80 produced excellent metal extraction results, i.e., greater 85% of both nlckel and vanadlum removed.

A sample of raw (uncalcined) high purlty kyanite wa9 obtained from 2 Vlrginia Ryanite Co. The sample as received had the following composition:
L. O. I. - 0.34%
203 - 57.93% T~02 ~ 0.93X
S102 - 40.6g% CaO - 0.02%
Fe203 - l.OX MgO - 0.04%
K20 - 0.02X Na20 - O.O9X
and was about 90~ < 325 ~e~b.
Th~s material was ball ~illed 20 hours at 60~ solids with 0.3~
Calgon T dispersant added; Agates were uset as the grinding media at 5.6 tlmes weight of kyanlte. The solids in the resultant slurry, pH 7.5, had a particle size dlstributlon as below:

85% < 4 u 35 ~ 1 u 7J~ ~ 3 u 60 < 2 u The sample was spray dried with approximately 50~ 10~8.
Furthermore, the recovered product did not have the sppearance of ~icrospheres.
~ ~econd preparation was made as sbove except ~odium ~ilicate was added as binder to spray drier feed. The addltion level for N~" Brand ~odium silic&se was 1% based on the weight of the kyanlte. The ~pray dryer product ~as calcined at owo temperatures as below:
Calcination Temp. (Pereny Furnace) 1149C 1260C
Time at Temp. 1 hour 1 hour Product Hg Pore Volume (cc/g) 0.202 0.22 BET Surface Area (N2) (m2/g) 2.1 1.9 Mullite Index not meaningful - lnterfering peaks 59 EAI (X/sec.) 0.58 0.76 Av. Particle Size (micron~) 88 70 The ~ample calcined at 1260C wa~ impregnated with 0.6X Ni, 2.4% Y
by the aqueous impregnation procedure, followed by steaming at 760C, 4 hours. The snmple was extracted with reflux~ng 20% H2SO4 for I hour (liquid~solid weight ratio of 2/1) to yield 92.5X nickel removal and 91.8%
vanadlum re~oval but only 0.9~ A1203 coextraction (ba~ed on the A1203 content of the microspheres.) Large~ quantities of calcined kyanite from the above spray drier batch were prepared with the following properties.
CalcinatloD Temp. ~arrop Furnace) 1038C 114QC
Tlme at Temp. 1 hour 1 hour Hg ~ore Volume (cclgm) 0.26 0.23 Mullite Index(not meanlngful - interfering peaks) E U (~/sec.) 3.3 1.0 9) These s~mples were evaluated for agglomeratlon. When loaded to 3X
oetals both samples agglomerated severely.
A third preparation of kyanlte micro~pheres wa~ prepared by flrst fluid energy milling the raw material. This ~a8 done in a pllot plant fluid energy mill at the following settings:
High pressure steam - 110-125 pslg Super Heaters - 315C on both Feed Rate - 32t/Hour Feed Prassure - 80-90 psig ~rind Pressure - 75-8~ psig The fluid energy mllled product wa8 subsequently ball mllled 20 hourg, as before, to yield a slurry of average particle size 1.5 microns.
The ball mill product wa8 treated with '~ Brand sodium silicate ~3Z based on kyanite weight) and spray dried. The spray drier 6ettings were:
~5 Slurry Feed Rate - 0.2 relative Slurry ~eed Pressure - 35 psig Alr Pressure - 80 psig Inlet Temp. - 177C
Outlet Temp. - 52-57C
The spray drier product was calcined in the Harrop furnace to give the following propertles:
Calcination Temp. 1260C
Tlme at Temp. 1 hour Hg P. Volume (cctgm) 0.27 ~ET Surface ~rea (~2fg) 1.~
EAI (~J&ec.~ 1.4 ~ arger quantlties of calcined kyanite were prepared for agglomeration evaluation. These samples were prepared from microspheres prepared using 3X sodium silicate binder. The only differences between these samples and the previous ones were the increased residence time in the furnace and the hlgher level of sodlum silicate added a~ blnder.
Portions of the calcined mlcrospheres were tested for physical propertles.
Other~ were impregnsted by the water impregnation technique de~cribed above to a total metal loading of 5X and tested for agglomeratlon performance.
S Xesults are summarlzed below:
Ryanlte Micro~pheres Calclnatlon Condltlons (C/Hours)1148C/2 1~60C/213~1C/2 ~gglomeratio~ 5~ metals ~ mean (mlcron) 69.3 4.9 5.7 ~ medlan (mlcron) 54.7 4.9 5 5 Physlcal Properties, Clean Mlcrospheres Mullite index 0* 47 74 Hg Pore Yolume, cc/g 0.2667 0.27130.2834 Mean Pore Radius, Angstrom 3500 4400 5300 lS Surface ~rea, m2/g 2.0 1.7 1.3 *Interfering Peaks - value may not be ~eaningful.

