CA1145285A

CA1145285A - Hydrocarbons hydroprocessing with halloysite catalyst

Info

Publication number: CA1145285A
Application number: CA000359497A
Authority: CA
Inventors: Robert A. Van Nordstrand
Original assignee: Chevron Research and Technology Co
Current assignee: Chevron USA Inc
Priority date: 1979-09-26
Filing date: 1980-09-03
Publication date: 1983-04-26
Also published as: JPS5670091A; DE3033963A1; GB2059283B; GB2059283A; FR2465775B1; FR2465775A1

Abstract

ABSTRACT OF THE DISCLOSURE

?

A process is disclosed for hydrogen processing hydrocarbons with a halloysite catalyst.

Description

2~35 001 ~1~

002HYDROCARBONS ~YDROPROCESSING WIT~ ~ALLO ~ITE CATALYST

004~AC~CRO~=3 O~ r~E INVENTION`~
005The present invention concerns a cat~lysk composition 006 and its use for hydrogen processing hydrocarbons. In one 007 specific aspect, the invention concerns a catalyst containing 008 the fibrous form of the clay mineral halloysite and its use for 009 demetalizing and deasphalting heavy petroleum fractions.
010 Heavy hydrocarbon fractions such as petroleum 011 residua, bitumen, coal and shale oils, and the like, are known 012 to contain substantial amounts of contaminants such as sulfur, 013 nitrogen and metals, especially nickel and vanadium. Such 014 heavy fractions also typically contain a substantial fraction 015 of heat sensitive, normal heptane-~nsoluble hydrocarbonaceous 016 material conventionally termed "asphaltenes".
017 It has been suggested to upgrade contaminated heavy 018 oil fractions by hydrogen processing in order to remove the 019 metals, sulfur and nitrogen, but the presence of asphaltenes in 020 the oils often has an adverse effect on the activity of conven-021 tional hydroprocessing catalysts. Another problem encountered 0~2 in conventional heavy oil hydroprocessing when large concentra-023 tions of metals are present in an oil, is that the metals tend 0~4 to deposit rapidly on the catalyst surface and plug the pores 025 of conventional hydrogen processing catalysts, with a 0~6 consequent loss of catalytic activity for sulfur and nitrogen 027 removal. This has led to the suggestion that de~etalizing 028 guard beds should be used upstream of a hydrodesulfurizing 029 and/or hydrodenitrifying reactor.
030 Because of the tendency of metals to deposit on the 031 surfaces o~ hydrocarbon processing catalysts during processing 032 of heavy oils and the tendency of metals to plug the pores of 033 the catalysts, it is desirable to employ a hydrodemetalation 034 catalyst having a large fraction o its total pore volume 035 provided by pores having a diameter of greater than 200 036 Angstrom units, which are termed "macropores" herein. Manu-037 facture of satisfactory catalysts with a substantial fraction 52~5 001 ~2-002 of total pore volume in macropores is difficult, in that most 003 catalysts with a sa~isfactory pore size distribution for 004 demetalation are quite deficient in crush strength and 005 attrition resistance. The shaping procedures used for forming 006 suitable catalytic bodies also often have an adverse effect on 007 the macropores content of catalysts.
008 In order to overcome the adverse effects of asphalt-009 enes on hydrogen processing catalysts, e.g. from rapid coking 010 and from inhibition of hydrodesulfurization, it has been 011 suggested to use a solvent treatment to separate asphaltenes 012 prior to hydrodesulfurization or hydrodenitrification. The non-013 asphaltenes may be dissolved in a li~uefied light aliphatic, 014 such as propane, while the insoluble asphaltenes ara rejected.
015 Not only is solvent deasphalting relatively complex and 016 expensive, but it also has the disadvantage of rejecting 017 potentially valuable hydrocarbonaceous materials, since 018 asphaltenes can potentially be at least partially converted by 019 hydrocracking, catalytic cracking and the like. Thus, the 020 larger the fraction of asphaltenes in a given oil, the less 021 attractive solvent deasphalting becomes.
022 U.S. Patent No. 4,152,250 suggests the use of a 0~3 catalyst containing sepiolite (~eershaum) and transition metals 024 and/or Group IIB metals for hydrotreating and hydrodemetalizing 025 hydrocarbons~ Sepiolite is a magnesium silicate clay.
026 U.S. Patent No. 4,166,026, suggests a two-stage 027 process for hydrogen treating heavy hydrocarbon oils. In the 028 first stage, a catalyst is employed which contains such 029 naturally occurring magnesium silicates as sepiolite, 030 attapulgite or palygorskite or synthetic products closely 031 related to these minerals in composition and structure, 032 supporting metals from Groups VA, VIA and VIII. employed. The 033 catalyst employed in the second conversion stage uses a carrier 034 having at least 90% of its pore volume provided by pores having 035 diameters of 35-200 Angstrom units, supporting metals from 036 Groups VA, VIA and VIII.
037 The catalysts using magnesium silicates as supports ~52l35 which are described in No. 4,152,250 and No. 4,166,026, are preferably pre-pared by grinding the mineral to small size particles and then kneading an aqueously moistened dough formed from the mineral, after which the support is shaped.
Halloysite is an aluminosilicate clay-type mineral. It was first described by P. Bertheir in 1826. It occurs in various hydrated forms and in dehydrated form. The specific halloysites employed in the catalyst of the present invention are characterized by a tubular or flbrous morphology, al-though there are forms of halloysite which have a platey structure similar to 10 kaolinite or which have any of several other morphologies. The basic formula usually given for halloysite is A12Si2O5(OH)4. A fully hydrated form, formu-la A12Si2O5(OH)4.2H2O, is sometimes called "endellite". The nomenclature of halloysites is discussed in Clays and Clay Minerals, Vol. 23, pp 382-388 (1975). Halloysites are also discussed in Clay Minerology by R. E. Grim, published by McGraw-Hill (1968). A mixture of fibrous halloysite, platey halloysite and alumina has been used commercially as a catalytic cracking catalyst, both with and without a zeolite.
SU~IARY OF T~IE INVENlION
In one embodiment, the present invention concerns a process for hy-20 drogen treating a hydrocarbon feed by contacting the feed, at hydrogen treat-ing conditions, with a cat`alyst composition comprising shaped catalytic bod-ies including (1) dispersed rods of tubular-form halloysite and (2) at least one porous refractory inorganic oxide gel, the gel bonding the halloysite rods together in a rigid, substantially random mutual orientation in the cat-alytic bodies. In a preferred embodiment, the halloysite, catalyst is used for demetalizing a heavy oil and for selectively hydrocracking asphaltenes in the oil.
I have found that a shaped catalyst for hydrogen processing hydro-carbons possessing surprisingly high crush ~ .

