CA1198406A - Hydrocarbon conversion catalyst - Google Patents

Abstract

HYDROCARBON CONVERSION CATALYST
ABSTRACT OF THE DISCLOSURE

Hydrocarbon conversion catalyst comprising an active metallic component comprising at least one metal having hydrocarbon conversion activity and at least one oxygenated phosphorus component, and a support component comprising at least one porous refractory inorganic oxide matrix component and at least one crystalline molecular sieve zeolite compo-nent.

Description

\

HYDROCARBON CONVERSION CATALYSIS
BACKGROUND OF THE INVENTION
This invention relates to improved catalytic compositions having utility in hydrocarbon conversion processes. In a specific aspect, the invention relates to improved catalytic compositions having utility in hydrogen treating of hydrocarbon feed materials.
Catalytic compositions containing a catalytically active metallic component deposed on a non zeolitic, refractory inorganic oxide support are well known as are numerous uses therefore Familiar examples include petroleum and synthetic crude oil hydrotreating and hydrocracking catalysts comprising a Group VIM
and/or VIII metal such as cobalt, nickel, molybdenum and/or tungsten deposed on a non-zeolitic, refractory inorganic oxide such as alumina, silica, magnesia, etc. and olefin polymerization catalysts comprising a Group VIM metal deposed on silica or silica-alur.lina supports.
It also is known that the activity or performance of catalysts of the type described hereinabove for reactions such as hydrocracking, disproportionation and oligomeri~ation can be improved or modified by inclusion in the catalyst of a crystalline molecular sieve zealot component. Thus U.S. 3,649l523 ~Bertolacini et at.) discloses a hydrocarbon convert soon process, and particularly hydrocracking and disproportionation of petroleum hydrocarbon feed materials, carried out in the presence of improved catalysts comprising a metallic component having hydrogenating activity deposed on a support component comprising a large pore crystalline aluminosilicate and a porous support material such as alumina, silica or aluminum phosphate. U.S. 3,894,930 and U.S.
4,054,539 (both ensoul) disclose hydrocracking in the presence of improved catalysts comprising a metallic hydrogenating component and a support component comprising ultra stable large pore crystal-line aluminosilicate and silica alumina U.S.
3,876,522 (Campbell et at,) discloses preparation of lube oils by a process that includes a hydra-cracking step in which there are employed catalysts containing a composite of a crystalline alumina-silicate zealot component and a porous refractory Lo oxide component such as alumina or silica, such composite containing deposited or exchanged catalytic metals. U.S. 4,029,601 (Wise) discloses oligomeri-ration of alikeness using a cobalt oxide-active carbon composite supported on a refractory oxide such as silica or alumina and/or crystalline aluminosilicate zealots. Other processes in which catalysts comprise in catalytically active metals and a support combo-next comprising a porous oxide and a crystalline molecular sieve zealot are useful include isomer-ration of alkylaromatics and alkylation of aromatics and paraffins.
It also is known that the performance of various catalysts containing catalytically active metals deposed on a non-zeolitic, refractory inorganic oxide support component can be improved or modified by inclusion of phosphorus in the catalytically active metallic component or through the use of phosphorus compounds in catalyst preparation For example, U.S. 3,287,280 (Colgan et at.) discloses that the use of phosphoric acid solutions of nickel and/or molybdenum salts to impregnate non-zeolitic supports such as alumina or silica leads to improved dispersion of catalytically active metals on the support surface and improved results in hydrodesul~
furization of petroleum hydrocarbon feeds. The patentee also discloses that phosphoric acid residues remaining in the catalyst impart thermal stability thereto. U.S. 3,840~472 (Colgan) contains a similar disclosure with respect to the use of phosphoric acid impregnating solutions of active metal salts.
U.S. 4,165,274 (Kant) discloses a two step process for hydrotreating and hydrocracking tar sands oils wherein hydrotreating takes place in a first stage in the presence of an alumina-supportedl fluorine and phosphorus-containing nickel-molybdenum catalyst, lo after which hydrocracking is conducted in the presence of a catalyst-containing nickel and tungsten supported on a low-sodium, Y type molecular sieve support component. U.S. 3,985,676 (Refers et at.) discloses catalysts for polymerization of olefins prepared by deposition of various organophosphorus compounds of chromium onto high surface area non-zeolitic supports such as silica or silica-alumina followed by thermal activation of the result.
Notwithstanding similarities in the basic gala-lyric composition catalytically active metal come potent deposed on non-zeolitic refractory inorganic oxide support component into which phosphorus or crystalline molecular sieve zealot components have been incorporated according to the above-described proposals, the reported effects of the zealot and phosphorus components are, in many respects, surf-ficiently unrelated as to mitigate against attempting to combine the effects of the components into a single catalyst. For example, the improved hydra-cracking activity of the above-described zealot-containing catalysts typically would not be desired in a hydrodesulfurization or hydrodenitrogenation catalyst because in typical hydxotreating processes employing such catalysts it is preferred to limit cracking. Similarly, the improved hydrodesulfuri-ration activity of phosphorus-promoted catalysts such as those of Colgan et at. would be of little consequence within the context of a cracking, alkali-lion, isomerization or disproportionation process.
On the other hand, we have previously found what a phosphorus component incorporated into the hydra-jointing component of certain hydrotreating catalyst exerts a promotional effect with respect to donator-genation of high nitrogen feeds while crystalline molecular sieve zealot components incorporated into catalysts containing similar active metals but free of phosphorus exerts a promotional effect with respect to denitrogenation and hydrocracking react lions.
It also is known from Rob, Zealot Chemistry no Catalysis, AS Monograph 171, American Chemical Society, pages 294-297 (1976), that many crystalline molecular sieve zealots possess only limited stab-lily with respect to strong acids such as the pros-phonic acid used according to Colgan et at. Accord-tingly, it can be speculated that attempts to combine the promotional effects of phosphoric acid and cry-stalling molecular sieve zealots have been limited by concern over destruction of the zealot component.
U.S. 3,617,S28 (Hilfman), which is directed to preparation of supported nickel-containing catalysts by coextrusion of a phosphoric acid solution of nickel or nickel and Group VIM metal compounds and an alumina-containing carrier, suggests the use of carriers containing silica and alumina that are amorphous or zeolitic in nature Column lines 39-43. Crystalline aluminosilicate zealots specify icily disclosed by Hilfman are mordant, faujasite and Types A and U molecular sieves Column 3 lines 42-46. Hilfman does not address the effect of the acid on zealot integrity or crystallinity, nor is there any disclosure or suggestion as to whether I
any zealot employed in the disclosed preparations would remain intact in the final catalyst. In fact, none of the disclosed crystalline aluminosi:Licate zeolikes, or any other for that matter, is employed in the patentee's examples. Further, U.S. 3,706,6~3 (Michelson et at. '693) and U.S. 3,725,243 (sass eke alp) teach that exposure of zealots to strong acids such as phosphoric acid destroys zealot crystallinity and integrity. In fact, both Michelson et at. '693 and Hess et alp are directed specifically to catalyst preparations in which impregnation of crystalline aluminosilicate-containing supports with phosphoric acid solutions of salts of hydrogenating metals results in destruction ox zealot crystallinity.
Further, three of the four crystalline aluminosilicate zealots specifically disclosed by Hilfman (faujasite, mordant and Type A molecular sieve) are included among the crystalline aluminosilicate zealots that are preferred for use in Michelson et Allis and Hess et Allis zeolite-destructive preparations.
The aforesaid Rob publication teaches that among Zealot A, faujasite and mordant, only the latter exhibits appreciable acid stability.
U.S. 3,905,914 (Juries et at.) is directed to preparation of oxidation catalysts by mixing a vanadium compound, zirconium salt and hydrogen halide, and then adding phosphoric acid or a compound hydra-losable to phosphoric acid. The result is reflexed to form a gel which then is dried, or loused to impreg-Nate a suitable carrier, such as alumina, alundum, silica, silicon carbide, silica-alumina, zircon, zirconium phosphate and/or a zealot." Column 2 lines 47-51. Juries et at. does not identify any zealots nor do the patentee's examples illustrate preparation of a supported catalyst. Also, no con-side ration is given to acid stability of zealots I

