CA1056801A - Heavy crude conversion - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
This invention relates to a catalyst composition having enhanced selectivity suitable for the conversion and demetallization of feeds which contain large quantities of 1050°F.+ hydrocarbon materials characterized by comprising an admixture of from about 0.1 to about 10 weight percent of a Group IVA metal, or compound thereof, from about 5 to about 50 weight percent of a Group VIB metal, or compound thereof, from about 1 to about 12 weight percent of a Group VIII metal, or compound thereof measured as oxides, and a porous inorganic oxide support, said catalyst including a combination of properties comprising, when the catalyst composition is of size ranging from 1/500 to about 1/50 inch average particle size diameter, at least about 20 percent of its total pore volume of absolute diameter within the range of about 100 .ANG. to about 200.ANG.; when the catalyst composition is of size ranging from about 1/50 inch up to 1/25 inch average particle size diameter, at least about 15 percent of its total pore volume of absolute diameter within the range of about 150.ANG. to about 250.ANG.; when the catalyst composition is of size ranging from about 1/25 inch to about 1/8 inch average particle size diameter, at least about 15 percent of its total pore volume of absolute diameter within the range of about 175.ANG.A , a surface area ranging at least about 200 m2/g to about 600 m2/g and a pore volume ranging from about 0.8 cc/g to about 3.0 cc/g. The catalysts have certain critical ranges of physical characteristics inclusive of large uniform pore sizes, these having been shown to possess improved catalytic activity and selectivity for the hydroconversion of the 1050°F.+ materials of the heavy feeds and residue.Novel methods are described for use of such catalysts.

Description

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The ilydrotreating of hydrocarbon or hydrocarbonaceous feedstocks, including particularly heavy petroleum crudes and residua, is not new. In the ~ast, the lower molecular weight or gas oil portion of such feedstocks has been catalytically converted and upgraded to high value fuels, while the heavy ends or 1050 F.+ materials were split out, then generally used as low grade fuel or as asphaltic materials. The 1050 F.+ material, often termed "the bottom of the barrel," is of low commercial value, even less than an equivalent quantity of raw crude.
Other related applications which describe new and improved catalysts, and hydroconversion processes, or processes for cracking the 1050 F.+
hydrocarbon portion of heavy whole crudes and residua to yield therefrom lighter boiling usable products, particularly from unconventional heavy crudes and residua which contain appreciable amounts of sulfur and nitrogen, high quantities of the so-called heavy metals, e.g., nic~el and vanadium, as well as high "ConOcarbon," high carbon-to-hydrogen ratios, high asphaltenes, ash, sand, scale and the like, are applications Nos. 219,484, 21~,496, 219,552 and 219,553 filed February 6, 1975.
Processes for the conversion of feeds containing 1050~.+
hydrocarbon materials to lower molecular weight hydrocarbons are known. For exampley in one such known process, a hydrocarbon feed and gas are passed up-wardly through an ebullating bed of particulate catalyt1c solids. The process is thus conducted under conditions which establish a random motion of the catalytic particles in the liquid without carrying the solids out of the reactor.
Based on the solid si~e and density of the catalyst particles, and liquid density, velocity and viscosity, the mass of particulate solids is expanded from about 10 pe~cent greater volume than the settled state of the mass to perhaps two or three times the settled volume. While such process has been found useful in the treatment of such feeds, it too has its limitations.

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Thus, there are certain disadvantages associated with the activity of the catalysts used in such process.
It is thus particularly difficult to treat crudes or residuas which contain large amounts of 1050~.~ hydrocarbons and the hydroconversion of 1050F.+ hydrocarbon materials to lower boiling and more useful hydrocarbons presents an acutely difficult problem.
Supply and demand considerations, nonetheless, make it imperative that new and improved methods be developed for the hydroconversion of new types of heavy crudes and residua which contain great amounts of the 1050F.+ materials which crudes and residua cannot be handled by present hydroconversion processes.
These so-called heavy crudes are different from conventional crudes in at least four important aspects, each of which makes hydroconversion of such crudes by present methods entirely unfeasible - viz., they have (1) very high Conradson carbon (i.e., "Con. carbon") or carbon to hydrogen ratios (i.e., relatively high carbon and low hydrogen content), (2) very high metals content, parti-cularly as regards the amount o nickel and vanadium, (3) they are ultra-high in their content of materials boiling above 1050~., e.g., asphaltenes~ and even (4) contàin considerable amounts of sand and scale. Properties which readily distinguish these new materials from conventional crudes are thus:
high metals, high asphaltenes, high carbon:hydrogen ratios, and a high volume percent of hydrocarbons boiling above 1050~. The presence of the greater amounts of metals and the higher carbon content of the heavy crudes9 in parti-cular, makes any considerations regarding the processing of these materials most difficult and expensive. The high "Con. carbon" and carbon:hydrogen ratios are considerably higher than those o~ any presently usable hydrocarbon liquids.
It is an object of the present invention to provide new and improved catalysts, particularly useful in hydrocarbon conversion reactions, particularly reactions involving the hydroconversion of the 1050F.~ hydrocarbon --portion of heavy crudes and residua.

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A further object is to supply new and improved methods for the preparation of such catalysts.
Another object is to provide a new and improved hydrocarbon conversion process, or hydroconversion process useful in converting the 1050 F.+
hydrocarbon portion of feeds comprising heavy crudes and residua -to useful lower boiling products while simultaneously producing appreciable Con. carbon reduction, hydrodesulfuri~ation, hydrodenitrogenation and demetallization of the feeds.
These obJects and others are achieved in accordance with the present invention which embodies (a) novel catalysts which, although they possess certain common characteristics 9 are of two distinct types as relates to an essential combina-tion of properties regarding pore size ~or pore si~e distribution~, surface area and pore volume, this enabling each to perform its function in a unique manner, a first catalyst providing enhanced selectivity for conversion and demetallization of whole heavy crudes and residua, in the presence of added hydrogen, which contains relatively large quantities of 1050F.+ materials, i.e., asphaltenes (C5 insoluble) and other large hydrocarbon molecules, which are effectively converted to lower molecular weight products, and a second catalyst particularly suitable for the efficient conversion, demetalli~ation 20 ~ and Con. carbon reduction of hydrocarbon materials, particularly of a feed of `
character similar to the product resultant from a hydroconversion process utilizing said first catalyst. Conversion, as used herein, thus requires chemical alteration of the 1050F.~ hydrocarbon molecules to form lower mole~
cular ~eight molecules boilin~ below 1050F. (i.e., 1050F.-) and it is measured by the weight decrease in the amount of 1050F.~ hydrocarbons contained in the original feed times I00, divided by the amount of 1050F.+ material originally present in the feed. These catalysts in common comprise catalytically active amounts of a hydrogenation component which includes a Group ~7IB or Group ~III

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metal (especially, a Group VIII nonnoble metal), or both (Periodic Table of the Elements, E.H. Sargent and Co., Copyright 1962 Dyna-Slide Co.), particularly molybdenum or tungsten of Group VIB, and cobalt or nickel of Group VIII, and preferably a Group VI~ and Group VIII metal in admixture one metal with the o~her, or with other metals, or both, particularly Group I~ metals, composited with a refractory inorganic sup~ort, notably a porous, inorganic oxide support, particularly alumina, or more particularly gamma alumina, (i) said first catalyst, hereinafter termed "R-l"
catalyst for convenience, including a combination of properties comprising, when the catalyst is of size ranging up to 1/50 inch average particle size diameter, at least about 20 percent, preferably at least about 25 percent, and more preferably a~ least about 70 percent of its total pore volume of absolute diameter within the the range of about 100~ (Angstrom units) to about 200~;
when the catalyst is of size ranging from about 1/50 inch up to 1/25 inch a~erage particle size diameter, at least about 15 percent, preferably at least about 20 percent, and more preferably at least about 45 percent of its total pore volume of absolute diameter within the range of about 15 ~ to about 250~; when the catalyst is of size ranging from about 1/25 inch to about 1/8 inch average particle size diameter, at least about 15 percent, preferably at least about 20 percent, and more preferably at least about 30 per cent of its total pore volume of absolute diameter within the range of about 175~ to about 275~, wherein, in each o~
these catalysts of differing ranges of particle size distri-butions, the pore ~olumes resultant from pores of 50~, and ~. : ,.. . . ..... . .

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smaller, i.e., 50~-, are ininimized; and preferably, while in catalyst average particle size below 1/50 inch, the pore volume resultant from pores of diameter above 300~, i.e., 300~+, is minimized9 and in catalysts of average particle size above 1/50 inch, the pore volume resultant from pores above 350~, i.e., 350~+, is minimized; the surface areas and pore volumes of the catalysts being interrelated with particle size, and pore size distributions, surface areas ranging at least about 200 m2/g to about 600 m2/g, and preferably at least about 250 m2/g to about 450 m /g, with pore volumes ranging from about 0.8~to about 3.0 cc/g, and preferably from about 1.1 to about 2.3 cc/g (B.E.T.):
(ii) said second catalyst, hereinafter termed "R-2"
catalyst for conyenience, over the spectrum of particle sizes ranging to l/8 inch average particle size diameter, is one including a combination of properties comprising at least about 55 percent, and preferably at least about 70 per-cent of its total pore volume of absolute diameter within the range of about 100~ to about 200~; less than 10 percent, preferably less than 1 percent of the pore volume results from pores of diameters 50~~; less than about 25 percent, and preferably less than 1 percent of the total pore volume resuIts from po~es of diameters ranging 300~+; surface areas ranging from about 200 m2/g to about 600 m2/g, preferably from about 250 m2/g to about 350 m2/g, and pore volumes ranging from about 0.6 to about 1.5 cc/g, and preferably from about 0.9 to about 1.3 cc/g ~B.E.T.):
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(b) a novel method for the preparation o e said R-l and R-2 catalysts from an aqueous or alcohol synthesis sol comprising dispersing an aluminum halide in an aqueous or alcohol medium, and adding an organic reagent which combines with the halide and removes the halide from solution as an organic halide7 with control of water (or alcohol):aluminum salt ratios7 and control and removal of hydrogen halide acid generated with reaction, preferably with the additional incorporation of Group VIII noble metals or lanthanum or lanthanum series metal salts, or both, to provide the selective pore si~e distributions, particularly as relates to the formation of extrudates, with concurrent optimization of surface area and pore volume, as required for the production of R-l and R-2 catalysts; and (c) a conversion process, conducted with said R-l catalyst, in an initial or first reaction zone comprising one or more stages (and in one or more reactors) wherein a hydrocarbon or hydrocarbonaceous feed, e.g., a coal liquid, shale liquids, tar sands liquids, whole heavy crude or residua feed, containing 1050F.~ materials, especially one having the ~ollowing characteristics, Operable Preferred Range_ Range Gravity, API-5 to 20 0-14 :~ 20 Heavy Metals (Ni & V), ppm5-1000 200~600 - L050 F.+, Wt~%10-100 40-100 ~ Asphaltenes ~C
: insolubles~, W~.% 5-50 15-30 ` Con. Carbon, wt.% 5-50 10-30 is contacted, in the presence of hydrogen at severities sufficient to convert at least about 30 percent by weight and preferably from about 40 percent to about 60 percent of the 1050F.~ materials of the crude or residua present to - 6 - ~:

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1050F.- ma~erials, remove at least about 75 ~e~cent, and preferably from about 80 to about 95 percent, by weight oE the metals, preferably producing a product having the following characteristics:

Operable Preferred Range Range Gravity, API 14-30 15-25 Heavy Metals (Ni & V), ppm10-100 40-80 1050 F.~, Wt.%10-50 25-40 Asphaltenes (C
. insolubles), ~t.~ 3-20 5-15 Con. Carbon, wt.% 3-20 5-10 which product is suitable Eor further contact, in the presence oE hydrogen, in a second or subsequent reaction zone comprising one or more stages (and in one or more reactors) with said R-2 catalyst at severities sufficient to convert at least about 50 percent, and preferably from about 60 percent to about 75 percent of the 1050 F.~ materials of the crude or residua to 1050 F.- materials, remove at least about 90 percent, preferably from about 97 percent to about 100 per-cent, by weight of the metals, and reduce Con. carbon from about 50 percent to about 100 percent, and preferably from about 75 percent to about 90 percent, especially to produce a product having the following characteristics Operable Preferred Range ~ang~
Gravity, API 18-30 20-28 Heavy Metals (Ni & C 50 < 5 V),ppm 1050F.+, Wt.% . 5-30 10-25 Asphaltenes (C
insolubles), ~t.% ~ 3 Cl Con. Carbon~ Wt.% ~ 5 <3 ~" ` : ,, . . .

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In their optimum fo~ms, the absolute pore size diameter, of the R-1 catalyst, dependent on particle size, is maximized within the 100-200~, 150-250~, and 175--275~ ranges, and the R-2 catalyst within the 100-200~ range, respectively. It i5 not practical, of course, to eliminate the presence of all pores of sizes which do not fall within these ranges, but metllods of preparation are known, particularly methods of preparation according to this invention, which do indeed make it practical to produce catalyst particles of absolute pore size diameters highly concentrated within these desired ranges. The following tabulations show the pore size distributions, as percent of total pore volume, of marginal and preferred catalysts of this invention:

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' . ~ ' . , i :' ~ : , ., ' ' ' . , ' . : ' ` ~. . , . : ,' ' ' ' ', The R-1 and R-2 catalysts can be the same or different as regards their specific chemical composition, qualitatively or quantitatively, though certain different forms of these catalysts have been found to provide better results when used in the different and preferred process modes--viz. when R-l -is used in an initial or first reaction zone to process heavy crudes or residua, hereinafter referred to as "R-1 service," and when R-2 is used in a second or subsequent reaction zone to process, e.g. the product of said initial or first reaction zone (or feed of similar nature), hereinafter referred to as "R-2 service." In general, however, both the R-l and R-2 catalysts can comprise a composite of a refractory inorganic support material, preferably a porous in-organic oxide support with a metal or compound of a metal, or metals, selected from Group VIB or Group VIII, or both, the metals generally existing as oxides, sulfides, reduced forms of the metal or as mixtures of these and other forms.
Suitably, the composition of the catalysts comprises from about 5 to about 50 percent, preferably from about 15 to about 25 percent ~as the o~ide) of the Group VIB metal, and from about 1 to about 12 percent, preferably from about 4 to about 8 percent (as the oxide) of the Group VIII metal, based on the total weight (dry basls) of the composition. The preferred active metallic components, and forms thereof, comprise an o~ide or sulfide of molybdenum and tungsten of Group VIB, an oxide or sulfide of nickel or cobalt of Group VIII, preferably a mixture of one of said Group VIB and one of said Group VIII metals, admixed one with the other and inclusive of third metal components of Groups VIB, VIII and other metals, particularly Group IVA metals. The preferred R-l and R-2 catalysts are constituted of an admixture of cobalt and molybdenum, but in some cases the preferred R~2 catalysts may be comprised of ni.ckel and molybdenum. The nickel-molybdenum catalyst in R-2 service possesses very high hydrogenation activity and is particularly effective in reducing Con. carbon. Other suitable Group VIB
and VIII metals include, for example, chromium, platinum, palladium, iridium, . ,: .. : . ~ . . ...... .. . ' . . . . : .

