CA1059110A - Heavy crude conversion - Google Patents

Abstract

ABSTRACT

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 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 composition including a combination of properties comprising, when the catalyst composition is of size ranging 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 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. to about 275.ANG.; surface areas ranging at least about 200 m2/g to about 600 m2/g and pore volumes ranging from about 0 6 cc/g to about 3.0 cc/g.
In use, the catalyst is contacted with a heavy metals containing hydrocarbon feed in the presence of added hydrogen 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.

Description

The hydrotreating of hydrocarbon or hydrocarbon-aceous feedstocks, including particularly heavy petroleum crudes and residua, is not new. In the past, the lower molecular weight or gas oil portion of such feedstocks has been catalytically convert-ed 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 t 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 1050F. + hydrocarbon portion of heavy whole crudes and residua to yield therefrom lighter boiling usable products, particularly from unconventional heavy crudes and residua which contain appre-ciable amounts of sulfur and nitrogen, high quantities of the so-called heavy metals, e.g., nickel and vanadium, as well as high "Con. carbon," high carbon-to-hydrogen ratios, high asphaltenes, ash, sand, scale, and the like, are copending Applications Nos.
219,484, 219,496, 219,526 and 219,552 filed March 6, 1975.
Processes for the conversion of feeds containing 1050 F+
hydrocarbon materials to lower molecular weight hydrocarbons are known. For example, in one such known process, a hydrocarbon feed and gas are passed upwardly through an ebullating bed of particulate catalytic solids. The process is thus conducted under conditions ., ~
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ch establish a random motion of the catalytic particles in the liquid without carrying the solids out of the reactor. Based on the solid size and density of the catalyst particles, and liquid density, velocity and viscosity, the mass of particulate solids is expanded from about 10 percent 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. Thus, there are certain dis-advantages associated with the activity of the catalysts used in such process.
It is thus particularly difficult to threat crudes or residuas which contain large amounts of 1050F. ~ hydrocarbons and the hydroconversion of 1050F. ~ hydrocarbon materials to lower boiling and more useful hydrocarbons presents an acutely difficult problem.

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,, " ' 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 hydroconver-sion 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, particularly as regards the amount of nickel and vanadium, (3) they are ultra-high in their content of materials boiling above 1050F., e.g., asphal-tenes, and even (4) contain considerable amounts of sand and scale.
Properties which readily distinguish these new materials from con-ventional crudes are thus: high metals, high asphaltenes, high carbon: hydrogen ratios, and a high volume percent of hydrocarbons boiling above 1050F. The presence of the greater amounts of metals and the higher carbon content of the heavy crudes, in part-icular, makes any considerations regarding the processing of thesematerials most difficult and expensive. The high "Con. carbon" and carbon: hydrogen ratios are considerably higher than those of any presently usable hydrocarbon liquids.

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- ~059110 It is an object of the present invention to provide new and improved catalysts, particularly useful in hydrocarbon conversion reactions, particularly reactions involvinq the hydro-conversion of the 1050F. + hydrocarbon portion of heavy crudes and residua.
A further object is to supply new and improved ,~
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-' 1059110 m_chods 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 1050F.~ hydrocarbon portion of feeds comprising heavy crudes and residua to useful lower boiling products while simultaneously producing appreciable Con. carbon reduction, hydro-desulfurization, 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, are of two distinct types as relates to an essential combination of properties regarding pore ; size (or pore size 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 (C5insoluble) and other ~ 20 large hydrocarbon molecules, which are effectively converted to j lower molecular weight products, and a second catalyst particularlysuitable for the efficient conversion, demetallization and Con.
carbon reduction of hydrocarbon materials, particularly of a feed of character similar to the pr~duct resultant from a hydroconversion s ~ - 4 -.
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,', . , ' : ' ' ' ' " ' . '. . :.'.-,'' ' ."'' - ' '. ' '' , ' , , ' ,: ' process utilizing said first catalyst. Conversion, as used herein, thus requires chemical alteration of the 10500F. t hydrocarbon molecules to form lower molecular weight molecules boiling 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 100, divided - 4a -,, -, ., , :
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bl the amount of 10500F. + material originally present in the feed. These catalysts in common comprise catalytically active amounts of a hydrogenation component which includes a Group VIB or Group VIII metal (especially, a Group VIII nonnoble metal), or both (Periodic Table of the Elements, E. H. Sargent and Co., Copy-right 1962 Dyna-Slide Co.), particularly molybdenum or tungsten of Group VIB , and cobalt or nickel of Group VIII, and preferably a Group VIB and Group VIII metal in admixture one metal with the other, or with other metals, or both, particularly Group IVA metals, composited with a refractory inorganic support,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, prefer-ably at least about 25 percent, and more preferably at least about 70 percent of its total pore volume of absolute diameter within the range of about 100A (Angstrom units) to about 200A; 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, prefer-àbly 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 150A to about 250A; when the catalyst is of size . -- 5 --.
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-- 1059~10 ging 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 percent of its total pore volume of absolute diameter - 5a -.. . . . . .. ..

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, ~" 1059110 thin the range of about 175 ~ to about 275 A; wherein, in each of these catalysts of differing ranges of particle size distri-butions, the pore volumes resultant from pores of 50A, and smaller, i.e., 50A-, are minimized; and preferably, while in catalyst average particle size below 1/50 inch, the pore volume resultant from pores of diameter above 300A, i.e., 300 A+, is minimized, and in catalysts of average particle size above 1/50 inch, the pore volume resultant from pores above 350A, i.e., 350A~, 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 convenience, over the spectrum of particle sizes ranging to 1/8 inch average particle size diameter, is one inclu-ding a combination of properties comprising at least about 55 per-cent, and preferably at least about 70 percent of its total pore volume of absolute diameter within the range of about 100A to about 200A; less than 10 percent, preferably less than 1 percent of the pore volume results from pores of diameters 50A-; less than about 25 percent, and preferably less than 1 percent of the . ~

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, total pore volume results from pores of diameters ranging 300 A ;
surface areas ranging from about 200 m2/g to about 600 m2/g, pre-ferably from about 250 m2/g to about 350 m /g, and pore volumes ranging from about 0.6 to about - 6a -- - - - , . . .. . . . .

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(b) a novel method for the preparation of 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 halide, with control of water (or alcohol): aluminum salt ràtios , and control and removal of hydrogen halide acid generated wi~th reaction, pre-ferably with the additional incorporation of Group VIII noble metals or lanthanum or lanthanum series metal salts, or both, to provide the selective pore size distributions, particularly as relates to th formation of extrudates, with concurrent optimiza-tion 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 1050 F.
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Operable Preferred Range Range Gravity, API-5 to 20 0-14 Heavy Metals (Ni & V), ppm5 - 1000 200-600 1050 F. ~ , Wt.~ 10 - 100 40-100 Asphaltenes (C
insolubles), W~.% 5 - 50 15-30 Con. Carbon, wt.% 5 - 50 10-30 - 7a -:, . . . . .
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, ' "''' ' ,', ' , ' ' , ': ', -105~110 . contacted, ln the presence ~f 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 10500F. + materials of the crude or`residua present to 1050F. - materials, removed at least about 75 percent, and preferably from about 80 to about 95 percent, by weight of the metals, preferably producing a product having the following characteristics:

operable Preferred Range Range Gravity, API 14-30 15-25 Heavy Metals (Ni ~ V), ppm 10-100 40-80 1050F.~ , Wt.% 10-50 25-40 Asphaltenes (C
insolubles), Wt. % 3-20 5-15 Con. Carbon, wt.% 3-20 5-10 which product is suitable for further contact, in the presence of 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 10500F.
+ materials of the crude or residua to 1050F. - materials, remove at least about 90 percent, preferably from about 97 percent to about 100 percent, 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 p_oduce a product having the following characteristics:
Operable Preferred Range Range Gravity, API 18-30 20-28 Heavy Metals (Ni & V), ppm <50 <5 - 8a -~.. . .
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3 1050F.+> Wt.% 5-30 10-25

4 Asphaltenes (C5 insolubles), Wt.% ~3 ~ 1 -6 Con. Carbon, Wt.% ~5 C3 7 In their opt~mum forms, the absolute pore size 8 diameter, of the R-l catalyst, dependent on particle size, O . O O
9 is maximized within the 100-200A, 150-~50A, and 175-275A
ranges, and ~he R-2 catalyst within the 100-200A range, 11 respectively. It is not practical, of course, to eliminate 12 the presence of all pores of sizes which do not fall with-13 in these ranges, but methods of preparation are known, 14 particularly methods of preparation according to this in-vention, which do indeed make it practical to produce 16 catalyst particles of absolute pore size diameters highly 17 concentrated within these desired ranges. The following 18 tabulations show the pore size distributions, as percent 19 of total pore volume9 of marginal and preferred catalysts of this invention:

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~ ~QS9110 ~ The R-l and R-2 catalysts can be the same or differ-ent 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 differ-ent and preferred process modes--viz. when R-l is used in an init-ial or first reaction zone to process heavy crudes or residua, hereinafter referred to as "R-l 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 re-fractory inorganic support material, preferably a porous inorganic oxide support with a metal or compound of a metal, or metals, selected from Group VIB or Group VIII, or both, the metals general-ly 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, prefer-ably from about 15 to about 25 percent (as the oxide) 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 basis) of the composition. The preferred active metallic components, and forms thereof, comprise an oxide or sulfide of molybdenum and tungsten of Group VIB, an oxide or sulfide of nickel or cpbalt of Group VIII, preferably a ;. :

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`'^ -- 1059110 ~ ture of one of said Group VII3 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 - 12a -1059~10 1 catalysts may be compr~sed of nickel ~nd molybdenum. The 2 nickel-molybdenum cat~lyst in R-~ service po~se~ses very 3 high hydrogenation acti~ity and ij particularly effective 4 in reducing Con. carbon. Other ~uit~ble ~roup YIB and VIII
metals include9 for example, chroml~m~ platin~m3 palladium, 6 iridium9Osmium, ruthenium9 rhodium9 and the like. The in-7 organic ox~de support~ suitably compri~e alumina9 silica, 8 zirconia, magnesia, boria, phosphate, titania, ceria, thoria 9 and the like. The preferred support is alumina~ preferably gamma alumina, which in R-2 service is preferably stabilized 11 with silica in concentration ranging from about 0.l to about l2 20 percent, prefarably from about l0 to about 20 percent, 13 based on the total weight (dry basis~ alumina-silica compo-4 sition ~inclusi~e of metal components). The catalyst compo-sition can be in the form of beads~ aggregates of various 16 particle sizes, extrudates, tablets or pellets, depending 17 upon the type of process and condition~ to which the catalyst -18 is to be exposed. -~
19 Particularly preferred catalysts ~re compoæites of n~ckel or cobalt oxide with molybdenum~ used in the follow-21 ing approximate proportionsO from About 1 to about 12 weight 22 percent, preferably from about 4 to about 8 weight percent 23 of nickel or cobalt oxides9 and from about 5 to about 50 24 weight percent, preferably from about lS to about 25 weight percent of molybdenum oxi~e on a suitable support~ such as 26 alumina. A particularly preferred support for R~2 catalyst 27 comprises alumina containing from ~bout l0 to about 20 per-28 cent sllica The catalyst i3 sulfided to fcrm the most active 29 species.
Ihe Group VIB and Group ~I~l metal component~, ~d-31 mixed one component with the other or with a third or great-32 er number of metal component~, can be compo~ited or intimate-- 13 ~

` 1~59110 1 ly aæsociated with the porou~ inorganic o~lde ~upport or 2 carr~er by various technique~ known to the art9 ~uch as by 3 impregnation of a ~upport with the metals, lon exchange9 4 coprecipitation of the metal~ with the ~lumlna in the sol or gel form, and the like. For example~ a preformed aluml~a 6 support can be impregnated by an "incip~ent wetne~s" tech-7 nique, or technique wherein a metal, or metal~, is contained 8 in a ~olution in measured amo~nt and the e~tire solution is 9 ab~orbed into the support which ~ then dried, calcined, etc., to form t~e cataly~tO Also, for example9 the catalyst composite can be formed from a cogel by adding together l2 suitable reagen~s such a~ ~altQ of the Grsup VT~R or Group 13 VIII metals, or both9 and ammoni~m hydroxide or ammonium 4 carbon te, and a salt of alumin~m ~uch as aluminum chloride or aluminum sulfate to form aluminum hydroxide. The alum-6 inum hydroxide containing the salts of the ~roup~ VIB or 7 Group ~III metals, or both~ and additional metalg ~f de-8 sired can then be heated, dried~ formed into pellets, or 19 extru~ed, and then calcined in nitrogen or ~her generally inert atmosphereO C~talyst~ f0rmed from cogel~ do not 21 p~ssess pore ~ize di~tr~bution~ as uniorm a~ tho~e formed 22 by impregnation metho~.
23 The cataly~t~ can be u~ed in the r~action ~ones a~
i4 fi~ed beds, ebullati~g bed~ or in ~lurry ~o~m within bedsO
When used in the form of f~Ked bed~, the part~cle ~ize diam-26 eter of the cataly~ts generally ranges from about l/32 to 27 about l/8 inch9 preferably about 1/16 ~nchO ~hen u~ed a8 28 ebulldting beds the cataly~t gener~lly range about l/32 inch 29 dlameter and ~m~ller, and when used as l~rry bed~ the par~
ticle size~ generally range from about lO0 tG about 400 31 microns. m~ bulk dens~ty of the R~l catalyst gener~lly 32 ranges from about 0,2 to abGut 0.6 g/~C9 preferably from 1~ ~

1 about 0.2 to about O.S g/cc, depending on particle ~ize, 2 and that of the R-2 catalyst ranges from about 0.3 to about 3 0.8 g/cc, preferably from about 0.35 to about 0.55 g/cc.
4 The catalysts of this invention further compri~e a metal, or metals, of Group IVA, or compounds thereof. ~he 6 catalysts will thu~ compri~e germanium, tin, or lead, or 7 admixture of such metal~ w~th e~ch other or with other metals, 8 or both, in combination with the Group VIB or Group VIII
9 metals, or admixture thereof. ~he Group IVA metals act as promoters for R-l and R-2 catalysts in enhancing the rate 1 of demetallization of a feed. Of the Group IVA metals 9 ger-12 manium i8 particularly preferred. Suitably, the Group IVA ` - -13 metal comprises from about O.Ol to about lO percent, prefer-14 ably from about 2.0 to about 5 percent of the cataly~t, based on the total weight (dry basis) of the compositionO The 6 Group IVA metals must be incorporated within the catalyst 7 by impregnation. ~-8 A feature of both the R-l and R-2 catalysts is 19 t~t each i9 of very high surface area and contains ultra-high pore volume, this provid~ng an extremely great number 21 of active metal siteg. Thi~, in combination with the se-22 lected pore size distributions of the R~l and R~2 catalysts, ';
23 provides catalysts admirably suitable for t~le d~metallization 24 and hydroconversion of feeds of the charac~eristics des~
cribed, which feeds usually conta~n additional high concen-26 trations of sulfur and nitrogenO In R 1 service, in util~
27 izing R-l catalyst in its most preferr~d form~ the number 28 of pores ranging between about 100-2-/SA absolute pore ~ize 29 diameter is maximized, dependent on particle size, as is 8urface area and pore volume consistent with practical cata-31 lyst preparation procedure~ and with regard to the part~cle32 cru~h ~trength requirements of the process. Moreover, the - ~ 15 ~