and there is no indication whether any zealot used in the disclosed catalyst preparation would remain intact.
Similar to the Michelson et at. '693 and Hess et at. patents discussed hereinabove, U.S. 3,749,663, 3,749,664 and 3,755,150 (all ~ickelson) are directed Jo impregnation of support materials with phosphoric acid solutions of salts of catalytically active metals. Although none of these patents discloses 10 impregnation of support materials containing a zoo-file component, each patent expressly cautions against exposure of supports containing aluminum ions to phosphoric acid at relatively low pi stating that reaction of the acid and aluminum degrades the sup-15 port, fouls the impregnation solution and results in formation of undesirable chemical forms in the finished catalyst. (See Michelson '663 at Column 8 lines 60-69, Michelson '664 at Column 8 lines 6-15, Michelson '150 at Column 9 lines 12-21.) U.S. 3,836,561 (Young) also deals with acid treatment of crystalline aluminosilicate zealots.
According to Young, alumina-containing compositions, including those containing crystalline aluminosilicate zealots, are reacted with aqueous acids including 25 hydrochloric, sulfuric, nitric, phosphoric and various organic acids, at a pi below about 5 in the presence of an ionizable salt that is soluble in the aqueous phase, and then the result is washed, dried and calcined. The result of such treatment 30 is removal of aluminum from the alumina-containing composition, replacement thereof with metallic cations if the ionizable salt is one containing cations that can be exchanged into the zealot, increased porosity and decreased bulk volume of the catalyst.
35 The resulting compositions are said to have utility as absorbents, ion exchange resins, catalysts and 1 1.9~ ?~, catalyst supports. Acid-stable zealots and the effects of acid treatment on zealot crystallinity are discussed at Column 2 lines 61-68. Of course, Young's acid treatment differs from the use of pros-phonic acid according to the patents discussed here-in above in that Young's purpose is to remove aluminum from the composition rather than to incorporate phosphorus into it. It also differs from the patents discussed hereinabove in that the disclosed compost-lions lack a catalytically-active metallic component deposed on the alumina-containing carrier.
Other patents and publications that may be of interest to the present invention in disclosing treatment of crystalline molecular sieve zealots or compositions containing the same with phosphoric acid and other phosphorus compounds to incorporate phosphorus into the zealot are U.S. 3,962,364 (Young) and U.S. 4,274,982, 4,276,437 and 4,276,438 (all Chum). According to these patents, suitable phosphorus compounds include halides, oxyhalides, oxyacids, and organophosphorus compounds such as phosphines, pros-whites and phosphates. Incorporation of phosphorus according to these patents is reported to improve para-selectivity in alkylation reactions. Chum '982 further discloses treatment of the phosphorus-containing zealots with magnesium compounds. Chum '437 discloses impregnation of the phosphorus treated compositions with solutions of gallium, iridium or thallium compounds. Chum '438 contains a similar disclosure with respect to impregnation of compounds of silver, gold and copper. Both patents disclose use of acid solutions of the metals as impregnating solutions, with hydrochloric, sulfuric and nitric as well as various organic acids being disclosed.
None of these patents discloses or suggests the use of phosphoric acid impregnating solutions nor is there any suggestion of a catalyst containing an active metallic component which contains phosphorus.
Rather, the respective patentees' phosphorus is incorporated into the zealot British 1,555,928 (Convene et aloe discloses crystalline silicates of specified formula having utility in a wide range of hydrocarbon conversiorls~
Impregnation of the silicates with catalytic petals is disclosed as is promotion or modification with halogens, magnesium, phosphorus, boron, arsenic or antimony, (Page 6 lines 33-54); with incorporation of phosphorus into the silicate to improve alkylation selectivity, as in the above-described Chum patents, being specifically disclosed.
It also is known that phosphine or other organ-phosphorus complexes of various metal salts can be employed in preparation of various supported catalyst compositions. or example, U.S. 3,703,561 (Kubicek et aloe discloses catalysts for olefin disproportional lion comprising a reaction product of (1) an organ-aluminum halide, aluminum halide or combination thereof with each other or with another organometallic halide and (2) a mixture of a salt of copper, silver or gold with a completing agent which may be an organophosphine. Reaction of components I and

(2) is conducted in the presence of a solvent for the reactants, in the substantial absence of air and at temperatures low enough to avoid decomposition ox the reactants. It also is disclosed to provide the catalysts in supported form by impregnating a support such as a non-zeolitic, refractory inorganic oxide or a elite with the reaction product, or by impregnation with one of the reactants followed by addition of the other. Kubicek et at. also states that if such supported catalysts are to be activated by calcination the calcination should take place I

prior to impregnation with the active species, i.e., the reaction product of components (1) and 12)~ It is unclear whether residues of any or~anophosphine compound used in preparation of the catalysts of Kubicek et at. would remain in association with the active metallic species In any event, the catalyst preparation according to this patent is conducted under conditions designed to avoid conversion ox any such organophosphine residues to an oxygenated phosphorus component such as that required according to the present invention.
U.S. 3,721,718 (Hughes et at.) and U.S.
4,010,217 (Zuech) contain disclosures similar to that of Kubicek et at. with respect to use of organ-phosphorus complexes of various metal salts in prepay ration of olefin disproportinativn catalysts. Like - Kubicek et at., both Hughes et at. and Zuech contem-plate supported catalysts; however, both patentees also state that if activation by calcination is desired, it should be accomplished by calcination of support prior to incorporation of active metals.
Another patent disclosing the use of metal complexes in catalyst preparation is U.S. 3,~49,457 (Haag et at.) which is directed to preparation of carboxylic acids by hydrogenolysis of esters The catalysts of Haag et at. comprise a hydrogenating metal component and a solid acid component such as a zealot which components may be employed as a loose physical admixture or ho combining the two components into a single particle Various methods for combining the two components into a single part-ale are disclosed at Column 6 line 64-Column 7 line OWE One of these involves mixing a solution of a metal pi-complex with the acid solid and then deco-posing the complex to form elemental metal and depositing the elemental metal onto the acid solid.

A specific metal complex employed in this preparative scheme is tetra(triphenylphosphine)palladium(II) dibromide. Another preparative method useful with respect to zeolitic acid solid components involves incorporation of the hydrogenation component by conventional methods such as ion exchange or impreg-nation. None of the disclosed methods would Rosetta in association of an oxygenated phosphorus component with the metallic component of the patentees' gala-lust.
U.S. 4,070,403 Homier discloses a hydra-formulation catalyst comprising a cobalt compound and a zeolite-alumina hydrosol dispersion. The cobalt compound is chemically bonded to the alumina zealot dispersion by a vapor-phase impregnation technique Suitable cobalt components of the disk closed catalysts include various salts such as halides, nitrate and various carboxylates as well as organophosphine complexes. Homier does not disk close or suggest the presence ox an oxygenated pros-chorus component in the final catalyst, nor does the patentee attribute any promotional effect to phosphorus.
It can be appreciated from the foregoing that efforts to include both a crystalline molecular sieve zealot component and a phosphorus component in catalysts comprising an active metal component deposed on a non-zeolitic refractory inorganic oxide component in such a manner that the promotional effects of both the phosphorus and the zealot are retained have been largely unsuccessful. In those instances in which an attempt has been made to incur-prorate a promoting phosphorus component through the use of phosphoric acid impregnating solutions of compounds of active metals, such use of phosphoric acid in conjunction with a crystalline aluminosilicate zeolite-containing composition often results in destruction of the crystalline aluminosilicate zealot component. Other proposals such as those involving use of organophosphorus complexes of various metal 5 salts to aid impregnation or deposition of active metals into or onto support result in only incidental, if any, incorporation of phosphorus into the final catalyst, and phosphorus so incorporated appears lacking in promotional effect.
It would be desirable to provide an improved catalytic composition in which both phosphorus and crystalline molecular sieve zealot components are present in a form capable of exerting a promotional effect. It is an object of this invention to provide an improved catalytic composition A further object of the invention is to provide for the use of such catalytic compositions in hydrocarbon conversion processes. A still further object is to provide for the preparation of catalysts in which improved performance is attained through incorporation of crystalline molecular sieve zealot and phosphorus components. Other objects of the invention will be apparent to persons skilled in the art from the following description and the appended claims.
We have now found that the objects of this invention can be attained by incorporation of an oxygenated phosphorus component into the catalytically active metallic component of a catalytic composition and incorporation of selected crystalline molecular sieve zealot components into the support component of the composition. Advantageously, the crystalline molecular sieve zealot components of the invented catalysts are derived from acid-tolerant crystalline molecular sieve zealots, and accordingly, phosphorus component can be incorporated without substantial destruction of zealot integrity or crystallinity.