2~3~
001 ~4~

002 strength and attrition resistance, and having an advantageously 003 high proportion of its total pore volume in 200-1000 Angstrom 004 macroporès, can be provided by employing dispersed rods of 00S tubular form halloysite as a matrix, skeleton or framework in 006 the catalyst particles. The halloysite rods are bonded to-007 gether, using a suitable refractory inorganic oxide gel, such 008 as silica or alumina, in random orientation to form the rigid, 009 three-dimensional matrix. Shrinkage and deformation of the 010 microporous gel binder during drying of the catalyst particles 011 provides a large fraction of 200-1000 Angstrom macropores in 012 the catalyst, while the rigid framework of halloysite rods 013 provides the catalyst bodies with excellent mechanical strength 014 properties such as crush strength and attrition resistance.
015 The catalyst provides excellent hydrodemetalation and 016 hydroconversion of asphaltenes, and can be used in conveniently 0~7 larger-sized catalytic bodies without encountering the 018 diffusion and mechanical strength problems found in previous 019 catalysts.
020 DE~AILED DESCRIPTION OF THE INVENTIOW
021 The catalyst composition employed in the present 022 invention includes two essentia:L components: (1) dispersed 023 rods of tubular halloysite, and (2) an inorganic oxide gel for 024 bonding the rods.
025 The tubular ~orm of halloysite is readily availablè
026 in natural deposits. It can also be synthesized, i~ desired, 027 in a known manner. In its natural state halloysite often 028 comprises bundles of tubular rods or needles consolidated or 029 bonded together weakly in parallel orientation. In order to 030 ma~e the halloysite suitable for use in the present catalyst, 031 bundles o~ parallel, consolidated rods must be broken up, so 032 that the halloysite rods are unconnected, or dispersed. As 033 used herein, the term "dispersed rods", means halloysite rods 034 which have been substantially completely disassociated from 035 other rods, so that each halloysite rod is freely movable with 036 respect to other rods. Dispersal of the rods can be accom-037 plished, when necessary, by grinding, milling, kneading and the ~ tS 2 ~ 5 001 -5~