:- 1059~0 1 n~m~r of pores which are 3maller than 50~ and preferably 2 those greater than about 30Q~r or about 350A when the aver-3 age particle size diameter excee~3 about 1/~0 inchg are mini-4 mized. R-l catalyst of ~uch character ~as thus proven out-standing, even under the stringent requirements of R-l ser-6 vice, in retaining considerable quantities of heavy metal~7 while yet remaining active over extraordinarily long peri-8 ods. For example, the R-l c~taly~t, whan oper~ted at a 9 700F. start-of-run temperature (SOR~, has been shown suit-able for maintaining 1050F.~ conversion levels rsnging from about 20 to about 40 percent, and higher~ for period~ ranging 2 up to about 70 days, and longer. In fact, this catalyst9 at 3 the end of such period, h~ been found to retain Gver 150 14 percent of its own weight of heavy metals from whole he~vycrudes and residua feeds. Moreover, while accomplishlng 6 this, the R-l catalyst ~lso effectively removes much of the 7 sulfur and nitrogen in hydrodesulfur~zation and hydrode 18 nitrogenation reaction~. For example, w~ole heavy c~udes 19 and residua of the type characteri~ed often contain fro~
about 2 to about 7 weig~t pereen~g u~ally from about 3 to 21 about 6 per~ent sulfur9 and often from about Oa2 to about 22 0.8 percent, usually from about 0.~ ~o about 0O7 percent 23 nitrogen. Generally, from abGut 75 to about 95 percent of 24 the sulfur, and from about ~5 to about 6~ pexc~nt of the 2s nitrogen can be effectively removed from ~uch heavy crudes26 and residua ~n R-l ~ervice while obtaining high conver~ion.
27 The product of such reaction9 unlike the original feed pro-28 cessed over the R-l catalyst, i8 now suitable a~ feed to a 29 coker to provide greater yield~ of C3+ li~uid product th n would otherwise have been po~3ible by coking the original 31 feed, and the coke product is le~s sour and le~ contamin-32 ated by heavy metalsO For example, lt ha~ been fo~nd th~t - 16 ~

~0 59 1 1 0 1 by operating the R-l cataly~t at a stsrt-~f-run (~OR~ temper-2 ature of about ?00F, ~t a low ~pace velocity of about 0.~5-3 0.50 V/H/V, a product i8 obtained whtch is highly suitable 4 for coking. Compared to coking of the raw whole crude or ~-residuum, the C3~ liquid product yield i~ increa~ed from 86 6 to 97 vol. % and the coke yield is decrea~ed ~ome 70%. The 7 product coke contains only 205 wt. 70 sulfur comp~red to 5.9%
8 sulfur coke from coking of the raw feed.
9 The product of the reaction conducted at a space -velocity of 0.~5 V/Hr./V is also highly ~uited for processing in a resid catalytic crack~ng operation. T~e raw feed con-l2 tains too much heavy metal~ and ~on carbon for conventional 13 catalytic cracking. ~he product9 on the other hand, iB
14 low enough in heavy metals and Con. carbon to be converted in a resid catalytic cracking operationO Hence, the hydro-l6 converted product is fed directly to a fluid catalytic 17 cracker operating on a cheap amorpho~3 cataly~t at low once-18 through 430F. conversion ~caO ~5%~ but at high 950F.~
19 conversion (ca. 95%). The re~ult is t~at a 97% yield ~C3+~ -of a ~ynthetic crude suitable for f~rther proces~ing in con 21 ventional refinery equipment i~ obtain2dO ~oke yieldD pro-22 duced on the cracking cataly~t~ is 7.~ wto Z.
23 By operating the reactor) or reactor~, containing 24 the R-l c~talyst at a start-of-run temper~ture of about 750F. and at a space velocity of a~out 005 V/Hr./V9 a pro- -26 duct is made that i8 suitable for u~e in a c~alytic cracker 27 employing zeolite cracking cataly~tO By operatlng at about 28 an 80% 430F,- conver~ion, a C3+ yield of 107 volume percent 29 and a coke-on-catalyst yield of 705 wt, ~ can be obta~ned, However, the preferred mode of cperat~on i~ to remove 90%
31 of the metals from the raw feed with the R~l cataly8t at a 32 SOR temperature of about 750~0 and a high space velocity -17 ~

1 of about 1.0 V/Hr./V. This product is now suitable for R-2 service 2 to provide feeds which can be used directly in conventional commercial 3 petroleum operations, especially in conventional hydrocracking and 4 catalytic cracking operations for the production of gasoline and other light distillates. The product from R-2 should contain about 2 ppm 6 heavy metals, or less, with a Con. carbon of about 3.3 wt. /0. This 7 material, when converted in a catalytic cracker employing zeolite 8 catalyst at a catalyst makeup rate of 0~4 lb./Bbl. at about 80% 430F. ~
9 conversion~ will produce a yield of llO vol. Z C3+ and 6.7 we. % coke on catalyst.
11 In the preferred mode of operation (i.e.~ 750F. SOR and 12 1 V/Hr./V)~ this catalyst will have removed up to 90% and more of the 13 metals in tbe raw feed after an operation of 27 or more days, the 14 catalyst retaining over about 95% of its weight of metals from whole heavy crudes and residuum feeds. The amount of sulfur and nitrogen that 16 is removed is comparable to that presented in the preceding paragraph.
17 In utilizing R-2 catalyst, in its ~ost preferred form, the lô number of pores ranging between about 100_200R absolute pore size diame-19 ter is maximized, as is the surface area and pore volume consistent with practical catalyst preparation procedures and with regard to the crush 21 strength requirements of the process. This means, of course, that the 22 number of pores of diameter which are smaller than loOR (especially 23 50R-) or greater than about 200R are minimized, especially the 300~
24 pores. R-2 catalyst of such character has thus proven outstanding in R-2 service which~ while noe as stringent as R-l service, is nonetheless 26 rather severe, the R-2 catalyst retaining considerable quantities of 27 heavy metals while yet remaining active for Con. carbon &onversion ' ' ', ,' ~ ' . ' " ,.

1059110 , -.
1 over long periods. Moreover, the R-2 catalyst accomplishes this while achieving high hydrodesulfurization and hydrode-nitrogenation of the feed. For example~ operating at 650F. SOR
temperature and at a space velocity of 0.5 V/Hr./V, the R-2 catalyst reduces the metals content of the R-l product from a level of about 60 ppm to about 5 ppm, representing about 99%
metals removal based on total feed. At the same time, asphal-tenes 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 1050F.+ conversions, and conversion levels (based on raw feed) of 60% and higher have been obtained. The product of R-2 service is suitable as feeds for conventional petroleum processing operations, particularly hydrocracking and catalytic cracking operations. `
In a preferred method for the preparation of these novel catalysts, catalysts which at least meet the marginal requirements of R-l and R-2 catalysts as regards desired pore size ;
;: -distribution are prepared from al~mina 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 the `
synthesis reaction. Gel preparation without added metals, of course, requires subsequent incorporation, e.g., impregnation, of metals whereas in cogel preparation the metals are added at the time of gel formation. In such preparations, an aluminum halide, e.g., al~mlnum chloride, is first dispersed or slurried in water or alcohol in certain critical proportions, defined for convenience 29 in terms of the molar ratio of water (or - 19 _ /
"' ' ` .
.

1 alcohol~Oal~minwm halide dependent on w~ether it i~ des~red 2 to produce an R-l or R-2 ~ataly$tO ~he temperature of the 3 aluminum halide-w~ter ~or alco~ol~ ~l~rryp to which the de-4 ~red Group VIB and Group VIIT metals and other metal~9 can be added as m~y be desired as in forming of a cogel, iB
6 then l~wered. Normally, water is u~ed a8 the ~olvent, but 7 alcohols such as methanol can be used~ though pore si~es 8 tend towards the ~maller diameter~ w~th alcohol solvent~.
g It i~ al~o essential in the reaction to add a re~gent which will remove the halide from ~oluticn while maintaining pH
11 in the range of 5-8, thi~ being preferably accompl~shed by 12 addition of an ol~fin oxide, eOg~, ethylene ox~de, propyl-3 ene oxide~ and the like, which forms a halohydrin. The re-14 action is necessarily carried out at relatively law temper-ature, preferably from about 30F. to about 100F., and more ~6 preferably from ~bout 32F. to about 60F. The olefin oxide 17 i8 added in at least stoic~bmetric quant~tie~ in relation 8 to the amount of halide to be rem~ed from the solution9 19 and prefer~bly is added in molar exces~ to the ~olutionO In the preparation of cataly~t which dt lea~t meets the margin-21 al pore si~e distribution required of R-l catalyst9 the molar 22 ratio of olefin oxide:halide ranges from about 1.50l to t 23 about 2.0:1 and preferably from about l.Sol to about 1~7:1, 24 while the molar r~tio of water ~or alcohol~ aluminum halide 2s is maintained within a range of from about 1501 to about 30~
26 and preferably from about 1801 to about ~70010 In the prepa-27 ration of catalyst which at lea~t meet~ the marg~nal pore 28 size distribution required of R~2 catalyst, the molar ratio 29 of olefin oxide:chloride ranges from abowt 00301 to about 1.5:1, and preferably from about l~Ool to about l~20ol~ -31 while the molar r~tio ~f water ~or alcohol~oal~tmin~m halide 32 i8 maintained ~ithin a raIIge of ~om abo~t 2201 to about 3~
- 20 '~

.' 1059110 1 and preferably from about 26~1 to about 280l. Failure to 2 remove most of the h~ide, e.g., chlor~de, from the reaction 3 results in a failure to obtain the desire~ crystal growth, 4 failure to obtain the required pore size distributions, or failure to produce a crystal sufficiently stable to retain 6 such desired pore size distribution~ throughout ~ubsequent 7 steps required in completing the formation of the catalyst.
8 It is believed that the required cry~talline structure which 9 shall ultimately be produced from the sol is of a nature of boehmite, termed for convenience "pseudo-boehmite," and that 11 excessive halide concentration and high pH adversely affect l2 the proper form~tion of ~uch aluminum oxy hydroxide crystal- ;
13 line ~tructure.
14 After completion of the reaction, the temperature of the gel is raised to from about ambient to about 180F.
6 to form a 80l. Preferably, the ~ol is formed at essentially 7 ambient temperature, r~nging generally from about 70F. to 8 about 80F. and, on proper aging, pseudo-bsehmite is produced.
19 It i~ essential to age the gel at such temperature for ~t least about 6 hours, and preferably for about 24 hours to 21 about 72 hour~ while the gel ig in contact with it~ syneresis 22 liquid. Lesser periods of aging result~ in reducing the uni-23 formity of pore gizes9 and significantly lon er periods, 24 particularly periods in excess of 6 day~9 often produce~
bimodal distribution of the pore ~ailure to properly age 26 the gel, while it is in contact with the jyneresis liquid, 27 also produces a crystal ~tructure wh~ch is not sufficiently 28 ~table to retain the desired pArticle size distribution~
29 in the subsequent and necessary step~ of washing, drying and calcination.
31 It ha~ been discovered that Grcup VII~ noble 32 metals and lanthanum and lantnanum ~erie~ metals, or com-~ 21 -.
, , 1 pounds thereo~9 are admirably ~uit~ble a~ promoter~ for pro-2 viding narrow pore size distr~bution~ and, in conjunction 3 with control of the concentrAtion ~f the reactants employed 4 in the synthesis, the temperature~ and particularly the acidity of the synthesis ~olution, these promoter~ can be 6 used to provide R-l and R~2 cat~lyst~ of optimum pore ~ize 7 di~tributions. Catalysts which meet even the preferred 8 specifications of R-l and R-2 catalysts can thus be made g by incorporation of small amounts of ~roup ~IIB metal~ of Atomic Number 57 and greater, and Group VIII noble metals, 11 or both, or compounds or salts thereof, within the ~olution l2 during the synthesis. Exemplary of the former are such metals as lanthanum, and the rare earth metals of the lan-14 thanum series such as cerium, pra~eodymium, neodymium, promethium, samarium, europium~ gadolinium, terbium, dys- -l6 prosium, holmium, erbium, thulium, ytterbium and lutetium 17 Exemplary of the Group VIII noble metals are ruthenium, 18 rhodium, palladium, osmiuml iridium, and platinum9 which 19 metals are less preferred than the lanthanum series metal~
because of their greater co~tO ~uitably, ~uch metals9 or 21 compounds th~reof9 are added to the $olution, for prepara-22 tion of R-l and Ro2 catalysts, in molar ratios of promoter 23 metals:aluminum halide ranging from about OoOOl l to about 24 0.06:1, and preferably from about OoOl l to about 0003:1.
The reason for the effectivenes~ of the~e metals, partieu-26 larly the lanthanum metal~, generally added as ~oluble 27 salts, e.g., a~ halides, acetates, nitrates, sulfate~ e~c., 28 in producing the high uniformity of pore sizes in the de-29 sired ranges, when employed at the condit~ons defined9 i8 not understood.
31 The synere~is liquid, after the aging step) is 32 poured off of the gel or cogelO In the ca~e of a gel, the - 22 ~