I

Further, the phosphorus component is incorporated into the metallic component in a Norm capable of exerting a promotional effect. Thus, as demonstrated in the examples appearing hereinbelow, the catalysts ox the invention, wherein an oxygenated phosphorus component is incorporated into a catalytically active metallic component which it deposed on or associated with a support component comprising at least one crystalline molecular sieve Zulu component and a non-zeoliticl refractory inorganic oxide matrix component, are superior to catalyst compositions that are identical but for the inclusion of a pros-chorus component, or but for inclusion of the zealot component, in a variety of catalytic processes.
Accordingly, the overall effect of the phosphorus and zealot components on performance of the basic catalytically active composition comprising a metallic component and a non-zeolitic, refractory inorganic oxide component is greater than the effect of either component alone in a variety of reactions.
In addition to the patents and publications discussed hereinabove, U.S. 4,228,036 (Swift et at.) and U.S. 4,277,373 (Sawyer et at.) may be of interest to the present invention in disclosing catalytic compositions containing phosphorus and zealot components. Specifically, Swift et at.
discloses an improved catalytic cracking catalyst comprising an alumina-aluminum phosphate-silica matrix composite with a zealot component having cracking activity, such as a rare earth-exchanged Y-type crystalline alllminosilicate zealot Swift et at. does not disclose inclusion of an active metallic component into such catalysts. Further, in contrast to the catalysts of the present invention, wherein an oxygenated phosphorus component is included in an active metallic component, the pros-lo chorus component of Swift et Allah catalysts is included in a refractory oxide material.
Sawyer et at. discloses hydroprocessing kowtow lusts comprising a Group VIM and/or Viol metal combo-Nina composite with an ultrastahle Taipei crystal-line aluminosilicate zealot and an alumina-aluminum fluorophospha~e component. The catalyst also may contain an alumina gel-containing matrix although an essential component of Sawyer et Allis catalyst is he aluminum fluorophosphate component of the support, it also is to be noted that patentee disk cloves use of phosphomolybdic acid to impregnate a support containing a Y-type crystalline aluminosil-irate and alumina-aluminum fluorophosphate in Example 1 (see Column 5 lines 21-25). According to the example, however, it appears that there was no incorporation of a phosphorus component into the active metal component of the catalyst because the table at Column 5 lines 42-52 fails to report pros-chorus content other than that contained in the aluminum fluorophosphate component of the support.
Table 2 of Sawyer et at. also reports on a compare-live catalyst C containing specified levels of alum mine, Y-type zealot, nickel oxide, molybdenum oxide, and phosphorus peroxide For catalyst C to have been a fair comparator for the calcites of Sawyer et Allis invention, the phosphorus pent oxide component must have been present in a Mann r similar Jo the fluorophosphate component of the patentees' catalysts, i.e., as part of the support. As such, Sawyer et at. fails to discos or suggest a catalyst containing phosphorus as an essential part of the active metal component.
DESCRIPTION OF THE INVENTION
35 Briefly, the catalyst composition of this invent lion comprises (1) an active metallic component us comprising at least one metal having hydrocarbon conversion activity and at least one oxygenated phosphorus component; and (2) a support component comprising a least one non-zeolitic, refractory inorganic oxide matrix component and at least one crystalline molecular sieve zealot component.
According to a further aspect of the invention, such catalytic compositions are prepared by a method comprising (1) impregnating a support component comprising at least one non-~eolitic, refractory inorganic oxide matrix component and at least one acid-tolerant, crystalline molecular sieve zealot component with precursors to an active metallic component comprising a least one metal having hydra-carbon conversion activity and at least one oxygen-axed phosphorus component under conditions effective to retain substantial zealot crystallinity; and (2) calcining the result to convert active metallic component precursors to active form. According to a still further aspect of the invention, the above-described catalytic compositions are employed in hydrocarbon conversion processes in which a hydra-carbon-containi~g charge stock is contacted with the catalytic composition under hydrocarbon conversion conditions.
In another aspect the invention provide a process for denitrogenation of high nitrogen content hydrocarbon feeds comprising contacting the feed with hydrogen under denitrogenation conditions in the presence of a catalyst comprising an active metallic component comprising at least one metal having hydrogenation activity and at least one oxygenated phosphorus compoIIent~ and a support come potent comprising at least one non~zeolitic, porous refractory inorganic oxide matrix component and at least one crystalline molecular sieve zealot component. In preferred embodiments of such process the denitrogenation -aye-conditions are denitroyenation hyd.rotreating conditions and comprise a temperature of about 650 to about 760F, hydrogen pressure ox about 1000 to about 2500 pal, LHSV
of about 0.2 to about 4 and hydrogen addition rate ox S about 200Q to about 20,000 SCAB.
On treater detail, the invented catalytic come position comprises an active metallic component and a support component. Rowley proportions of these are not critical so long a the active metallic component is present in at least a catalytically effective amount. Optimum proportions for a given catalyst will vary depending on intended use. Use-f ugly, the active metallic component constitutes about 5 to about 50 wit% and the support constitutes about 50 to about 95 wit%, such weight percentages being based upon total weight of the catalytic come position.
The active metallic component of the invented catalyst comprises at least one metal having hydra-carbon conversion activity and at least one oxygenated phosphorus component. Suitable metals hiving hydra-carbon conversion activity include any of the metals typically employed to catalyze hydrocarbon conversion reactions such as those of Groups IBM II, IIIB-VIIB
and VIII. These can be present in the catalyst in elemental form, as oxides, as sulfides, or in other active forms. Combinations also are contemplated.
The Group VIM metals exhibit a high degree of siesta-ability to promotion by oxygenated phosphorus combo-next. Accordingly, preferred compositions are those in which the active metallic component comprises at least one Group VIM metal.
For a given catalyst, the preferred metal or combination of metals of the active metallic component will vary depending on end use. For example, in hydrogen processing of hydrocarbon feed materials such as petroleum or synthetic crude oils, coal or Bahamas liquids, or fractions thereof, preferred metals are those of Groups VIM and VIII such as chromium, molybdenum, tungsten, nickel, cobalt, iron, platinum, rhodium, palladium, iridium and combinations thereof. Oxides and sulfides of these are most preferred from the standpoint of catalytic performance. In processes for denitrogenation hydra-treating or denitrogenation hydrocracking, combine-lions of nickel or cobalt with molybdenum and cry-mum give particularly good results. Particularly good results in hydrocracking processes are attained using catalysts containing combinations of cobalt and molybdenum, nickel and molybdenum, or nickel and tungsten as the metals of the active metallic I

component. In mild hydrocracking processes such as catalytic dew axing and catalytic cracker feed hydra-cracking processes, preferred metals of the metallic component are combinations of nickel and molybdenum.
In addition to the above described catalytically active metal component, the active metallic component of the invented composition contains at least one oxygenated phosphorus component which ma be present in a variety of forms such as one or more simple oxides, phosphate anions, complex species in which phosphorus is linked through oxygen to one or more metal or metals of the active metallic component or compounds of such metal or metals, or combinations of these. The specific form of the oxygenated pros-chorus component is not presently known; accordingly, for purposes hereof, phosphorus contents are cowlick-fated and expressed in terms of Pros.
Content of the metal and phosphorus components of the active metallic component is not critical although phosphorus component preferably is present in at least an amount effective to promote hydrocarbon conversion activity of the metal or metals of the metallic component. In general, the metal or metals of the metallic component, calculated as oxide of the metal or metals in a common oxidation state, e.g., Cry, Moo, WOW, No, Coo make up about 3 to about 45 White of the total catalyst weight while phosphorus component, expressed as Pros, makes up about 0.1 to about 20 wt.% of the total catalyst.
Within these broad ranges, preferred levels of metal and phosphorus component will vary clependiny on end use. For example, catalysts useful in hydrogen processing of petroleum or synthetic crude oils, coal or Bahamas liquids, or fractions thereof prefer-by contain about 5 to about 35 wt.% Group VIM and/or VIII metal expressed as common metal oxide, and about 0.5 to about 15 wt.% oxygenated phosphorus component expressed as POW. Of course, higher and lower levels of metal Andre phosphorus component can be present; however, below about 5 White metal oxide, hydrogenation activity can suffer while above about 35 White, improvements in activity typically do not compensate for the cost of the additional metal. Similarly, below about 0.5 wt.% phosphorus component, calculated as Pros, promotional effect may be insignificant while above about 15 White, the phosphorus component may adversely affect hydrogen-lion activity or performance For high nitrogen feed stocks, the hydrogenating metal preferably makes up about 10 to 40 White of overall catalyst while phosphorus content as Pros makes up about 0.5 to about 15% of overall catalyst weight. For mild hydrocracking r hydrogenating metal preferably makes up about 5 to about 30 wt.% of overall catalyst weight while phosphorus content as Pros makes up about 0.1 to about 10 wt.% of overall catalyst weight.
The support component of the invented catalytic composition comprises a non-zeolitic, refractory inorganic oxide matrix component and at least one crystalline molecular sieve zealot component. Suit-able non-zeolitic, refractory inorganic oxide matrix components are well known to persons skilled in the art and include alumina, silica, silica-alumina, alumina silica, magnesia, zircon, titanic, etch, and combinations thereof. The matrix component also can contain adjutants such as phosphorus oxides, boron oxides, fluorine and/or chlorine. Matrix components that are preferred are those comprising alumina, owing to the availability and strength thereof. More preferably the matrix component is alumina, or a combination of alumina and silica.
The support component of the invented catalytic composition also comprises at least one crystalline molecular sieve zealot component. This component of the support component is derived from at least one acid-tolerant crystalline molecular sieve zealot.
For purposes hereof, an acid-tolerant crystalline molecular sieve zealot is defined as one that retains substantial crystallinity on exposure to phosphoric acid at pi down to about 3 to 4 and contains surf-ficiently low levels of cations capable of reacting with aqueous phosphoric acid to form insoluble metal phosphates capable of plugging the zealots pores as to avoid substantial plugging. Both naturally occurring and synthetic zealots are contemplated.
As with the metals of the metallic component of the invented catalysts, the specific zealot component to be included in a given catalyst will vary depending on intended use ox the catalytic composition.
Examples of acid tolerant, crystalline molecular sieve zealots include faujasite-type crystalline aluminosilicate zealots selected from the ultra stable Y-type crystalline aluminosilicate zealots in acid and ammonium forms/ AMS-type crystalline boron silicate zealots, ZSM~type crystalline aluminosili-gate zealots and mordenite-type crystalline alumina-silicate zealots.

I

The ultra stable crystalline aluminosilicate zealots typically are faujasite~type zealots that exhibit improved stability at elevated temperatures, such stability being imparted by exchanging original alkali metal cations with ammonium salt, calcining Jo convert the zealot to hydrogen form, steaming or calcining again, exchanging with ammonium salt once again and finally calcining. Specific examples of ultra stable Y type crystalline aluminosilicate lo zealots include zealot ZEUS, which it described in detail in U.S. 3,293,192 (Maker et at.) and U.S.

3,44~,070 (McDaniel et Allah Y-type crystalline aluminosilicate zealots in hydrogen or ammonium form also exhibit sufficient acid-tolerance as to be suitable for purposes of the present invention.
When used in preparation of catalysts, Y-type zealots in ammonium form are converted to acid form.
Crystalline borosilicate zealots of the AS-type are described in detail in commonly assigned U.S. 4,269,813 clout).
A specific example of this material is crystalline borosilicate zealot RMS-lB which corresponds to the formula:
owe 0.2 M2/nO:B2O3 ysio2 ZOO
wherein M is at least one cation having a valence of n, Y ranges from 4 to about 600 and Z ranges from 0 to about 160. AS lo provides an X-ray pattern that comprises the following X-ray diffraction lines and assigned strengths:

d (A) Assigned Strength 11.2 _ 0.2 WIVES
10~0 0.2 W-MS

30~2 0.05 US
3.70 0.05 MS
3.S2 0.05 M-MS
2.97 0.02 W-M
1.99 -I 0.02 VW-M

Crystalline aluminosilicate zealots of the ZSM-type are well known and typically contain silica and alumina in a molar ratio of at least 12-1 (Sue) and have average pore diameters of at least about 5 I. Specific examples ox crystalline aluminosilicate zealots of the ZSM type include crystalline aluminosilicate zealot ZSM-5, which is described in detail in U.S. 3l702,886; crystalline aluminosilicate ZSM-ll, which is described in detail in U.S. 3,709,979; crystalline aluminosilicate zealot ZSM-12, which is described in detail in U.S.
3,832,449; crystalline aluminosilicate elite ZSM-35, which is described in detail in U.S. 4,016,245;
and crystalline aluminosilicate zealot ZSM~38, which is described in detail in U.S. 4,046.859.