002 like. It is strongly preferred that dispersal is carried out 003 in the presence of an aqueous hydrogel or sol precursor of the 004 inorganic oxide gel component, with the halloysite being worked 005 as a slurry. For example, a colloid mill can be used 006 satisfactorily in many cases to disassociate the individual 007 rods. Dispersion is facilitated by mechanical agitation of the 008 halloysite in an aqueous medium. A dispersion procedure can 009 conveniently be carried out in the presence of an aqueous 010 precursor of the inorganic oxide gel component, as by milling a 011 slurry of fibrous halloysite in the presence of an inorganic 012 oxide precursor sol. It is to be noted that ylatey forms of 013 halloysite are not suitable for use as substitutes for the 014 halloysite rods employed in the present catalyst.
015 Preferably, the halloysite rods used in the catalyst 016 have a length to diameter ratio of about 5:1 to about 100:1.
017 The rod diameter, for this purpose, is taken as the largest 018 diameter of the rod normal to t:he length. If the average 019 length:diameter ratio of available rods is higher than desired, 020 it can be decreased by grinding the halloysite to a finer 021 particle size.
022 The length of halloy~iite rods used in a catalyst is 023 also preferably maintained within a range proportionate to the 024 size of the catalytic bodies, or particles, to be formed from 025 the halloysite and inorganic oxide. If the length of the rods 026 is too great in comparison to the average diameter of the 027 catalyst bodies to be formed, then the shaping procedure can 028 tend to cause a uniform, parallel mutual orientation of the 029 halloysite rods in the shaped catalyst. This is particularly 0~0 the case when extrusion is used for shaping. Preferably, the 031 average length of the halloysite rods used is between about 2%
032 to about 10~ of the average diameter of the shaped catalytic 033 bodies into which the catalyst is for~ned. Rods shorter than 2%
034 of the catalyst particle diameter are usually quite satis-035 factory, but rods larger than 10% are usually not satisfactory.
036 In addition to the halloysite component of the 037 present catalyst, a porous, refractory inorganic oxide gel com~
038 ponent is also used. Suitable refractory inorganic oxide gels 5~

002 are well known to those skilled in the art. Examples of 003 suitable inorganic oxides are silica, alumina, magnesia, 004 zirconia, titania, boria, and the like. Mixtures of two or 005 more inorganic oxides are also suitable. Preferred inorganic 006 oxides are silica, alumina and silica-alumina. The gel 007 material preferably has a substantial fraction of its total 008 pore volume in micropores having pore diameters in the range 009 from 1 to 200 Angs~rom units. The inorganic oxide gel may be 010 provided or derived from a natural material such as a clay or 011 may be a synthetic material such as synthetic silica-alumina 012 cogel. Suitable additional materials which may be used include 013 kaolin clays, bentonite clays, the ~ype of layered clays 014 discussed in U.S. Patents No. 3,252,757, No. 3,252,889 and No.
015 3,743,594, montmorillonite clays, mixed or platey halloysite 016 clays, etc.
017 The dispersed halloysite rods and the inorganic oxide 018 gel may be combined in any suitable conventional manner. For 019 example, the rods may be added to an aqueous solution of a 020 precursor of the inorganic oxide, after which a hydrogel of the 021 inorganic oxide is formed, and the resulting mass is then 022 shaped and dried conventionally. Or, the halloysite component 023 can be added to a previously precipitated hydrogel which has Q24 not hardened, and the rods and gel can be mechanically mixed 025 prior to shaping. Another suitable combination technique is to 026 combine the rods with a properly peptized powder of an 027 inorganic oxide, again with mechanical mixing to homogenize the 028 resulting mass.
~29 Pre~erably, the amount of the inorganic oxide com-030 ponent is about 10 weight percent to about 50 weight percent of 031 the amount of the halloysite rods in the final catalyst com-032 position.
033 ~n essential function of the inorganic oxide gel com-034 ponent is to act ~s a bonding agent for holding or bonding the 035 halloysite rods in a rigid, three-dimensional matrix or 036 skeletal arrangement. The inorganic oxide provides a rigid 037 link between the halloysite rods, which are randomly oriented ~5~