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osmium, ruthenium, rhodium, and the li~e. The lnorganic oxide supports suitably comprise alumina, silica, ~irconia, magnesia, boria, phosphate, titania, ceria, thoria and the like. The preEerred support is alumina, preferably gamma alumina, which in R-2 service is preferably stabilized with silica in concentration ranging from about 0.1 to about 20 percent, preferably from about 10 to about 20 percent, based on the total weight (dry basis~ alumina-silica composition (inclusive of metal components). The catalyst composition can be in the form of beads, aggregates of various particle sizes, extrudates, tablets or pellets, depending upon the type of process and conditions to which the catalyst is to be exposed.
Particularly preferred catalysts are composites of nickel or cobalt oxide with molybdenun~, used in the following approximate proportions:
from about 1 to about 12 weight percent, preferably from about 4 to about 8 weight percent of nickel or cobalt oxides; and from about 5 to about 50 weight percent, preferably from about 15 to about 25 weight percent of molybdenum oxide on a suitable suppoxt, such as alumina. A particularly preferred support for R-2 catalyst comprises alumina containing ~rom about 10 to about 20 percent silica. The catalyst is sulfided to form the most active species.
The Group ~IB and Group VIII metal components, admi~ed one component with the other or with a third or greater number of metal components, can be composited or intimately associated with the porous inorganic oxide support or carrier by Yarious techniques known to the art, such as by impregna-tion of a support with the metals9 ion exchange, coprecipitation of the metals with the alumina in the sol or gel form, and the like. For example, a pre-formed alumina support can be impregnated by an "incipient wetness" technique, or technique wherein a metal, or metals, is contained in a solution in measured amount and the entire solution is absorbed into the support which is then dried, calcined, etc., to form the catalyst. Also, for example, ~he catalyst composite ,. ~ .

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can be formed from a cogel by adding together suitable reagents such as salts of the Group VIB or Group VIII metals, or both, and ammonium hydroxide or ammonium carbonate, and a salt of aluminum such as aluminum chloride or aluminum sulfate to form aluminum hydroxide. The aluminum hydroxide containing the salts of the Groups VIB or Group VIII metals, or both, and additional metals if desired can then be heated, dried, formed into pellets, or extruded, and then calcined in nitrogen or o~her generally inert atmosphere. Catalysts formed from cogels do not possess pore size distributions as uniform as those formed by impregnati.on me~hods.
The catalysts can be used in the reaction zones as fixed beds, ebullating beds or in slurry form within beds. When used in the form of fixed beds, the particle size diameter oE the catalysts generally ranges from about 1/32 to about 1/8 inch, preferably about 1/16 inch. When used as ebullating beds the catalyst generally range about 1/32 inch diameter and smaller, and when used as slurry beds the particle sizes generally range from about 100 to about 400 microns. The bul~ density oE the R-l catalyst generally ranges from about 0.2 to about 0.6 g/cc, preferably from about 0.2 to about 0.5 g/cc~, depending on particle size, and that o the R~2 catalyst ranges from about 0.3 to about 0.8 g/cc, preferably rom about 0.35 to about 0.55 g/cc.
The catalysts oE this inventlon further comprise a metal, or metalsj of Group IVA, or compounds thereof. The catalysts will thus comprise germanium, tin, or lead, or admixture of such metals with each other or with other metals, or both, in combination with the Group VIB or Group VIII metals, or admixture thereof. Tlle Group IVA metals act as promoters for R-l and R-2 catalysts in enhancing the rate of demetallization of a feed. Of the Group IV~ -metals, germanium is particularly preferred. Suitably, the Group IVA metal compxises from about 0.01 to about 10 percent, preferably Erom about 2.0 to about 5 percent of the catalyst, based on the total weight (dry basis) of the ;

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composition. The Group IV~ metals ~ust be incorporated within the catalyst by impregnation.
A feature of both the R-l and R-2 catalysts is that each is of very high surface area and co~tains ultra-high pore volume, this providing an extremely great nllmber of active metal sites. This, in combination with the selected pore size distributions of the R-1 and R-2 catalysts, provides catalysts admirably suitable for the demetallization and hydroconversion of ~eeds oE the characteristics described, which feeds usually contain additional high concen-trations of sulfur and nitrogen. In R-l service, in utilizing R-l catalyst in its most preferred form, the number of pores ranging between about 100-2752 absolute pore size diameter is maximized, dependent on particle size, as is surface area and pore volume consistent with practical catalyst preparation procedures and with regard to the particle crush strength requirements of the process. Moreover, the number of pores which are smaller than 50~, and pre-ferably those greater than about 300~, or about 350~ when the average particle size diameter exceeds about 1/50 inch, are minimized. R-l catalyst of such character has thus proven outstanding, even under the stringent requirements of R-l service, in retaining considerable quantities of heavy metals while yet remaining active over extraordinarily long periods. For example, the R-l catalyst, when operated at a 700F. start-of-run temperature ~SOR), has been shown suitable for maintaining 1050 F.+ conversion levels ranging from about 20 to about 40 percent, and higher, ~or periods ranging up to about~70 days, and longer. In fact, this catalyst, at the end oE such period, has been found ~-to retain over 150 percent of its own weight of heavy metals from whole heavy crudes and residua feeds. Moreover, while accomplishing this, the R-l catalyst also effectlvely removes much o~ the sulfur and nitrogen in hydrodesulfurization and hydrodenitrogenation reactions. For example, whole heavy crudes and residua of the type characterized often contain from about 2 to about 7 weight percent, .: - 1~ -, : . - , :, . . .: . ~ .: :.: . ,: .- ~ : .
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usually from about 3 to about 6 percen~ sulfur, and often from about 0.2 to about 0.8 percent, usually from about 0.3 to about 0.7 percent nitrogen. Generally, from about 75 to about 95 percent of the sulfur, and from about 25 to about 60 percent of the nitrogen can be effectively removed from such heavy crudes and residua in ~-1 service while obtainin~ high conversion. The product of such reaction, unlike the original feed processed over the R-l catalyst, is now suitable as feed to a coker to provide greater yields of C3 liquid product than would otherwise have been possible by coking the original feed, and the coke product is less sour and less contaminated by heavy metals. For example, it has been found that by operating the R-l catalyst at a start-of-run ~SOR) temperature of about 700~. at a low space velocity of about 0.25-0.50 Y/~l/V, a product is obtained which is highly suitable for coking. Compared to coking of the raw whole crude or residuum, the C3~ liquid product yield is increased from 86 to 97 vol. % and the coke yield is decreased some 70%. The product coke contains only 2.5 wt. % sulfur compared to 5.9% sulfur coke from coking of the raw feed.
The product of the reaction conducted at a space velocity of 0.25 V/Hr./V is also highly suited for process~ng in a resid catalytic cracking operation. The raw feed contains too much heavy metals and Con.carbon for con-ventional catalytic crackingO The product, on the other hand, is lo~ enough inheavy metals and Con. carbon to be converted in a resid catalytic cracking operation Hence, ~he hydroconverted product is fed directly to a fluid catalytic cracker operating on a cheap amorphous catalyst at low once-through 430 F. conversion (ca. 25%) but at high 950 F. conversion (ca. 95%). The result is that a 97% yield (C3+) of a synthetic crude suitable for further processing in conventional refinery equipment is obtained. Coke yield, produced on the cracking catalyst, is 7.5 wt. %.

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By operating the reactor, or reactors, containing the R-1 catalyst at a start of-run temperature of about 750F. and at a space velocity of about 0.5 V/Hr./V, a product is made that is suitable for use in a catalytic cracker employing zeolite cracking catalyst. By operating at about an 80%
430 F. conversion, a C3 yield of 107 volume percent and a coke-on-catalyst yield of 7.5 wt. % can be obtained. However, the preEerred mode of operation is to remove 90% of the metals from the raw feed with the R-l catalyst at a SOR
temperature of about 750 F. and a high space velocity of about 1.0 V/Hr./~.
This product is now suitable for R-2 service to provide feeds which can be used directly in con~entional commercial petroleum operations, especially in con-ventional hydrocracking and catalytic cracking operations for the production of gasoline and other light distillates. The product from R-2 should contain about 2 ppm heavy metals, or less, with a Con. carbon of about 3.3 wt. %. This material, when converted in a catalytic cracker employing zeolite catalyst at a catalyst makeup rate of 0.4 lb.tBbl~ at about 80% 430F. conversion, will produce a yield of 110 vol. % C3~ and 6.7 wt. % co~e on catalyst.
In the preferred mode of operation (i.e., 750F. SOR and 1 V/Hr./~), this catalyst will have removed up to 90~ and more of the metals in the raw feed after an operation of 27 or more days, the catalyst retaining over about 95% of its weight of metals from whole heavy crudes and residuum feeds.
The amount of sulfur and nltrogen that is removed is comparable to that pre-sented in the preceding paragraph.
In utilizing R-2 catalyst, in its most preferred form, the number of pores ranglng between about 100-200~ absolute pore size diameter is maximized, as is the surface area and pore volume consistent with practical catalyst preparation procedures and with regard to the crush strength require-ments of the process. This means, of course, that the number of pores of d~ameter which are smaller than 100~ (especially 50~-) or greater than about - , , . ~ , , , . ,:

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200~ are minimized, especially the 300~ pores. ~-2 catalyst of such character has thus proven outstanding in R~2 service which, while not as stringent as R-l service, is nonetheless rather severe, the R-2 catalyst retaining considerable quantities of heavy metals while yet remaining active for Con. carbon conversion over long periods. Moreover, the R-2 catalyst accomplishes this while achieving high hydrodesulfurization and hydrodenitrogenation of the feed. For example, operating at 650 F. SOR temperature and at a space velocity of 0.5 V/Hr./V, the R-2 catalyst reduces the metals content of the ~-l product from a level of about 60 ppm to about 5 ppm, representing about 99% metals removal based on total feed. ~t the same time, asphaltenes are reduced to near 1 wt. ~ which is necessary for obtaining Con. carbon levels of 2-3 wt. %, based on product.
Sulfur level reaches about 0.3 wt. %, representing over 90% removal of sulfur based on the raw feed. The catalyst is also effective for effecting 1050 F.
conversions, and conversion levels (based on raw feed) of 60% and higher have been obtained. The product of ~-2 service is suitable as feeds for conventional ~petroleum processing operations, particularly hydrocracking and catalytic crack-ing operations.
In a preferred method for the preparation of these novel cata-lysts, catalysts which at least meet the marginal requirements of R-l and R-2 catalysts às regards desired pore size distribution are prepared from alumina in a synthesis reaction, as gels or cogels wherein certain critical conditions must be observed as regards the concentration of reactants in the synthesis solution, the acidity of the synthesis solution, and the temperature of ~he synthesis reaction. Gel preparation without added metals, of course, requires subsequent incorporation, e.g., impregnation9 of metals whereas in cogel pre-paration the metals are added at the time of gel formation. In such preparations, an aluminum halide, e.g., aluminum chloride, is first dispersed or slurried in water or alcohol in certain critical proportions, de~ined for convenience in ~ : :~ .
' . ~' :. ~ ' ' , ' ~.', ,' . ; ' 0~
terms of the molar ratio of water (or alcohol):aluminum halide dependent on whether it is desired to produce an R-l or R-2 catalyst. The temperature of the aluminum halide-~ater (or alcohol) slurry, to which the desired Group ~IB and Group VIII metals and other metals, can be added as may be desired as in forming of a cogel, is then lowered. Normally, water is used as the solvent, but alcohols such as methanol can be used, though pore sizes tend towards the smaller diameters with alcohol solvents. It is also essential in the reaction to add a reagent which will remove the halide from solution while maintaining pH in the range of 5-8, this being preferably accomplished by addition of an olefin oxide, e.g., ethylene oxide, propylene oxide, and the like, which forms a halohydrin. The reaction is necessarily carried out at relatively low temper-ature, preferably from about 30F. to about 100F., and more preferably from about 32 F. to about 60 F. The olefin o~ide is added in at least stoichiometric quantities in relation to the amount of halide to be removed from the solution, and preferably is added in molar excess to the solution. In the preparation of catalyst which at least meets the marginal pore size distribution required of R-l catalyst, the molar ratio of olefin oxide:halide ranges from about 1.5:1 to about 2.0:1 and preferably from about 1.5:1 to about 1.7:1, while the molar ratio of wate~ (or alcohol):aluminum halide is maintained within a range of f~om about 15:1 to about 30:1, and preferably from about 18:1 to about 27:1.
In the preparation of catalyst which at least meets t~le marginal pore size distribution required of R-2 catalyst, the molar ratio of olefin oxide:chloride ranges from about 0.3:1 to about 1.5:1, and preferably from about 1.0:1 to about 1.2:1, while the molar ratio of water (or alcohol):aluminum halide is maintained within a range of from about 22:1 to about 30:1, and preferably from about 26:1 to about 28:1. Failure to remove most of the halide, e.g., chloride, from the reaction results in a failure to obtain the deslred crystal growth, failure to obtain the required pore size dls-tributions, or failure to produce a crystal : . . : : :

: . :. . : : .: : .::

- ~05680~ -sufficiently stable to retain such desired pore size distrlbutions throughout subsequent steps required in completing the formation of the catalyst. It is believed that the required crystalline structure which shall ultimately be produced from the sol is of a nature of boehmite, termed for convenience "pseudo-boehmite," and that excessive halide concentration and high pH ad-versely affect the proper formation of such aluminum oxy hydroxide crystallinestructure.
After completion of the reaction, the temperature of the gel is raised to from about ambient to about 180~. to form a sol. Preferably, the sol is formed at essentially ambient temperature, ranging generally from about 70 F. to about 80F. and, on proper aging, pseudo-boehmite is produced. It is essential to age the gel at such temperature for at least about 6 hours, and preferably for about 24 hours to about 72 hours while the gel is in contact with its syneresis liquid. Lesser periods of aging results in reducing the uniformity o pore siæes, and significantly longer periods, particularly periods in excess of 6 days, often produces bimodal distribution of the pores. Failure to properly age the gel, while it is in contact with the syneresis liquid, also produces a crystal structure which is not sufficiently stable to retain the desired particle size distributions in the subsequent and necessary steps of washing, drying and calcination.
It has been discovered that Group VIII noble metals and lanthanum and lanthanum series metals, or compounds thereof, are admirably suitable as promoters for providing narrow pore size distributions and, in conjunction with control of the concentration of the reactants employed in the synthesis, the eemperature, and particularly the acidity of the synthesis solution, these promoters can be used to provide R-l and R-2 catalysts of optimum pore siæe di~tributions Catalysts which meet even the preferred specifications of R~
and R-2 catalysts can thus be made by incorporation o~ small amounts of Group IIIB

`

metals of Atomic Numbe~- 57 and greate~, and Grou~ VIII noble metals, or both, or compounds or salts thereo~, wlthin the solution during the synthesis.
Exemplary of the former are such ~etals as lanthanum, and the rare earth metals of the lanthanum series such as cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbiunl and lutetium. Exemplary of the Group VIII noble metals are ruthenium, rhodium, palladium, osmium, iridium, and platinum, which metals are less pre-ferred than the lan-thanum series metals because of their greater cost. Suitably, such metals, or compounds thereof, are added to the solution, for preparation of R-1 and R-2 catalysts, in molar ratios of promoter metals:aluminum halide ranging from about 0.001:1 to about 0.06:1, and preferably from about 0.01:1 to about 0.03:1. The reason for t~e effectiveness of these metals, particularly the lanthanum metals, generally added as soluble salts, e.g., as halides, acetates, nitrates, sulfates, etc., in producing the high unirormity of pores sizes in the desired ranges, when employed at the conditions defined, is not understood.
The syneresis liquid, after the aging step, is poured off of the gel or cogel. In the case of a gel, the gel can next be crushed to the desired particle size, air dried, then thoroughly washed. It is particularly preferred to wash the gel or cogel with alcohol, to remove contaminants, after which the catalyst is air dried at room temperature, and then dried at mild temperatures, e.g., at about 175-225F. for about 3 to 6 hours, then calcined, e.g., by heat-ing at about 800-llO0 F. for about 1 to 4 hours, and, the gel, then impregnated with a predeterminéd amount of the desired metal, or metals. The washing step is critical in the formation of the desired pore size distribution. Gènerally, isopropanol or one of the intermediate alcohols, e.g., n-propyl isobutyl and the like promotes th~ formation of the desired pore sizes. Methanol, on the other hand, forms smaller pores generalIy, e.g., 0-100~, and hexyl alcohol forms ,-. . :

. ,,, . , . . , . , . . , .. , ,,, . . . ~ .. ,. . . .. , ~ , . , ,. .. , . . . - .