Mordenite-type crystalline aluminosilicate zealots also can be present in the catalytic combo-session of the present invention. Suitable mordant-type crystalline aluminosilicate zealots are disk closed in U.S. 3,247,098 (Timberline), U.S. 3,281,483 (Buoyancy et at.) and U.S. 3,299,153 (Adams et at.).

Synthetic mordenite-~tructure crystalline aluminosil-Jo irate zealots, such as whose designated Zillion and available from the Norton Company of Worcester, Massachusetts, also are contemplated according to the invention.
Synthetic crystalline molecular sieve zealots often are synthesized in alkali metal form, i.e., having alkali metal cations associated with framework species. For purposes of the present invention, the original form as well as various exchanged forms such as the hydrogen (acid), ammonium and metal-exchanged forms are suitable. Crystalline molecular sieve zealots can be converted to acid form by exchange with acids or by indirect means which typic gaily involve contacting with ammonium or amine salts to form ammonium-exchanged intermediate species which can be calcined to acid form. Metal exchanged zealots are well known as are methods for preparation thereof. Typically, zealot is contacted with a solution or solutions containing metal cations capable of associating with framework metallic species As noted hereinabove, crystalline molecular sieve zealot components present in the catalysts of the present invention contain only insubstantial levels of metals capable of reacting with aqueous phosphoric acid to form insoluble metal phosphates capable of plan the pores of the support component. Accordingly, preferred metal-exchanged crystalline molecular sieve zealots are those in which the exchanged metals are nickel, cobalt, iron or a Group VIII
noble metal. In catalysts intended for use in hydra-gun processing of petroleum or synthetic crude oils, coal or Bahamas liquids, or fractions thereof, pro-furred crystalline molecular sieve zealot combo-newts of thy invented catalysts are those in acid or polyvalent metal ion exchanged form, and especially the former.

* Trade mark.