002 in a three-dimensional mutual orientation. The resulting rigid 003 skeletal framework provides a catalyst body with high crush 004 strength and attrition resistance.
005 After a mass of mixed halloysite and inorganic oxide 006 gel, e.g. as a hydrogel, or other gel precursor has been shaped 007 into the desired form, as by extruding, pilling, hot oil sphere 003 formation or like conventional technique, the resulting 009 cata~ytic bodies may be dried and/or calcined in a conventional 010 manner, if desired. Extrusion is a preferred shaping technique 011 for forming the present composition into suitable catalytic 012 bodies.
013 When conventional catalyst bases, such as inorganic 014 oxide gels, are heated during drying and/or calcination, the 015 microporous inorganic oxide component tends to shrink, 016 resulting in a catalyst which is structurally stable, but which 017 has few pores with diameters greater than 200 Angstrom units.
018 The presence of the halloysite framework, or ~atrix, in the 019 present catalyst prevents such uniform shrinkage o~ the gel 020 component. The result is a catalyst with a large fraction of 021 i~s pore volume provided by pores with diameters in the range 022 from 200 Angstroms to 1,000 Angstroms. Preferably, the 023 relative proportions of the halloysite and inorganic oxide ~el 024 components in the catalyst (and the proportion of catalytic 025 metals, if used) are adjusted so that the final catalyst bodies 02~ have at least 40% of their total pore volume supplied by pores 027 with diameters between 200 and 1,000 Angstroms. Pore si~e 028 distribution and pore volume may be determined by the mercury 029 porosimitry method, as described in U.S. Patent No. 3,853,789, 030 or, if appropriate, by the BET nitrogen adsorption method 031 described in JACS 60, 309 (1939) and 73, 373 (1951). Pores in 032 the 200-1000 Angstrom range are particularly suitable when the 033 present catalyst is employed in the preferred use, hydrode-034 metalation and hydroconversion of asphaltenes in heavy oils.
035 The total surface area of the present catalysts is not 036 particularly critical for most uses; however, a surface area 031 between about 10 and 200 s~uare meters per gram is preferred.