, ' 1 gel can next be cru~hed to the desired particle size, air 2 dried, then thoroughly washed. It i~ particularly pre-3 ferred to wash the gel cr cogel with ~lcohol, to remove 4 contaminantg, after which the cataly~t is air dried at room temperature, and then dried at mild temperatures, e.g.~ at 6 about 175-225F. for about 3 to 6 hours, then calcined, 7 e.g., by heating at about 800-1100F. for about 1 to 4 8 hours, and, the gel, then impregnated with a predetermined 9 amount of the desired metal, or metal~. The washing step is critical in the form~tion of the de~ired pore size dis-11 tribution. Generally, isopropanol or one of the intermed-l2 iate alcohols, e.g., n-propyl i~obutyl and the like promotes 13 the formation of the desired pore sizes. Methanol, on the 14 other hand, forms smaller pores generally, e.g.9 O-lOQA, and hexyl alcohol forms larger pore~, e.g., 300t~. Nixtures of l6 water and intermediate alcohols also favor the formation of 17 O-lOQA pores.
8 Impregnation of the alumina can be done prior or 19 subsequent to the calcinaticn step. If sub~equent to the calcination step, it i~ best to allow the calcined alumina 21 to equilibrate with the moisture in the air for 4-6 hour~
22 pricr to impregnation to avoid damage to the pore structure. ~;~
23 It is imperative that the ~mpregnation be done with a non-24 aqueous solution, e.g., alcohol, rather than water solution.
If water solution~ are u~ed~ the pore structure will readily -~
26 shrink to the O lOQA pore diameter range during subsequent 27 drying and calcination. The catalytic me~als9 eOg., Co and 28 Mo, are dissolved in alcohol, eOg., methanol9 and preferably 29 isopropanol, and the solution imbibed into the aluminaO
Drying for 16-24 hours in air at ambient condi~ions, then 31 drying for about 3-6 hour~ at 175 225F., and then calcin-32 in8 at 800-1100F. for 1~4 hours, will preser~e the de~ired ~ 23 -, . . , ~

',:' 1~59110 1 pore structure. The catalyst ls then crushed and ~creened 2 to the desired particle si7e for testlng, usually 14-35 3 mesh (Tyler).
4 Extrudates of outstanding strength and quality, which meet the requirements of both R-l and R-2 catalysts, 6 can be prepared in accordance with a preferred and novel 7 method of this invention which embodies extrusion of a gel 8 or cogel of preselected pore size distributions falling 9 within the R-l and R-2 cataly~t ranges, cr which contains pores of size distribution suff~ciently large that when the 11 gel is sub~ected to extrusion at the required conditions the 12 reduction in the si~e of the pores caused by the extrusion 13 and aging step~ will reduce the pore sizes such as to cause 14 them to fall within the R-l and ~-2 catalyst rangesO The gel or cogel, at the time of extrusion, is of critical 16 liquids-solids content (generally produced by drying~, it 17 has been previously aged within syneresis liquid for pre-18 selected periods at conditions involving critical time9 19 temperature, or time-temperature relationsh~p~ and, after extrusion9 the extrudate is dried to provide a critical 21 liquid-solids content and, in a preferred embodiment, then ~.
22 re~urned to syneresis liquid, without wash~g, and aga~ ged 23 for specific critical periods at conditions involving cr~ti- -24 cal time, temperature, or time-temperature relationship~
In the preparation of an extrudate9 a gel or cogel 26 is initially prepared from a sol, preferably one containing 27 a Group VIII noble metal, or metals, or lanthanum and lan~
28 thanum series metals, or admixture~ thereof~ in the range of 29 proportions previou~ly described, by varying the molar ratios of water (or alcohol):aluminum halide and olefin oxldeo 31 halide9 and al80 within the ranges described consistent with 32 the requirement~ of producihg an R~l catalyst, if an R-l - 24 ~

, ,, ' ' ~

1 catalyst is desired, or with the requirements of producing 2 an R-2 catalyst, if an ~o2 catalyst is desired~ Sub~equent 3 to form~tion of a gel or cogel of the required properties, 4 the gel or cogel is init~ally ~ged in ~yneresis liquid at critical time, temperature, or time-temperature relationships 6 sufficient to increase the crush strength of the finished 7 particle and to provide the desired pore si~e distribution 8 of the gel or cogel, or to preserve such pore si~e di~tri-9 bution sufficiently that when sub~ected to extrusion and further aging at the required conditions the reduction in 11 size of the pore~ caused by the extrusion will produce pore l2 size distributions falling within the R-l and R-~ catalyst 13 ranges. Thi8 i~ accompli~hed in part by the presence of the Group VIII noble metals or lant~num series metals, or both, which inhibits or tend~ to inh~bit the normal tendency 16 to reduce the sizes of the pores during the nece~sary step, 17 or steps, of aging. The cr~h ~trength i~ lncreased, and 18 pore size distribution pre~erved by aging the gel or cogel 19 prior to extrusion, preferably cont~in~ng the Group VI~I
or lanthanum series metal~, or both9 in syneresis liquid 21 (l~ for an initial time period ranging at least 6 hours, and 22 up to about 30 days, or longer, preferably for a period of 23 from about l day to about 6 days, and mcre preferably from 24 about 24 hours to about 72 hours9 at generally ambient temper-atures, i.e.9 about 50F. to about 80~.9 or by ag~n~l~2 26 at elevated temperatures ranging from about 80~F. to about 27 180F., preferably from about lO0F. to about l60F., or by ~-28 aging (3) at a combination of time temperature reiationships 29 within these ranges of expre~s conditlon~O It is preferred, however, to subject the gel or cogel to an init~al aging 31 for a rather short period, ~a~ preferably from about l to 3 32 days or, more preferably, from about 24 hours to abcut 30 - 2~ ~

1 hours, at ambient conditions, or ~b) at higher temperatures 2 ranging from about 80F. to about 180F., preferably 100F
3 to about 160F. for shorter periods, preferably ranging from 4 about 10 hou~ to about 24 hour~, and more preferably from about 15 hours to about 20 hours~ and then to extrude, dry 6 the extrudate to a critical liquid-solids content, and there 7 after again su~ect the extrudate to a sub~equent aging in 8 syneresis liquid.
9 The gel or cogel, after the init~al aging period, lo is separated from the syneresi~ liquid and partially dried 11 by standard techniques, e.g., as described, to produce a l2 gel or cogel contain~ng from about 12 percent to about 40 13 percent, and preferably from about 15 percent to about 25 4 percent solids content, based on the total weight of the gel or cogel with its occluded liquid. The gel or cogel is l6 preferably cru~hed to less than 10 mesh (Tyler series) par-l7 ticle si~es and then extruded througk a die to produce ex-8 trudates of desired diameter, and the extrudates are then 19 cut into desired lengths. Efforts, on the one hand, to ex-trude a gel or cogel having too low a solids content gener- - -21 ally prcve unsucces~ful or, if successful, the extrudates - ~
22 will be of poor quality and msy even deteriorate and crumble ~ -23 on subsequent aging in syneresis liquid. Extrusion of a gel 24 of too high solids content adversely affects the pore size distribution previously developed in the gellation, the crush 26 strength and the larger pores generally ~eing substantlally 27 reduced in size7 After extrusion, and formation of the ex-28 trudate, the extrudate must again be dried to a solid~ con-29 tent of ~25 wt, %O If the extrudate i~ to be subsequently aged, a~ preferred, the extrudate, after drying, i8 then 31 directly transferred, without washing, to the syneresis 32 liquid, In the subsequent aging ~n ~eresis liquid, the - ~6 o 1 extrudate is ag~in treated at critical time, temperature9 2 or time~temperature relationships to preserve the required 3 Rol and R~2 pore size distributionsO Suitably9 this is ac 4 complished by aging the extrudate in the syneresis liquid (1) for a period ranging at least 6 hours~ and up to about 6 30 day~9 or longer, preferably for a period ranging from 7 about 1 day to about 6 days, and more preferflbly from about 8 24 to about 72 hours at ambient conditions, or by aging 9 (2) at elevated temperatures ranging from about 80F. to 10about 180F., preferably from about 100F. to about 160F., 1 for periods ranging from about 10 hours to about 24 hours, 2 preferably from about 15 hours to about 20 hours, or by 3 aging (3) at a combination of time~temperature relationships 14 within these express conditions. The extrudate is then a~
gain necessarily dried to provide a solids content of ~25 , . , l6 wto %, and then washed9 preferably with alcohol. Failure 17 to dry the gel to the required solids content c~n produce 18 di~integration of the particles in washingO A gel or cogel 19 properly aged, properly dried to the required liquids~solids 2Q content, properly extruded9 without washing~ and then agfl~n 21dried to the required solids content9 the extrudate subse~ -22 quently aged fcr the required periodD and then dried to the 23 required solids content prior to washing wi~l provide extru~
24 dates of superior strength and quality.
25A low torque extruder9 Model 0O810 Research Ex~
26 truder manufactured by Welding Engineers of King cf Prussia9 27 Pennsylvania, has been found to produce extrudates of out 28 standing quality when produced pursuant to these specifica~
29 tions. Extrudates of superior cru~h strength c~n be formed in producing both R~l and R02 types of catalysts. After 31 passage through a die to provide s~apes of predetermined 32 selected diameter~ particul~rly for use Ln ebullst~ng and ~2 7 1 fixed beds9 the extrudates can be cut in the desired lengths, 2 dried to critical sol~ds content, aged in the syneresis liq-3 uid and again dried to control solids content, washed, pre-4 ferably in alcohol as previou~ly described, again dried~
calcined and, where de~ired, the so-formed extrudate then 6 impregnated with the desired metal, or metal~, or with an 7 additional metal, or metals.
8 The metals-containing catalyst, whether formed as 9 a gel or cogel9 can then be contacted with hydrogen and hydrogen ~ulfide, or hydrogen ~ulfide precursor, or both, 11 in situ or ex situ9 in a subsequent ~tep9 or ~tep~l to re-12 duce and sulfide all or part of the metal salts and activate 13 the catalystO The sulfiding is generally carried out by 14 passing hydrogen sulfide in admixture with hydrogen through a zone of contact with the catalyst. The temperature of l6 sulfiding is not especially critical9 but i3 generally car-l7 ried out in the range of about ~00 to about 900F., prefer-8 ably from about 600Fo to about 750F. The t~me required 19 for the sulfiding of the metals is generally short and not ~ -more than an hour, or at least no more than cne to four hours 21 is generally required to complete the sulfiding. Typically, 22 in sulfiding the catalyst, the cataly~t is contacted with a 23 dilute gaseous solution, eOg., about 5 to about 15 percent, 24 preferably from about 8 to about ~ percent, of hydrogen sulfide in hydrogen, or hydrogen plus other nonreactive gases, 26 and the contacting i8 continued until hydrogen sulfide is de-27 tected in the effluent gas0 Such treatment convert~ the 28 metals on the catalyst to the sulfide form9 Sulfur-contain-29 in8 hydrocarbons, such as gas oils and the like, may be used a~ hydrogen ~ulfide precursorsc 31 In accordance with the present hydroconver~ion pro-32 cess? the R-l catalyst is contacted in a reaction zone with 28 ~

.

1 a hydrocarbon or hydrocarbonaceous feed9 e.g., a liquid de-2 rived from coal by hydrogenation, shale or tar sand liquids, 3 a heavy crude or residua feed, in the pre~ence of hydrogen, 4 at conditions of severity sufficient to achieve the de~ired conversion of the 1050F.+ materials to lower molecular 6 weight, or 1050F.- materials, and ~imul~aneously to remove 7 at lea~t about 80 weight percent, and preferably from about 8 85 weight percent to about 90 weight percent of the heavy 9 metals, particularly vanadium and nickel, from the feed.
Removal of the heavy metals is enhanced by the combination 11 of condition~, particularly that of temperature, w~ich en-l2 hances the conver~ion and result~ in ~ome cleavage and re-13 duction in the size of the asphaltenes9 and the selective 14 pore size distribution of the R 1 catalyst, the 100 275A
pore size openings accepting asphaltenes ranging from small l6 to relatively large size, with regard to whether or not such 17 molecules were origin lly of such 8 i2e or reduced in 8 i~e by 8 the eonditions cf reactionO ~he small to relatively large 19 ~ize asphaltene~ readily diffuse~ with hydrogen, into the depths of the catalyst particles wherein hydrocon~er~ion re-21 action egre$sing from the particle9 along with unreacted 22 materials, dS more highly hydrogenated lower boiling products.
23 In conduct~ng the reactionD the R 1 catalyæ~ is 24 generally employed in one or more stages of a reactor, or reactors, ligned in series ~which can an~ us~ally does in 26 clude one or more stand-by or swing reactors9 as desired3.
27 The R-l catalyst, after be~ng reduced and ~ulfided generally 28 in situ within the reactor, is cperated under contitions, 29 the ma3Or variables of which are tabulat~d for convenience, ag follows , . ,, , ,.,. , ,:

.

~059110 1 Operable Preferred ,, 2 Tem erature, ~F., E.I.T.~l~
3 ~tart-of-Run 700 750 4 End-of-Run 850 800 Pressure, psi 2000-10,000 2000-5000 6 Hydrogen Rate, ~CF/B 3000-20,000 3000-109000 7 Space Velocity, LHSV 0.25-5.0 0.5-1.0 8 (1) Equivalent I~ thermal Temperature (E.I.T.~
9 The hydrocarbon or hydrocarbonaceous feed, i.e., coal liquid, shale or tar sand liquid~, he~vy crude or re-11 sidua, is rendered by R-l service more suitable a~ a feed 12 or use in a coking proces~ or a resid catalytic cracking 13 process. Preferably, however, the product of R-l service 14 i8 rendered a suitable grist for R-2 service, and thereby made suitable as a feed for use in conventional petroleum 16 refining processes, especially as a feed for a hydrocracking 17 or catalytic cracking operationO The R-2 catalyst, as here-18 tcfore suggested, is of pore si~e distribution select~ve of -~
19 a range of asphaltene molecules smaller than those accepted within the pores of the R-l cataly~t. m e asphalteneg in 21 the R-l product are generally smaller than those of the raw 22 feed and can quite readily diffuse ~nto ths pore~ of the R-2 23 catalyst. The R-2 reactor is ~pecifically designed t3 re-24 move the remaining metals such that the product will contain C 5 ppm metals and<2-3 wto % ConO carbon. ~ cnditions are 26 needed that favor the hydrogenation of the fused benzene 27 rings of the asphaltene fragments followed by the cracking 28 and dealkylation of the saturated ring~O In thi~ way, Con.
29 carbon can be effectively reduced to the desired levelO
These conditions also favor the removal of the very refrac-31 tory remaining metal~. Conditions ~avoring this type of re-32 action are l~w ~tart-of-run temperature, eOgO 650;700F., 33 at high hydrogen partial pressure, eOgO, 2000~5000 psigO