Content of non-zeolitic, porous refractory inorganic acid matrix component and crystalline molecular sieve zealot component in the support component of the invented composition are not critical. Broadly, the matrix component constitutes about 5 to about 95 White of the support, and likewise, the zealot component can constitute about 5 to about 95 White of the support. Preferably, the content of the non~zeolitic matrix component is at least about 10 wit% in order to ensure that the support component will exhibit sufficient strength and pry-steal integrity to allow shaping of the component or final catalyst into a form suitable for intended use. Of course, even at less than about 10 White matrix component, suitable catalytic performance can be attained in applications amenable to use of catalyst in finely divided form.
In terms of overall catalyst weight of the invented catalytic composition, preferred matrix content ranges from about 10 to about 90 wit% and preferred zealot content ranges from about 5 to about 90 wit%. Within these ranges, precise levels of matrix and zealot components that are more pro-furred for a given catalyst will vary depending on intended use. For use in mild hydrocracking, the matrix component content preferably ranges from 40 to about 95 wt.% of the support while zealot content ranges from about 5 to about 60 White of the support component.
The support component of the invented catalytic composition can be prepared by any suitable method.
A preferred method comprises blending acid-tolerant zeolitic component, preferably in finely divided form, into a sol, hydrosol or hydrogen of at least one inorganic oxide and adding a golfing medium such as ammonium hydroxide with stirring to produce -23~
a gel. It also is contemplated to add the zealot component to a slurry of the matrix component, In either case, the result can be dried, shaped I
desired, and then calcined to firelight the support come pennant Suitable drying temperatures Lange frornabout 80 to about 350F (about 27 to about 177C) and suitable drying times range from seconds to several hours. Calcination preferably is conducted at a temperature of about 800 to about 1,200F (about lo 427 to about ~49C) for about l/2 to about 16 hours.
Shaping of the support component can be conducted if desired, preferably after drying or calcining.
Another suitable method for preparing the support component of the invented composition comprises physically mixing particles of the matrix and zealot components, each preferably in finely divided form, followed by thorough blending of the mixture.
The invented catalytic composition is prepared by a method comprising (l) impregnating the above-described support component with precursors to the active metallic component under conditions effective to retain substantial elite crystallinity; and (2) calcining the result.
Impregnation of support component with precursors to the active metallic component can be conducted in a single step or in a series of separate steps which may be separated by drying and/or calcination steps, provided that impregnation with at least one metal precursor takes place prior to or simultaneously with impregnation with phosphorus component precursor.
If the active metallic component contains more than one metal, precursors can be impregnated simultan-easily, in sequence or by various combinations of simultaneous and sequential impregnations. Phosphorus component precursor or precursors can be included with one or more of the metal precursors, or one or more separate phosphorus component precursor impreg-nation steps can be included between or after the metal precursor impregnation steps It also it contemplated to impregnate either the porous refract tory inorganic oxide matrix component or the zeoliticcomponent with precursors to the active metallic component and blend the result with the other combo-next.
The mechanics of impregnating a support with metallic component precursors are well known to persons skilled in the art and typically involve contacting a support with one or more solutions of one or more precursors in amounts and under conditions effective to yield a final composition containing the desired amount of metal or metals. Suitable solvents for the impregnating solution or solutions include water and various low boiling alcohols in which the precursors are soluble. Water is preferred over alcohols from the standpoint of cost. In the case of simultaneous impregnations of metal and phosphorus component precursors a more preferred solvent is aqueous phosphoric acid.
Metal precursors useful in preparation of the invented catalytic compositions are well known to persons skilled in the art and include a wide range of salts and compounds of the metals that are soluble in the impregnating solvent and convertible to the desired form on calcination. Examples of useful salts include organic acid salts such as acetates, formats and preappoints; nitrates; androids;
sulfates; and ammonium salts.
Useful precursors to the oxygenated phosphorus component en materials capable of reaction with the metal or metals of the metallic component or compounds of such metal or metals, or precursors thereto, so as to incorporate into the metallic component or metallic component precursor a phosphorus containing species what can be converted to an oxygenated phosphorus component. From the standpoint of maximizing the promotional effect of the oxygenated phosphorus component, the preferred phosphorus come potent precursor is one containing or capable of liberating phosphate anions as these are sufficiently reactive with the metal or metal precursors to yield the desired promotional effect. Specific examples of such phosphorus anion sources include phosphoric acid and salts thereof such as ammonium dihydrogen phosphate and diammonium hydrogen phosphate. Other phosphorus component precursors contemplated according to the invention, though less preferred from the standpoint ox attaining maximum promotional effect, include organophosphorus compounds such as partial and full esters of the aforesaid oxyacids such as organophosphates and organophosphites; other organ-phosphorus compounds such as phosphines, and other phosphoric oxyacids such as phosphorus and phosphinic acids.
Impregnation of the support component with pro-cursors to the metallic component is conducted under conditions effective to avoid substantial destruction of crystallinity of the crystalline molecular sieve zealot component. Preferably, such conditions include a temperature that is high enough to maintain the metal and/or phosphorus come potent precursors in solution in the impregnating solvent though not so high as to decompose sup h precursors or have substantial adverse effects on the support component. More preferably, impregnating temperatures range from about 40 to about 200F.
pi of the impregnating solution or solutions to be used also is important from the standpoint of insuring retention of substantial zealot crystallinity when I
phosphoric acid or other phosphate anion source is employed as a phosphorus component precursor and/or impregnating solvent. In such cases, pi preferably is sufficiently high that only insubstantial destruct lion of zealot crystallinity takes place during the preparation. Of course, the precise pi at which substantial decomposition of crystallinity will occur will vary somewhat depending upon the choice of zealot component. In general, however, pi should be above about 2 in order to insure retention of sufficient zealot crystallinity to insure desirable catalytic performance. Most preferably, pal ranges from about 2.5 to about 6 in order to insure retention of a high degree of zealot crystallinity while also insuring the desired association of the pros-chorus and metal components of the active metallic component.
Following impregnation of the support component with metallic component precursors, it is preferred to dry the impregnated support. It also is contem-plated to dry the support subsequent to any interim-dilate impregnating steps in a multi step impregnation.
Preferred drying temperatures range from about I
to about 350F (about 27 to about 177C), with pro-furred drying times ranging from a few seconds inspire drying operations to several hours in convent tonal driers.
Following impregnation of the support with precursors to the metallic component and any optional drying steps, the impregnated support is subjected to calcination in order to convert at least a portion of the metal or metals of the metallic component to the active form and to convert phosphorus precursors to oxygenated phosphorus component. Calcination is conducted in an atmosphere containing molecular oxygen at a temperature and for a period of time effective to attain the desired conversion. Prefer ably, calcination temperatures range from about 800 to about 1,200F (about 427 to about 649C). Pro-furred calcination times range from about 1/2 to about 16 hours.
As a result of the above-described preparation, there is attained a catalytic composition comprising (l) a metallic component comprising at least one metal having hydrocarbon conversion activity and at lo least one oxygenated phosphorus component, and I
a support component comprising at least one Nan zeolitic, refractory inorganic oxide matrix component and at least one crystalline molecular sieve zealot component. Preferred compositions are those in which the zealot component exhibits at least about 40% crystallinity as compared to compositions identi-eel but for inclusion of phosphorus component More preferably, such relative crystallinity is at least about 75% in order to ensure desirable catalyst performance.
The compositions of this invention have utility in a wide range of hydrocarbon conversion processes in which a charge stock comprising hydrocarbon is contacted with the catalyst under hydrocarbon convert soon conditions. The invented catalysts are paretic-ularly useful in processes for hydrogen processing of hydrocarbon feed materials such as whole petroleum or synthetic crude oils, coal or Bahamas liquids, and fractions thereof. The process of the invention is described in further detail with reference to hydrogen processing of such feed materials.
Petroleum and synthetic crude oil feeds that can be hydrogen processed according to this aspect of the invention include whole petroleum, shale and tar sands oils, coal and Bahamas liquids and fractions thereof such as distillates, gas oils and residuals fractions.
Such feed materials are contacted with the catalyst of the invention under hydrogen processing conditions which will vary depending upon the specific feed to be processed as well as the type of processing desired. Broadly, hydrogen treating temperatures range from about 350 to about 850F (about 177 to about 455C), hydrogen pressures range from about 100 to about 3,000 prig (about 7 to about 210 kg/m2) and feed linear hourly space velocities range from about 0.1 to about 10 volumes of feed per volume of catalyst per hour. hydrogen addition rate generally ranges from about 200 to about 25,000 standard cubic feet per barrel (SCAB).
Hydrocarbon feed materials treated under mild hydrocracking conditions are whole petroleum or synthetic crude oils, coal or Bahamas liquids, or fractions thereof. Substantial levels of impurities such as nitrogen, sulfur, oxygen and/or waxy combo-newts may be present in the feeds. Typical feeds contain up to about 1.5 wt.% nitrogen and/or oxygen, up to about 12 wit% sulfur and/or sufficient waxy components, e.g., n-paraffins and isoparaffins, to exhibit pour points of at least about 30F. Specific examples of useful feeds include heavy and light vacuum gas oils, atmospheric and vacuum distillates and disaffiliated and hydrotrPated residual fractions.
Mild hydrocracking conditions vary somewhat depending on the choice of feed as well as the type of processing to be conducted. Dew axing mild hydra cracking conditions are employed when it is desired to reduce n paraffin and isoparaffin content of the feed without substantial cracking of desirable art-mattes, naphthenes and branched paraffins. Dewaxingmild hydrocracking conditions preferably include a temperature of about 650 to about 800F, hydrogen pressure of about B00 to about 2500 psi, linear hourly space velocity (LHSV) of about 0.2 to about 5 and hydrogen addition rate of about 1000 to aback 20,000 standard cubic feet per barrel (SCAB).
The catalytic dew axing mild hydrocracking process can be included as part of a multi step process for preparation of lube oils wherein catalytic dew axing is conducted in combination with other conventional processing steps such as solvent extraction, solvent dew axing, hydrocracking or hydrotreating to obtain lube oil base stocks of relatively low pour point and high viscosity index and stability According to a preferred aspect of the invention, however, there is provided an improved process for preparation of lube oil base stocks of high viscosity index low pour point and sufficiently low sulfur and/or nitrogen content to exhibit good stability consisting essentially of catalytically dew axing a feed, and preferably a petroleum or synthetic crude oil distillate fraction having a pour point of about 50 to about 150F and containing up to about 5 White sulfur, 0.5 wt.% oxygen and/or 0.5 White nitrogen in the presence of the aforesaid catalyst. Conditions according to this aspect of the invention typically are somewhat more severe than those in catalytic dew axing operations conducted as part of a multi step process. Preferred conditions according to this aspect of the invention include temperature ranging from about 700 to about 800F, hydrogen pressure of about 1200 to about 2000 psi, LHSV of about 0.2 to about 2 reciprocal hours and hydrogen addition rate of about 2000 to about 10,000 SCAB. A preferred catalyst according to this aspect of the invention is one in which the shape selective zeolitic cracking component is a crystalline borosilicate component of the AMS-lB type in hydrogen form, and the hydra-yenating metal of the active metallic component comprises a molybdenum component and a nickel come potent.
Catalytic cracking feed mild hydra racking conditions are employed when it is desired to remove nitrogen and/or sulfur from the feed as well as crack hydrocarbon components thereof to lower boiling components. Such conditions include temperatures ranging from about 650 to about 760~F, hydrogen pressures ranging from about 500 to about 2000 psi, LHSV ranging from about 0.2 to about 4 reciprocal hours and hydrogen addition rates ranging from about 1000 to about 20,000 SCAB. Preferred catalytic cracking feed mild hydrocracking conditions include a temperature ranging from about 690 to about 740F, hydrogen pressure of about 800 to about 1600 psi, LHSV of about 0.5 to about 1 reciprocal hour and hydrogen addition rate of about 1000 to about 15,000 SCAB.
The process can be conducted in either fixed or expanded bed operations using a single reactor or series thereof as desired.
Catalysts that are preferred for use in the mild hydrocracking process of the present invention are those in which the active metallic component comprises at least one metal of Group VIM or VIII, the non-zeolitic matrix component comprises alumina or silica-alumina and the shape selective crystalline molecular sieve elite component comprises a crystal-line aluminosilicate zealot of the ZSM-type or a crystalline borosilicate zealot of the Mistype as these exhibit high activity for hydrogenation and cracking. More preferably, the hydrogenation metal of the active metallic component is nickel, cobalt, chromium, molybdenum or tungsten or a comb-nation thereof and is present in an amount ranging from about 10 to about 30 wit% calculated as metal oxide and based on total catalyst weight Preferred support compositions contain about 60 to about 90 wit% alumina or silica-alwnina having dispersed therein about 1.0 to about 40 wit% shape selective crystalline molecular ivy zealot.
Most preferably, the hydrogenating metal of the active metallic component of the catalyst employed comprises a combination of nickel and molybdenum.
Best results in terms of mild hydrocracking are attained using catalysts contain about 1 to about 7 wit% No, about 10 to about 20 wit% Moo, about 0.1 to about 5 White oxygenated phosphorus component, calculated as POW, and a support comprising about 65 to about 85 wit% alumina having dispersed therein about 15 to about 35 White crystalline borosilicate zealot of the AMS-type, especially HAMS-lB.
hydrocarbon feed materials treated under hydra-cracking conditions are gas oil boiling range hydra-carbons derived from petroleum or synthetic crude oils, coal liquids or Bahamas liquids. Preferred feeds are those boiling from about 400 to about 1000F and containing up to about 0.1 White nitrogen and/or up to about 2 White sulfur. Specific examples of preferred gas oil boiling range feeds include petroleum and synthetic crude oil distillates such as catalytic cycle oils, virgin gas oil boiling range hydrocarbons and mixtures thereof.
Hydrocracking conditions vary somewhat depending on the choice of feed and severity of hydrocracking desired. Broadly, conditions include temperatures ranging from about 650 to about 850F, total pressures ranging from about 1000 to about 3000 psi, hydrogen partial pressures ranging from about 300 to about 2500 psi, linear hourly space velocities (LHSV) ranging from about 0.2 to about 10 reciprocal hours and hydrogen recycle rates ranging from about 5,000 to about 20,000 standard cubic feet per barrel of feed (SKIFF). Hydrogen consumption broadly ranges from about 500 to about 3000 SCAB under such condo-lions. Preferred conditions in hydrocracking of catalytic cycle oils, virgin gas oils, and kimono-lions thereof to gasoline boiling range products include a temperature ranging from about 675 to about 775F, total pressure of about 1500 to about 2500 psi, hydrogen partial pressure of about 1000 to about 1500 psi, space velocity of about 0.5 to about 4 reciprocal hours and hydrogen recycle rate of about 10,000 to about 15,000 SAAB, with hydrogen consumption ranging from about 1000 to about 2000 SCAB.
The process can be conducted in either fixed or expanded bed operations using a single reactor or series thereof as desired.
Catalysts that are preferred for use in the hydrocracking process of the present invention are those in which the active metallic component comprises at least one metal of Group VIM or VIII, the non-zeolitic matrix component comprises alumina, orsilica-alumina and the crystalline molecular sieve zealot component comprises a low sodium, ultra stable Y-type crystalline aluminosilicate zealot, as these exhibit high activity for hydrogenation and cracking over prolonged periods of time. More preferably, the hydrogenation metal of the active metallic come potent is nickel, cobalt, chromium, molybdenum or tungsten or a combination thereof and is present in an amount ranging from about 8 to about 25 wit%, calculated as metal oxide and based on total catalyst weight. Preferred support compositions contain about 40 to about 80 wit% alumina or silica-alumina having dispersed therein about 20 to about 60 wit%
low sodium, ultra stable Y-type crystalline alumina-silicate zealot.
Most preferably, the hydrogenating metal of the active metallic component of the catalyst employed comprises a combination of cobalt and molybdenum, nickel and molybdenum or nickel and tungsten, jest results are attained using catalysts containing about 0.5 to about 6 White oxygenated phosphorus component, calculated as Pros and a hydrogenatlny component containing about l to about 4 wit%, Coo or No and about 3 to about 15 wit% Moo; or about l to about 4 wit% No and about 15 to about 25 wit% WOW;
and a support comprising about 50 to about 70 White alumina or silica-alumina having dispersed therein about 30 to about 50 wit% low sodium ultra stable Y type crystalline aluminosilicate zealot component, such weight percentages of hydrogenating metal oxides being based on total catalyst weight, and such matrix and zealot weight percentages being based on support weight.
Hydrocarbon feeds treated under denitrogenation, hydrotreating or hydrocracking conditions are those containing substantial levels of nitrogen compounds.
Preferred feeds are those containing at least about 0.4 White nitrogen. Specific examples of preferred high nitrogen feeds include whole shale oils and fractions thereof such as shale oil resins, vacuum and atmospheric distillates and naphtha fractions.
Whole petroleum crude oils, tar sands oils, coal and Bahamas liquids suitably high in nitrogen, as well as various fractions thereof, also are par-titularly well suited for use.
Denitrogenation conditions vary somewhat depend-in on the choice of feed as well as the type of processing to be conducted. Denitrogenation hydra-treating conditions are employed when it is desired to reduce nitrogen content of the feed without sub-staunchly cracking thereof and include a temperature of about 650 to about 760F, hydrogen pressure of about 1000 to about 2500 psi, linear hourly space velocity (LHSV) of about 0.2 to about 4 volumes of feed per volume of catalyst per hour (Herr) and hydrogen addition rate of about 2U00 to about 20,000 standard cubic feet per barrel (SKIFF). Preferred denitrogenation hydrotreatiny conditions include a temperature ranging from about 6B0 to about 750F, hydrogen pressure of about 1400 to about 2200 psi, LO of about 0~3 to about 3 and hydrogen rate of about 4000 to about 10,000 SCAB as these result in desirable reductions in product nitrogen while avoid-in exposure of the catalyst to conditions so severe as to adversely affect catalyst lifetime.
Denitrogenation hydrocracking conditions are employed when it is desired to remove nitrogen from the feed as well as crack higher boiling Components thereof to lower boiling components. Denitrogenation hydrocracking temperature ranges from about 720 to about 8~0~F, hydrogen pressure ranges from about 1000 to about 2500 psi, LHSV ranges from about 0.2 to about 3 and hydrogen addition rate ranges from about 4,000 to about 20,000 SCAB. A particularly preferred application in which denitrogenation hydra-cracking conditions are employed is in conversion of whole shale oils or fractions thereof to jet fuel. Preferred conditions for such an application include a temperature ranging from about 750 to about 82QF, hydrogen pressure of about 1200 to about 2200 psi, LHSV of about 0.3 to about 1 and hydrogen addition rate of about 5000 to about 10,000 SCAB.
The process can be conducted in either fixed or expanded bed operations using a single reactor or series thereof as desired.
Catalysts that are preferred for use in the denitrogenation hydrotreating or hydrocracking process are those in which the hydrogenating metal of the active metallic component is nickel, cobalt, chromium, molybdenum, tungsten or a combination thereof, the non-zeolitic matrix component comprises alumina or silica-alumina and the crystalline molecular sieve zealot component comprises an ultra stable I-type crystalline aluminosilicate zealot, a crystal line aluminosilicate zealot ox the ZSM-type or a crystalline borosilicake zealot of the Mistype as these exhibit high activity for denitrogenation hydrotreating and hydrocracking. More preferably, the hydrogenation metals of the active metallic component comprise a combination of nickel and Malibu-denim or a combination of cobalt or nickel, chromium and molybdenum and are present in an amount ranging from about 10 to about 30 White calculated as metal oxide and based on total catalyst weight, and the support component contains about 40 to about 80 wit%
alumina or silica-alumina having dispersed therein about 20 to about 60 White crystalline molecular sieve zealot component, such weight percentages being based on support weight.
Most preferably, the catalyst employed in the denitrogenation process contains about 1 to about 5 wit% No and about 12 to about 20 wit% Moo; or about 1 to about 5 White Coo or No, about 2 to about 10 wit% Cry and about 12 to about 20 White Moo; and about 0.5 to about 8 White oxygenated phosphorus come potent, expressed as Pros; and a support containing a dispersion of about 30 to about 60 wit% ultra stable Y-type crystalline aluminosilicate zealot, AS-type crystalline borosilicate zealot or ZSM-type crystalline aluminosilicate zealot in about 40 to about 70 wit% alumina or silica alumina Ultra stable Y-type crystalline aluminosilicate zealots give best results in denitrogenation hydrocracking applique-anions.