, .,. . .,:. .. , ~ ,. : , : . . . ..

~56~
larger pores, e.g., 30 ~ . ~ixtures o-~ water and intermediate alcohols also favor the formation of 0-100~ pores.
Impregnation of the alumina can be done prior or subsequent to the calcination step. If subsequent to the calcination step, it is best to allow the calcined alumina to equilibrate with the moisture in the air for 4-6 hours prior to impregnation to avoid damage to the pore structure. I- is imperative that the impregnation be done with a non-aqueous solution, e.g., alcohol, rather than water solu-tion. If water solutions are used, the pore structure wlll readily shrink to the 0-100~ pore diameter range during sub-sequent drying and calcinationO The catalytic metals, e.g., Co and Mo, are dissolved in alcohol, e.g., methanol, and preferably isopropanol, and the solution imbibed into the alumina. Drying for 16-24 hours in air at ambient conditions, then drying for about 3-6 hours at 175-225 F., and then calcining at ~00-1100F. for 1-4 hours, will preserve the desired pore structure. The catalyst is then crushed and screened to the desired particle size for testing, usually 1~-35 mesh (Tyler).
Extrudates of outstanding strength and quality, which meet the require~ents of both R-l and R-2 catalysts, can be prepared in accordance with a preferred and novel method o~ this invention which embodies extrusion of a gel or cogel of preselected pore size distributions falling within the R-l and R-2 catalyst ranges, or which contains pores of size distribution sufficiently large that when the gel is subjected to extrusion at the required conditions the reduction in the size of the pores caused by the extrusion and aging steps will reduce the pore sizes such as to cause them to fall within the R-l and R~2 catalyst ranges. The gel or cogel, at the time of extrusion, is of critical liquids-solids content (generally produced by drying), it has been previously aged within syneresis liquid for preselected periods at conditions involving critical time, temperature, or time-temperature relationships and, aftes , . .,, . I .,: . . , ~ ~ , , : - .

: ' ,'' '' ';'' ' '' ' '"' :'' ',;' " '''' ~ ~ ' ; " '' ' ' '"

~S68~
extrusion, the extrudate is dried to provide a critical liquid solids content and, in a preferred embodiment, then returned to syneresis liquid, without washing, and again aged for specific critical periods at conditions involving critical time, temperature, or time-temperature relationships.
In tle preparation of an extrudate, a gel or cogel is initially prepared from a sol, preferably one containing a Group VIII noble metal, or metals, or lanthanum and lanthanum series metals, or admixtures thereof, in the range of proportions previously described, by varying the molar ratios of water (or alcohol):aluminum halide andiolefin oxide: halide, and also within the ranges described consistent with the requirements of producing an R-l catalyst, if an R-l catalyst is desired, or with the requirements of producing an R-2 catalyst, if an R-2 catalyst is desired. Subsequent to formation of a gel or cogel of the required properties, the gel or cogel is initially aged in syneresis liquid at critical time, temperature~ or time-temperature relationships sufficient to increase the crush strength of the finished particle and -to provide the desired pore size distribution of the gel or cogel, or to preserve such pore size distribution sufficiently that when subjected to extrusion and further aging at the required conditions the reduction in size of the pores caused by the extru-sion will produce pore size distributions falling within the R-l and R-2 catalyst ranges. This is accomplished in part by the presence of the Group VIII noble metals or lanthanum series metals, or both, which inhibits or tends to inhibit the normal tendency to reduce the sizes of the pores during the necessary step, or steps, of aging. The crush strength is increased, and pore size distribution preserved by aging the gel or cogel prior to extrusion, preferably containing the Group VIII or lanthanum series metals, or both, in syneresis liquid (1) for an initial time period ranging at least 6 hours, and up to about 30 days, or longer? preferably for a period of from about 1 day to about 6 days, and more preferably from about 24 hours to about 72 hours, at generally ambient temperatures, .: : : : ' ,, . ., :. . : .: . - : : . : .: :

i.e., about 50E. to about 80 ~., o~ by aging (2~ at elevated tempe~atures ranging from about 80F. to about 180F., preferably from about 100F. to about 160F., or by aging (3) at a combination of time-temperature relationships within these ranges of express conditions. It is preferred, however, to subject the gel or cogel to an initial aging for a rather short period, (a) preferably from about 1 to 3 days or, more preferably, from about 24 hours to about 30 hours, at ambient conditions, or Cb) at higher ~emperatures ranging from about 80F. to about 180F., preferably 100F. to about 160F. for shorter periods, preferably ranging from about 10 hours to about 2~ hours, and more preferably from about i5 hours to about 20 hours, and then to extrude, dry the extrudate to a critical liquid-solids content, and thereafter again subject the extrudate to a subsequent aging in syneresis liquid.
The gel or cogel, after the initial aging period, is separated from the syneresis ]iquid and partially dried by standard teclmiques, e.g., as described, to produce a gel or cogel containing from about 12 percent to about 40 percent, and preferably from about 15 percent to about 25 percent solids content, based on the total weight of the gel or cogel with its occluded liquid.
The gel or cogel is preferably crushed to less than 10 mesh ~Tyler series) particle sizes and then extruded through a die to produce extrudates of desired diameter, and the extrudates are then cut into desired lengths. Efforts, on the one hand, to extrude a gel or cogel having too low a solids content generally prove unsuccessful or, if successful, the extrudates will be of poor quality and may even deteriorate and crumble on subsequent aging in syneresis liquid.
Extrusion of a gel of too high solids content adversely affects the pore size distribution previously developed in the gellation, the crush strength and the larger pores generally being substantially reduced in size. After extrusion, and formation of the extrudate, the extrudate must again be dried to a solids content of ~ 25 wt. %. If the extrudate is to be subsequently aged, as preferred, _ 23 -:- . - . ~ . . . .
,, . ~ I

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- :.
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.

~ 6~

the extrudate, after drying, ls then directly trans~erred, without washing, to the syneresis liquid. In the subsequent aging in syneresis liquid, the extru-date is again treated at critical time, temperature, or time-temperature relationships to preserve the required R-] and R-2 pore size distributions.
Suitably, this is accomplished by aging the extrudate in the syneresi~ liquid (1) for a period ranging at least 6 hours, and up to about 30 days, or longer, preferably for a period ranging from abou, 1 day to about 6 days, and more preferably from about 24 to about 72 hours at ambient conditions, or by aging (2) at elevated temperatures ranging from about 80F. to about 180F., pre~
ferably from about 100F. to about 160~., for periods ranging from about 10 hours to abou~ 24 hours, preferably from about lS hours to about 20 hours, or by aging (3) at a combination of time-temperature relationships within these express conditions. The extrudate is then again necessarily dried to provide a solids content of ,25 wt. %, and then washed, preferably wlth alcohol. Failure to dry the gel to the required solids content can produce disintegration of the particles in washing. A gel or cogel properly aged, properly dried to the required liquids-solids content, properly extnlded, without washing, and then again dried to the required solids content, the extrudate subsequently aged for the required period, and then dried to the required ~olids content prior to Z0 washing will provide extrudates of superior strength and quality.
A low torque extruder, ~odel 0.810 Research Extruder manufactured by Welding Engineers of King of Prussia, Pennsylvania, has been found to produce extrudates of outstanding quality when produced pursuant to these specifications.
Extrudates of superior crush strength can be formed in producing both R-l and R-2 types of catalysts. After passage through a die to provide shapes of pre~
determined selected diameter, particularly for use in ebullating and fixed beds, the extrudates can be cut in the desired lengths, dried to critical solids content, aged in the syneresis liquid and again dried to control solids content9 .. . i , , .. ,, . . , . . . ; .

washed, preferably in alcohol as previously described, again drie~, calcined and, where desired, the so-formed extrudate then impregnated with the desired metal, or metals, or with an additional metalg or metals.
The metals-con-taining catalyst, whether formed as a gel or cogel, can then be contacted with hydrogen and hydrogen sulfide, or hydrogen sulfide precursor, or both, in situ or ex situ, in a subsequent step, or steps, to reduce and sulfide all or part of the metal salts and activate the catalyst.
The sulfiding is generally carried out by passing hydrogen sulfide in admixture with hydrogen through a zone of contact with the catalyst. The temperature of sulfiding is not especially critical, but is generally carried out in the range of about 500 to about 900F., preferably from about 6~0F. to about 750~.
The time required for the sulfiding of the metals is generally short and not more than an hour, or at least no more than one to four hours is generally required to complete the sulfiding. Typically~ in sulfiding the catalyst, the catalyst is contacted with a dilute gaseous solution, e.g., about 5 to about 15 percent, yreferably from about 8 to about 12 percent, of hydrogen sulfide in hydrogen, or hydrogen plus other nonreactive gases, and the contacting is con-tinued until hydrogen sulfide is detected in the effluent gas. Such treatment converts the metals on the catalyst to the sul:eide form. Sulfur-containing hydrocarbons, such as gas oils and the like, may be used as hydrogen sulfide precursors.
In accordance with the present hydroconversion process, the ~-1 catalyst is contacted in a reaction zone with a hydrocarbon or hydro-carbonaceous feed, e.g~, a liquid derived from coal by hydrogenation, shale or tar sand liquids, a heavy crude or residua feed, in the presence of hydrogen, at conditions of severity suEficient to achieve the desired conversion of the " ` ' ` ' ' :

56~Z~D~

1050F.~ materials to lower molecular weightZZ or 1050 F.- materials, and simultaneously to remove at least about 80 weight percent, and preferably from about 85 weight percent to about 90 weight percent of the heavy metals, parti-cularly vanadium and nickel, from the feedO Removal of the heavy metals is enhanced by the combination of conditions, particularly that of temperature, which enhances the conversion and results in some cleavage and reduction in the size of the asphaltenes~ and the selective pore si7e distribution of the R-1 catalyst, the 10C-275~ pore si~e openings accepting asphaltenes ranging from small to relatively large size, with regard to whether or not such mole-cules were originally of such size or reduced in size by the conditions ofreaction. The small to relatively large si2e asphaltenes readily diffuse, with hydrogen, into the depths of the catalyst particles wherein hydroconversion reaction egressing from the particle, along with unreacted materials, as more highly hydrogenated lo~er boiling products.
In conducting the reaction, the R-l catalyst is generally employed in one or more stages of a reactor, or reactors, aligned in series (which can and usually does include one or more stand-by or swing reactors, as desired). The R-l catalyst, after being reduced and sulfided generally in situ ~ithin the reactor, is operated under conditions, the majo~ variables of which are tabulated for conveniencè, as Eollows:
Operable Preferred Temperature, F., E.I~T.( ) Start-of-Run 700 750 End-of-Run 850 800 Pressure, psi 2000-10,000 2000-5000 Hydrogen Rate, SCF/B 3000-20,000 3000-10,000 Space ~elocity, LHS~ 0.25-5.0 0.5-1.0 (1) Equivalent Isothermal Temperature (E.I.T.) ,', . ' .

: ,, . ., . ~ .. ;, . . , ,:
.. , .~ ... ,. ~

:, ,' ~' ' : . ., ' ' ' ' ' " , , . .: , , , , : ,, ,' , . ' , ' ~: , ~613~

The hydrocarbon or hydrocarbonaceous feed, i.e., soal liquid, shale or tar sand liquids, heavy crude or residua, is rendered by R-l service more suitable as a feed for use in a coking process or a resid catalytic crack-ing process. Preferably, however, the product of R-l service is rendered a suitable grist for R-2 service, and thereby made suitable as a feed for use in conventional petroleum refining processes, especially as a feed for a hydro-cracking or catalytic cracking operation. The R-2 catalyst, as heretofore suggested, is of pore size distribution selective of a range of asphaltene molecules smaller than those accepted within the pores of the R-l catalyst.
The asphaltenes in the R-l product are generally smaller than those of the raw feed and can quite readily diffuse into the pores of the R-2 catalyst. The R-2 reactor is specifically designed to remove the remaining metals such that the procluct will contain ~ 5 ppm metals and ~2-3 wt. % Con. carbon. Conditions are needed that favor the hydrogenation of the fused benzene rings of the asphaltenefragments followed by the cra~king and dealkylation of the satura-ted rings. In this way, Con. carbon can be effectively reduced to the desired level. These conditions also favor the removal of the very refractory remaining metals.
Corlditions favoring this type of reaction are low start-of-run temperature~ e.g.
650-700F.~ at high hydrogen partial pressure, e.g., 2000-5000 psig.
In contrast to tne R-l catalyst, the R-2 catalyst removes less metals and Con. carbon on an absolute basis but percentage-wise it removes aboutthe same amount of the metals. This is also true of the sulfur and nitrogen removal reactions. However, this catalyst is more effective on the most re-fractory molecules a~d must be quite active to accomplish this reaction, espe-cially at the low temperature required.
The R-2 catalyst, which differs from R-l catalyst, is effective in the hydroconversion of smaller molecules, far more so than an R-l type catalyst. ~lbeit it has pores maximized within a ranee of diameters smaller ,., . .. . . , . . ~, -: . , , ' . 1 ~3~S6~

than the R-l catalyst, it does not encounter d~ffusion problems with the con-version material produced in R-l service. The smaller pores prevent the very large asphaltene molecules from entering the pores which severely diminish the much needed hydrogenation function of the catalys-t.
In R-2 service, the R-2 catalyst is generally employed in one or more stages of a reactor, or reactors aligned in series. The R-2 catalyst, after being reduced and sulfided generally in situ within the reactor, is operated under conditions, the major variables of which are tabulated Eor con-venience as follows:
Operable Preferred Temperature, F., E.I.rr.
Start-of-Run 600 650 End-of-Run 850 775 Pressure, psi 2000-10,000 2000-5000 Hydrogen Rate, SCF/B 3000-20,000 3000-10,000 Space Velocity, LHSV 0.25-5 0.25-2.0 ~ The invention will be more fully understood by reference to the following selected nonlimiting examples and comparative data which illustrate its more salient features. ~ll parts are given in terms of weight units except as otherwise specified.
Examples 1-7, immediately following 9 describe preparation of a series of R-l and R-2 catalysts, inclusive of gels and cogels, wherein pore size distribution is controlled and set during gellation. Examples 1-4 thus describe the preparation of gel type catalysts under varying conditions which favor the formation of R-l or R-2 catalysts, respectively. Catalysts A and B
are thus R-l pre-catalysts, and Catalysts E and F are R-2 pre-catalysts. Example 5 describes preparation of R-1 catalysts, prepared from cogels, including Group VIB and VIII metals. Examples 6-7 describe preparation of vastly improved gel type catalysts of both the R-l and R-2 types.