, ~059110 1 In contrast to the R-l catalyst, the R-2 cat~lyst 2 removes less metals and Con. carbon on an absolute basis 3 but percentage-wise it removes about the same amount of the 4 metals. This is also true of the sulfur and nitrogen re-moval reactions. However, this catalyst is more effective 6 on the most refractory molecules and must be quite active 7 to accomplish this reaction, especially at the low tempera-8 ture required.
9 The R-2 catalyst, which differs from R-l catalyst, is effective in the hydroconversion of smaller molecules, 11 far more 80 than an R-l type catalyst. Albeit it has pores 2 maximized within a range of diameters smaller than the R-l 3 catalyst, it does- not encounter diffusion problems with the 14 conversion material produced in R-l service. The smaller pores prevent the very large asphaltene molecules from enter-l6 ing the pores which severely diminish the much needed hydro-l7 genation function of the catalyst.
18 In R-2 service, the R-2 catalyst is generally em-l9 ployed in one or more stage~ of a reactor, or reactors aligned -in series. The R-2 cat~lyst, after being reduced and sulfided 21 generally in situ within the reactor, i~ operated under con-22 ditions, the ma~or vari~bles of which are tsbulated for con-23 venience as follows:
24 Operable PreSerled Temperature, F., E.I.T.
26 Start-of-Run 600 650 27 End-of-Run 850 775 28 Pressure, psi 2000~10,000 2000~5000 29 Hydrogen Rate, SC~/B 3000-209000 3000-10,000 Space Velocity, LHSV 0.2505 0.25-2.0 31 The invention will be more fully under~tood by 32 reference to the following selected nonlimiting examples 33 and comparative dat~ which illu~trate its more salient 10591~0 1 feAtures. All p~rts are given in term~ of weight unit~
2 except as otherwise specified.
3 Exampleæ 1-7, immedlately following, describe 4 preparation of a serie~ of R-l and R-2 catalysts, inclu~ive of gels and cogels, wherein pore size distribution is con~ -6 trolled and set during gellation. Examples 1-4 thus das-7 cribe the preparation of gel type catalysts under varying 8 conditions which favor the formation of R-l or R-2 catalysts, 9 re8pecti~ely. Catalysts A and B are thus R-l pre-catalysts, and Cataly~ts E and F are R-2 pre-catalyst~. Example 5 describes preparation of R-l cataly~ts~ prepared from co-l2 gels, including Group VIB and VITI metals. Examples 6-7 13 descri~e preparation of va~tly ~mproved gel type catalysts 14 of both the R-l and R-2 types.
Exa les 1-4 (Preparation of Gel-TYPe CatalYsts A.B,E and F) l6 In à first series of preparation~, 1160 gram por-17 tion~ of AlC13-6H20 were weighed9 tran~ferred to large glas~
8 beakers9 and then slurried in portions of deioni~ed w~ter 19 ranging from 1501 to 2701. The several portions of ~lurried material were each then cosled to 35F., and ga~eous ethyl-21 ene oxide was then introduced at a ;rate of 12,5 grams per 22 minute until sufficient ethylene oxide had been added to pro-23 vide molar ratios of C2H40/HCl ranging from lol to 1.6.
24 The resulting clear ~olutionæ were then allowed to slowly warm to an ambient temperature of 75F., a rigid 26 gel having begun to form after about 1 hcur. The gel~ were -27 permitted to age at this temperature fcr period~ ranging 24 - - -:. ~
28 to 72 hours, each in contact with its own syneresis liquid,~`
29 the 3yneresis liquid having become vi~ible as a stratified layer above the blocks of solidified gel~ and between the 31 glass walls and side bound~ries of the ~olidified gel~ which 32 shrink away from the glass and exude the ~ynere~is liquid~ -- 32 ~

.
,. . . . . . . .
. ' ' ' ,; ,' , '', "' '' '' ', ' 1 The gels, after the ~g~ng period, were each then 2 separated from its respective syneresis liquid by merely 3 pouring of the liquid. The gels, having the appearance of 4 dry blockæ of material, were then crushed into p rticulate ma~se~9 and each then thoroughly w~shed with 5 gallons of 6 isopropyl alcohol containing 1000 cc NH40H in a column or 7 by succe~ive decantation. The washing was continued in 8 each in~tance until the effluent from the column was free 9 of chloride, as determined by testing for chloride with 8il-ver nitrate test solution. The particulate mas8es were then ll thoroughly dr~ed in air for 1S-2$ hours and 190F. for l2 periods ranging between 6 and 24 hours9 and thereafter cal-13 cined at lOOODF. for perio~ of from 2 to 4 hours.
14 The materials formed in these synthe~is reactions, which were found admirably suitable as ~upports for use in 6 the prepar~tion of both R-l and R-2 catalysts, are charac-7 terized in Table I as R-l ~atalysts A and B and R-2 Cataly~t~
8 E and F, respectively.
19 ~amPle 5 (Preparation of ~o~el-Type Catalvsts D and D~) T~e foregoing procedure was repeated, except that 21 in this instance two cogels were separately prepared, each 22 according to the following specifics~ 1160 gram~ of AlC13 23 6H20 wa8 81urried in 500 cc deionized water and9 after addi-24 tion of one-half of the required amount of ethylene oxide, solutions were added which cont~ined (a~ 64.2 grams of 26 CoC12~6H20 di~solved in 200 cc H20 and ~b~ 95 grams of 27 phosphomolyb~ic acid dis~olved in 200 cc H20. The balance 28 of the ethylene oxide was then added. The final preparation 29 of a catalyst, which contained 6 wt. % CoO and 20.5 wto ~/o MoO3, was then completed, these cataly~t~ being identified 3l as Catalysts D and ~' in Table I.

- 33 ~

10591~0 1 Example~ 6-7 ~Preparatlon ~ Improved ~el-~ype ~at~lysts C
2 and ~
3 Examples 1-4 were again repeated except that in 4 this instance 1.0 wt. % rhodium or 3.5 wt. % lant~anum was slurried with the Alc13-6H20 in preparation of the sol.
6 The catalysts formed in this manner sre ~dentified in Table 7 I as Catalysts C and G, re~pectively.
8 The data pre4ented by reference to Table I thus 9 $how that cataly~ts, h~ving only a marginal amount of pore 8izes in diameters le88 than 5QA, i.e., 5QA-, and with 11 a large amount9 preferably a max~mum of pore ~izes in diam-12 eters ranging 150-250A can be prepare~ by maintaining molar 13 ratios watercaluminum chloride of about 15 to 30, preferably 14 18 to 27; molar ratios ethylene oxideoHCl of about 1.5 to 2, lS preferably 1.5 to 1.7; and by aging the catalysts for periods 16 ranging from about 1 to 3 days, preferably from 1 to 2 days.
17 In preparing catalysts with smaller pores, these data show 18 that such catalyst can be also prepared with a minimum of 19 pore sizes of diameter within the 50A-and 30QA~ range~, and with a maximum of pore sizes of diameter ranging from about 21 10~ to 200A. Thi~ is accompli~hed by maintain~ng a molar 22 ratio of wateroalum~num halide ranging about 22lto 309 pre-....
23 ferably 26 to 28; a molar r~tio of ethylene oxideOHCl of ~ -24 about 0.!3 to 1.5~ preferably 1 to 1~29 ~nd by aging the cata-lyst for periods ranging about 1 to 3 days, preferably 1 to 26 2 days. ~hi8 limited aging im~r~ve~ ~he uniformity of pore 27 size distributions with the desired ranges, a~ relate~ to 28 the preparation of gels and cogel~. ~he use of trace me~als 29 such a~ Group VIII noble metal~ or lanthanum and lanthanum series metals is also ound to ~ncrease the uniformity and 31 maximization of the desirdble pore si~e distr~bution~0 More-32 over, catalysts h~ving very large pores can be prepared . .
,,, ' ' ', '~

1 having a minimum of pore si2es rang~ng 50A- and 350~+, 2 and with a large amount, preferably a maximum of pore sizes 3 of diameter ranging 115-275A suit~bly by preparation of a 4 cogel as described, e.g., in Example 5, with subsequent ex-trusion of a particulate mass of the cogel to provide an ex-6 trudate. Extrusion of cogel of Ex~mple 5 can thus be em-7 ployed to provide extrudates of 1/l6 inch p~rticle si~e 8 diameter ha~ing the properties, e.g.9 of Catalyst XX as des-9 cribed by reference to Table IV, Examples 10-17.
Once the gel i8 ~et by observing conditions which 11 favor the desired range~ of pore si2e distributions, it is 12 al~o important to wash the gel sufficiently to remove essen-13 tially all traces of halldes ~nd gyneresis liquid Failure 14 to accomplish this removal will result in a losg of the de-veloped pore siz~ distributions. An alcohol wash has been l6 found particularly effective in such capacity, the C2 to C6 17 alcohols, particularly the C~ or isopropyl alcohol, having 18 been found particularly effective in preserving the developed 19 pore size distribution thrDughout the subsequent steps re-quired in completing the preparation of the catalyst~.
21 m e actual water content of the alcohol used ln 22 the wash W8S found to have a profound effect on the pore 23 size di~tributions, the surface areas and pore volumes of 24 the catalysts, and on subsequent drying it was found that these properties vary dependent on the amount of water, if 26 any, contained in the alcohol wash, As with the syneresis 27 liquid, if the wash alcohol contains water9 the pore volume 28 shrink~ with cnly minor attend~nt reduct~on in surface area~
29 The result i8 a reduction in the average size of the poreg.
mhus, becauge w~ter decreases pore size distribution and 31 pore volume, it is generally preferred to use anhydrous al-32 cohol or ~atdlyst preparation~. The following example~

`:- 1059110 ~, 1 demonstrate the effect of water on these properties, e~pec-2 ially on pore volume and pore size distributions ~n the al-3 cohol wa$hing and drying sequenceO
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.

1 Example 8 2 A ~eries of gel type catalysts ~, I, J, K, L) 3 was prepared, the preparation ~tep~ employed and the com-4 position of thèse catalysts being s~milar to that previously described with regard to Catalyst B, except that these cata-6 lysts were a~ed somewhat longer during the period of gella-7 tion. In the preparation of the~e catalysts, except as re-8 gards Cataly6t H, however, water in varying concentrations 9 wa~ added to the isopropyl alcohol used as a wa~h. The re-sults of these runs are tabulated as follows:
11 TABLE II ~ -Catalyst H I J K L
13 H20 in Alcohol ~Yol.~/0) 0 2.5 5 10 25 14 Surface Area, m2/gm 382 393 398 3?3 354 Pore Volume, cc/gm 2.071.93 1.82 1059 0.92 l6 Avg. Diameter, A
17 (4 PV/SA x 104) 217 197 183 112 104 18 These data thus show th~tg with isopropyl alcohol, 19 pore volume is decre~sed as the water content of the alcohol increases from 2.5 to 25 percent (vol.~ with only nominal 21 change in the surface areaO The result is to decrea~e the 22 average size of the pores.
23 The presence of w~ter i~ also fo~nd to decrease 24 the pore volume and pore size di~tribution~ during the lm-pregnation steps, wherein the hydrogenation~dehydrogenation 26 and other catalytic components are added to alumina supportsO
27 For best results, it ha~ been fo~nd desirable to add the 28 metals by impregnation o the supports with non~queous 29 solution6 of the metals salt~, prefer~bly alcohol solution6.
Water, however, should not be usedO ~he pre~ence of water 31 ha~ been found to decrease both pore volume and pore size 32 distribution dra~tica~ly. It i5 thu~ believed that water r , 1 enters the pores, redi~solves and, during drying9 ~ome of 2 the redistributed alumina forms deposits within the pores.
3 Thus, some shrinkage of the previously developed pore sizes 4 results from the use of water during the impregnation step and hence its use is preferably avoided. The following 6 example thus presents data showing preparation of a cobalt-7 molybdenum on alumin~ catalyst by impregnation of a suitable 8 alumina support with a metals-containing methanol solution.
9 Comparison is made between the surface area, pore volume lo and pore size distribution of the catalyst and the unim- ;
11 pregnated support from which the fini~hed catalyst was made.
l2 ExamPle 9 13 Alumina prepared pursuant to the procedure u~ed 14 in preparation of Catalyst E was split into two portions, one, a precatalyst or support, termed for convenience l6 Catalyst 0, and a ~econd 100-gram portion, termed Catalyst 17 P, which was impregnated with a ~olution containing 3204 18 grams of CoC12-6H20 and 47.6 grams of phosphomolybdic acid 19 dissolved in 162 cc of methanol. Catalyst P wa~ ~ubsequently dried at room temperature and at 190F. and then calcined 21 for 2 hours at 1000F. The two catalysts are compared in 22 Table III, as follows:
23 Catalyst 0 P
24 Wt. % CoO - 6 Wt. % MoO3 -- 20.5 26 Wt. % P~05 -- 1 27 Surface Area, m2/gm 336 246 28 Pore Volume9 cc~gm 0O99 0~61 29 Pore Vo~ume, Distribut~on % in 50A-Po~es - 307 31 50-150~ Pore~ 9~3 5g.4 32 150-250A Pores 4 31.9 33 250~350~ Pores ~~ 4~7 34 350A+ Pores -- 0~3 These data thu~ show that considerable pore vol-36 ume shrinkage occurred, partlcularl~ in the 50~150~ pore ~ 39 -1 diameter ranges even as a result of using alcohol. This 2 shrinkage must be compen~atedror by forming in the gel or 3 cogel pores of larger pore size distribution than ultimately 4 desired realizing that the shrinkage shall constitute a com-pensating factor. The shr~nkage can be further minimized 6 by using C2 to C6 alcohols, preferably i~opropyl alcohol, 7 as the solvent.
8 The following examples and demonstration~ describe 9 preparation of a series of extrudates from cogels (and gels), and define certain critical features required to obtain ex-11 trudates of good quality meeting the requirements of R-l and l2 R-2 catalysts. The technique of m~king catalysts in the form 13 of extrudates i8 particularly applicable to the formation of 14 catalysts in the l/50-l/25 and l¦2S-l/8 inch particle ~ize ranges, and sphere forming techniques, particularly as des-l6 cribed hereinafter, are particularly applicable to the forma- - -17 tion of cat~lygts in the l/500-l¦S0 inch particle size ranges.
18 In making catalysts with the desired narrow pore size dis-19 tributions, as ~hown9 it i~ nece~sary to l~mit the time cf aging because aging produces shrinkage of pore size but9 on 21 the other hand, aging is essential if extxu~te$ of good 22 strength are to be made, particularly extrudate~ of high crush 23 strength, especially cru~h strength in exce~s of 7 pounds.
24 High crush strength is desirable, or necessary, in certain types of processes. Thus, techniques are described w~ich 26 have been found to speed up the aging proce~ and to counter-27 act the effect of aging which tends to decrea$e the pore 28 sizes of the catalysts. Y~e aging proces~ can thus be car-29 ried out by (l) contact of the gel or cogel with syneresi~
liquid at ambient conditions for period~ ranging to about 30 31 days, and longer; (2) contact of the extrudPte, or pelletized 32 form of the gel or cogel, for periods ranging to abowt 30 ~OS9110 1 days, or longer, in the synere~i~ liquid, (3) contact of 2 the gel or cogel in synere~s liquid in an initial step 3 prior to contact of the extrudate, or pelletized form of the 4 gel or cogel, in syneresis liquid, as described in (1) and (2), which is preferred; (4~ by h~gh temperature contact 6 of the gel or extrudate (or pelleti~ed form of the gel or 7 cogel), or both, by (5) a combination o~ the~e steps; and 8 (6) Group VIII noble metals, or lanthanum and rare earth 9 metals of the lanthanum series, are preferably included in the gellation step to counteract the pore shrinkage effect 1 of aging on pore size distribution. In these data, it will 2 also be observed that (7) critical ~olids contents are re-3 quired prior to or sub~equent to certain steps to avoid de-4 terioration or weakening of the gel or extrudate. These in-clude: (a) drying to about 12-40 wt. % solid~ prior to ex-6 tru3ion~ or pelletizing of the gel or cogel, (b) drying to 7 25+ wt. % solids prior to the ag~ng of extrudates, or pel-8 letized gel or cogel, in synere~i~ liquid, And ~c) again 19 drying to 25+ wt. % solids prior to alcohol washing.
ExamPles 10-17 .
21 Portions of gel, or eogel, compri~ing metAl~ and 22 alumina, were each prepared by raising the temperature of 23 8018 prepared by reaction between aqueous slurr~es of alum-2~ inum chloride and ethylene oxide a~ described for the ini-tial preparation of Catalysts D and D' ~Example 5~ The 26 portions of cogel were each u~ed to prepare a ~eries of 27 cataly~ts defined in Table IV below9 referred to as Cata-28 lysts AA, BB, CC, DD, EE, FF ~a gel~, GG ~A gel), XX and YY0 29 The portions of cogel (or gel) were each aged at 75F, (except Catalyst EE which was aged at 160F.), prior 31 to extru~ionD ~n its own synere~is liquid for periods rang-32 ing from 24 hours (1 day~ to 30~ ~ay60 T~e portions of cogel ~ 41 ~