52~35 002 The catalyst may also include one or more known cata~
003 lytically active metals, such as transition metals. A metal 004 component can be added to the halloysite and inorganic oxide 005 during ~ormation of the shaped catalyst bodies, as by including 006 an aqueous solution or suspension of the metal in an aqueous 007 liquid used for forming a hydrogel of the inorganic oxide or by 008 comulling a solid metal-containing powder with the inorganic 009 oxide and/or halloysite components prior to or after the 010 halloysite and inorganic oxide are combined. Alternatively, a 011 catalytically active metal can be added to the catalyst 012 particles after shaping and preferably after stabilization of 013 the catalyst bodies by drying and calcination.
014 One preferred group of catalytically active metals 015 for use in catalysts of the invention is the group including 016 chromium, molybdenum, tungsten and vanadium. Preferably one or 017 more of these metals is present in the catalyst in a total 018 amount of 0.1 to 10 weight percent of the total catalyst 019 weight, including the catalyti.claly active metal or metals.
020 Another preferred group of catalytically active 021 metals for use with the present catalyst is the group including 022 iron, nickel and cobalt. Preferably, one or more of these 023 metals is included in the catc~lyst particles in a total amount 024 of from 0.1 to 10 weight percent of the total catalyst weight, 025 including the catalytically ac:tive metal or metals.
026 Particularly preferably, the catalyst particles 027 include ~rom 0.1 to 10 weight percent of at least one metal 028 from both of the preferred groups. Combination of molybdenum 0~9 and cobalt, molybdenum and nickel, tungsten and nickel t 030 vanadium and nic~el are examples. The catàlytically active Q31 metals may be present in reduced form or as one or more metal 032 compounds such as the oxide, sulfide or sulfate.
033 According to the invention, the catalyst is employed 034 for hydrogen treating a hydrocarbon feed. The catalyst is 035 versatile and can be used for a variety of hydrogen treating 036 operations on a wide selection of hydrocarbon feeds. Pref-037 erably the hydrocarbon feed is a heavy oil or fraction such as z~s 002 a crude oil, petroleum atmospheric or vacuum distillation 003 residuum, coker distillate oils, heavy petroleum cycle oil, 004 synthetic oils or fractions of synthetic oils such as bitumen, 005 coal oil, shale oil or the like. Especially suitable feeds are 006 oils containing more than 10 ppm (wt) of metals such as nicke~
007 and vanadium. Asphaltic fractions, e.g., oils containing 10 008 weight percent or more of asphaltenes, are also especially 009 suitable for upgrading according to the process employing the 010 pr~sent catalyst. Especially suitable feeds are those oils 011 having an API Gravity below about 25, or a Conradson carbon 012 residue of at least 7~. Particularly suitable heavy oil feeds 013 are those in which at least 10 weight percent of the oil boils 014 at a temperature above 550~C. Such heavy oils are not the only 015 preferred feeds, however, since the present catalyst can be 016 used effectively for demetalizing lighter oils, such as 017 potential catalytic cracking feeds boiling in the range from 018 roughly, 210C to 550C, especially gas oils with a substantial 019 fraction boiling in the range from 250C to 475C.
020 The catalyst of the invention is particularly useful 021 for catalytically hydrogen treating hydrocarbon feeds. In 022 hydrogen treating, which may also be called hydroprocessing or 023 hydroconversion, the oil ~eed to be treated is mixed with 024 hydrogen, and the mixture is contacted with the catalyst in a 025 suitable reaction zone at hydrogen treating conditions.
026 Generic hydrogen treating conditions include a 027 reaction zone temperature in the range from about 200C to 028 540C, a total pressure in the range from about 1 atmosphere to 029 about 300 atmospheres, with a hydrogen partial pressure of from 030 0 to 200 atmospheres, a hydrogen-to-oil feed ratio of from 0 to 031 9000 standard cubic liters per liter of oil (SCLL), and a 032 liquid hourly space velocity (LHSV) of about 0.1 to about 25 033 volumes per hour per volume of catalyst.
034 Among the speci~ic hydrogen treating, hydrocon-035 version, or hydrogen processing operations for which the 03~ present catalyst is particularly suitable are hydrocracking, 037 hydrodesulfurization, hydrodenitrification, hydrodemetalation ~52~35 002 and hydroconversion of asphaltenes. ~he present catalyst is 003 especially suitable for use in hydrodemetalizing heavy oils and 004 in selectively hydrocracking asphaltenes from asphaltinic 005 stocks. Reaction conditions used in hydrodemetalation and 006 asphaltenes cracking preferably include a temperature in the 007 range from 200 to 500C, a hydrogen pressure of 20 to 300 008 atmospheres, a hydrogen-to-feed oil rate.of 1000 to 100,000 009 standard cubic feet per barrel ~SCFB) and a LHSV of about 0.1 010 to 5.
011 The hydroconversion processes carried out with the 012 present catalyst may be performed in a ba~ch-type or, 013 preferably, a continuous-type system. The catalyst may be used 014 in the form of a slurry in the feed, a fixed bed, a moving bed, 015 an ebullated or fluidized bed. Suitable conventional reaction 016 zones, such as reactor vessels, are well known to those skilled 017 in the art. In the case of a fixed bed operation, the feed oil 018 and hydrogen can be contacted with the catalyst bed in, for 019 example, upward flow, downward flow or radial flow.
020 In one preferred embodiment, the present catalyst is 021 used in carrying out the first stage of a two-stage hydrocon-022 version operation. Using the present catalyst in the first 023 stage at hydrodemetalation conditions in a first reaction zone, 024 the feed oil is primarily freed from a large fraction of its 025 metals and the asphaltenes content of the oil is substantially 026 reduced, without substantial desulfurization. In the second 027 stage, the primary hydroconversion carried out is hydrodesulfur-028 ization, using conventional hydrodesulfurization conditions and 029 a conventional hydroprocessing catalyst selected for its hydro-03n desulfurization activity in a second reaction zone. In such a 031 two-stage operation, suitable hydrodesulfurization conditions 032 for use in the second stage include a temperature of 150C to 033 425C, a hydrogen pressure oE 5 to 15 atmospheres, a hydrogen-034 to-feed oil rate oE up to 2,000 SC~B and a liquid hourly space 035 velocity of 0.1 to 5.
036 The following Illustrative Embodiments describe 037 preferred embodiments of the preparation of the present 038 catalyst and its use in demetalizing a heavy hydrocarbon feed.