The present invention is described in further detail in the hollowing examples, it being understood that the same are for purposes of illustration and not limitation.

A support component containing 30 wt.% ultra stable Y-type crystalline aluminosilicate zealot obtained from the Davison Chemical Division of W. R. Grace and Co. dispersed in 70 wt.% alumina was prepared by mixing 15,890 g alumina sol Lowe wt.% alumina dry weight) with 681 g ultra stable Taipei zealot.
To the result was added a solution of 400 ml water and 400 ml concentrated N~40H while stirring rapidly to form a gel. The resulting gel was dried overnight at 250F in air, ground to lo mesh, mulled with water, extruded to 5/64" particles, dried overnight at 250F in air and calcined at 1000 in air for three hours.
A solution prepared by dissolving 8.30 g (N~4)2Cr2O7 in 49 ml water was added to 72.77 9 of support component and allowed to stand for 1 hour after which the result was dried in air at 250F
for l hour.
Subsequently, 18.40 g (NH4)6Mo70~4 OWE, 5.85 9 Cowan 6H20 and 8.6 g 85% phosphoric acid (H3PO4) were dissolved in 35 ml water to form an impregnating solution having a pi of about 3. The impregnating solution was added to the chromia-impregnated support and the mixture was allowed to stand for l hour after which the result was dried in air at 250F
for l hour and calcined in air at 1000F for l hour.
The resulting catalyst contained 5.0 wit% Cry, 15.0 White% Molly 1.5 wt.% Coo and 5.5 wt.% oxygenated phosphorus component, calculated as PRO.

A support component containing 50 White ultra-stable Y-type crystalline aluminosilicate zealot Davison) dispersed in 50 wt.% alumina was prepared substantially according is the procedure of Example 1 using 3863 g alumina sol (10 White alumina) and 386.5 9 ultra stable Y-type zealot.
solution prepared by dissolving 16.6 g (NH~)2Cr~O7 in 90 ml water was added to 148.98 y of the support component and allowed to stand for 1 hour. The result was dried in air at 250F for 1 hour and calcined in air at 1000F for 1 hour.
Subsequently, 36.8 g (NH4)Mo7O~4 4H20, 11.70 g Cowan and 13.02 g 85~ H3PO4 were dissolved in 67 ml water to form an impregnating solution having a pi of about 3. This solution was added to the Crimea impregnated support and the result was allowed to stand for 1 hour after which the result was dried in air at 250F for 1 hour and calcined in air at 1000F for 1 hour.
The resulting catalyst contained 5.0 White% Cry, 15.0 wt.% Moo, 1.5 wt.% Coo and 4.0 wt.% oxygenated phosphorus component, calculated as P25.

An impregnating solution having a pi of about 5.0 was prepared by dissolving 34.80 g cobalt nitrate, 42.45 9 ammonium molybdate and 16.63 g phosphoric acid in 600 ml distilled water r after which total volume of the solution was brought to 660 ml with distilled water. The impregnating solution was added to 331 g of a premixed support component con-twining 41 wt.% ultra stable Y-type crystalline alum-no silicate zealot and 59 wt.% silica-alumina and stirred vigorously for a short time The result was dried in air at 250F for several hours, ground to pass a 28 mesh screen, formed into 1/8" pellets and calcined in air for 1 hour at FOE for 1 hour at 750F and for 5 hours at 1000F.

The resulting catalyst contained 9.13 White%
Moo, 2.36 wt.% Coo and 2.3 wt.% phosphorus component, calculated as Pros.

A support component containing 35 wt.% ultra stable Y-type crystalline aluminosilicate zealot Davison) dispersed in 65 wit,% silica alumina con-twining 71.7 wt.% silica was prepared in two batches by blending 4160 g of silica-alumina slurry containing about 2.5 wt.% solid with 54.4 g of the elite component for about 5 to 10 minutes and then filter-in, drying the solid in air at 250F overnight, grinding the dried solid to pass through a 3Q-mesh screen and calcining in air at 1000F for 3 hours.
lo An impregnating solution was prepared by disk solving 35.4 9 cobalt nitrate, 41~6 g ammonium Malibu-date and 4.6 y phosphoric acid in 472 ml distilled water, 290 g of the support component were contacted with the impregnating solution after which the result was dried in air at 250F overnight, ground to 28 mesh, formed into 1/8" pills and calcined in air at 500F for 1 hour, at 700F for 1 hour and at EYE
for 5 hours.
The resulting catalyst contained 2.6 wt.% Coo 9.6 wt.% Moo and 0.6 White oxygenated phosphorus component, calculated as Pus 147.84 g support component containing 20 wt.%
Mistype crystalline borosilicate zealot dispersed in 80 wt.% alumina was impregnated with a solution prepared by dissolving 22.09 9 (NH4)2Mo7O2~ OWE
and 13.63 g Nina in 68 ml distilled water and adding drops 7~44 g 85% H3PO~ thereto while stirring. A small amount of water was added to the impregnation mixture and the result was allowed to stand for 1 hour. The result was dried in air at 250F overnight, and then impregnated with 22.09 g (NH4)2Mo7O24.4H2O, 13.63 g Nina, and 7.44 9 85~ H3PO~ in 68 ml distilled water. The result was allowed to stand for 2 hours, dried in air at 250F
and calcined at 1000F.
The resulting catalyst contained 17.70 White%
Moo, 3.44 wt.% No and 4.35 White oxygenated pros-chorus component, calculated as Pros, and had a surface area of 242 mug and pore volume of 004802 cc/g.