" , . .. . ~ ., . ....... : : .
, ~ . .

Examples 1-4 (Preparat.ion of Gel-Type Catalysts ~B~E and F) In a first series of preparations, 1160 gram portions of A1C13.6H20 were weighed, transferred to large glass beakers, and then slurried in portions of deionized water ranging from 15:1 to 27:1. The several portions of slurried material were each then cooled to 35 F., and gaseous ethylene oxide was then introduced at a rate of 12.5 grams per minute until sufficient ethylene oxide had been added to provide molar ratios of C2H40/HCl ranging from l.l to 1.6.
The resulting clear solutions were then allowed to slowly warm to an ambient temperature of 75F., a rigid gel having begun to form after about 1 hour. The gels were permitted to age at this temperature for periods ranging 24 to 72 hours, each in contact with its own syneresis liquid, the syneresis liquid having become visible as a stratified layer above the blocks of solidified gels and between the glass walls and side boundaries of the solidified gels which shrink away from the glass and exude the syneresis liquid.
The gels, after the aging period, were each then separated from its respective syneresis liquid by merely pouring off the liquid. The gels, having the appearance of dry blocks of material, were then crushed into parti-culate masses, and each then thoroughly washed with 5 gallons of isopropyl alcohol containing 1000 cc NH40H in a column or by successive decantation. The washing was continued in each instance until the effluent from the column was free of chloride, as determined by testing for chloride with silver nitrate test solution. The particulate masses were then thoroughly dried in air for 15-25 hours and 190F. for periods ranging between 6 and 24 hours, and thereafter calcined at 1000F. for periods of from 2 to 4 hours.
The materials formed in these syn-thesis reactions, which were found admirably suitable as supports for use in the preparation of both R-l and R-2 catalysts, are characterized in Table I as R-l Catalysts ~ and B and ' ' '~ , ' ''' ';'':-' " ' ' ., ~ . , .
:' , , : ' .,''`,. , '', ,' ',: .
.... ,:, ,,: , ,, . . .. ~ . . :

R-2 Catalysts E and F, respectively.
Example 5 (Preparation of Cogel~Type Catalysts ~ and D'?
The foregoing procedure was repeated, except that in this instance two cogels were separately prepared, each according to the following specifics: 1160 grams of A1C13.6H20 was slurried in 500 cc deionized water and, after addition of one-half of the required amount of ethylene oxide, solutions were added which contained (a) 64.~ grams of CoC12.6H20 dissolved in 200 cc H20 and (b) 95 grams of phosphomolybdic acid dissolved in 200 cc H20. The balance of the ethylene oxide was then added. The final preparation of a catalyst, which contained 6 wt. % CoO and 20.5 wt. % MoO3, was then completed, these catalysts being identified as Catalysts~D and D' in Table I.
Examples 6-7 (Preparation of Improved Gel-Type Catalysts C and G) -~
Examples 1-4 were again repeated except that in this instance 1.0 wt. % rhodium or 3.5 wt. % lanthanum was slurried with the AlC13.6H20 in preparation of the sol. The catalysts formed in this manner are identified in Table I as Catalysts C and G, respectively.
The data presented by ~eference to Table I thus show that catalysts, having only a marginal amount of pore sizes in diameters less than 50~, i.e., 50~-, and with a large amount, preferably a maximum of pore sizes in diameters ranging 150-250~ can be prepared by maintaining molar ratios water:
aluminum chloride of about 15 to 30, preferably 18 to 27; molar ratios ethylene oxide:HCl of about 1.5 to 2, preferably 1.5 to 1.7; and by aging the catalysts for periods ranging from about 1 to 3 days, preferably from 1 to 2 days. In preparing catalysts with smaller pores 9 these data show that such catalyst can be also prepared with a minimum of pore sizes of diameter within the 500A- and 300~ ranges, and with a maximum of pore sizes of diameter ranging from about 100~ to 200~. This is accomplished by maintaining a molar ratio of water:
aluminum halide ranging about 22 to 30, preferably 2G to 28; a molar ratio of -, ` ~ . ' ',' ': ' ' . ,, , " , ~ " ., ," ,".,. ~ , .. " " ~ ,.. ... .. . . .

~35~

ethylene oxide:HCl of about 0.3 to 1.5, ~efe~ably 1 to 1.2; and by aging the catalyst for periods ranging about 1 to 3 days, preferably 1 to 2 days. This limited aging improves the uniformity of pore size distributions with the desired ranges, as relates to the preparation of gels and cogels. The use of trace metals such as Group VIII noble metals or lanthanum and lanthanum series metals is also found to increase the uni~ormity and maximization of the desirable pore size distributions. Moreover, catalysts having very large pores can be prepared having a minimum o pore sizes ranging 50~- and 350A~, and with a large amount, preferably a m~ximum of pore sizes o diameter ranging 175-275~
suitably by preparation of a cogel as described, e.g., in Example 5, with sub-sequent extrusion of a particulate mass of the cogel to provide an extrudate.
Extrusion of cogel of Example 5 can thus be employed to provide extrudates of 1/16 inch particle size diameter having the properties, e.g., of Catalyst XX
as described by reference to Table IV, Examples 10-17.
Once the gel is set by observing conditions which favor the desired ranges of pore sixe distributions, it :is also important to wash the gel sufficiently to remove essentially all traces of halides and syneresis liquid.
Failure to accomplish this removal will result in a loss of the developed pore 5ize distributions. An alcohol wash has been found particularly effective in such capacity, the C2 to C6 alcohols, particularly the C3 or isopropyl alcohol, having been found particularly effective in preserving the developed pore size distribution throughout the subsequent steps required in completing the pre-paration of the catalysts.
The actual water content of the alcohol used in the wash was found to have a profound effect Oll the pore size distributions, the surface areas and pore volumes of the catalysts, and on subsequent drying it was found that these properties vary dependent on the amount of water, if any, contained in the alcohol wash. As with the syneresis liquid, iE the wash alcohol contains .

water, the pore volume shrinks with only minor ~ttendant reduction in surface area. The result is a reduction in the average size of the pores. Thus, because water decreases pore size distribution and pore volume, it is generally preferred to use anhydrous alcohol for catalyst preparations. The following examples demonstrate the effect oE water on these properties, especially on pore volume and pore size distributions in the alcohol washing and drying sequence.

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o~ ~ a) t~
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i~ ~ 00 I ~rl O ~rl `I OI ~ 1--C"l I~ ~ O ~1 C~ ~ ~ ~ o ¢ t~
~0 C C) o ~ ~o ~~ ~ ~ GO g - alu, ,~I ~o 1~ o ~ ~ ~ o .
U~ ~ o h ~d ~ O ~O ,~ O ~ a O a a O
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xample 8 A series of gel type catalysts (-tl, I, J, K, L) was prepared, the preparation steps employed and the composition of these catalysts being similar to that previously described with regard to Catalyst B, except that these catalysts were aged somewhat longer during the period of gellation. In the preparation of these catalysts, except as regards Catalyst H, however, water in varying concentrations was added to the isopropyl alcohol used as a wash.
The results of these runs are tabulated as follows:
T~BLE II
Catalyst H I J K L
H20 in Alcohol (Vol.%) o 2.5 5 10 25 Surface Area, m2/gm 382 393 398 373 354 Pore Volumej cc/gm 2.07 1.93 1.82 1.59 0.92 ~vg. Diameter, ~
(4 PV/S~ x 104) 217 197 J :L83 112 104 These data thus show that, with isopropyl alcohol, pore volume is decreased as the water content of the alcohol increases Erom 2.5 to 25 per-cent (vol.) with only nominal change in the surface area. The result is to decrease the average size of the pores.
The presence of water is also Eound to decrease the pore volume and pore size distributions during the impregnation steps, wherein the hydro-genation-dehydrogenation and other catalytic componen-ts are added to alumina supports, For best results, it has been found desirable to add the metals by impregnation of the supports with nonaqueous solutions of the metals salts, preferably alcohol solutions. Water, however, should not be used. The presence of wate~ has been found to decrease both pore volume and pore slze distribution drastically. It is thus believed that water enters the pores, redissolves and, , " ' ' , : i , ,. , ; . : , .. ,: ,: , ' :'' ' ' ' . ' ,` ' ., ' , .' ,'~ ~' ' ' ' ., " ' ' :;' .

during drying, some of the redistributed alumina ~orms deposits within the pores.
Thus, some shrinkage of the previously developed pore sizes results from the use of water during the impregnation step and hence its use is preferably avoided.
The following example thus presents data showing preparation of a cobalt-moly-bdenum on alumina catalyst by impregnation of a suitable alumina support with a metals-containing methanol solution. Comparison is made between the surface area, pore volume and pore size distribution of the catalyst and the unimpregna-ted support from which the finished catalyst was made.
Example 9 Alumina prepared pursuant -to the procedure used in preparation of Catalyst E was split into two portions, one, a precatalyst or support, termed for convenience Catalyst 0, and a second 100-gram portion, termed Catalyst P, which was impregnated with a solution containing 32.4 grams of CoC12.6H20 and 47.6 grams of phosphomolybdic acid dissol~ed in 162 cc of methanol. Catalyst P was subsequently dried at room temperature and at 190F. and then calcined for 2 hours at 1000F. The two catalysts are compared in Table II, as follows:
Catalyst 0 P

Wt. % CoO -- 6 Wt. % MoO3 -- 20.5 Wt. % P205 -- 1 Surface Area, m /gm 336 246 Pore ~olume, cc/gm 0.99 0.61 Pore Volume, Distribution % in 50~ Pores -- 3.7 50-150~ Pores 95.3 59.4 150-250~ Pores 4.7 31.9 250-350~ Pores -- 4.7 350~ Pores -- 0 3 These data thus show that considerable pore volume shrinkage occurred, particularly in the 50-150~ pore diameter ranges even as a result of using alcohol. This shrinkage must be compensated for by forming in the gel or cogel pores o~ larger pore size distribution than ultimately desired realizing - 35 ~

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that the shrinkage shall constitute a compensating factor. The shrinkage can be further minimized by using C2 to C6 alcohols, preferably isopropyl alcohol, as the solvent.
~ he following examples and demonstrations describe preparation of a series of extrudates from cogels (and gels), and define certain critical features required to obtain extrudates of good quality meeting the requirements Df R-l and R-2 catalysts. The technique of making catalys-ts in the form of extrudates is particularly applicable to the formation of catalysts in the 1/50-1/25 and 1/25~1/8 inch particle size ranges, and sphere forming techniques, particularly as described hereinafter9 are particularly applicable to the forma-tion of catalysts in the 1/500-1/50 inch particle size ranges. In making catalysts with the desired narrow pore size distributions, as shown, it is necessary to limit the time of aging because aging produces shrinkage of pore size but, on the other hand, aging is essential if extrudates of good strength are to be made, particularly extrudates of high crush strength, especially crush strength in excess of 7 pounds. High crush strength is desirable, or necessary, in certain types of processes. Thus, teclmiques are described which have been found to speed up the aging process and to counteract the effect of aging which tends to decrease the pore sizes of the catalysts. The aging process can thus be carried out by (1) contact of the gel or cogel with syneresis liquid at ambient conditions for periods ranging to about 30 days, and longer; (~) contact of the extrudate, or pelleti~ed form of the gel or cogel, for periods ranging to about 30 days, or longer, in the syneresis liquid; (3) contact of the gel or cogel in syneresis liquid in an initial step prior to contact of the extrudate, or pelleti~ed form of the gel or cogel, in syneresis liquid, as described in (1) and (2), which is preferred; (4) by high temperature contact of the gel or extrudate (or pelletized form of the gel or cogel), or both, by (5) a combination of these steps; and (6) Group YIII noble metals, or lanthanum and rare earth : - 36 -, ;'; ~ . , ', , 1, '. ' ' :; :~ ", ' ' .

metals of the lanthanum serles, are preferably included in the gellation step to counteract the pore shrinkage effect of aging on pore size distribution. In these data, it will also be observed that (7) critical solids contents are re-quired prior to or su~sequent to certain steps to avoid deterioration or weaken-- -ing of the gel or extrudate. These include: (a) drying to about 12 40 wt. %
solids prior to extrusion or pelletizing of the gel or cogel, (b) drying to Z5~ wt. % solids prior to the aging of extrudates, or pelle-tized gel or cogel, in syneresis liquid, and (c) again drying to 25~ wt. % solids prior to alcohol washing.

Examples 10-17 Portions of gel, or ~ogel, comprising metals and alumina, were each prepared by raising the temperature of sols prepared by reaction between aqueous slurries of aluminum chloride and ethylene oxide as described for the initial preparation of Catalysts D and D' (Example 5). The portions of cogel were each used to prepare a series of catalysts defined in Table IV below, referred to as Catalysts AA, BB, CC, DD, EE, FF (a gel), GG (A gel) 9 XX and YY.
The portions of cogel (or gel) were each aged at 75 F. (except Catalyst EE which was aged at 160F.), prior to extrusion, in its own syneresis li~uid for periods ranging from 24 hours (1 day) to 30t days. The portions of cogel (or gel) were then dried in air for a time sufEicient to provide twenty percent solids content, based on the total weight o~ the gel. In these cases, to prepare Catalysts GG, XX and YY, the aged gel (or cogel) was crushed to ~10 mesh particle size before extrusion. After extrusion in a Model 0.810 Research ~xtruder manufactured by Welding Engineers of King of Prussia, Pa., using a 1/16 or 1/32-inch diè, some o~ the extrudates were then further dried in air for a time sufficient to provide a twenty-five percent solids content, based on the total weight o~ the cogel (or gel), Some of the extrudates were then returned, without washing, to the syneresis liquid from which they were originally removed, ~'""' ' '. . . : ,' :' ' .: ,. ' -, . :
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immersed therein and aged at 75F. for one day. The extrudates were again dried in air to 25 wt. % solids content, then subsequently washed in isopropyl alcohol, oven dried in air at 190F., and finally calcined at 1000~.
These several portions of gel or cogel, the manner in which each was treated, and the properties of the series of catalysts, i.e., Catalysts AA, BB, CC, DD, EE, FF, GG, XX and YYJ produced therefrom, respectively, are : -referred to in Table I~ below. The table shows, in the first two rows of figures, the number of days that each of the catalysts was aged in syneresis liquid prior to extrusion, and the number of days, if any, that each of the extrudates was aged in syneresis liquid subsequent to extrusion. The next two rows of figures indicate, respectively, the solids content of the cogel (and gel) before extrusion, and subsequent to extrusion. The next row of figures, also given under "Extrusion Conditions" gives, respectively, the percent solids of the cogel (and gel) prior to the alcohol wash. Isopropyl alcohol was used as the wash liquid in each case. The last seven rows of figures give the properties of the several extrudates. The pore diameter, for convenience, is also listed in terms of average pore size as calculated by the conventional formula 4 x 10 times pore volume divided by surface area. For the 1/16 inch extrudate, 175-275~ pores are given where for 1/32 inch extrudates 150-250~

pores are given. As discussed later, these are the important ranges for the particle sizes.