- lOS9110 1 (or gel) were then dried in air for a t~me sufficient to 2 provide twenty percent solids content, ba~ed on the total 3 weight of the gel. In these cases, to prepare Catalysts GG, 4 XX and YY, the aged gel (or cogel) wa~ crushed to C~0 mesh particle size before extrusion. After extrusion in a Model 6 0.810 Research Extruder manufactured by Welding Engineers of 7 Ring of Prussia, Pa., u5ing a 1/16 or 1/32-inch die, some of 8 the extrudates were then further dried in air for a time 9 sufficient to provide a twenty-five percent solids content, 0 based on the total weight of the cogel ~or gel). Some of 1 the extrudates were then returned, without washing, to the l2 synere~is liquid from which they were originally removed, 13 immersed therein ~nd aged at 75F. for one day. The extru-14 dates were again dried in air to 25 wt. % solids content, then subsequently washed in isopropyl alcohol, oven dried l6 in air at 190F., and finally calcined at 1000F.
7 These several portions of gel or cogel, the manner 8 in which each was treated, and the properties of the series 19 of catalysts, i.eO, Catalysts M ~ BB, ~C9 9 E~, FF, GG, --XX and YY, produced therefrom, respectively, are referred to 21 in Table I~ below. The table showQ, ~n the fir~t two row~
22 of figures, the number of days that each of the cataly~ts 23 was aged in syneresis liquid prior to extrusion, and the 24 number of days, if any, that each of the~extrudates was aged in syneresis liquid sub~equent to extru~ion. The next 26 two rows of figures indicate, respectively, ~he ~olid~ con-27 tent of the cogel ~and gel) before ex~rusion, and ~ubsequent 28 to extrusionr The next row of figures, also g~ven under i 29 "~xtrusion Conditions" give~, respectively, the per~ent solids of the cogel (and gel) prlor to the alcohol wash.
31 I~opropyl alcohol was used as the wa~h liquid in each case3 32 The last seven rows of fig~re~ glve the propertie~ of the 1 several extrudatesO The pore diameter, for convenience, is 2 also listed in terms of average pore size as calculated by 3 the con~entional formula 4 x 104 times pore vol~me di~ided 4 by surface area. For t~e 1/16 inch extrudate, 175-275A
pores are given where for 1/32 inch extrudates 150-250A
6 pores are given. As discu~ed later, these are the import-7 snt ranges for the particle si~es.

~ ~3 ~

,, ' ' ' ' ~ ..

1 These data show that Catalyst AA possesses a re-2 asonably good pore size distribution in that it has low 3 pore volume in the 0-50A pores and 35QA~ pores and reason-4 ably good pore volume in 175-275A pores~ It also has good surface area and pore volume. Unfortunately~ it has low 6 strength, i.e., 1.3 lbs., but by allowing the cogel to age 7 for 3 days prior to extrusion ~Catalyst BB), the strength 8 can be markedly improved to 4.2 lbs. Catalyst CC demonstrate~
9 the shrinkage of pores when cogel is aged 30+ days prior to extrusion. The strength is excellent at 10.7 lbs. but the 11 low pore volume (0.83 cc/g) and excessive pores in the 12 0-50A confirm an excessive shrinkage due to long term aging.
13 Cataly~t 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 0-50A pores were l6 excessive due to poor temperature control during~the sol 17 fonming step. It is important to control the sol forming 18 temperature at 40050F. to m~nimize these pores. As shown 19 by Cataly~t XX, a good extrudate is fonmed (~.4 lbs.~ by good sol temperature control and aging of the extrudate~ in 21 syneresis liquid. This catalyst had low pore volume in 22 0-5QA and 350A+ pores and high pore volume ~n 175-275A poresO
23 Further improvements in strength can be obtained 24 by aging the gel (or cogel) at high temperature for short times as with Catalyst EEo By aging at 160F., a catalyst 26 with 14 lbs. crush strength was formedO However, excec$ive 27 pore volume shrinkage occurred resulting in exces~ive pore 28 volume in the O-SOA pores and a low total pore volume 29 (0,92 cc/gm).
Catalysts can also be prepared by first extruding 31 a gel followed by impregnation of that extruda~e with cata-32 ly~t mRtals~ This is demonstrated by Cataly~ts ~;F nd GG
- ~5 ~

~05~1~0 1 These data are for the gels prior to impregnation. Good 2 strength was obtained (4-8 lbs ) but pore volume shrinkage 3 occurred. Pore volume in 0-5QA range is not unduly exce~s-4 ive, however, One example of a 1132-inch catalyst is given 6 ~Catalyst YY). Strength is below that desired (3.7 lbs.) 7 but for 1/32-inch extrudates it has a good pore size dis~
8 tribution with minimum 0-50A pores and 35aA~ pores and a 9 large amount of pore volume is 150-25 ~ pores which are best for 1/32-inch particles.
11 Spheres are the preferred forms of catalysts for l2 use in ebullating beds and slurry reactors ~reaction zones), 13 the si~e thereof ranging about 1150 inch particle size 14 diameter, and smaller. Spheres, of course, can be utilized in a fixed bed (e.g., in particle size diameter ranging l6 about 1/32-1/8 inch), but most often are utilized in ebullat-17 lng bed and slurry reactors where particle si~e diameters 18 st often r~nge 1/32-1/250 inch, and sm ller~ A very ef-19 fective range for spheres in ebullating ~nd slurry reactors is from about 1~0 to about 500 micron diameters. There are ~1 sever~l known techniques for forming sphere~, to wit: -22 (1) prilling, (2) gelling in a column9 ~3) centrifugal force, 23 (4) gelling in a stirred vessel, or tank, and the likeO In 24 the preferred stirred tank method, a sol (gel or cogel~ is heated and aged, while agitated, in a mineral oil bath gen-26 erally at temperatures ranging from about 75Fo to about 27 150F , preferably from about 100Fo to about 125Fo The 28 amount of mineral oil~sol, on a volume basis, ranges gener 29 ally from about 5:1 to about 20:1a preerably from about 8:1 to about 12:1. The amount of agitation of the bath, and the 31 height and diameter of the tank, i8 selected to provide 32 particles of desired size Such techrlique is described in ~ 46 1~5~10 1 greater detail in Examples 18-2C, below.
2 ExamPle~ 18-20 3 Portions of cogel, which contain metals and alum-4 ina, or portions of gel which contain alumina, were each pre-~ pared first by forming a sol as disclosed in the preparation 6 of Catalysts D and D~ (Ex~mple S), and the sols were then 7 added to a stirred vessel containing mineral oil.
8 The preparation of the sols was as described by 9 reference to Examples 1-5, the slurried material formed by reaction between the aluminum salt and ethylene oxide having 11 been removed from the beakers at temperatures of about 35F., l2 and the temperature adjusted to about 55-65F. over a period 13 of one-quarter hour prior to introduction of the portion of 14 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 l6 period of one-quarter hour to avoid gelling prior to the ., 17 introduction.
18 The amount of m~neral oilosol, on a vol~me basis, 19 was maintained at 10:1, and the temperature w~s maintained at 100-150F. Turbine type agitators using various blade 21 designs were employed, the size of the particles produced 22 being controlled by blade design, ~es~el design, and the 23 speed of revolution (revolutions per m~nute, RPM~ Gf the 24 blade.
..
For the formation of relatively small particles 26 (e.g., 100-200 microns) a single blade turbine operated at 27 250 RPM proved best. For larger particles (eOg~9 300-~00 28 microns), a six blade turbine at 75 ~PM proved best~ The 29 design of the ~essel is critical. It was found that the ratio of the height of the vessel ~H) to its diameter ~D~
31 i.e., H/D, should range between about 105-1O2, preferably 321:4 to 103. The design of the turbine should be such that O 47 ~

.
"' ' '' ` '' ' :`' ., ` . ~ . , .

-1059~0 1 the ~mpeller abuts the walls and bottom of the vessel. The 2 ratio of the height of the impeller (HI~ to the height of 3 the vessel, HI/H, should range from about 1:2 to about 4:5, 4 preferably from about 2:3 to about 3:4.

- 5 It is found that as the sol is added to the min-

6 eral oil, smsll spheres form in the oil. After completion

7 of sol addition9 the agitator is allowed to con~inue agi-

8 tating for at least 30 minutes, preferably for a period

9 ranging up to 2 hours. During this time, the spheres are gelled. The spheres are next separated from the oil, and 11 the solids particles either spread out over a solid surface 12 to age, or surface washed to remove the mineral oil to avoid 13 agglomeration of the solids particlesO Suitably, the spheres 14 can be surface washed with varsol or isopropyl alcohol, or both, to avoid agglomeration, but care must be taken to l6 avoid removal of syneresis liquid from the pores as opposed 17 to mere removal of the surface oil. The spheres are aged 18 for about 1 day. After this, the spheres are washed in 19 isopropyl alcohol, with or without added ammonia, oven dried at 190F., and then calcined at 1000F. for 4 hours. -~
21 Catalysts UU, W and WW9 SO produced, are charac-22 terized as ~aving the following properties: ~

~ .
,~

~059110 2 C~talyst ~u~a~ w ~b3 WW~C) 3 Vol.of M~neral Oil, cc 1000 10,000 10,000 4 ~ol~ of sol 9 CC 100 1000 1000 Mixin~
6 Turbine 1 Blade 6 Blades 6 Blades 8 ~ellation Temp., F. 150 100 120 9 ~atalYst ~oPerti~s '~'R~r7D~or~li Tg ~78 24~ 330 11 Pore Volume, cc/g 0054 0~49 1.15 12 Avg. Pore Dia. 5 A 85 80 139 13 Pore SOize Dist. 9 % PV in 14 O-SQA O -- -- 1.9 100-200A -- -- 33~8 16 300~+ __ __ 21.0 17 Particle ~i~e, microns 100-200 100-500 100-300 18 (a ~ rinse/No NH~ in w~sh 19 (b Rinse, no NH3 In wa~h (c~ No rinse, NH3 in wash 21 Catalyst W was formed ~n quantity with a l-blade 22 turbine at high RPM (250~ and high temperature (150F.~.
23 The particles were small due to high ~PM and impeller de~ign.
24 l~e low surface area and pore volume are due to high gella-tion temper~ture (150F.) and the act that NH3 was excluded 26 from the i~opropyl ws~h. Cat~lyst W was made in a larger 27 vessel with a 6-blade ~mpeller operated at 100 RPM and 100F
28 m e c~taly~t spheres were rin~ed with ~ar~ol and i~opropanol 29 in this case to avoid agglomerationD and no ammonia was in-cluded in the wash Due to the lower RPM and impeller de-31 sign, particle size was increased to 100~00 microns ~ue 32 to the improper rinse ~i.e., vPrsol and isopropanol pretreated 33 spheres prior to aging~ and the lack of ~H3 in the w~sh, the 34 surface area and pore vol~me are lower than de~lr2dO ~ata-ly~t ~W repre~ent~ an excellent ~pherLcal catalygt prepared 36 by this technique. By forming the ~phere~ in the larger 37 ve~sel u~ing the 6-bLade turbine at 100 RPM and 120F., 38 ~pheres rQnglng in sl~e from lOQ-300 micr~n~ were made.

~ 49 0 ~OS9~10 1 Eurther, by carefully handling the spheres before aging to 2 avoid agglomeration without the use of varsol and isopro-3 panol rinse, the resulting spheres possessed good surface 4 area and pore volume. In addition, 50A pores and 300A+
pores were minimized while maximiæing 100-200A pores which 6 are highly desirable for particles in this size range. By 7 decreasing the RPM to 75, particle size is further increased 8 to 300-400 microns.
g Example ~1 Runs were conducted with each of Catalyst D, Q
11 and R, of 1/32 inch average particle size, by contact with 12 Cold Lake and Jobo Crudes, respectively, in a reactor which 13 contained the catalysts as fixed beds~ The runs were each 14 conducted at two different temperature levels, at approxi- -mately the same pressure level of 2250 psig, at two differ- -l6 ent flow velocities and at hydrogen rates varying between 17 5500-8500 SCF/Bo The following Table VIII shows the pro- ~ ' 18 duct inspections at the end of two different time periods, 19 the conditions of reaction being given at the time the pro-ducts were withdrawn for analysis, 21 Shown immediately below in Table VI are the anal-22 yses for Cold Lake and Jobo crudes. In addition, the cat~-23 lyst inspections for Catalysts Q and R are given in Table 24 VII. Catalyst Q is a commercially available hydrodesulfur-i~ation catalyst having most of its pore volume in the 0-26 lOOA region. Catalyst R was made in a manner simiLar to 27 Catalyst D but with longer aging of the gel .~ 0 lOS9~10 2 ~EED ANALYSES
3 Gold Lake Crude JoboCrude Kuwait Resid.
4 Gravity, API 11.1 8.5 16.5 Sulfur, Wt. % 4~ 5 3.8 3.6 6 Carbon~ Wto % 83.99 83.92 84.64 7 Hydrogen, Wt~ % 10.51 10.49 11.41 8 Con.Carbon, Wt. %12.0 13.8 9.0 g Asphaltenes, Wt. % 17.9 17.7 --Nitrogen, Wt. % 0O46 0.68 0.22 ll Metal~ PPm 12 Ni 74 97 12 14 Distillation 1 mm IBP, F. 463 518 451 16 5% (Vol.) 565 627 577 22 % Recovered 56.4 50.8 64.0 23 % Residue 42.4 48.2 36.0 24 FBP, F. 1047 1047 1047 BLE VII

27 Cataly~t R Q
28 Surface Area, m2/g 362 260 "~ .
29 Pore Volume, cc/g 1.79 0.50 Pore Volume Di~tribution, 31 % P~e Volume in O
32 0-5QA Pores lo 4 11~ 1 33 50-150A 10.9 79~5 34 150-250~ 1706 6~1 2500-3SQR 23. 4 ~ ~ 8 36 350A+ 46 7 1.5 37 % CoO 6 3.5 38 % MoO3 20 12.0 ,.