The catalysts prepared in Examples 1 and 2 were tested for denitrogenation and hydrocracking activity in an automated processing unit that included a vertical, tubular downfall reactor having a length of 32" and inner diameter of 1/4". The unit included automatic controls to regulate hydrogen pressure and flow, temperature and feed rate. Catalyst was ground to 14-20 mesh and loaded into a 10-12" segment of the reactor and sulfide therein by passing, 8 vowel HIS in hydrogen over the catalyst at 300 psi for 1 hour at 300F followed by 1 hour at 400F and then 1 hour at 700F. The reactor then was heated to operating temperature, pressured with hydrogen and a high nitrogen feed generated in situ from oil shale was pumped into the reactor using a Rusks pump. The feed had the following properties:
APT Gravity I 23.8 Nitrogen (wt.%) 1.27 Sulfur (wt.%) 0.65 Oxygen (wt.%) 1.40 Pour Point (OF) 60 Simulated Distillation (~) IBP--360F 2.0 360--650~' 42.5 650F~ 55.5 operating conditions and results for each run are shown in Table I. In addition to runs with the I

catalysts from Examples 1 and 2, comparative runs were conducted using comparative catalysts A-C which were prepared according to the general procedure of Examples 1 and 2 but without the use of phosphoric acid in the case of A and B and without a zealot component in the case of C. Compositions of catalysts A-C were as hollows:
A) :L0.0 White Cry, 15.0 wt.% Moo and 1.5 wt.% Coo supported on a dispersion of 30 White ultra-stable Y-type crystalline aluminosilicate elite (Davison) in 70 White alumina;
B) 10.0 wit n Cry, 15.0 wt.% Moo and 1.5 wt.% Coo supported on a dispersion of 50 White ultra-stable Y-type crystalline aluminosilicate zealot dispersed in 50 wt.% alumina;
C) 5.0 White Cry, 15.0 wt.% Moo, 1.5 wt.%
Coo and 4.6 wt.% oxygenated phosphorus component, calculated as Pros, supported on alumina.

Catalyst 1 A 2 B C
Tempt (OF) 760 760 780 780 760 Pressure tPsi~ 1800 1800 18001300 1800 LHSV (Harley 0.5 0.5 0.50.5 0.5 Days on Oil 6 9 7 6 6 Liquid Product (9)184 239 124190 198 APT gravity I 40.0 36.5 49.449.6 37.0 Pour Point (OF) 70 80 40 15 75 Sulfur (ppm) 2 110 6 26~ 57 Nitrogen (ppm) 1.7 173 0.7 3 85 Simulated Distillation (~) IMP -350F 14.5 lQ.7 44.5 42.0 9.0 350--~5~ 60.0 54.3 53.~520~ 55.0 650F+ 2505 35.0 2.55.4 36.0 As can be seen from the table, catalysts 1 and 2 according to the invention exhibited superior denitrogenation and desulfurization activity as I

compared to all three comparative catalysts. Further, cracking activities of catalysts 1 and 2 were superior to those of comparative catalyst A and B, respective-lye as evidenced by the simulated distillation data showing reduced 650F~ content. Cracking activities of 1 and 2 also were superior to that of catalyst C
which lacked a zealot component.

The catalysts prepared in Examples 3 and 4 were -tested for hydrocracking activity in a vertical, tubular, downfall reactor having a length of 19-1/2"
and inner diameter of 0.55" and equipped with a pressure gauge and DO cell to control hydrogen flow and a high pressure separator for removal of products.
The reactor was loaded with 18.75 g catalyst, immersed in a molten salt-containing heating jacket at 500F
and pressured to 1250 pi with hydrogen. Temperature was held at 500F for two hours and then feed was pumped to the reactor with a Milton Roy pump.
Temperature was slowly increased to 680F, held there overnight and then raised to operating tempera-lure of 710-730F. Feed rate (LHSV) was 1-2 hurl Runs were conducted for two weeks with periodic sampling.
The feed used in all runs was a mixture of 70 White light catalytic cycle oil and 30 White% light virgin gas oil having the following properties:
APT Gravity to) 25.3 Nitrogen (ppm) 304 Sulfur two.%) 1.31 Initial Boiling Point tF~ 404 Final Boiling Point (OF) 673 In addition to the runs conducted using the catalysts of Examples 3 and 4, comparative runs were conducted using comparative catalysts A C which are described below:

A) 2.5 wt.% Coo and 10.2 wt.% Moo supporter on a dispersion of 35 White ultra stable Y-type crystal-line aluminosilicate zealot in 65 White alumina prepared substantially according to the procedure of Example 3;
B) commercial hydrocracking catalyst containing 2.63 wt.% Coo and 10.5 wt.% Moo supported on the base used in Example 3 obtained from the Davison Chemical Division of W. R. Grace and Co.;
C) 2.6 wt.% Coo and 10.0 wt.% Moo supported on a dispersion of 35 wt.% ultra stable Y-type crystal-line aluminosilicate zealot (Davison) in 65 White alumina and prepared substantially according to the procedure of Example 4.
~ydrocracking activities of the catalysts were determined on the basis of temperature required to convert 77 wt.% of the feed to gasoline boiling range products (up to 380F). Activities relative to comparative catalyst C are reported in Table 2.

CATALYST RELATIVE ACTIVITY INCREASE ( % ) 3 14ds 44

4 138 I
As can be seen from the table, the phosphorus-promoted, ~eolite-containing catalysts of the invent lion exhibited significantly improved hydrocracking 0 activity as compared to the comparative catalysts.

Activity of the catalyst of Example 5 for mild hydrocracking was tested in an automated pilot plant consisting of a downfall, vertical pipe reactor of about 30" length and 3/8" inner diameter equipped with four independently wired and controlled heaters, a pressure step down and metering device for introduce lion of hydrogen and an outlet pressure control loop to control withdrawal of hydrogen. The catalyst of Example 5 was calcined in air at luff for about 2 hours and then screened to 14-20 mesh. The reactor was loaded to a height of twelve inches with glass balls after which about ten inches were loaded with 16 cm3 of catalyst. lass balls were added to fill the reactor.
The reactor was heated 300F and a gaseous mixture of 8 volt HIS in hydrogen was passed over the catalyst at 200 psi and 0~8 ft3/hr. After an hour, temperature was raised to 400F, and after another hour, to 700F. After one hour at 700F, flow of the gaseous mixture was discontinued and a hydrogen flow of 12,000 SCAB at 1200 psi was begun.
Heavy vacuum gas oil was pumped to the reactor at 10.2 cc/hr using a positive displacement pump. After passage through the reactor, product exited the reactor through a high pressure gas-liquid separator via a valve with a control loop designed to maintain a constant liquid level in the high pressure swooper-ion. Feed properties were as follows:

APT Gravity I 18.6 Pour Point (OF) 110 Viscosity (cyst at 100~C) 11.~8 Carbon (wt.%) 84.94 Hydrogen (White 11.63 Nitrogen (White) 0.166 Sulfur (wt.%) 2.98 Simulated Distillation I
IMP

10% 727 20% 788 40% 863 80% 977 90~ 1000 -I
Paraffins (wt.%) 19.7 Naphthenes (wt.%) 34.7 Monoaromatics (White) 12.6 Polyaromatics and 33.0 Heterocyclics (White) In addition to the catalyst from Example 5, a comparative catalyst (A) containing 3.5 wt.% Nil 10 wt.% Cry and 15 wt.% Moo supported on a dispel-soon of I woo% rare earth-exchanged ultra stable Y-type zealot in 80 White alumina was tested. Another run was conducted using a catalyst (B) containing 20 wt.% Moe 3.5 wt.% No and 3.0 White oxygenated phosphorus component, calculated as Pros, supported on alumina Operating conditions and results are shown in Table 3.

RUN NO SAMPLE NO. 1/1 1/2 1/3 TEMPT (OF) 700 740 740 PRESSURE (psi) 1200 1200 1200 LHSV (Harley) 0.625 0.625 0.625 HYDROGEN (SCAB) 12000 12000 12000 HOURS ON OIL. 136 352 496 APT GRAVITY I 28.0 33.6 32.9 POUR POINT (OF) 80 -70 ~60 VISCOSITY (cyst it 100C) 4.71 2.51 2.55 CARBON (wt.%) 87~00 86.90 87.05 HYDROGEN (White) 12.93 13.09 12.94 SULFUR (ppm) 633 137 86 NITROGEN (ppm) 135 8.8 14 SIMULATED DISTILLATION

5% 329 165 168 I 631 ~27 448 50% 797 696 707 80% 907 860 863 95% g90 967 961 % DESULFURIZATION 97.9 99.5 99.7 % DENITROGE~ATION 91.9 99.5 99.2 HYDROGEN CONSUMED (SCAB) 795 1045 940 YIELD (wt.%) IBP-360F 5.5 14.8 13.6 360-650F 17.9 25.7 24.7 650F+ 75.4 53.9 55.3 ';~

ABLE 3 (Continued) RUN NO SAMPLE NO. 1/4 1/5 1/6 _ TEMPT (OF) 690 730 730 PRESSURE (psi) 1200 1200 800 LHSV (Harley) 0.625 0.625 0.625 HYDROGEN (SCAB) 12000 12000 12000 APT GRAVITY I 26.6 30.3 28.2 POUR POINT (OF) 95 30 55 VISCOSITY (cyst at 100C) 6.07 3.88 3.89 CARBON (wt.%) 87.09 87~02 87~26 HYDROGEN to 12.80 OWE 12.66 SULFUR (ppm) 660 88 368 NITROGEN (ppm) 409 29 338 SIMULATED DISTILLATION
IMP 409 ND* ND
5% 584 ND ND
20~ 716 ND ND
50% 830 ND ND
80% 928 ND ND
95% 999 ND ND
DESULFURIZATION 97.7 99.7 98.7 % DENITROGENATION 60.2 98~2 79.6 HYDROGEN CONSUMED (SCAB) 700 930 635 YIELD (White) 360-650F 10.4 ND ND
650F+ 88.9 ND ND
*ND stands for not determined.