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.' . ' . ' ' '~ '" " . ' , ', '. , ' '' ' '', ;',' .,, ' . ""':.;', . " ' ' , " ' '' '' ~'' "' "" ' ", ,'.; ' ''' " ' ' -These data show that Catalyst ~A possesses a reasonably good pore size distribution in that it has low pore volume in the 0-50~ pores and 350~+ pores and reasonably good pore volume in 175-275~ pores. It also has good surface area and pore volume. Unfortunately, it has low strength~ i.e., 1.3 lbs., but by allowing the cogel to age for 3 days prior to extrusion (Catalyst BB), the strength can be markedly improved to 4.2 lbs. Catalyst CC
demonstrates the shrinkage oE pores when cogel is aged 30~ days prior to extrusion. The strength is excellent at 10.7 lbs. but the low pore volume (0.83 cc/g) and excessive pores in the 0-50~ confirm an excessive shrinkage due to long term aging. Catalyst DD shows that by aging the extrudates in the syneresis liquid, a catalyst with fair strength is formed (3.7 lbs.). In this case, however, the 0-50R pores were excessive due to poor temperature control during ~he sol forming step. It is important to control the sol forming temperature at 40-50F. to minimize these pores. As shown by Catalyst XX, a good extrudate is formed (4.4 lbs.) by good sol temperature control and aging of the extrudates in syneresis liquid. This catalyst had low pore volume in 0 50~ and 350~ pores and high pore volume in 175-275~ pores.
Fllrther improvements in strength can be obtained by aging the gel (or cogel) at high temperature for short times as with Catalyst EE. By aging at 160F., a catalyst with 14 lbs. crush strength was formed. However, excessive pore volume shrinkage occurred resulting in excessive pore volume in the 0-50~ pores and a low total pore volume (0.92 cc/gm).
Catalysts can also be prepared by first extruding a gel followed by impregnation of that extrudate with catalyst metals. This is demonstrated by Catalysts FF and GG. These data are for the gels prior to impregnation.
Good strength was obtained (4-8 lbs.) but pore volume shrinkage occurred. Pore volume in 0-50~ range is not unduly excessive, however, .. .. . : .
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One example of a 1/32-inch catalys~ is given (Catalyst YY).
Strength is below that desired (3.7 lbs.) but for 1/32-inch extrudates it has a good pore size distribution with minimum 0-50~ pores and 350~ pores and a large amount of pore volume is 150-250~ pores which are best for 1/32-inch particles.
Spheres are the preferred forms of catalysts for use in ebullat-ing beds and slurry reaotors (reaction zones), the size thereof ranging about 1/50 inch particle size diameter, and smaller. Spheres, of course, can be utilized in a fixed bed (e.g., in particle size diameter ranging about 1/32-1/8 inch), but most often are utili~ed in ebullating bed and slurry reactors where particle size diameters most often range 1/32-1/250 inch, and smaller.
A very effective range for spheres in ebullating and slurry reactors is from about 100 to about 500 micron diameters. There are several known techniques for forming spheres, to wit: (1) prilling, (2) gelling in a column, (3) centri-fugal force, (4~ gelling in a sti~red vessel~ or tank, and the like. In the preferred stirred tank me~hod, a sol (gel or cogel) is heated and aged, while agitated, in a mineral oil bath generally at temperatures ranging ~rom about 75 F. to about 150 F., preferably Erom about 100 F. to about 125 ~. The amount of t~ineral oil:sol, on a volume basis, ranges generally from about 5:1 to about20:1, prefer~bly from about 8:1 to about 12:1. The amol1nt of agitation of the bath, and the height and diameter of the tank, is selected to provide part~cles of desi~ed size. Such technique is described in greater detail in Examples 18-20, below.
Examples 18-20 Portions of cogel, which contain metals and alumina, or portions -of gel which contain alumina, were each prepared first by ~orming a sol as disclosed ln the preparation of Catalysts D and D' (Example 5), and the sols ~ere then added to a stirred vessel containing tnineral oil.

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Ihe preparatlon o~ tiie sols was as described by reEerence to Examples 1-5, the slurried material formed by reaction between the aluminum salt and ethylene oxide having been removed from the beakers at temperatures of about 35F., and the temperature adJusted to about 55-65~. over a period of one-quarter hour prior to lntroduction of the portion o~ sol into the vessel containing the mineral oil. The sol was added slowly, i.e., at a rate of about 5-75 cc/min., over a period o~ one-quarter hour to avoid gelling prior to the introduction.
The amount of mineral oil:sol, on a volume basis, ~as maintained at 10:1, and the temperature was maintained at 100-150F. Turbine type agitators using various blade designs were employed, the size of the particles produced being controlled by blade design, vessel design, and the speed of revolu-tion (revolutions per minute, RP~) of the blade.
For the formation of relatively small particles (e.g., 100-200 microns) a single blade turbine operated at 250 RP~ proved best. For larger particles (e.g., 300-400 microns), a six blade turbine at 75 RP~ proved best.
The design of the vessel is critical. It was found that the ratio of the height of the vessel (H) to its diameter (D), i.e., H/D, should range between about 1:5-1:2, preferably 1:4 to 1:3. The design of the turbine should be such ; 20 that the impeller abuts the walls and bottom of the vessel. The ratio o~ the height of the impeller (HI) to the height of the vessel, HI/H, should range from about 1:2 to about 4:5, preferably fro~l about 2~3 to about 3:4.
It is found that as the sol is added to the mineral oil, small spheres form in the oil. After completion of sol addition, the agitator is allowed to continue agitating for at least 30 minutes, preferably for a period ranging up to 2 hours. During this time, the spheres are gelled. The spheres are next separated ~rom the oil, and the solids particles either spread out over a solid sur~ace to age, or surface washed to remove the mineral oil to ., . : . . . . .

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avoid agglomeration of the solids particles. Suitably, the spheres can be surface washed with varsol or isopropyl alcohol, or both, to avoid agglomeration, but care must be taken to avoid removal of syneresis liquid from the pores as opposed to mere removal of the surface oil. The spheres are aged for about 1 day. After this, the spheres are washed in isopropyl alcohol, with or without added an~onia, oven dried at 190F., and then calcined at 1000F. for 4 hours.
Catalysts W , W and WW, so produced, are characterized as having the following properties:
T~BLE V

Catalyst uu(a) W (b) ww(c) ~ol. of Mineral Oil, cc lO00 10,000 10,000 Vol. of sol, cc 100 1000 1000 Mixing Turbine 1 Blade 6 Blades 6 Blades Gellation Temp., F. 150 100 120 Catalyst Properties Surface Area, m~~g 278 244 330 Pore Volume, cc/g 0.54 0.49 1.15 Avg. Pore Dia., A 85 80 139 Pore Size Dist., % PV in 0-50~ 1.9 100-200~ 33.8 -- 21.0 Particle Size, microns 100-200 100-500 100-300 , . .. . .
(a) No rinse/No NH3 in wash (b) Rinse, no NH3 ln wash (c) No rinse, NH3 in wash Catalyst W was formed in quantity with a l-blade turbine at high RPM (250) and high temperature (150F.). The particles were small due to high RPM and impeller design. The low surface area and pore volume are due to high gellation temperature (150F.) and the fact that NH3 was excluded from the isopropyl wash. Catalyst W was made in a larger vessel with a 6-blade impeller operated at 100 RPM and 100 F. The catalyst spheres were rinsed with varsol . .
.

and isopropanol in this case to avo~d ~gglomer~tion, and no ammonia was included in the wash. Due to the lower P~M and impeller design, particle size was in-creased to 100-500 microns. Due to the improper rinse (i.e., varsol and iso-propanol pretreated spheres prior to aging) and the lack of NH3 in the wash, the surface area and pore volume are lower than desired. Catalyst WW represents an excellent spherical catalyst prepared by this technique. By forming the spheres in the larger vessel using the 6-blade turbine at 100 RP~ and 120F., spheres ranging in size from 100-300 ~icrons were made. Further, by carefully handling the spheres before aging to avoid agglomeration without the use of varsol and isopropanol rinse, the resulting spheres possessed good surface area and pore volume. In addition, 50~ pores and 300~ pores were minimized while maximizing 100-200~ pores which are highly desirable for particles in this size range. By decreasing the RPM to 75, particle size is further in-creased to 300-400 microns.
Exam~
Runs were conducted with each of Catalyst D, Q and R, of l/3~
inch average particle size, by contact with Cold Lake and Jobo Crudes, respec-tively, in a reactor which contalned the catalysts as fixed beds. The runs were each conducted at two different temperature levels, at approxima~ely the same pressure level of 2250 psig, at two different flow velocities and at hydrogen rates varying between 5500-8500 SC~/B. The following Table ~III shows the product inspections at the end of two different time periods, the conditions of reaction being given at the time the products were withdrawn for analysis.
Shown immediately below in Table VI are the analyses for Cold Lake and Jobo cru~es. In addition, the catalyst inspections for Catalysts Q and R are given in Table VII. Catalyst 0~ is a commercially available hydrodesulfur-ization catalyst having most of its pore volume in the 0-lO0~ region. Catalyst R was made in a manner similar to Catalyst D but with longer aging of the gel.

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TABLE VI
FEED ~N~LYSES
Cold Lake Crude Jobo Crude Kuwai-t Resid.
Gravity, API 11.1 8.5 16.5 Sulfur, Wt. % 4.5 3.8 3.6 Carbon, Wt. % 83.99 83.92 84.64 Hydrogen, Wt. %10.51 10.49 11.41 Con.Carbon, Wt. % 12.0 13.8 9.0 Asphaltenes, Wt. % 17.9 17.7 --Nitrogen, Wt. %0.46 0.68 0.22 Metals, ppm Ni 74 97 12 Distillation, l mm IBP, F. 463 518 451 5% (Vol.) 565 627 577 712 '798 737 % Recovered 56.4 50.8 64.0 % Residue 42.4 48.2 36.0 FBP, F. 1047 1047 1047 TABLE VII
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CATALYST INSPECTIONS
Catalyst R Q
Surface Area, m /g 362 260 Pore Volume, cc/g 1.79 0.50 Pore Volume Distribution, % Pore Volume in 0-50R Pores 1.4 11.1 50-150R 10.9 79.5 150-250~ 17.6 6.1 250-350~ 23.4 1.8 350~ 46.7 1.5 ; -% CoO 6 3.5 % ~oO3 20 12.0 :.~

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These data thus show that Catalyst Q, the commercial hydro-desulfurization catalyst, is completely unsuitable for the treatment of these heavy crudes at hydroconversion conditions, although Catalysts D and, to a lesser extent, Catalyst R are well suited for such purpose. Whereas Catalyst Q does efFectively hydrodesulfurize the cured in some cases, the data clearly show that it is entirely unsuitable for removal of heavy metals, for the reduction of Con. car~on, and for the conversion of asphaltenes.
In other comparative runs, for purposes of demonstra-tion, Kuwait residua, a more conventional crude characteriæed as a light ~rabian eedstock, the inspections on which are given in Column 4 of Table V, above, Catalyst Q and Catalyst D were compared at similar but varying conditions in hydrodesulfurization reactions with the results described in Table IX, below.
T~BLE I~

Temperature, ~. 650-750 F.
Pressure, psig 2000 Hydrogen Pate, SCF/Bbl. 4000 Catalyst Q Catalyst D

Days on Oil 26 26 ~verage Temperature, F. 710 710 Space ~elocity, V/Hr./V 0.4 0.6 0.4 0.2 Product Ins~ections Gravity, ~API 24.8 22.7 23.6 24~1 Sulfur, Wt. % 0.25 0.64 0.45 0.28 Nickel, ppm 5.3 2.7 1.1 0.2 Vanadium, ppm 12.5 5.4 2.3 1.7 Nitrogen, Wt. % 0.09 0.17 0.16 0.14 .
These data sho~ that Catalyst Q is better for desulfurization (and denitrogenation) of a light feedstock than Catalyst D which is less satis-factory. However, the catalyst of the invention (Catalyst D) is superior in metals removal even for this light feed.

Example 22 Diffusion plays a very l~portant role in the conversion of asphaltenes and removal of nickel and vanadium from heavy crudes. This is due to the larger size of the diffusing molecules. Since sulfur is found in smaller molecules, the sulfur removal reaction is much less restricted ~y diffusion.
This is demonstrated in the following example. A catalyst was prepared in a manner similar to that used in the preparation of Catalys-t D. This catalyst is designated Catalyst AAA. Properties of this catalyst are given in the table below:
CAT~LYST AAA

Surface Area, m /g 366 Pore Volume, cc/g 1.33 Pore Volume Distribution, %

0-50~ Pores 4-3 50-100~ 10.0 100-150~ 13.3 150-175~ 5.2 175-200~ 6.5 200-250~ 13.4 250-275~ 6.3 275-300X 6.9 300-350~ 9.7 350~ 24.7 CoO 6 ~ ~1003 20 ~ This catalyst was divided into three parts, each crushed, and si~ed to provide particles having average diameters equal to 1/85, 1/43 and 1/29 inch, respec-tively. Each of these catalysts was loaded into reactors and used to hydro-convert Cold Lake Crude~ the properties of which are given in Table VI.
Conditions for the tests were 775 F., 2250 psig, 2.6 V/Hr./V and 6000 SCF/B
hydrogen gas rate. ~roduct inspections were obtained after 20 hours on oil and are shown below:

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Catalyst Size, Inch 1~85 1/43 Sulfur, Wt. % 0.37 0.37 0.40 ~sphaltenes, ~t. % 1.1 2.3 3.5 Nickel, ppm 3.1 5.9 11.2 Vanadium, ppm 1.0 9.0 19.1 These data show that the asphaltene, nickel and vanadium removal reactions are strongly dependent upon catalyst particle size indicating strong diffusion limitations. On the other hand, sulfur appears to be much less dependent upon particle size. It is found from these data that as particle size increases it is desirable to increase the size of the pores to decrease the diffusion limita-tions with larger particles. On the other hand, as particle size is decreased it is desirable to decrease the pore size, since less diffusion resistance will be encountered. ~hus, larger particles (e.g., 1/16 inch) will require larger pores (e.g., 175-275~) and smaller particles (e.g. 1/64 inch) will require smaller pores (e.g., 100-200~) while intermediate particles (e.g., 1/32 inch) will require intermediate po~es (e.g., 150-250~).
The following examples show that R-l catalyst can be used to treat 1050F.~ in heavy crudes or residua at a variety of conditions ranging ~rom hydrotreating, with minor canversion of the 1050 F.~ materia1s~ through hydroconversion conditions wherein a major amount o~ the 1050 F.~ material is converted to lower boiling products.
Examples 23-29 Catalyst D, the R-l catalyst o~ Example 5, having an average particle size of 1/32 inch, was used for treating Jobo Crude (Table VI) in a series of runs wherein the severity of the reaction was gradually increased principally by a combination of decreased space veloclty and increased tempera-ture to obtain increasing rates of conversion. In Examples 23-26 the start-of-run (SOR) temperature was set at 650F., and gradually increased during the operation to maintain a given reaction Xate. In Exa1nples 27-29 the start-of-run .