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~d C4 E~cqE~

~ 52 .

1 The~e data t~u~ ~h~w that Catalyst Q9 the commer-2 cial hydrodequlfurization eataly~t~ is completely unsuitable 3 for the treatment of the~e heavy crudes at hydroconversion 4 conditions~ although Catalyst~ D andg to a le~er extent, Cataly~t R are well 3uited for such purpo~e. Whereas Cata- ;~
6 lyst Q doe~ effectively hydrodesulfurize the crude in some 7 cases~ the data clearly 5how that it is ent~rely unsuitable 8 for removal of heavy metals~ for the reduction of Con. car~
9 bon, and for the conver~ion of a~phAltenes.
In other compar~tive run~ for purposes of demon-11 strationD K~wait residua9 a more conventional crude char~
12 acterized a~ a light Arabian feed~toc~, the in~pections on 13 which are given ~n Column 4 of Table V~ above9 C~talyst Q ~-14 and Cataly~t D were compared at qimilar but varying condi~ --tions in hydrodesulfurization reaction~ with the results l6 described in Table IX9 below.

~_ . .
18 Temperature9 F~ 650~750F.
19 Pre~ure, psig 2000 Hydrogen Rate9 SCF~Bbl. 4000 21 ~ _ ___5~oL-~LC ~D_ _~
22 Day~ on Oil 26 26 23 Average TemperaturegF. 710 710 24 Spaee Velocity~V/Hr./V 0.4 ~o6 0~4 0~2 Product In~pections 26 Grav~tya ~PI ` 24.8 22.7 23.6 24.1 27 Sulfur~ Wt. % 0.25 0.64 0.45 0.28 28 Nickel9 ppm S.3 2.7 1.1 0.2 29 Vanad~um~ ppm 12.5 5.4 2.3 1.7 Nitrogen~ Wt.% 0.09 0017 0.16 0.14 31 The~e data ~how that Catalyst Q is better for de~
32 sulfurizati,~n (and denitrogenation) of a light feedstock 33 than Cataly~t D w~ich i~ le~s ~atisfactory. Howeverc the 34 cataly~t of the invention (Cataly~t D~ i3 superior in metals removal even for thi~ 1~ ght feed .
36 l~ Xfl~ 2 37 Dlffu~lon pla~s a very impDrtarlt role in the con-~ 5;3 ~

1 version of asphaltenes and removal of nickel and vsnadium 2 from heavy crudes. This is due to the larger size of the ; 3 diffusing moleculesO Since sulfur is found in smaller 4 molecules9 the sulfur removal reaction is much less re-stricted by diffusion. This is demonstrated in the follow-6 ing example. A catalyst was prèpared in a manner similar 7 to that used in the preparation of Catalyst D. This cata-8 lyst i8 designated Catalyst AAA. Properties of this cata-9 lyst are given in the table below:
CATALYST AAA
11 Surface Area9 m2/g 366 12 Pore Volume, cc/g 1.33 13 ~
14 o-soA Pores 4.3 50~100A 10.0 16- 100~150A 13.3 17 150-17sA 5.2 18 17so200A 6.5 19 200~250A 13.4 250OZ75A 6.3 21 275~300~ 6.9 22 300O350A ~.7 23 350a~ 2407 24 % CoO 6 % MoO3 20 26 This catalyst was divided into three partsa each crushed, 27 and sized to provi~e particles having average diameters 28 equal to 1/85, 1/43 and 1/29 inch, respectively. Each of 29 these catalysts was loaded into reactors and used to hydro-convert Cold Lake Crude, the properties cf which are given 31 in Table VI. Conditions for the tests were 775F.9 2250 32 psig, 2.6 V/Hr./V and 6000 SCF/B hydrogen gas rate. Product 33 inspections were obtained after 20 hours on oil and ~re 34 shown belowo Catalyst Size, Inch 1/85 l!43 l/~g 36 Sulfur, Wt. % 0.37 0037 0040 - 37 Asphaltenes, Wto % 1.1 2.3 3.5 38 Nickel, ppm 301 5.9 11.2 39 Vanadium~ ppm loO 9.0 19.1 - 54 ~

.

, ~OS9~10 These data show that the asphaltene, nickel and vanadium re-moval 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 limitations 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 encoun-tered. Thus, larger particles (e.g., 1/16 inch) will require larger pores (e.g., 175-275A) and smaller particles (e.g. 1/64 inch) will require smaller pores (e.g., 100-200~) while interme-diate particles (e.g., 1/32 inch) will require intermediate pores (e.g.~ 150-250R).
The following examples show that R-l catalyst can be used to treat 1050 F. + in heavy crudes or residua at a variety of conditions ranging from hydrotreating, with minor conversion of ~
the 1050 F.+ materials~ through hydroconversion conditions wherein a ma~or amount of the 1050 F. + material is converted to lowerboiling products.
Examples 23-29 :, Catalyst D, the R-l catalyst of 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 spaced velocity and increased temperature to obtain in-creasing rates of conversion. In Examples 23-26 the start-of-run (SOR) temperature was set at 650 F., and gradually increased during the operation to maintain a given reaction rate. In Examples 27-29 the start-of-run temperature was 700 F. These and other conditions of operation of the several runs, and the inspections obtalned 1 on the product~ of the series of reactions are given in 2 Table X, below. Data are shown for Examples 23~26 at 662F.
3 after 517 hours on oil. Data for Examples 27~29 are at 4 736F. after 80S hours on oil. In this series of runs, Ex-amples 23 through 26 can be considered as essentially hydro-6 treating runs9 and Examples 27 through 29 as hydroconver-7 sion runs.
8 _ABLE X
9 Pressure~ psig 2250 Hydrogen Rates, SCF/Bbl. 6000 11 Temperature, F. (SOR) 12 Examples 17~20 650 13 Examples 2~3 700 14 Example No. 23 24 25 26 27 ~8 29 Space VelO, 16 V/H/V 0O79 0.590O39 0.19 0.98 0.49 0.24 17 Product 18 In~ections 19 Gravity,UAPI 12~4 130414.1 16.0 15.4 18.1 21.4 Sulfur9WtO% 2.56 2.231.87 1.11 1.45 0.78 0.15 21 Nitrogen~Wt.% 0.65 0.620.60 0O55 0.56 0.49 0026 22 Con.Carbon, 23 Wt.~ 10.4 11.010.3 7O9 803 603 308 24 Asphaltenes9 t Wt.% 10.6 lOoO9O3 5O~ 7.8 402 -~
26 Metals~ ppm 27 ~ 52.2 48.23809 2905 2803 16.1 501 28 V 24206 207.2 18~.0 1070i 143.4 7200 0.8 291050F.+,Conv.~
Wt.% 1.8 12.17O~ 13.4 21~9 33O4 46.6 31 1050Fo+
32 QuaIity 33 ~ Wto% 3O47 3O092 83 1089 2051 1.49 0O30 34 Con.Carbon, Wt.% 23.3 22.720.4 1705 21.3 1804 10~4 36 Yc~ls~p~
37 Ni 10806 11205 97O9 6504 86.2 59.0 8.7 38 V 504~4 476.0 391.~ 24803 34105 ~96.8 9.5 39 Metal on Cat.
Wt.7O* 115 60 75 ~ 168 100 -~
41 *Wt. % on fresh catalyst at end of operation~
42 The~e data thus sh~w that relatively high tempera-43 ture i~ required to obtain high rate~ of hydroconver~ion of 44 the 1050F.+ materials, and conversely that low temperatures cannot provide adequate conversion rates~ even with rela~
46 tively low space velocitie~O The product of Examples 23 47 through 26 i~ unsuitable for coker feed because the metals ~ 56 -1 content is too high~ and un~uitable even flS fuel becau~e of 2 the high ~ulfur content. The product of Example 26 is of 3 marginal utility as a coker feedD but coke produced from 4 such product would nece~sarily be of poor quality. The 8ul-fur content is too high for u~e ~8 fuel9 and further treat-6 ment i8 requlred to render the product suitable a8 a fuel 7 oil. As to the serie~ of hydroconvers~on reactions, the 8 data show that the product of Example 29 is of good quality, 9 and even ~uitable a~ a feed for a resid catalytic cracker using amorphous ~lica~alumina catalysts. The product of 11 Examples 28 and 29 can be split into 1050F.+ and 1050F.~
l2 fractions, and the 1050F.+ fraction coked a~ presented in 13 Example 30 below. Best use of the Example 28 product re-14 quires that it be treated in R~2 service to obtain a m~terial having from 2 to 3 wt. % Con. carbon and <5 ppm metals, l6 preferably < 2 ppm metals~ which material can then serve as 17 a p~ime feed for * convention~l hydrocracker or catalytic 8 cracker. The product of Example 29 ~s a marginal feed for a 19 conventional hydrocr&cker or catalytic cracker. The product of Example 29 ~ 8 a prime fe2d for a resid catalytic cracker 21 as pre~ented in Exam~le 38.
22 The product of Example 27 i3 m~rginally suitable 23 for R~2 service, or as a margi~al feed for U8~ ~n a coker.
24 None of the products of Exflmple~ 27 through 29 ~ ~uitable for direct use in a conventional hydrocracker or catalytic 26 cracker.
27 The following example illustrate~ certain advan-28 tages in use of the product of Example 29 *3 coker feed.
29 Example 30 Case A Jobo crude was split into two fractions, 31 1050~.+ and 1050F.~ fraction~. Yield~ for coking the 32 1050~.+ fraction were predicted u~ing correl~tionsO The 1 total yields were then cslculated by mathematical blending.
2 Case B: The Example 29 product was separated into 3 1050F.~ and 1050~F.~ fractions. Yields for coking the 4 1050F.+ fraction were predicted u~ing c~rrelations. The total liquid yields were calculated by mathematical blending.
6 The re~ults of the~e calculations are given in 7 Table XI belowo 9 Basis~ 50 MBID of Jobo Crude Ca8e A Case B
11 C3, ~ Lb-/D 0.87 0.44 l2 C4, B/D 893 777 13 C5/430F.9 R¦D 4~434 39446 430/650F.~ B~D 89323 11~950 650/1050F.9 B~D 28~108 31~703 l6 Coke9 T/D 19223 (5.9% S) 373 (2.5% S) 17 C3+ Yield9 Vol. % 86 97 18 The~e comparat~ve data ~how that the C3+ volume 19 percent y~eld of product i~ 97 when coking the 1050F.+
product of Example 29 vis~a~vis the 86 C3+ volume percent 21 yield obtflined when coking the 1050FO~ material of the Jobo 22 crude per se9 an 11 volume percent improvement in C3+ liquid 23 yield. Moreover9 both the coke and the liquid product re~ ~
24 sulting from eoking the ~xample 29 1050F.~ material vi~a~ ~-vis the 1050F.+ material from the original Jobo crude i8 ~ ~ ~
26 superior.
27 The following pre~ent~ ~ ~eries of runs which ~how 28 that products c~n be produced from 1050F.~ heavy crudes and 29 residua by react~on with an R~l c~taly~t which are admirflbly suitsble as feeds for Ro2 service. In the following series 31 of dat~, the in~tlal temperature of the several runs is fur~
32 ther inere~sed as contra~ted with the runs of preceding ~ 5~ ~

, 1 ~xa~ples 27 through 29. The space velocity is then gradual-2 ly decre~sed~ and as ~pace velocity ic lowered9 it will be 3 observed that product quality improves.
4 Ex~mple 31 A series of runs9 viz.~ Example 319 Runs 1-4, was 6 conducted u~ing an R~l type catalyst9 identical to Catalyst 7 D previou~lY de~cribed (Example 5), except that the catalyst 8 contained 0.35 wt. % Sn (by imprègnation) in addition to co-9 balt and molybdenum. Again particles averaging 1/32 inch diameter were used. Jobo crude (T~ble V) was contacted in 11 each instance with the catalyst at a start of~run tempera-12 ture of 760F. 9 the temperature being increased during the 13 operations 8t an average rate of from about 1.8 to 2.2F.
14 per day to m~intain a substantially constant rate of reac-tion for a given run. The following data, given in Table 16 XII, below9 were obtained ~t a temperature of 765F. after 17 166 hours on oil.

~ ,, 19 Pressure9 psig 2250 Hydrogen Rate9 SCF/Bbl 6000 21 Run NoO 1 2 3 4 22 Space Veloc~ty, 23 V/HrOlV 1.90 1045 0.91 0.46 24 Product Ins~ection -Gravity, API 1703 1703 1805 ~OD7 26 Sulfur, Wto% 1.29 1.08 0080 0.20 27 Con Carbon9 Wt.% 7.6 7.0 7.1 4.0 28 A~phaltenes 9 Wt-% 6-1 6.2 4O8 1.9 29 Metals. D~m Ni 29.2 24.8 17.2 207 31 V 26.1 93.9 4609 0O9 32 1050+F-,Conv- 9 33 Wt.% 44O3 38.2 43O5 5606 34 1050~F. QufllitY
~ Sulfur; ~-t~ 1098 1081 1.48 0.43 36 Con~C~rbon, wt.% 26.0 2107 2403 17.2 37 Met~ls~ PPm 38 ~ ~ 96.8 73~5 64.5 2006 39 V 363.4 308.0 189.0 1.5 Met~l on CatO,Wt.%* 69 88 91 46 41 *Wt.% on fresh ~at~at end of operation. Run~ terminsted 42 st dlfferent time~ on oil.