TABLE 3 (Continued) RUN NO SAMPLE NO. 2/1 2/2 2/3 ___ _ CATALYST B B e TEMPT (OF) 740 780 780 PRESSURE (psi) 1200 1200 1200 LM~V (Harley) 0.68 0.68 0.68 HYDROGEN (SCAB) 12000 12000 12000 HOW'S ON OIL 128 320 488 APT GRAVITY I ND* 32.5 33.2 POUR POINT (OF) 100 100 90 VISCOSITY (cyst at 100C~ND 2.10 2.30 CARBON two.%) 86.78 86.97 87.06 HYDROGEN White) 13.19 13.02 12.93 SULFUR (ppm) 240 70 16 NITROGEN (ppm) 22 3 SIMULATED DISTILLATION

5% 343 244 267 20% 572 440 462 50% 769 656 67~
80~ 869 827 841 95% 985 931 941 % DESULFURIZATION 99.2 99.8 99.9 % DENITROGENATION 98.7 99.8 99.9 HYDROGEN CONSUMED (SCFB)990 940 870 YIELD (wt.%) IBP-360F 5.6 12.0 11.4 360-659F 22.9 37.2 34.3 650F+ 70.1 48.0 51.6 *ND stands for not determined.

I

TABLE 3 (Continued) RUN NO SAMPLE NO. 3/1 3/2 _ _ CATALYST A A
TEMPT (OF) 740 780 PRESSURE (psi) 1200 1200 LHSV (Harley) 0.625 0.625 HYDROGEN (SCAB) 12000 12000 APT GRAVITY I 29.7 30.3 POUR POINT (OF) 105 100 VISCOSITY (cyst at 100C)3.84 2.98 CARBON (wt.%) 87.01 87.16 HYDROGEN (wt.%) 12.97 12.82 SULFUR (ppm) 102 79 NITROGEN (ppm) 76 137 SIMULATED DISTILLATION

5% 36~ 322 20% 606 558 80~ 905 882 95~ 990 969 DESULFURIZATION 99.7 99.1 DENITROGENATION 95.3 91. 6 HYDROGEN CONSUMED (SCFB)82 5 890 YIELD (wt.%) IBP-360F 4.8 6.0 360-650F 20.1 23.3 650F~ 74.0 64.9 *ND stands for not determined As can be seen from the table, all three catalysts exhibited high desulfurization activity and catalysts 5 and B showed good denitrogenation.
Cracking activity, as indicated by the yield data, was generally comparable for catalysts 5 and B, both of which were superior to eatalysks A.
Catalyst 5 was superior to both comparative catalysts in terms of selective cracking of waxy eompon~nts as evidenced by the reductions in pour point in runs using catalyst 5. Catalyst 5 also was superior in terms of overall performance in that comparable or better results were achieved with that catalyst at lower temperatures than those used in the comparative runs.

A series of catalyst compositions was prepared from various erys~alline molecular sieve zealot and matrix components and aqueous phosphoric acid soul-lions of various metal salts (pi about 3) according to the general procedure of Examples 1-5. A second series of catalysts was prepared in similar fashion to entwine identical levels of metals and support components but no phosphorus (pi about I
Samples of the catalysts were analyzed by X-I ray diffraction to determine the effect of phosphorieaeid on retention of zealot erystallinity. For each pair of catalysts (with and without phosphoric and impregnation) of identical metals and support content, intensity of one or more X-ray bands err-touristic of the zealot component and not subjeetto interference by the metals of the catalysts were measured.
For each pair of catalysts, composition and crystallinity of the phosphorus eomponent-eontaining catalyst relative to that of the phosphorus free composition is reported in Table 4.

RELATIVE
CRYSTAL-SAMPLE COMPOSITION (wt.%) LUNATE
(%~
A 3.5% No, 18~ Moo, 3.4% Pros/ 86 50 US, 50~ AYE

B 3~5% No, 18~ Moo, 3-4% P2s/ 78 50% v, 50% AYE

C 3.5% No, 18% Moo, 3-4% P2s/ 86 50~ ZSM-5~3), 50% AYE
D 1.5~ Coo 10% Cry, 15% Moo, 79 4.6~ Pus HAMS-lB(4), 60~ AYE

E 1.5~ Coo 10% Cry, 15% Moo, 88 4.6~ P20s/30~ US, 70% Aye .
(1) Ultra stable Y-type crystalline aluminosiLicate zealot.
(2) Y-type crystalline aluminosilicate zealot.
(3) Crystalline aluminosilicate zealot ZSM-5.
(4) Crystalline borosilicate zealot HAMS-lB.
As can be seen, crystallinity of the compositions according to the invention was quite high relative to compositions identical but for inclusion of pros-phonic acid in preparation. 3.5% No, 18.0% Moo, 3.5~ P20s/30% US, 70~ AYE exhibited 66~ crystal-tinily relative to a dispersion of 30% US in 70~
Aye .

Claims (16)

1. A catalytic composition comprising (1) an active metallic component comprising at least one metal having hydrocarbon conversion activity and at least one oxygenated phosphorus component, and (2) a support component comprising at least one non-zeolitic, porous refractory inorganic oxide matrix component and at least one crystalline molecular sieve zeolite component comprising a crystalline borosilicate zeolite.

2. The composition of claim 1 wherein the metal having hydrocarbon conversion activity comprises at least one Group IB, II, IIIB-VIIB or VIII metal.

3. The composition of claim 2 wherein the active metallic component comprises at least one metal having hydrogenation activity.

4. The composition of claim 1 wherein the oxy-genated phosphorus component is present in an amount ranging from about 0.1 to about 20 wt.%, expressed as P2O5 and based on total weight of the composition.

5. The composition of claim 2 wherein the metal having hydrocarbon conversion activity comprises at least one hydrogenation metal selected from the group consisting of chromium, molybdenum, tungsten, iron, cobalt and nickel.

6. A catalytic composition comprising (1) an active metallic component comprising about 5 to about 35 wt.% of at least one hydrogenating metal and about 0.5 to about 15 wt.% of at least one oxygenated phosphorus component, expressed as P2O5, and (2) a support component comprising alumina, silica or a combination of alumina and silica and at least one crystalline molecular sieve zeolite component comprising a crystalline borosilicate zeolite.

7. A method for preparing a catalytic composition comprising impregnating a support component comprising at least one non-zeolitic, refractory inorganic oxide matrix component and at least one acid-tolerant crystalline molecular sieve zeolite component comprising a crystalline borosilicate zeolite, with precursors of an active metallic component comprising at least one metal having hydrocarbon conversion activity and at least one oxygenated phosphorus component under conditions effective to retain substantial zeolite crystallinity, and calcining the resulting impregnation product.

8. The method of claim 7 wherein the precursors to the active metallic component comprise phosphoric acid or a salt thereof having a pH of at least about 2, and the support component is impregnated with such phosphoric acid or salt simultaneously with, or subsequent to, impregnation with at least one metal precursor.

9. A process for denitrogenation of high nitrogen content hydrocarbon feeds comprising contacting the feed with hydrogen under denitrogenation conditions in the presence of a catalyst comprising an active metallic component comprising at least one metal having hydrogenation activity and at least one oxygenated phosphorus component, and a support component consisting essentially of at least one non-zeolitic, porous refractory inorganic oxide matrix-component selected from the group consisting of alumina, silica, zirconia, titania, magnesia and combinations thereof and at least one crystalline molecular sieve zeolite component, wherein the high nitrogen content feed is a whole petroleum or synthetic crude oil, coal, shale or biomass liquid, or a fraction thereof containing at least about 0.4 wt.% nitrogen.

10. The process of claim 9 wherein denitrogenation conditions are denitrogenation hydrotreating conditions and comprise a temperature of about 650° to about 760°F., hydrogen pressure of about 1000 to about 2500 psi, LHSV
of about 0.2 to about 4 and hydrogen addition rate of about 2000 to about 20,000 SCFB.

11. The process of claim 9 wherein denitrogena-tion conditions are denitrogenation hydrocracking conditions and comprise a temperature of about 720° to about 820°F., hydrogen pressure of about 1000 to about 2500 psi, LHSV of about 0.2 to about 3 and hydrogen addition rate of about 4000 to about 20,000 SCFB.

12. The process of claim 9 wherein the hydrogenation metal of the active metallic component comprises at least one metal of Group VIB or VIII.

13. The process of claim 12 wherein the crystalline molecular sieve zeolite component comprises an ultrastable Y-type crystalline alumino-silicate zeolite, a crystalline borosilicate zeolite of the AMS-type or a crystalline aluminosilicate zeolite of the ZSM-type.

14. The process of claim 13 wherein the hydrogenating metal of the active metallic component comprises nickel-molybdenum, chromium-molybdenum-cobalt or chromium-molybdenum-nickel.

15. The process of claim 14 wherein the support component comprises a dispersion of ultrastable Y-type crystalline aluminosilicate zeolite in alumina or silica-alumina.

16. The process of any of claims 9, 11 and 13 wherein the high nitrogen content feed comprises a whole shale oil or a shale oil fraction.