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temperatu~e Was 700F. These ~nd other conditions o~ operation of the several runs, and t~e inspections obtained on the products of the series of reactions are given in Table X, below. Data a~e shown for Examples 23-26 at 662F. after 517 hours on oil. Data for Examples 27~29 are at 736F. after 805 hours on oil. In this series o~ runs, Examples 23 through 26 can be considered as essentially hydrotreatin~ runs, and Examples 27 through 29 as hydroconversion runs.
T~BLE X

Pressure, psig 2250 Hydrogen Rates, SCF/Bbl. 6000 Temperature, F. ~SOR) Examples 17-20 650 Examples 21-23 700 ~xample No. 23 24 25 26 27 28 29 Space Vel., VlH/V 0.79 0.59 0.39 0.19 0.98 0.49 0.24 Product Inspections Gravity, API 12.4 13.4 14.1 16.0 15.4 18.1 21.4 Sulfur, Wt. %2.56 2.23 1.87 1.11 1.45 0.78 0.15 Nitrogen, Wt. % 0.65 0.62 0.60 0.55 0.56 0.49 0.26 Con. Carbon, Wt. % 10.4 11.0 10.3 7.9 8.3 6.3 3.8 Asphaltenes, Wt. % 10.6 10.0 9.3 5.4 7.8 4.2 --Metals 9 ppm ~i 52.2 48.2 38.9 29.5 28.3 16.1 5.1 V O 242.6 207.2 183.0 107.5 1~l3.4 72.0 0.8 1050 F.~, Conv., Wt.% 1~.8 12.2 7.5 13.4 21.9 33.4 46.6 1050F.
Quality S~lfur,Wt. %3.47 3.09 2.83 1.89 2.51 1.49 0.30 Con.Carbon, Wt. % 23.3 22.7 20.4 17.5 21.3 18.4 10.4 ~-Metals, ppm Ni 108.6 112.5 97.9 65.4 86.2 59,0 8.7 504.4 476.0 391.5 248.3 341.5 196.8 9.5 ~e~al on Cat.
Wt.%* 115 60 75 -- 168 100 --*Wt. % on ~esh catalyst at end o~ ope~ation.

- 50 ~

., .. , , ~ . . , . : .~ . ........... . .
., . . , . , ~ , ..

These data thus show that relatively high temperature i9 required to obtain high rates of hydroconversion of the 1050 F.~ materials, and con-versely that low temperatures cannot provide adequate conversion rates, even with relatively low space veloclties. The product of Examples 23 through 26 is unsuitable for coker feed because the metals content is too high, and un-suitable even as fuel because of the high sulfur content. The product of Example 26 is of marginal utility as a coker feed, but coke produced from such product would necessarily be of poor quality. The sulfur content is too high for use as fuel, and further treatment is required to render the product suitable as a fuel oil. As to the series of hydroconversion reactions, the data show that the product of Example 29 is of good quality, and even suitable as a feed for a resid catalytic cracker using amorphous silica~alumina catalysts.
The product of Examples 28 and 29 can be split into 1050~.~ and 1050F.-fractions, and the 1050F.~ fraction coked as presented in Example 30 below.
Best use of the Example 28 product requires that it be treated in R-2 service to obtain a material having from 2 to 3 wt. % Con. carbon and <5 ppm metals, preferably C2 ppm metals, which material can then serve`as a prime feed for a conventional hydrocracker or catalytic cracker. The product of Example 29 is a marginal feed ~or a conventional hydrocracker or catalytic cracker. The product o~ Example 29 is a prime feed for a resid catalytic cracker as pre~
sented in Example 38.
The product of Example 27 is marginally suitable for R-2 service or as a marginal feed for use in a coker. None of the products of Examples 27 ;~
through 29 is suitable for direct use in a conventional hydrocracker or catalytic cracker.
The following example illustrates certain advantages in use of the product of Example 29 as coker ~eed.

~, , . ; ::

Exam~le 30 Case A: ~obo crude was split into two fractions, 1050F.+ and 1050F.- fractions. Yields for coking the 1050F.+ ~raction were predicted using correlations. The total yields were then calculated by mathematical blending.
Case B: The Example 29 product was separated into 1050 F.+
and 1050 F.- ~ractions. Yields for coking the 1050 ~.+ ~raction were predicted using correlations. The total liquld yields were calculated by mathematical blending.

The results o~ these calculations are given in Table XI below:
TABLE XI
Basis: 50 MB/~ o~ Jobo Crude Case ~ Case B
-C3, M Lb./D 0.87 0.4 C4, B/D 893 777 C5/430 F., B/D ~,434 3,446 430/650F., B/D 8,323 11,950 650/1050F., B/D 28,108 31,703 -Coke, T/D 1,223 (5.9% S) 373 (2.5% S) C3 Yield, Vol. % 86 97 These comparative data show that the C3 volume percent yield of product is 97 ~hen coking the 1050 F.~ product of Example 29 vis-a-vis the 86 C3 volume percent yield obtained when coking the 1050F.+ material o~ the Jobo crude per se, an 11 volume percent improvement in C3+ liquid yield.

Moreover, both the coke and the liquid product resulting from coking the Example 29 1050 F.+ material vis-a~vis the 1050 F.+ material from the original Jobo crude is superior.

` - 52 ,-. '.

... . . . . . . . . .

The following presents a series of runs which show -that products can be produced Erom 1050F.~ heavy crudes and residua by reaction with an R-l catalyst which are admirably suitable as feeds for R-2 ser~ice. In the follow- -ing series of data, the initial temperature of the several runs is further increased as contrasted with the runs of preceding Examples 27 through 29. The space ~elocity is then gradually decreased, and as space velocity is lowered, it will be observed that product quality improves.
Example 31 A series of runs, vi~., Example 31, Runs 1-4, was conducted using an R 1 type catalyst, identical to Catalyst D previously described (Example 5), except that the catalyst contained 0.35 wt. % Sn (by impregna~ion) in addition to cobalt and molybdenum. Again particles averaging 1/32 inch diameter were used. Jobo crude (Table V) was contacted in each instance with the catalyst at a start-of-run temperature of 760F., the temperature being increased during the operations at an average rate of from about 1.8 to 2.2 F.
per day to maintain a substantially constant rate of reaction for a given run.
The following data, given ln Table XII, below, were obtained at a temperature of 765F. after 166 hours on oil.

.~ . .

., . ' . ' ,, , ,, ' ' .

~-~t TABL~
Pressure, psig 2250 Hydrogen Rate, ~C~/Bbl 6000 Run No. 1 2 3 4 Space Velocity V/Hr./V 1.90 1.45 0.91 0.46 Product InsPection Gravity, API 17.3 17.3 18.5 20.7 Sulfur, Wt. % 1.29 1.08 0.80 0.20 Con Carbon, Wt. % 7.6 7.0 7.1 4.0 Asphaltenes, Wt. % 6.1 6.2 4.8 1.9 Metals, ppm Ni 29.2 24.8 17.~ 2.7 V 26.1 93.9 46.9 0.9 1050+F., Con~., Wt.% 44.3 38.2 43.5 56.6 1050+F., Quality Sulfur, Wt. % 1.98 1.81 1.48 0.43 Con Carbon, Wt. %26.0 21.7 24.3 17.2 Metals, ppm Ni 96.8 73.5 64.5 20.6 V * 3630~ 308.0 189.0 1.5 Metal on Cat~, Wt.%69 88 91 46 *Wt.% on fresh cat at end o~ operation~ ~uns terminated at different times on oil.
It is thus apparent by reference to Runs 3 and 4, as contrasted with Runs 1 and 2, ~hat temperatures above about 750 F., at space velocities about 1, can provide an R-2 feed of desirable quality. Suitably, the R-2 feed ~ is about 90 Wt. % demetalli~ed, and hence the product of R-l service is usually one containing metals below about 60 ppm, which metals content can be further reduced in R-2 service to 5 ppm or less. Also, Con. carbon at levels o~ about 7 Wt. % can be reduced to levels ranging about 2-3 Wt. ~ as required for use in R-2 service. In operating at these condltions, the ~-1 catalyst was found suitable for about 3-4 weeks of continuous R-l ser~ice.
The product of ~xample 31, Run 4, on the other hand, can ba fed directly to a catalyticcracker employing zeolite catalyst as shown by reference to Example 38, if desired. The product produced in Example 29, described by .. .. .

~5~

reference to Table X, is a ~ri~e feed ~o~ resld caLalytic cracking as shown in Example 38.
Example 32 Several catalysts of varying pore si~e distribution were obtained for demonstrative purposes. Catalysts S and T are commercially available alumina which was impregnated with cobalt and molybdenum salts and then dried and calcined at conditions similar to that used in Example 9.
Catalyst V, the catalyst of the invention, was pre~ared in a manner similar to that used for Catalyst D described by reference Example 5. A portion of each having an average particle size of 1/32 inch was then employed in a fixed bed reactor for hydroconversion o~ whole ~obo crude to measure the effective-ness of each in R-1 service. The pore size distributions of each of these several catalysts, termed Catalysts S, T, U, and V for convenience, the conditions under which the hydroconversion runs were conducted, and product data are tabu-lated in Table XIII, as follows:
TABLE XIII
(a) ~escription of Catalysts:
Catalyst S T U V

Surface ~rea, m2/g 250 217 259(()) 362 Pore Volume, cc/g 0.55 0.53 0.58 1.51 Pore Volume Distribution, %
.
0-50~ Pores 4.3 10.7 5.0 2.8 50-150~ 73.8 33.0 40.5 15.7 150-250~ 12.2 22.6 33.1 25.2 250-350~ 5.4 16.8 15.~ 27.3 35 ~ 4.3 16.9 6.1 29.1 % CoO 3 3 r 6 6 % MoO3 13 21~- 20 20 (b) Process Conditions:
Temperature, F. 789 (after 665 hours on oil, 750 F. SOR) Space Velocity, V/Hr./V 1.0 Gas Rate, SCF/BBl 6600 - . . . .
- . : , , :, . :, ..
:: . ''. .' . ~ . ' ' , ' ,; , , : . .. . .

-~5~

(c) Product Inspections:
Catalyst S T U V

Product Inspection Sulfur, ~t. % l.l63 1.254 l.588 1.074 Metals, ppm Ni 27.9 28.1 23.8 21.1 V 72.1 83.1 49.9 38.0 Metal on Cat., Wt. %* 43 41 62 99 (1) Data obtained from pore size distribution measurement due to problem with single point nitrogen measurements for surface area and pore volume.
* Wt. % on fresh cat at 665 hours on oil.
- These data thus show that Catalyst V, an R-l catalyst, which inter alia, contains greater than 20% of its total pore volume in the 150~ to 250~ range, less than 5% of its pore volume in 0-50~ pores and less than 30%
of its pore volume in the 350~ range, is far superior to the other catalysts none of which are R-1 catalysts, in terms of both sulfur and metals removal, but particularly as relates to metals removal, in terms of metals removal an average of about 35% less of Catalyst V is required to remove the same amounts of metals as would be removed by the other catalysts.
The following example shows that as total pore volume in the 150-250~ range is increased, the catalyst becomes even more effective in terms of removing metals.
Example 33 The following data are illustrative of that obtained from two different R-l catalysts, one (Catalyst W) of which contains 56.7% of the pores in the 150-250~ range and the other (Catalyst D), also described by reference to Table I except that it contains 0.3 wt. % Sn, by impregnation) of which contains 44.1% of its total pore volume in pore sizes ranging 150-250~. Each is used at similar conditions for the hydroconversion of Cold hake Crude (Table VI). Catalyst W was prepared similarly to Catalyst C except that La was ~ - .

: : , - :

'. ' . ' '. ., , . :.. , - , ~ : ,, .

- - \

not included. The gel was impregnated by the methods of Example 9. Both catalysts were constituted of particles averaging 1/32 inch diameter. The description of these catalysts in terms of their pore size distributions, the conditions of the run and the inspections on the products from the runs are given in Table XIV below:
TABLE XIV
(a) Description of catalyst:

Catalyst 2 _ W ~1~ D
Surface Area, m /g 271'(1) 330 Pore Volume, cc/g 1.22 1.23 Pore Volume Distribution, %

0~50~ __ 1.5 50-150~ 3.0 15.5 150-250~ 56.7 44.1 250-350~ 25.3 33.0 3502f 15.0 5.9 % CoO 6 6 % MoO3 20 20.5 (b) Process Conditions:
Temperature, F. 750 F. (210-240 hours on oil) Pressure, psig 2250 Hydrogen Rate, SCF/Bbl. 6000 Space Velocit~, V/Hr./V 0.5 (c) Product Inspections:

Catalyst O W D
Gravity, ~PI 23.4 24.0 Sulfur, Wt. % 0.16 0 09 Con Carbon, Wt. % 2.5 2.1 Asphaltenes, Wt~ % 0.9 1.2 Metals, ppm (Ni and V) 2.0 5.8 1050F.f Sulfur, Wt. % 0.29 0.26 Con Carbon, Wt. % 8.0 9.7 _etals, ppm Ni 1.7 6.6 V 4.7 ~ 9.3 (1) Data obtained from pore size distribution measurements due to problems with nitrogen measurements for surface area and pore volume.

. .:,::, . ., . : . ., . . ` .
; , ~ : , . , :. ; - , , : ' . ': . , . : , : -`
3S~

The advantages of maximizing pores within t~e 150-250X pore diameter range for demetallization is thus clearly illustrated. Catalys-ts similar to Catalyst W, but with higher pore volume in the 150-250~ pore dia-meter range, and greater surface area, provide even greater improvements.
The following additionally shows that a Group IV~ metal is effective in increasing the rate of demetallization of the catalysts of this invention.
Example 34 Two catalysts were prepared, each at the same conditions and identical in composition one to the other~ except that one contained 3 wt. %
germanium by impregnation and the other did not. These catalysts, identified as Catalyst V and V', are similar in their composition (except as to the presence of germanium in Catalyst V~) and in their physical characteristics as relates to pore ~olume and pore size distribution, and method of preparation which is the same as that of Catalyst D identified by reference to Table I.
A~erage particle size for both catalysts was 1/32 inch. Each catalyst was employed for the hydrocon~ersion of Jobo crude, at conditions very similar to those used in Example 32 to provide products as identi~ied in Table X~, below:
TABLE ~V
.
Process Conditions:
Temperature, F. 778 F. (496 hours on oil) Pressure, psig 225 Space Velocity, V/H/V 1.0 Hydrogen Rate, SCF/B 6000 Catalyst V V~

Promoter ~ None 3% Ge Product Inspection Sulfur, Wt. % 1.098 1 308 Metals, ppm Ni 19.4 14,6 V 34,1 23.

- , . . .. . ~, . - - . . : .... . ... . . .