~ 59 -1 It is thus apparent by reference to Runs 3 and 4, 2 as contrasted with Runs l and 29 that temperatures above a 3 bout 750F., at spsce velocities about 19 can provide sn 4 R~2 feed of de~irable quality~ Suitably, the R-2 feed is sbout 90 Wt. % demetallized, and hence the product of R-l 6 service is usually one containing metals below about 60 ppm, 7 which metal~ content can be further reduced in R-2 service 8 to 5 ppm or le~s. Also, Con. carbon at levels of about 7 9 Wt. % can be reduced to levels ranging about 2-3 Wt. % as required for use in R~2 serviceO In operating at these con-11 dition~g the R~l catalyst was found suitable for about 3-4 l2 weeks of cont~nuous R~l servlce.
13 The product of ExAmple 319 Run 49 on the other 14 hand, can be fed directly to a catalytlc cracker employing zeolite catalyst as shown by reference to Example 38, if 16 desired. The product produced in Example 29, described by 17 reference to Table X, is a prime feed for resid catalyt~c `~
18 cracking as shown In Example 38.
19 Example 32 Several catalyst~ of varying pore size distribu~
21 tion were obtained for demonstrative purposes~ Catalysts S
22 ~nd T are commercially available alumina which was impreg~
23 nated with cobalt and molybdenum ~alts and then dried and 24 calcined at conditions similar to that used in Example 9.
Catalyst V, the catalyst of the invention9 was prepared in 26 a msnner similar to that used for Catalyst D described by 27 reference Example 5. A portion of each hav~ng an average 28 particle size of 1~32 inch was then iemployed in ~ fixed bed -~
29 reactor for hydroconversion of whole Jobo crude to measure the effectivene~s of each in R~l service. The pore size 31 distributions of eaeh of these several catalysts, termed 32 Catalysts S, T~ U, and V for convenience~ the conditionA

~ 60 ~

'` 1059110 , 1 under w~ich t~e hydrocon~er~ion run~ were conducted, and 2 product data are tabulated in Table XIII,a~ follows~
3 ~A8LE ~
4 ~a9 De~cripti~n of ~atalysts:
Catalyst S T U V
6 Surface Area9 m2/g 250 217 259(1) 362 7 Pore Volume, cc/g 0~55 0.53 0.58(1) 1.51 8 Pore Volume Distribution, 7~
9 0-5QA ~ores 4~ 3 10. 7 S. 0 2. 8 50-lSOA 73. 8 33.0 40.5 15.7 11 150-~5Q~ 12.2 22.6 33.1 25.2 12 250~,35ai~ 5~4 1608 15.4 27.3 13 350A+ 4.3 16.9 6.1 29.1 `
14 % CoO 3 3 6 6 % MoO3 13 21 20 20 16 ~b~ Process ~onditionso 17 ~emperature, F. 789 (after66~ hours on 18 oil,~750F. SOR) 19 Space Velocity, V/Hr.~,V 1.0 Ga~ Rate, ScFtBBl 6600 21 (c~ Product Inspection~
22 Catalyst S T U V
23 Product Inspection .-24 ~ulfur, ~. Z~ 1.163 lo 254 1.588 1.074 Metals, ppm -;
26 Ni ~ 2709 28.1 23.8 21.1 27 V 72.1 83.1 ~9 9 3800 28 Metal on Cat.,~tO7~ 43 41 62 99 29 ~1~ Data obt~ined frDm pore s~æe distr~bu~io~ measurement due to problem with ~ingle point nitrogen m~asurements 31 for ~urface area and pore volume~
32 * ~t. % on fresh cat at 665 hour~ on oil.
33 ~hese data thu~ sho~ that Catalyst V, an R-l cata-34 lyst, which inter alia, contains greater than 20~ of its total pore volume in the 150A to 250A range, less than 5% of it~ pore 36 volume in 0 50A pores and less th~n 3070 of it~ pore volume in 37 the 350A+ range, is far superior to ~he ot~er catalyst~ none 38 of which are R~l cataly tSJ in term~ of both ~ulfur and metals 39 removal9but particulQrly as rel~tes to metals remo~al, in terms ~ of metals removal an aver~ge of about 35% less of Catalyst V
required to remove the ~ame amou~t of metal~ a~ would be n~

~ 61 moved by the other catalysts.
2 The following example shows that as total pore vol-3 ume in the 150-250A range is increased, the catalyst becomes t 4 even more effective in terms of remov~ng metals.
Example 33 6 The following data are illustrative of that ob-7 taine~ from two different R-l catalysts, one (Catalyst W) of which contains 56.7% of the pores in the 150-250A range and g the other (Catalyst D), also described by reference to Table I except that it contains 0.3 wt. % Sn, by impregnation) 11 of which contains 44.1% of its total pore volume in pore 12 sizes ranging 150-250A. Each is used at similar conditions 13 for the hydroconversion of Cold Lake Srude (Table VI).
14 Catalyst W was prepared similarly to Catalyst C except that ~ ~
La was not included. The gel was impregnated by the methods - -16 of Example 9. Both catalysts were constituted of particles 17 averaging 1/32 inch diameter. The description of the~e . .
18 catalysts ~n terms of their pore si e distributions, the 19 conditions of the run and the inspection~ on the products from the ruIls are given in Table XIV belowo ~-21 ~ :-22 (a) De~cription of c~talysto 23 Catalyst W 3~ `
24 Surface Area, m2/g ~7~
Pore Volume, cc/g lo 22 ~1~ lo 23 226 Pore Volume Distribution~ % 1 5 28 50-150~ ~,o 15,5 29 ~50-250~ 56.7 44O1 2500-350A 25.3 33~0 31 350A+ 1500 5Og 32 7 CoO 20 20~5 34 (b) Process Conditions.
Temperature, F. 750Fo (210-240 hours on oil) 36 Pres~ure, psig 2250 37 Hydrogen R~te, SCF/B~l, 6000 38 Space Velocity, V/Hr,/V 0O5 1 A~'E XI~? ~Contd~
2 ~c~ Product Inspections~
3 Catalyst W D
4 Gravity, APl 23.4 24.0 Sulfur, Wt. % ~ ~.16 0.09 6 Con ~arbon~ Wt. % ~.5 2.1 7 Asphaltenes, Wt. % 0.9 1.2 8 Metals, ppm (~i and ~ ~.o 5.8 9 105OGF.~
~ul~rur, Wt. % 0.29 0.26 11 Con Carbon, Wt. b 8.0 9.7 12 Metals, ~m 13 Ni 1.7 6.6 14 V 4.7 9.3 (1) Data obtained from pore si e distribution measurements 16 due to problems with nitrogen measurements for surface 17 area and pore volume.
18 The advantages o~ maximi~ing pores within the 19 150-250A pore diameter range for ~ etalJi~ation is thus clearly illustrated. Catalysts similar to ~atalyst W, but 21 with higher pore volume in the 150-25QA pore diameter range, 22 and greater s~rface are~, provide even greater imp~ovements. ~-23 The followi~g additionally shows that a Group IVA
24 metal i8 effective in increasing the rate of demetalliza-tion of the catalysts of this invention.
26 Example 34 27 ~wo catalyst~ were prepared, each at the same con-28 ditions a~d ident,ical in composition one to the other, ex-29 cept that cne contained 3 wt. ~ ~ermani~m by impregnation and the other did not. Ihese catalysts, identified as 31 Catalyst V ~nd V~, are similar in their composition (except 32 as to the pr~sence of ~ermanium in Cataly~t ~ nd in 33 their p~.ysical characterictics a~ relates to po~e ~olume and pore size di~ribltion, and method of p~eparation which is the same 2S that of Catalyst D ide~tified by reference 36 to Table I. Average particle size for both catalysts 37 was 1/32 inch. Each catalyst ~as employed for the hydro-38 conversion of Jc~o cr~de, at conditions very similar to tho~e used in Example 32 to provide product~ a~ ldentified in Table XV, below:

lOS9110 l TABLE XV
2Process Condition~o 3Temperature~ F. 778F. (4~6 hours on oil) 4Pressure, psig 2250 Space Velocity, V/H/V 1.0 6 `Hydrogen Rate, SCF/B 6000 7 Catalyst V V' 8 Promoter None 3Z Ge 9 Product InsPection Sulfur, Wt. % 1.098 1.308 11 Metals, ~m 12 Ni 19.4 14.6 13 V 34.1 23.1 14 The rate of demetallization of Catalyst V' ùsed for hydroconver~ion of the crude is thus appreciably in~
16 creased as contrasted with Catalyst V which does not con-17 tain the germanium promoter.
18 The following examples are exemplary of an R-2 19 catalyst of preferred composition, the catalyst being des-cribed as used in a typical R 2 service situation for hydro-21 conversion of an R~l product resultant from the treatment ~ -22 of a whole Jobo crude by contaet with R-l catslyst as typi-23 cal R~l service conditions. The performance of the R-2 cata-24 lyst i~ aompared with an R-l catalyst for similar use, and with a commercially available catalyst in similar service.
26 Example 35 27 Runs were made wherein whole Jobocrude (Table VI) 5' `.
28 was introduced into an R~l reactor containing a fixed bed 29 of R-l catalyst (Cataly~t V) and treated at hydroconver~ion conditions, the R-l product produced being defined in Column 31 2 of Table XVI, belowO

33 (fl) Conditions of Operationo 34 R 1 Reactor:
` Temperature, F. 750 (SOR) 36 Pressure, psig 2250 37 Hydrogen Rate,SCF/Bbl. 6000 38 Space VelocityJV/H/V 1.0 ~ 6/~ ~

~!~ntd) 2 ~-1 Producto 3 ~:ravity, API 16.8 4 Sulfur, Wt. % 1.40 Carbon, Wt~ % 86.44 6 Hydrogen, Wt.% llo 25 7 Con.Carbon,Wt.% --8 Asphaltenes, Wt.% 5O49 9 Metals, ppm Ni 24.6 12 Nitrogen, Wt. ~ 0.577 13 ~L~
14 IBP ~00 5% 455 16 ~ 515 22 % Recovered 65 23 % Residue 35 The R-l product, characterized in Table XVI (b), 26 was then successively passed over Catalyst V (Example 34), 1~ 27 having particles averaging 1/32 inch diameter, at a start-28 o-run temperature of 750F., 6000 S~F/Bbl H2, 2250 psig 29 and with space velocities varying from 0.49 to 1.93 V/Hr./V.
Data shown in Table XVII are for products withdrawn from 31 the reactor at 755F. after 161 hours on oil.
32 TABLE ~III
.
33 V/Hr./V 0O49 0.83 0.95 1.93 34 Product InsPections Gravity, API 2305 19.8 18~3 17.5 36 Sulfur, Wto % 0.10 0.38 0~71 1.05 37 Asphaltenes, Wt.% 0.86 2.48 3.88 4.32 38 Metals, ppm 39 Nl 1.7 9.5 1406 18.0 V 0.1 0.3 5.7 37.3 41 These results show that the R-l type of catalyst 42 is not ideally suited for R-2 service. High temperatures ;~
43 and low space velocities are required to reach the R-2 cats-44 lyst target of ~5 ppm metals and 2-3 wt. % Con. carbon (~1 wt, % asphaltenes~.
46 A catalyst with maximum pores in the 100-200A

~059110 1 r~nge i8 preferred for R-2 service as shown in the next 2 example. In addition9 it is preferred to operate at lower 3 temperature where equilibrium favors aromatics saturation 4 enhancing Con Sarbon removal.
Example 36 6 The R-l product characteriæed in Table XVI (b) 7 was succe~sively passed over Cataly~t V and a commercially 8 available hydrotreating Catalyst X which is characterized 9 in Table XVIII (a~. The catalysts, veraging 1/32 inch in particle diameter, were evaluated at a start-of-run temper-11 ature of 700F., 6000 ~¢F/B H2, ~250 psig and 0.5 V/Hr./V.
12 Data shown in Table XVIII (b) are for products withdrawn 13 from the reactor at 700F. after 93 hours on oilO

.
(a) Description of Catalyst X
16 Surface Area, m2/g 222 17 Pore Volume, cclg 0.58 18 Pore Volume Distribution, %
19 O-SOA pores lo 6 50-lOO~o 32.9 ~:
21 10020QA Slo 8 22 200-30oA g o 23 300~+ ~07 24 % NiO 3 0 % MoO3 18.0 26 (b~ Characterization of R 2 Product 27 Catalyst X V ~-....
28 ~59~e5L~
29 Gravit-y, VAPI 2007 19 8 Sulfur, Wt. ~/0 00207 00282 `
31 Asphaltenes, Wt. % 0083 lo 29 ;~
32 Metals, PPm 33 ~ Ni ` 707 8.4 34 V Ool 0~1 35 The data show that the commercial Ni~Mo catalyst with 52%
36 of its pores in the 100-200A region is more active for sul-37 fur, asphaltene and metals removal at the conditions than 38 the R~l catalyst which has less of it8 pores in 100-200A

- 66 w 1 region.
2 The catalyst of the invention for R-2 service 3 wherein pores in the 100-200A region are further maximized 4 is shown to be superior to the co.~ ercially available cata-lyst (Catalyst X) in Example 37.
6 Exam~ole 37 7 The R-l product (Table XVI lbl) was successively 8 passed over Catalyst X (Commercial catalyst of Example 36) 9 and Catalyst P (Example 9), having average particle size diameters of 1/32 inch, at 650F. start-of-run temperature, 11 6000 SCF/B H2, 2550 psig and 0.5 V/Hr~/V. Catalyst Y i8 12 characterized in Table XIX (a) and the product inspection 13 for product withdrawn at 650F. after 48 hours.on oil is ::.
14 shown in Table XIX.
.. TABLE XIX
16 (a) Description of Catalyst Y
17 Surface Area, m2/g 212 18 Pore Volume, cc/g 0O43 -19 Pore Volume Distribution~ % .
0-50~ ~ores .8Ol 21 50~100~ 1904 22 100~200A 58O3 23 200~300A 13Ol 24 300A+ lol % NiO 6 26 % MoO3 20 27 (b) Characterizatfon of R~2 Product 28 Catalyst X Y P
29 Product InsPection Gravity, API 1805 1806 1808 31 Sulfur, Wt. % 00436 0O533 00287 32 Asphaltenes, Wt.% 2.1 205 1.7 33 Met~ls, oom 34 Ni 9O4 9O0 600 V 2.8 0O9 0O7 36 These data thus show the advantage for having less than 10%
37 of the pore volume in 0~50A pores and greater than 55% of 38 the pore volume in 100~200A pores and less than 25% of its 1059~0 ~ r 1 pores in 300~+ poresO Cat~lyst Y with 58% of its pores in 2 the 100-200A region shows some ~dvantage for demet~llization 3 over Catalyst X which h~d 52% of its pore volume in 100~200~
4 pores. Both were Ni/Mo c~talysts~ Catalyst P, a Co/Mo C~tfl- -lyst with 5870 of its pore volume in 100~200~ pores and 3.7%
6 of its pore volume in 0-50R pores and 1.6% of its pores in 7 300A+ pores was the most outstanding catalyst for R-2 ser- -8 vice-9 Example 38 .