~5285 003 Naturally occurring halloysite clay is obtained and 004 crushed in dry form to one-half inch diameter particles. The 005 particles are slurried in water at a water:halloysite volume 006 ratio of 9:1 and subjected to further comminution in conven~
007 tional clay handling apparatus, such as a blunger, to provide 008 halloysite particles of less than 5 micron diameter. Silt and 009 sand particles larger than 5 microns are settled out of the 010 dispersion. The halloysite is then concentrated by filtration 011 to provide a wet filter cake. An alumina hydrogel slurry is 012 prepared conventionally, as by peptizing a commercially 013 available boehmite alumina (e.g. Catapal) by violent agitation 014 with a peptizing agent such as nitric acid or formic acid. The 015 hydrogel may alternatively be prepared by precipitation from an 016 a~ueous solution of alu~linum nitrate by addition of a base such 017 as ammonium hydroxide. After appropriate washing to remove 018 undesired ions, the hydrogel is mixed with suE~icient water to 019 provide 15 weight percent alumina in a slurry. A mixture of 020 halloysite and alumina hydroc~el is then formed by addiny the 021 filter cake to the hydrogel slurry at a halloysite:alumina 022 weight ratio of 3:1. The rods of halloysite are then 023 dispersed, randomly oriented and homo~eneously Inixed with the 024 alumina. Proper blending of the components is important in 025 order to obtain the advantageous physical properties desired in 026 the final catalyst. A preferred blending-dispersing procedure 027 is, first, to agitate the halloysite-alumina mixture violently 02~ in a Waring blender, Cowles dissolver, or the like, for about 029 20 minutes. At this stage the solids should be in slurry form 030 in water with about 25 weight percent solids. Proper dispersal 031 of the halloysite rods is indicated by a slurry viscosity of 032 above that of water. The halloysite rods in the slurry are 033 then further dispersed by passing the slurry two or three times 034 through a stone colloid mill, e.g., a Morehouse mill, or the 035 like. Clearance of the mill should be adjusted to provide a 036 temperature rise of 6 to 10C during each pass, indicating 037 sufEicient shear for proper dispersion of the rods in the 038 mixture.

, ~ , 002 The slurry is then placed in a steam heated partially closed 003 vessel to reduce the water content of the slurry to about 50 4 weight percent. The water content is adjusted for best results 0;05 in shaping. In the case of extrusion, the mixture is then 006 extruded to form particles of about 1.~ to 4 millimeters 007 diameter. The extrudate is then dried for about one hour at 008 150C and then calcined at 565C for about 2 hours. The 009 resulting catalytic bodies have a pore volume of about 0.7 to 010 1.0 cc~g. About ~0% of the pore volume is provided by pores 011 with diameters above 200 Angstrom units, as measured by 012 nitrogen desorption isotherm. The catalyst is effective as 013 prepared or can be impregnated with a sufficient amount of an 014 aqueous solution of ammonium molybdate to provide 5 weight 015 percent molybdenum (as elemental metal), and with a sufficient 016 amount of an aqueous cobalt nitrate solution to provide 2.5 017 weight percent cobalt (as elemental metal) in the finished 018 catalyst.