. ~

The rate of demetaIlization o~ Catalyst V' used for hydro-conversion of the crude is thus appreciably increased as contrasted with Catalyst V which does not contain the germanium promoter.
The following examples are exemplary of an ~-2 catalyst of pre-ferred composition, the catalyst being described as used in a typical R-2 service situation for hydroconversion of an R-l product resultant from the treatment of a whole Jobo crude by contact with R-l catalyst as typical R-l service conditions. The performance of the R-2 catalys~ is compared with an R-l catalyst for similar use, and with a commercially available catalyst in similar service.
Example 35 Runs were made wherein whole Jobo crude (Table VI) was intro-duced into an R-l reactor containing a fixed bed of R-l catalyst (Catalyst V) and treated at hydrocon~ersion conditions, the R-l product produced being defined in Column 2 of Table ~VI, below:
T~BLE X~I
(a) Conditions o~ Operation:

R-l Reactor:
Temperature, ~. 750 ~SO~) Pressure, psig 2250 2 Hydrogen Rate, SCF/Bbl. 600V
Space Velocity, V/H/V l.O
(b) R-l Product:

Gravity, API 16.8 Sulfur, Wt. % 1.40 Carbon, Wt. % 86.44 Hydrogen, Wt. % 11.25 Con.Carbon, Wt. % --~sphaltenes, Wt. % 5.49 Metals, ppm Ni 24.6 V 39.7 Nitrogen, Wt. % 0.577 TABLE XVI (Cont'd) Distillation~ Wt. %

5% 4S5 g44 % Recovered 65 % Residue 35 The R-1 product, characteri~ed in Table XVI (b), was then successively passed over Catalyst V ~Example 34), having particles averaging 1/32 inch diameter, at a start-of~run temperature of 750F., 6000 SCF/Bbl H2, 2250 psig and with space velocities varying from 0.49 to 1.93 V/Hr./V. Data shown in Table XVII are for products withdrawll from the reactor at 755F. after 161 hours on oil.
TABLE XVII
V/Hr./V 0 49 0.83 0 95 1.93 Product Ins~ections Gravity, API 23.5 19.8 18.3 17.5 Sulfur, Wt. % 0.10 0.38 0.71 1.05 Asphaltenes, Wt. % 0.86 2.48 3.88 4.32 Metals~ ~pm ~i 1.7 9.5 1406 18.0 V 0.1 0.3 5.7 37.3 These results show that the R-l type of catalyst is not ideally -~ suited for ~2 service. High temperatures and low space velocities are required to reach the R-2 catalyst target of < 5 ppm metals and 2-3 wt. % Con. carbon ~< 1 wt. % asphaltenes).
A catalyst with-maximum pores in the 100-200~ range is preferred for ~-2 service as shown in the next example. In addition, it is preferred to operate at lower temperature where equilibriam ~avors aromatics saturation enhancing Con. Carbon removal.

' :'' ', ':" ' "' ''' ' ' "' ' ' ' ,,',' ~' ', "'''"'.."' '. ' ' ,'.".' ' .'' ' ' "' '. '' ' ' "~' .'' ' '','`'' . '' : , ' : .. .i . ' ' '; . " " '. ~ ' ' ' ~ " : ' ' ' ' , :. : . ., . , . :. .: , . , . ,: : :.
. . . . ..

Example 36 The R~l product characteri~ed in Table XVI ~b) was successively passed over Catalyst V and a commercially available hydrotreating Catalyst V
and a commercially available hydrotreating Catalyst X which is characterized in Table XVIII (a). The catalysts, averaging l/32 inch in particle diameter, were evaluated at a start-of-run tempe~ature of 700 ~., 6000 SCF/B H2, 2250 psig and 0.5 V/Hr~/V. Data shown in Table XVIII (b) are for products withdrawn from ~he reactor at 700F. after 93 hours on oil.
T~BLE X~III
(a) Description of Catalyst X

Surface Area, m /g 222 Pore Volume, cc/g 0.58 Pore Volume Distribution, %

0-50~ Pores 1.6 50-l00~ 32.9 100-200~ 51.8 200-300~ 9.0 300~+ 4.7 % NiO 3.0

3 18.0 ~b) Characterization of R-2 Product Catalyst X V

Product Inspection Gravity, API 20.7 19.8 Sulfur, Wt. % 0.207 0.282 : Asphaltenes, Wt. %0.83 1.29 Metals, ppm Ni 7.7 8.4 V 0.1 0.1 The data sho~ that the commercial Ni/Mo catalyst with 52~ of its pores in the 100-200~ region is more active for sul~ur, asphaltene and metals removal at the conditions than the R~l catalyst which has less o~ its pores in 100-200 _ 61 -1 region.
2 The ca~alyst of th~ inventlon for R 2 sen~ire 3 whereln pores in the 100~200A region are further maximized

4 is shown ~o be super~or to the commercially ~va~lable cata-lyst (Catalyst X) ln Ex~mple 37O
6 ~
.

7 The R~l product (Table XVI [b~) was successively 8 pa~sed over Catalyst X (Commercial catalyst of Example 36) 9 and Cat~lyst P (Exampl~ 9) 9 having average partlcle size diameters of 1/32 inch9 ~t 650F. start~of-run temperature, lL 6000 SCFjB H2, 2550 psig ~nd 0O5 V/Hr./VO Cat~lyst Y is 12 ch~racterized in T~ble XIX (a) and the product inspection 13 for produet withdrawn at 650Fo after 48 hours .on oil is 14 shown in Table XIX.
... .... .. .
TABLE XIX
16 (a) Description of Catalyst Y
17 Surfaee Area, m2~g 212 18 Pore Volume, cc/g 0O43 19 Pore Volume Dis~ributlon %
__ .
0~50~ ~ores 8O1 21 $0~100A 1904 ~2 ~00~00~ 58O3 23 200~300~ 13O1 .
24 30~A~ l o l % Niû 6 26 /0 MoO3 20 27 (b) Char~cteriz~t~on of R~2 Product ~8 ~at~lyst ~ X Y P
29 ~3559b5 ~E~:~l~ .
~ravity, API 1805 1806 1808 31 ~ulur~ Wtr % 00436 00533 00287 3~ Asphaltenes, Wt~% 2~1 2~5 107 33 Met~ls ~m 34 ~ 904 9OO 600 ~ .
V ~8 0O9 0O7 36 These d~t~ thus show the advant~ge for h~ving less th~n 10%~ -37 of the pore volume ln O~SOA pores ~nd greater th~n 55% of 38 the pore vvlume in 100~200A pores and less than 25% of it~

. .1 ~2 .. . . . , . . , ., ,.. , , ~ . . ..

., 1 pores in 300A+ poresO Catalyst Y wi~h 58% of its pores in 2 the 100~200A reglon sh~ws some advantage for demetallization 3 over Cakalyst X whleh had 52% of its pore volume in 100-200A.
4 poresO Both were NiiMo catalysts~ Cat~lyst P9 a Co/Mo c~t~

- 5 lyst with 58% of its pore volume ;n 100~200~ pores and 3O7%
~ of its pore vol~me in 0~50A pores and 1.6% of its pores in 7 300A-~ pore~ was the most outstanding catalyst for R~2 ser~
8 vice.

The conditions for the R~l reactor c~n be varied 11 ~o yield product whieh is ~uitable for coking~ for resid --12 catalytic cracking by contac~ with amorphous ~ilic2 alumina 13 (3A)9 for use in z~olite catalytic cracking or for further 14 treatment in the R~2 reactor to produce a product contain~
ing C5 ppm metal~9 preferably ~2 ppm met~ls, with a Con.
16 carbon of less than 3 wt- %. ~he material from R~2 ~ervice 17 i~ suitable for conversion ~n a conventional catalytic 18 cr~cking or hydro~r~cking unit. Results of such runs are 19 summarized in Table ~X~ below.
TABL~ XX
21 Jobo Feed ~ 2250 pSig9 6000 SCFIB H2 22 R~l R-l/R~2 23 R-l R~l Plus Plu~
24 Plu~ Plu~ Zeolytic Zeolytic :~
Proce~s ~ ~ ~ ~L~ clc .
26 R~l Condition~ ~:
27 SOR TempO,FO ~ 700 700 760 760 28 Space Velocity, 29 V/Hr-/Y G ~ D 0O4 0.25 0O5 1.0 ~ uc~
. .
31 Sul~ur3Wt~% 0.6~ 0O32 0O22~ ) 0 D 76( ) 32 Metal~ 9 ppm ~ 62 10 5 60 33 Con.Carbon 34 Wto% ~ 5.3 308 4.~ 605 :, ~3 ., ~

1 TAB (Continued) 2 R~l R~l/R~2 3 R~l R~l Plus Plus 4 Plus Plus Zeolyt~c Zeolytic ~ 3A C/C C/C C/C
, 7 430Fo~ ~nv.~
8 % ~ 25 80 ~0 9 Catalyst Addition 11 Rate9 12 Lb/Bo ~ 0 0O4 13 ~ ~ ~i N ee~

V31 % 86 97 97 107 110 1~ Wt.70 1308 404 705(3) 7.5(3) 6.7(3) 18 Su~ in 19 Cdke, 7.0 Wt.% 5 .9 2 o5 21 (1) Analyses averaged fo.r total run3 life expected to be 22 greater than 2 mvnths.
~3 (2) Analyse~ averaged for total run, life expected to be 24 3~4,wee~.
(3) Cok~ m~ke on cat Cracking (C/'C) catalyst.
26 These d~ta show that coking of raw Jobo crude ~7 result~ in 86 vol. % yi~ld of C3+ and a,l3.8 WtJ ~/0 y~el~
28 of sour coke (509% S~0 When the crude is treated in R~l st 29 700Fo and at 0~4 V/HrO/V09 the product is a prime coker feed~ Coking the feed increases the C3~ yield to 97 volO%
31 and reduces the coke to 404% ~2.5% S)u ~ublished dat~ and ~ ~-32 correlati~ns show that if the sever~ty of R~l is lncre~sed 33 by reducing the space veloclty to 0~25 V/HrO~V~ the product 34 is then suit~ble for re$id c~ta1ytic cr~cking us~-ng ~m~r~
phous S102/A1203 catalyst~ The yields produced are 97 vol.%
36 C3~ and 7.5 wto% cokeO If the severity of R~l i9 furth~r 37 increased to 76~F~ and 005 V~HrO~V/ khe product is suit~
38 able for c3taly~ic cracking using zeoli~e cracking cata~yst.
39 In this i~stance9 the yields produced are 107 vo10 % C3+

and 7.5 wt~ v~O coke. Moreover9 using the preferring re~c~n , . . . . . . . . .
.. ..

1 sequenees of R~ltR~2 ca~alysts3 this product can be cata 2 ly~ically craeked using zeolite catalysts to produce yields 3 of llO volO % C3 and 6~7 wt. % coke D These results show 4 the wide versa~ility and capabllities of these catalysts and - 5 processes.

6 It is ~pparent that various modifications and

7 changes can be made wlthout departing the spirit and scope

8 of the present invention.

9 Pore size distributions9 as percent of total pore volume, for purpose of the present invent~on are measured by 11 nitrogen adsorption wherein nitrogen is adsorbed at ~arious 12 pre~sures us~ng the Aminco Adsorptomat Cat. No. 4~4680, and 13 mNltiple sample acces~ory Cat. No~ 4~4685. The detailed 14 pro~edure is described in the ~minco Instruction Manual No.
~: ;1S 861~A furnished with the instrumeni:. A descr~p~ion of thè
16 Adsorptomat prototype instrument alld procedure is given in 17 Analytic~l C4emistry9 Volume 32J p~lge 5329 April l960.
18 An outline of the procedure i~ given here~ includ-19 ing sample preparationO
From 0.2 ~o loO g~ of sample is used and ~he iso~
21 therm is run in the ad30rption mode only. All sampleg are 22 placed on the preconditioner beore ana~ysis where they are 23 out~ga~sed and dried at 190Co under vacuum (lO 5 torr) for 24 5 hours. Ater pretreatment the weighed sample is charged to the Ad~orpt~mate and pumped down to 10~5 torr~ At thls 26 point~ th~ instrum0nt.i~ set in the autom~tic adsorption mode 27 to charge ~ s~andard volume of gas to the catalyst. This i5 28 done by charging a predetermined num~er of volumes as doses 29 and ~hen allowing time or adsorption of the nitrogen to re~ch equilibrium pressure. rrhe pressure ls measured in ~ -31 ~enm3 of its ratiQ to ~he saturation pressure o:E boiling 32 liquld nitrogen. Three do~es are injected ~nd 8 minutes ,: . . .. . . . . .

6~ 0 ~

1 allowed for equilibration of each measured relative pressure.
2 The dosing and equilibration are continued until a pressure 3 ratio of 0.97 ;s exceeded and maintained for 15 minutes.
4 The run îs then automatically terminated.
The data obtained with the dead space factor for 6 the sample, the vapor pressure of the liquid nitrogen bath, 7 and the sample weight are sent to a digital computer which 8 c~lculates the volume points of the isotherm, the BET area, 9 and the pore size distribution of the Barrett, Joyner, and Halend~ m~thodO [Barrett, Joyner, ~nd Halenda9 J~ Am, Chem.
ll Soc. 73, p. 373.] It is believed th~t the B~rrettg Joyner, 2 8nd Halenda method is as complete a treatment as can be ob~
tained~ based on the assumptions of cylindrical pore~ and 14 the validity of the Kelvin equation.
Hydrocarbon or hydrocarbonaceous feedstocks wkich l6 c~n be treated pursuant to the practice of this invention .~- . ... . . .
17 include he~vy p~troleum crudes, synthetic crudes derived l8 from coal, shale~ tar sands, heavy oils and tars which con-19 tain relatively high concentrations-of asphaltenes9 high carbon:hydrogen ratios9 high metals con~ents~ considerable 21 amounts of sand and s~ale9 considerable amounts of 1050F.+
22 materials 9 and generally high sulfur and nitrogan~ -:

,'~.

... :
: ~ .

Claims (50)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A catalyst composition having enhanced selec-tivity suitable for the conversion and demetallization of feeds which contain large quantities of 1050°F.+ hydrocarbon materials characterized by comprising an admixture of from about 0.1 to about 10 weight percent of a Group IVA metal, or compound thereof, from about 5 to about 50 weight percent of a Group VIB metal, or compound thereof, from about 1 to about 12 weight percent of a Group VIII metal, or compound thereof, measured as oxides, and a porous inorganic oxide support, said catalyst including a combination of properties comprising, when the catalyst com-position is of size ranging from 1/500 to about 1/50 inch average particle size diameter, at least about 20 percent of its total pore volume of absolute diameter within the range of about 100.ANG. to about 200.ANG.; when the catalyst composition is of size ranging from about 1/50 inch up to 1/25 inch average particle size diameter, at least about 15 percent of its total pore volume of absolute diameter within the range of about 150.ANG. to about 250.ANG.; when the catalyst composition is of size ranging from about 1/25 inch to about 1/8 inch aver-age particle size diameter, at least about 15 percent of its total pore volume of absolute diameter within the range of about 175.ANG. to about 275.ANG., a surface area ranging at least about 200 m2/g to about 600 m2/g and a pore volume ranging from about 0.8 cc/g to about 3.0 cc/g.

2. A catalyst composition according to claim 1 further characterized in that the said catalyst comprises from about 2 to about 5 percent of a Group IVA metal, or com-pound thereof, from about 15 to about 25 percent of a Group VIB metal, or compound thereof, and from about 4 to about 8 percent of a Group VIII metal, or compound thereof, measured as oxides.

3. A catalyst composition according to claim 2 futher charac-terized in that said Group IVA metal is germanium, said Group VIB metal is selected from the group consisting of molybdenum and tungsten and said Group VIII metal is selected from the group consisting of nickel and cobalt.