The conditions for the R~l reactor can be varied 11 to yield product which i8 suitable for coking, for re~id 12 catalytic cracking by contact with amorphous silica alumina 13 (3A), for use in zeolite catalytic cracking or for further 14 treatment in the R-2 reactor to produce a product contain-ing ~5 ppm metals9 preferably ~2 ppm metals, with a Con.
16 carbon of less than 3 wt. %. The material from R~2 service 17 is suitable for conversion ~n a conventional catalytic ~ -18 cracking or hydrocracking unit. Results of such runs are 19 summarized in Table XX9 below.

TABLE XX
21 Jobo Feed 2250 pSig9 6000 SCF/B H2 22 R~l R~l/R~2 23 R~l R~l Plus Plus 24 Plus Plus Zeolytic Zeolytic Process Cokln~ Coking 3A CJC C/C C/C _ 26 R-l Conditions 27 SOR Temp.,F. o- 700 700 760 760 28 Space Velocity, 29 V/Hr./V. ~ 0-4 0.25 0O5 l.D
Av~. R-l Product 31 Sulfur,Wt.% -~ 0.6~1) 0.32~) Oo22(2) 0-76(2) 32 Metals, ppm ~ 62 10 5 60 33 Con.C~rbon, 34 Wt.% -~ 5.3 3.8 4.0 6.5 ~ 68 ~

lOS9110 1 TABLE XX (Continued) 2 R-l R-l/R-2 3 R~l R l Plus Plus 4 Plus Plus Zeolytic Zeolytic Coking Coking 3A C/C C/C C/C
6 Cstalytic Cra ~in~ Conditions 7 430F.+ C4nv~
8 % __ __ 25 80 80 9 Catalyst Addition 11 Rate, 12 Lb/B. ~ 1.0 0.4 13 Estimated Yields 54 gol % 86 97 97 107 110 Coke, 7.5(3) 7-5~3) 6.7(3) 18 Su~ in 19 Coke, Wt.% 5-9 2.5 -o O~ ;
21 (1) Analyses averaged for total run; life expected to be 22 greater than 2 months.
24 (2) Analyses averaged for total run, life expected to be (3) Coke make on cat Cracking (C/C) catalyst.
26 These data show that coking of raw Jobo crude 27 results in 86 vol. % yield of C3+ and a 13.8 wt. % yield 28 of sour coke (5.9% S). When the crude is trea~ed in R~l at 29 700F. and at 0.4 V/Hr./V.9 the product is a prime coker feed. Coking the feed increases the C3~ yield to 97 vol.%
31 and reduces the coke to 4.4% (2.5% S). Published data and 32 correlations show that if the severity of R~l is increased 33 by reducing the space velocity to 0.25 V~Hr.~V9 the product 34 is then suitable for resid catalytic cracking using amor-phous SiO2/A1203 catalyst. The yields produced are 97 vol.%
36 C3+ and 7~5 wt.% coke. If the severity of R~l is further 37 increased to 760Fo and OOS V/HrO~V9 the product is suit-38 able for catalytic cracking using zeolite cracking catalyst.
39 In this instance, the yields produced are 107 vol. % C3+
and 7.5 wt. % coke. Moreover, using the preferring reac~n ~ 69 ~

~ ~ ` ~
~059~10 1 sequences of R-l/R~2 catalysts, this product can be cata- -2 lytically cracked using zeolite catalysts to produce yields 3 of 110 vol. % C3+ and 6.7 wt. % coke. These results show 4 the wide versatility and capabilities of these catalysts and proces~es.
6 It is apparent that various modifications and 7 changes can be made without departing the spirit and scope 8 Of the present invention.
9 Pore size distributions, as percent of total pore volume, for purpose of the present invention are measured by 11 nitrogen adsorption wherein nitrogen is adsorbed at various l2 pressures using the Aminco Adsorptomat Cat. No. 4~4680, and 13 multiple sample accessory Cat. No. 4 4685. The detailed 14 procedure is described in the Aminco Instruction Manual No.
lS 861-A furnished with the instrument. A description of the l6 Adsorptomat prototype instrument and procedure is given in 17 Analytical Chemistry, Volume 32J page 532a April 1960.
18 An outline of the procedure is given here, includ-19 ing sample preparation.
From 0.2 to 1.0 g. of sample is used and the iso~
21 therm is run in the adsorption mode only. All samples are 22 placed on the preconditioner before analysis where they are 23 out-gassed and dried at l90~C. under vacuum (10 5 torr) for 24 5 hours. After pretreatment the weighed sample is charged to the Adsorptomate and pumped down to 10~5 torr. At this 26 point, the instrument is set in the automatic adsorption mode 27 to charge a standard volume of gas to the catalystO This is 28 done by charging a predetermined number of volumes as doses 29 and then allowing time for adsorption of the nitrogen to reach equilibrium pressure. The pressure is measured in 31 terms of its ratio to the saturation pressure of boiling 32 liquid nitrogen. Three doses are in~ec~ed and 8 minutes ~ 70 ~

. .

1 allowed for equilibration of each measured relative pressur~
2 The dosing and equilibration are continued until a pre~sure 3 ratio of 0.97 is exceeded and maintained for 15 minutes.
4 The run is 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 calculates the volume points of the isotherm, the BET area, ` -9 and the pore size distribution of the Bflrrett, Joyner, and Halenda method. [Barrett, Joyner, and Halenda, J. Am. Chem.
11 Soc. 73, p. 373.] It is believed that the Barrett, Joyner, l2 and Halenda method is as complete a treatment as can be ob-13 tained, based on the assumptions of cylindrical pores and 14 the valid~ty of the Kelvin equation.
Hydrocarbon or hydrocarbonaceous feedstocks which l6 can be treated pursuant to the practice of this invention 17 include heavy petroleum crudes, synthetic crudes derived ;
18 from coal, shale, tar sands, heavy oils and tars which con-19 tain relatively high concentrations of asphaltenes~ high carbon:hydrogen ratios, high metals contents, considerable 21 amounts of sand and scale, considerable amounts of 1050F.+
22 materials, and generally high sulfur and nitrogen.

Claims (36)

1. A catalyst composition having enhanced selectivity suitable for the conversion and demetallization of feeds which contain large quantities of 1050°F+ hydrocarbon materials charac-terized by comprising an admixture of 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 composition including a combination of properties compri-sing, when the catalyst composition is of size ranging 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 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. to about 275.ANG.; surface areas ranging at least about 200 m2/g to about 600 m2/g and pore volumes 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 said catalyst composition comprises from about 15 to about 25 weight percent of said Group VIB metal, or compound thereof, and from about 4 to about 8 weight percent of said Group VIII metal, or compound thereof, measured as oxides.

3. A catalyst composition according to claim 2 further characterized in that 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:
Distribution of Pore Diameters 0-50.ANG. 20%
100-200.ANG. 20%
300.ANG.+ 30%

Pore Volume, cc/g 0.8-1.4 Surface Area, m2/g 300-450

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:
Distribution of Pore Diameters 0-50.ANG. < 2%
100-200.ANG. >70%
300.ANG. < 1%

Pore Volume, cc/g 1.1-1.7 Surface Area, m2/g 325-550

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:

Distribution of Pore Diameters 0-50.ANG. <10%
100-200.ANG. >25%
300.ANG.+ <25%
Pore Volume, cc/g 0.9-1.5 Surface Area, m2/g 310-500

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 character-ized as follows:
Distribution of Pore Diameters 0-50.ANG. <10%
150-250.ANG. >15%
350.ANG.+ <35%
Pore Volume, cc/g 1.1-1.7 Surface Area, m2/g 320-475

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 character-ized as follows:
Distribution of Pore Diameters 0-50.ANG. <5%
150-250.ANG. >20%
350.ANG.+ <30%
Pore Volume, cc/g 1.3-1.9 Surface Area, m2/g 340-575

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:
Distribution of Pore Diameters 0-50.ANG. <1%
150-250.ANG. >45%
350.ANG.+ <7%
Pore Volume, cc/g 1.5-2.1 Surface Area, m2/g 360-600

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 diameter is characterized as follows:
Distribution of Pore Diameters 0-50.ANG. <5%
175-275.ANG. >15%
350.ANG.+ <40%
Pore Volume, cc/g 1.3-1.9 Surface Area, m2/g 340-500

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:
Distribution of Pore Diameters 0-50.ANG. <4%
175-275.ANG. >20%
350.ANG.+ <35%
Pore Volume, cc/g 1.5-2.1 Surface Area, m2/g 350-600

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:
Distribution of Pore Diameters 0-50.ANG. <3%
175-275.ANG. >30%
350.ANG.+ <25%
Pore Volume, cc/g 1.8-2.3 Surface Area, m2/g 370-650

13. A catalyst having enhanced selectivity for conversion, demetallization, and for Con carbon reduction of hydrocarbon feeds which contain substantial quantities of 1050°F+ hydrocarbon materials 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, measured as oxides, 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 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 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. A process for the demetallization and conversion of the 1050°F+ materials of a heavy metals containing hydrocarbon feed to 1050°F- material comprising contacting said feed, in the presence of added hydrogen, with a catalyst characterized as comprising admix-ture of 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 includ-ing a combination of properties comprising when the catalyst is of size ranging from about 1/500 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 diam-eter, 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.

17. The process of claim 16 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.

18. The process of claim 16 or claim 17 wherein the feed is characterized as follows:
Gravity, °API -5 to 20 Heavy Metals, ppm 5-1000 1050°F+, wt.% 10-100 Asphaltenes (C5 insoluble), wt.% 5-50 Con Carbon, wt.% 5-50

19. The process of claim 16 or claim 17 wherein the feed is characterized as follows:
Gravity, °API 0 to 14 Heavy Metals ppm 200-600 1050°Ft,wt.% 40-100 Asphaltenes (C5 insoluble), wt.% 15-30 Con Carbon, wt.% 10-30

20. The process of claim 16 or claim 17 wherein the conditions of the reaction are characterlzed as follows:
Temperature, °F (E.I.T.) Start-of-Run ` 700 End-of-Run 850 Pressure, Psi 200-10,000 Hydrogen Rate, SGF/B 3000-20,000 Space Velocity, LHSV 0.25 5.0

21. The process of claim 16 or claim 17 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:
Distribution of Pore Diameters 0-50.ANG. <20%
100-200.ANG. >20%
300.ANG.+ <30%
Pore Volume, cc/g 0.8 1.4 Surface Area, m2/g 300-450

22. The process of claim 16 or Claim 17 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:

Distribution of Pore Diameters 0-50.ANG. <10%
150-250.ANG. >15%
350.ANG.+ <35%
Pore Volume, cc/g 1.1-1.7 Surface Area, m2/g 320-475

23. The process of claim 16 or Claim 17 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:
Distribution of Pore Diameters 0-50.ANG. <5%
175-275.ANG. >15%
350.ANG.+ <40%
Pore Volume, cc/g 1.3-1.9 Surface Area, m2/g 340-500

24. The process of claim 16 wherein the Group VI
metal of the catalyst is molybdenum, and the Group VIII
metal of the catalyst is cobalt.

25. A process for the demetallization, conver-sion and reduction of the Con. carbon content of the 1050°F.+
materials of a heavy metals containing heavy crude or re-sidua feed to 1050°F.- material comprising contacting said feed, in the presence of added hydrogen, with a catalyst characterized as comprising an ad-mixture 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 includ-ing B 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 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, re-move at least about 90 percent of the heavy metals from the feed, and reduce Con. carbon from about 50 percent to about 100 percent.

26. The process of claim 25 wherein from about 60 percent to about 75 percent of the 1050°F.+ material is con-verted to 1050°F.-, from about 97 percent to about 100 per-cent of the metals are removed from the feed, and Con. car-bon is reduced from about 75 percent to about 90 percent.

27. The process of claim 25 or claim 26 wherein the product of the reaction is characterized as follows:
Gravity °API 18-30 Heavy Metals,ppm <50 1050°F.+, Wt.% 5-30 Asphaltenes (C5 insoluble), Wt. % <3 Con. Carbon, Wt. % <5

28. The process of claim 25 or claim 26 wherein the conditions of the reaction are characterized as follows:

Temperature, °F. (E.I.T.) Start-of-Run 700 End-of-Run 850 Pressure, Psi 2000-10,000 Hydrogen Rate, SCF/B 3000-20,000 Space Velocity, LHSV 0.25-5.0

29. The process of claim 25 or claim 26 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 dia-meters 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.

30. The process of claim 25 or claim 26 wherein the Group VI metal of the catalyst is molybdenum, and the Group VIII
metal of the catalyst is nickel.

31. The process of claim 25 wherein said catalyst com-prises from about 10 to about 20 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.

32. The process of claim 25 wherein the feed is characterized as follows:

Gravity °API 15-25 Heavy Metals, ppm 40-80 1050°F.+, Wt. % 25-40 Asphaltenes (C5 insoluble), Wt. % 5-15 Con-Carbon, Wt. % 5-10

33. The process of claim 25 wherein the product of the reaction is characterized as follows:
Gravity,°API 20-28 Heavy Metals, ppm <5 1050°F.+, Wt.% 10-25 Asphaltenes (C5 insoluble), Wt. % <1 Con. Carbon, Wt. % <3

34. A process for the demetallization and con-version of the 1050°F.+ materials of a heavy metals contain-ing heavy crude or residua feed to 1050°F.- material com-prising contacting in the pregence of added hydrogen, a feed characterized as follows:
Gravity, °API -5 to 20 Heavy Metals, ppm 5-1000 1050°F.+, Wt. % 10-100 Asphaltenes (C5 insoluble), Wt. % 5-50 Con. Carbon, Wt. % 5-50 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, when the catalyst is of size ranging from about 1/500 up to l/50 inch average particle size diam-eter, at least about 20 percent of its total pore volume of absolute diameter within the range of about 100.ANG. to a-bout 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 a-bout 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, characterized as fol-lows:
Gravity, °API 14 to 30 Heavy Metals, ppm 10-100 1050°F.+, Wt.% 10-50 Asphaltenes (C5 insoluble) Wt.% 3-20 Con Carbon, Wt. % 3-20 into contact with a catalyst characterized as comprising a composite 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, or admixture of said Group VIB and Group VIII metals, or compounds thereof, and a porous inorganic oxtde support, said catalyst includ-ing 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, 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.

35. 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 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 com-pound thereof, measured as oxides, and a porous inorganic oxide support, said catalyst composition including a combination of properties comprising, when the catalyst composition is of size ranging 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 composition is of size ranging from about 1/50 inch up to l/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.
to about 275.ANG.; surface areas ranging at least about 200 m2/g to about 600 m2/g and pore volumes ranging from about 0.6 cc/g to about 3.0 cc/g.

36. A process for the demetallization and conversion of the 1050°F+ materials of a heavy metals containing hydrocarbon 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 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 from about 1/500 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 0.6 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.