020 The catalyst prepared as described in ILLUSTRATIVE
021 EMBODIMENT I is employed for hydrodemetalizing a heavy, metals 022 and asphaltenes containing petroleum fraction and for 023 simultaneously selectively hydrocracking the heptane-insoluble 024 ' asphaltenes in the petroleum fraction. The catalyst is 025 employed as a fixed bed in a conventional hydroconversion 026 system. The feed is mixed with hydrogen and passed over the 027 catalyst bed at a temperature of about 410C with a hydrogen 028 partial pressure of about 135 atmospheres. The LHSV employed 029 is about 1.5 per hour. A hydrogen/oil ratio of about 1000 030 nanoliters per li~er is employed. The product oil is analyzed 031 and found to be substantially lower in vanadium, nickel and 032 heptane-insoluble components than the feed.

Claims

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

1. A process for hydrogen treating a hydrocarbon feed which comprises contacting said feed, at hydrogen treating conditions, with a catalyst compri-sing shaped catalytic bodies including (1) dispersed rods of tubular halloy-site and (2) at least one porous refractory inorganic oxide gel, said gel bon-ding said rods together in a rigid, substantially random mutual orientation in said catalytic bodies.

2. A process as defined in claim 1 wherein said inorganic oxide gel is present in said composition in an amount between 30 and 50 weight percent of said rods.

3. A process as defined in claim 1 wherein the average length of said rods is between 2% and 10% of the average diameter of said shaped catalytic bodies.

4. A process as defined in claim 1 wherein at least 40 percent of -the total pore volume in said catalytic bodies is provided by pores with diameters between about 200 Angstrom units and 1,000 Angstrom units.

5. A process as defined in claim 1 wherein said rods have an average length:diameter ratio between about 5:1 and 100:1, said diameter being the maximum diameter of said rods normal to said length.

6. A process as defined in claim 1 wherein said catalytic bodies further include from about 0.1 to about 10 weight percent of at least one metal selec-ted from chromium, molybdenum, tungsten and vanadium.

7. A process as defined in claim 1 wherein said catalytic bodies further include from about 0.1 to about 10 weight percent of at least one metal selec-ted from iron, nickel and cobalt.

8. A process for hydrodemetalizing a hydrocarbon feed which comprises contacting said feed, at hydrodemetalizing conditions, with a catalyst includ-ing (1) dispersed rods of tubular halloysite and (2) from 10 to 50 weight per-cent, based on said rods, of at least one porous refractory inorganic oxide gel, said gel bonding said rods together in a rigid, substantially random mutual orientation in said catalytic bodies.

9. A process as defined in Claim 8 wherein said inorganic oxide gel is present in said composition in an amount between 10 and 50 weight percent of said rods.

10. A process as defined in claim 8 wherein the average length of said rods is between 2% and 10% of the average diameter of said shaped catalytic bodies.

11. A process as defined in claim 8 wherein at least 40 percent of the total pore volume in said catalytic bodies is provided by pores with diameters between about 200 Angstrom units and 1,000 Angstrom units.

12. A process as defined in claim 8 wherein said rods have an average length:diameter ratio between about 5:1 and 100:1, where the diameter is the maximum diameter of said rods.

13. A process as defined in claim 8 wherein said catalytic bodies fur-ther include from about 0.1 to about 10 weight percent of at least one metal selected from chromium, molybdenum, tungsten and vanadium.

14. A process as defined in claim 8 wherein said catalytic bodies fur-ther include from about 0.1 to about 10 weight percent of at least one metal selected from iron, nickel and cobalt.