4. The catalyst composition of any of claims 1-3 wherein the catalyst of particle size diameter ranging from about 1/500 to 1/50 inch particle size diameter is characterized as follows:

5. A catalyst composition according to any of claims 1-3 further characterized in that the catalyst composition of particle size diameter ranging from about 1/500 to 1/50 inch particle size diameter is characterized as follows:

6. A catalyst composition according to any of claims 1-3 further characterized in that the catalyst composition of particle size diameter ranging from about 1/500 to 1/50 inch particle size in diameter is characterized as follows:

7. The catalyst of any of claims 1-3 wherein the catalyst composition of particle size diameter ranging from about 1/50 to 1/25 inch particle size diameter is characterized as follows:

8. The catalyst of any of claims 1-3 wherein the catalyst composition of particle size diameter ranging from about 1/50 to 1/25 inch particle size diameter, is characterized as follows:

9. The catalyst of any of claims 1-3, wherein the catalyst of particle size diameter ranging from about 1/50 to 1/25 inch particle size diameter is characterized as follows:

10. The catalyst of any of claims 1-3 wherein the catalyst of particle size diameter ranging from about 1/25 to 1/8 inch particle size dia-meter is characterized as follows:

11. The catalyst of any of claims 1-3 wherein the catalyst of particle size diameter ranging from about 1/25 to 1/8 inch particle size diameter is characterized as follows:

12. The catalyst of any of claims 1-3 wherein the catalyst of particle size diameter ranging from about 1/25 to 1/8 inch particle size diameter is characterized as follows:

13. A catalyst having enhanced selectivity for conversion, de-metallization, and for Con carbon reduction of hydrocarbon feeds which contain substantial quantities of 1050°F.+ hydrocarbon materials comprising an admixture of from about 2 to about 5 percent of a Group IVA metal, or compound thereof, from about 5 to about 50 percent of a Group VIB metal, or compound thereof, from about 1 to about 12 percent of a Group VIII metal, or compound thereof measured as oxides, and a porous inorganic oxide support, said catalyst includ-ing a combination of properties comprising at least about 55 percent of its total pore volume of absolute pore diameters ranging from about 100.ANG. to about 200.ANG. less than about 10 percent of its total pore volume of absolute diameter within the range of 0 to 50.ANG., less than 25 percent of its total pore volume of absolute diameter 300.ANG.+, a surface area ranging at least about 200 m2/g to about 600 m2/g and a pore volume ranging from about 0.6 cc/g to about 1.5 cc/g.

14. The catalyst of claim 13 wherein said catalyst comprises the combination of properties wherein at least about 70 percent of the total pore volume of said catalyst is of pore diameter ranging from about 100.ANG. to about 200.ANG., less than about 1 percent of its total pore volume is of absolute diameter within the range 0 to 50.ANG., less than 1 percent of its total pore volume is of absolute diameter 300.ANG.+, surface area ranges at least about 250 m2/g to about 350 m2/g and pore volume ranges from about 0.9 cc/g to about 1.3 cc/g.

15. The catalyst of claim 13 wherein said catalyst comprises from about 2 to about 5 percent of a Group IVA metal, or compound thereof, from about 15 to about 25 percent of a Group VIB metal, or compound thereof, and from about 4 to about 8 percent of a Group VIII metal, or compound thereof, measured as oxides.

16. The catalyst of claim 13 wherein said Group IVA metal is germanium.

17. A process for the demetallization and conversion of the 1050°F.+ materials of a heavy metals containing heavy crude or residua feed to 1050 F.- material characterized by comprising contacting said feed, in the presence of added hydrogen, with catalyst characterized as comprising an admixture of from about 0.1 to about 10 percent of a Group IVA metal, or compound thereof, from about 5 to about 50 percent of a Group VIB metal, or compound thereof, from about 1 to about 12 percent of a Group VIII metal 7 or compound thereof, and a porous inorganic oxide support, said catalyst including a combination of properties comprising, when the catalyst is of size ranging from about 1/500 to 1/50 inch average particle size diameter, at least about 20 percent of its total pore volume of absolute diameter within the range of about 100.ANG. to about 200.ANG.; when the catalyst is of size ranging from about 1/50 inch up to 1/25 inch average particle size diameter, at least about 15 percent of its total pore volume of absolute diameter within the range of about 150.ANG. to about 250.ANG.; when the catalyst is of size ranging from about 1/25 inch to about 1/8 inch average particle size diameter, at least about 15 percent of its total pore volume of absolute diameter within the range of about 175.ANG. to about 275.ANG.; a surface area ranging at least about 200 m2/g to about 600 m2/g and a pore volume ranging from about 0.8 cc/g to about 3.0 cc/g, at severity sufficient to convert at least about 30 percent of the 1050°F.+
material to 1050°F.- material, while removing at least about 80 percent of the heavy metals from the feed.

18. The process of claim 17 wherein from about 40 percent to about 60 percent of the 1050°F.+ material is converted to 1050°F.-, and from about 85 percent to about 90 percent of the metals are removed from the bed.

19. The process of claim 17 or claim 18 wherein the feed is characterized as follows:

20. The process of claim 17 or claim 18 wherein the feed is characterized as follows:

21. The process of claim 17 or claim 18 wherein the conditions of the reaction are characterized as follows:

22. The process of any of claims 1-3 wherein the catalyst is comprised of particle size diameter ranging from about 1/500 to 1/50 inch particle size diameter, and further characterized as follows:

23. The process of any of claims 1-3 wherein the catalyst is comprised of particle size diameter ranging from about 1/50 to 1/25 inch particle size diameter, and further characterized as follows:

24. The process of any of claims 1-3 wherein the catalyst is comprised of particle size diameter ranging from about 1/25 to 1/8 inch particle size diameter, and further characterized as follows:

25. The process of claim 1 wherein the Group IVA metal is germanium, the Group VI metal of the catalyst is molybdenum, and the Group VIII
metal of the catalyst is cobalt.

26. A process for the demetallization, conversion and reduction of the Con. carbon content of the 1050 F.+ materials of a heavy metals contain-ing heavy crude or residua feed to 1050°F.- material comprising contacting said feed, in the presence of added hydrogen, with a catalyst characterized as comprising an admixture of from about 0.1 to about 10 weight percent of a Group IVA metal, or compound thereof, from about 5 to about 50 percent of a Group VIB metal, or compound thereof, from about 1 to about 12 percent of a Group VIII metal, or compound thereof and a porous inorganic oxide support, said catalyst including a combination of properties at least about 55 percent of its total pore volume of absolute diameter within the range of about 100.ANG. to about 200.ANG.; less than 10 percent of the pore volume results from pores of diameters 50A-; less than about 25 percent of the total pore volume results from pores of diameters ranging 300.ANG.+; surface areas range from about 200 m2/g to about 600 m2/g, and pore volumes range from about 0.6 to about 1.5 cc/g, at severity sufficient to convert at least about 50 percent of the 1050°F.+ material to 1050°F.- material, remove at least about 90 percent of the heavy metals from the feed, and reduce Con. carbon from about 50 percent to about 100 percent.

27. The process of claim 26 wherein from about 60 percent to about 75 percent of the 1050°F.+ material is converted to 1050°F.-, from about 97 percent to about 100 percent of the metals are removed from the feed, and Con. carbon is reduced from about 75 percent to about 90 percent.

28. The process of claim 26 or claim 27 wherein the product of the reaction is characterized as follows:

29. The process of claim 26 or claim 27 wherein the conditions of the reaction are characterized as follows:

30. The process of claim 26 or claim 27 wherein the catalyst comprises a combination of properties wherein at least about 70 percent of the total pore volume of said catalyst is of pore diameter ranging from about 100.ANG. to about 200.ANG., less than about 1 percent of its total pore volume is of absolute pore diameters ranging from 0 to about 50.ANG., less than about 1 percent of its total pore volume is of absolute pore diameters ranging 300.ANG.+, and the catalyst has a surface area ranging at least about 250 m2/g to about 350 m2/g and a pore volume ranging from about 0.9 cc/g to about 1.3 cc/g.

31. The process of claim 26 or claim 27 wherein the Group IV
metal of the catalyst is germanium, the Group VI metal of the catalyst is molybdenum, and the Group VIII metal of the catalyst is nickel.

32. A process for the demetallization and conversion of the 1050°F.+ materials of a heavy metals containing heavy crude or residua feed to 1050°F.- material comprising contacting in the presence of added hydrogen, a feed charac-terized as follows:

with a catalyst characterized as comprising an admixture of from about 0.1 to about 10 weight percent of a Group IVA metal, or compound thereof, from about 5 to about 50 percent of a Group VIB metal, or compound thereof, from about 1 to about 12 percent of a Group VIII metal, or compound thereof and a porous inorganic oxide support, said catalyst including a combination of properties comprising, when the catalyst is of size ranging up to 1/50 inch average particle size diameter, at least about 20 percent of its total pore volume of absolute diameter within the range of about 100.ANG. to about 200.ANG.; when the catalyst is of size ranging from about 1/50 inch up to 1/25 inch average particle size diameter, at least about 15 percent of its total pore volume of absolute diameter within the range of about 150.ANG. to about 250.ANG.; when the catalyst is of size ranging from about 1/25 inch to about 1/8 inch average particle size diameter, at least about 15 percent of its total pore volume of absolute diameter within the range of about 175.ANG. to about 275.ANG.; a surface area ranging at least about 200 m2/g to about 600 m2/g and a pore volume ranging from about 0.8 cc/g to about 3.0 cc/g, at severity sufficient to convert at least about 30 percent of the 1050°F. material to 1050°F.- material, while removing at least about 80 percent of the heavy metals from the feed, and feeding such feed, charac-terized as follows:

into contact with a catalyst characterized as comprising an admixture of from about 5 to about 30 percent of a Group VIB metal, or compound thereof, from about 1 to about 12 percent of a Group VIII metal, or compound thereof and a porous inorganic oxide support, said catalyst including a combination of properties comprising at least about 55 percent of its total pore volume of absolute diameter within the range of about 100.ANG. to about 200.ANG.;
less than 10 percent of the pore volume results from pores of diameters 50.ANG.-;
less than about 25 percent of the total pore volume results from pores of diameters ranging 300.ANG.+; surface areas range from about 200 m2/g to about 600 m2/g, and pore volumes range from about 0.6 to about 1.5 cc/g, at severity sufficient to convert at least about 50 percent of the 1050°F.+ material to 1050°F.- material, remote at least about 90 percent of the heavy metals from the feed, and reduce Con. carbon from about 50 per-cent to about 100 percent.

33. A process for the synthesis and preparation of catalyst having a combination of properties including a relatively high concentration of pores of uniformly large diameter, high surface area and pore volume com-prising dispersing a compound of a Group VIB and Group VII metal, said compound being thermally decomposable to form a metal oxide and aluminum halide salt in an aqueous or alcohol medium in molar ratio of water (or alcohol): aluminum halide ranging from about 15:1 to about 30:1 and, while maintaining the tempera-ture within a range of from about 30°F. to about 100°F., adding olefin oxide in molar ratio of olefin oxide:halide of from about 0.3:1 to about 2.0:1 while maintaining a pH in the range of from about 5-8 to effect removal of the halide from solution and form a sol, raising the temperature of the solution to substantially ambient temperature or higher to form a solid which separates from its syneresis liquid, aging the solid while in contact with syneresis liquid for a period of at least 6 hours, separating the solids from the syneresis liquid, and then washing, drying, calcining, dispersing a soluble salt of a Group IVA metal in an aqueous or alcohol medium, in amount sufficient to provide from about 0.1 to about 10 percent of the Group IVA metal, measured as its oxide, in the final catalyst, impregnating said solid with aqueous or alcohol medium containing said Group IVA salt, drying, calcining, and then recovering a product.

34. The process of claim 33 wherein the recovered product includes a combination of properties comprising, when the catalyst is of size ranging up to 1/50 inch average particle size diameter, at least about 20 per-cent of its total pore volume of absolute diameter within the range of about 100.ANG. to about 200.ANG.; when the catalyst is of size ranging from about 1/50 inch up to 1/25 inch average particle size diameter, at least about 15 percent of its total pore volume of absolute diameter within the range of about 150.ANG. to about 250.ANG.; when the catalyst is of size ranging from about 1/25 inch to about 1/8 inch average particle size diameter, at least about 15 percent of its total pore volume of absolute diameter within the range of about 175.ANG. to about 275.ANG.;
a surface area ranging at least about 200 m2/g to about 600 m2/g and a pore volume ranging from about 0.8 cc/g to about 3.0 cc/g.

35. The process of claim 33 or claim 34 wherein the recovered product is characterized as follows:

36. The process of claim 33 wherein one or more of the Group VIII noble metals, lanthanum or lanthanum series metals, or compounds or salts thereof, are added to the solution in molar ratio metal:aluminum halide ranging from about 0.001:1 to about 0.06:1 during the synthesis, and the recovered product is characterized as follows:

37. The process of claim 36 wherein the molar ratio metal:
aluminum halide ranges from about 0.01:1 to about 0.03:1 and the product re-covered is characterized as follows:

38. The process of claim 33 or claim 34 wherein the water (or alcohol):aluminum halide ratio ranges from about 18:1 to about 27:1.

39. The process of claim 33 or claim 34 wherein the temperature of the solution is raised to a temperature ranging from about 70°F. to about 80°F. in forming the solid.

40. The process of claim 33 wherein the temperature, after formation of the sol is completed, is maintained within a range of from about 70°F. to about 80°F., and aged for a period ranging from about 24 hours to about 72 hours.

41. The process of claim 33 wherein the Group IVA metal is germanium.

42. The process of claim 33 wherein a Group VIB metal or a Group VIII metal, or both, is added to the aqueous or alcohol medium during the synthesis.

43. The process of claim 42 wherein the Group VIB metal is molybdenum and the Group VIII metal is cobalt.

44. A process for the synthesis and preparation of catalyst having a combination of properties including a relatively high concentration of pores of uniformly large diameter, high surface area and pore volume com-prising dispersing a compound of a Group VIB and Group VII metal, said compound being thermally decomposable to form a metal oxide and an aluminum halide salt in the aqueous or alcohol medium in molar ratio of water (or alcohol):
aluminum halide ranging from about 22:1 to about 30:1 and, while maintaining the temperature within a range of from about 30°F. to about 100°F., adding olefin oxide in molar ratio of olefin oxide:halide of from about 0.3:1 to about 1.5:1 while maintaining a pH in the range of from about 5-8 to remove the halide from solution and form a sol, raising the temperature of the solution to substantially ambient temperature or higher to form a solid which separates from its syneresis liquid, aging the solid while in contact with syneresis liquid for a period of at least 6 hours, separating the solid from the syneresis liquid, and then washing, drying, calcining, dispersing a soluble salt of a Group IVA metal in an aqueous or alcohol medium, in amount sufficient to provide from about 0.1 to about 10 percent of the Group IVA metal, measured as its oxide, in the final catalyst, impregnating said solid with aqueous or alcohol medium containing said Group IVA metal, drying, calcining, and then recovering a product characterized as follows:

45. The process of claim 44 wherein the Group IVA metal is germanium.

46. The process of claim 44 wherein one or more of the Group VIII noble metals, lanthanum or lanthanum series metals, or compounds or salts thereof, are added to the solution in molar ratio metal:aluminum halide ranging from about 0.001:1 to about 0.06:1 during the synthesis, and the recovered product is characterized as follows:

47. The process of claim 46 wherein the molar ratio metal:
aluminum halide ranges from about 0.01:1 to about 0.03:1 and the product re-covered is characterized as follows:

48. The process of claim 44 wherein a Group VIB or Group VIII
metal, or both, is added to the solution during the synthesis to form a cogel.

49. The process of claim 48 wherein the Group VIB metal is molybdenum and the Group VIII metal is cobalt.

50. The process of claim 44 wherein the water (or alcohol):
aluminum halide ratio ranges from about 26:1 to about 28:1.