This example illu~trates the preparation of fluidizable microspherical contact ~aterial from mixtureo of hlgh purity kaolln clay wlth varlou~ calclned and hydrous aluminas. The clay ~aterials used were ~SP 600 ksolin clay, described above, and hard kaolln clay having a nomlnal partlcle ~i~e of about 80Z mlnus 2 mlcrons nd prepared, as described above, by centrifuglng a degritted waste stream of coar~e partlcle si~e fractlon of hard clay and recovering the fine slze fractlon. The aluminas were ~lcoa A-3 alumina (calcined ~lumina); and PG~ (fusion grade calcined alumlna) snd TGA, (~raDs~tlon gr~de alu-~Da) aluminas obtalned from Reynolds Metals Co~pany. The proportlo~ of alumlnas mlxed wlth cl~y was varled, ranging from about 15 to 75 parts by weight alumina (anhydrous ba8i~) to 100 parts by welght total mixture (try welght basls).
The procedure for preparlng contact material composed of clay-alumlna blends was as follows. An amount of tetrasodium pyrophosphate . - 60 -9~
corresponding to 0.5 wt.X of the clay componen~ of the blends was sdded to water. The pH of the ~olution of tetrasodium pyrophosphate, initially about 9.8, was then ad~usted to 7.0 by addition of concentrated phosphorlc acid.
Mlxtures of clay and alum~na were added to the resulting solution ln S - alaounts calculated to produce 60X sollds slurries. Slurry makedown was performed in a Cowles mixer. The slurries were then spray dried in a Stork-Bowen spray dryer. ~The operating conditlons of the spray dryer were:
lnlet temperature 250-260C, outlet temperature 110-120C, nozzle~pressure 35 p8ig, and pressure drop 6-7 ln. of water. Five hundred (500)g of each sample was calcined in the Harrop furnace st two different temperatures (1260~C and 1371C) for two hours.
Physical propertles were ~easured and some calcined microspheres were impregnated wlth metals and tested for extractability with acid and agglomeration. These results are presented in Table XYI. X-ray diffraction patterns indlcated that llttle if any mull~te formed beyond that expected from the clay component even with the 1371~C calcination treatment.
It will be understood that the term flne mlneral matter as used in the spec~ficatlon and clalms refers to particles that are about 10 microns or flner. The me~hods for measuring particles of such ~ize involve ~edlmentatlon and there are some differences normally encountered ln maklng measurements evon whon the same equipment te.g.. MICROTRA P analy~er) is used. For example, a partlcle may be reported aJ having a size of 10 mlcroDs (equivale~t ~pherlcal dla~eter) but others uslng the same equlpment ~ay report ~alues a~ higb ~8 15 mlcrons or a~ low as 7 microns. Particles 26 f~ner than about 2 icron~ are best measured by equipment such as a SEDIGRAPH9 ~00 ana b ze~. Particles larger than about 200 mlcrons can be measured by try ocreening. The term coarse ~lneral matter as used hereln refer~ to particles having a size grester than about 10 microns. Generally fluidlzable particles are in the 20- 200 micron size range and partlcle slze dis ibution a~ well as oize per se affect fluidizability.

Claims (24)

1. A process for upgrading a charge of a tar sand bitumen concentrate containing mineral matter including fine particles which comprises contacting said charge in a riser in the presence of a low boiling organic solvent diluent with finely divided attrition-resistant particles of a hot fluidizable substantially catalytically inert solid which is substantially chemically inert to a solution of mineral acid, the contact of said charge with said particles being at high temperature and short contact time which permits vaporization of the high hydrogen containing components of said bitumen, said period of time being less than that which induces substantial thermal cracking of said charges at the end of said time separating said vaporized product from said fluidizable particles, said fluidizable particles now bearing a deposit of both combustible solid, adherent particles of fine particles of mineral matter and metals, and passing said particles of inert solid with deposit of combustibles and fine particles of mineral matter to a regenerator to oxidize the combustible portion of said deposits, removing at least a portion of deposit of mineral matter and metals by removing said inert solid from said regenerator and contacting removed inert solid with a hot mineral acid, and recirculating fluidizable solid depleted at least in part of deposited mineral matter to contact with incoming charge of tar sand bitumen concentrate and diluent.

2. The process of claim 1 wherein said acid is sulfuric, hydrochloric or nitric.

3. The process of claim 1 wherein said inert solid comprises calcined clay or calcined kyanite.

4. The process of claim 2 wherein said bitumen concentrate contains from 2500 ppm to 20 percent fine mineral matter, based on the weight of said bitumen, calculated on a dry weight bests.

5. The process of claim 4 wherein said bitumen concentrate also contains water.

6. The process of claim 5 wherein said fine particles of mineral matter are present as an emulsion in said bitumen concentrate.

7. The process of claim 1 wherein said regenerator is provided with cyclones and high velocity air jets to attrite deposited mineral matter from said attrition-resistant microspheres, and recovering material removed by attrition from the regenerator.

8. The process of claim 1 wherein the mineral matter also includes coarse particles comprising quartz or diatomite.

9. The process of claim 1 wherein said vaporized product is further refined to produced one or more premium products such as gasoline.

10. The process of claim 1 wherein spent fluidizable inert contact material 18 withdrawn on a continuous or semi-continuous basis in order to maintain a predetermined average metal content in the circulating contact material and to prevent, in conjunction with said acid removal of mineral matter the buildup of high levels of metals as a deposit on said particles of contact material.

11. The process of claim 1 wherein said tar sand bitumen concentrate is prepared by wet processing such as flotation or gravity separation.

12. The process of claim 11 wherein wet processed tar sand bitumen is further processed by solvent extraction to recover a bitumen concentrate.

13. The process of claim 11 wherein said charge is diluted with at least a portion of the solvent used in the purification to obtain said concentrate, whereby the amount of solvent that is removed by fractionation from said concentrate prior to contact with said heated fluidizable solid is reduced or eliminated.

14. The process of claim 1 wherein said charge is diluted with light gas oil and/or gas recovered from the vaporized product obtained by contact of a previous charge of tar sand bitumen concentrate with hot fluidizable inert solid.

15. The process of claim 1 wherein said nickel and vanadium are also extracted with said solution of mineral acid without previously being subjected to any pretreatment to facilitate extraction of nickel or vanadium with mineral acid other than burning in air to remove residual carbon and to oxidize vanadium to the pentavalent valence state.

16. A process for upgrading a charge of a tar sand bitumen concentrate containing fine mineral particles and water which comprises contacting said charge in a riser in the presence of a low boiling organic solvent diluent with finely divided attrition-resistant particles of a hot fluidizable substantially catalytically inert solid consisting essentially of crystalline mullite and crystalline silica, said contact being carried out at high temperature and short contact time which permits vaporization of the high hydrogen containing components of said bitumen, said period of time being less than that which induces substantial thermal cracking of said charge, at the end of said time separating said vaporized product from said fluidizable particles, said fluidizable particles now bearing a deposit of both combustible solid, metals and adherent particles of fine mineral particles, reducing the temperature of said vaporized product to minimize thermal cracking and recovering said product for further refining to produce one or more premium products such as gasoline, passing said particles of inert solid with deposit of combustibles, metals and fine mineral particles to a regenerator to oxidize the combustible portion of the deposits, at least periodically withdrawing an additional portion of said particles from said burning zone and contacting them in an extraction zone with a solution of mineral acid selected from the group consisting of sulfuric, nitric and hydrochloric at elevated temperature to remove deposited mineral matter and metals from the tar sand bitumen without substantial coextraction of alumina from said attrition-resistant particles and without appreciably changing the size and hardness thereof, and reintroducing at least a part of the solid particles thus extracted from said extraction zone into said burning zone for recycle to said decarbonizing and demetallizing zone.

17. The process of claim 16 wherein said nickel and vanadium are also extracted with said solution of mineral acid without previously subjecting particles withdrawn from the burning zone to any pretreatment to facilitate extraction of nickel or vanadium with mineral acid other than burning in air to remove residual carbon and to oxidize vanadium to the pentavalent valence state.

18. The process of claim 16 wherein said particles are derived from kaolin clay.

19. The process of claim 16 wherein said particles are derived from kyanite.

20. The process of claim 16 wherein said particles also contain acid-insoluble alumina.

21. A process for upgrading a charge of a tar sand bitumen concentrate containing mineral matter, including particles of fine particle size, and water which comprises contacting said charge in a riser in the presence of a low boiling organic solvent with finely divided attrition-resistant particles of a hot fluidizable substantially catalytically inert acid-insoluble solid at high temperature and short contact time which permits vaporization of the high hydrogen containing components of said bitumen, said period of time being less than that which induces substantial thermal cracking of said charge, at the end of said time separating said vaporized product from said fluidizable particles, said fluidizable particles now bearing a deposit of both combustible solid metals and adherent particles of fine particle size mineral matter, immediately reducing the temperature of said vaporized product to minimize thermal cracking and recovering said product for further refining to produce one or more premium products such as gasoline, and passing said particles of inert solid with deposit of combustibles, metals and fine particle size mineral matter to a regenerator provided with cyclones and high velocity air jets to oxidize the combustible portions of the deposit and to heat said fluidizable particles and to attrite fine particle size mineral matter containing a portion of said metals from said attrition-resistant fluidizable particles, recirculating the heated fluidizable solid depleted at least in part of fine particle size mineral matter to contact with incoming charge, and recovering mineral matter removed by attrition from the regenerator.

22. The process of claim 21 wherein said material removed by attrition is recovered in a bag house, cyclone or scrubber downstream from the burner regenerator.

23. The process of claim 21 wherein spent fluidizable inert contact material is withdrawn on a continuous or semi-continuous basis in order to maintain a predetermined average metal content in the circulating contact material and to prevent, in conjunction with said attrition, the buildup of high levels of metals as a deposit on said particles of contact material.

24. The process of claim 21 including the step of leaching additional fine particle size mineral matter and removing metals on particles discharged from said regenerator prior to recirculating contact material to contact with incoming charge.