CA1168210A

CA1168210A - Residual oil processing catalysts

Info

Publication number: CA1168210A
Application number: CA000389349A
Authority: CA
Inventors: Donald S. Santilli
Original assignee: Chevron Research and Technology Co
Current assignee: Chevron USA Inc
Priority date: 1981-01-12
Filing date: 1981-11-03
Publication date: 1984-05-29
Also published as: GB2090766A; GB2090766B; DE3146306A1

Abstract

ABSTRACT OF THE DISCLOSURE

"RESIDUAL CIL PROCESSING CATALYSTS"
A porous ceramic composition suitable for use as a catalyst support for demetalation of asphaltene-containing feedstocks is made from the tubular form of the clay halloysite by dispersing the rods of that clay, either alone or in combination with a fibrous second clay and a binder oxide.

Description

8~10 RESIDUAL OIL PROCESSING CATALYSTS

BACKGROUND OF THE INVENTION
This invention relates to a catalyst for hydro-treatment and hydrodemetalation of hydrocarbonaceous feedstocks. More particularly, this invention relates to catalysts and catalyst supports fabricated from halloysite.
Impurities such as metals, sulfur and nitrogen are contained in hydrocarbonaceous materials including crude oils, heavy oils, cracked oils, deasphalted oils, residual oils, shale oils, coal and partially liquefied coal and the like. These impurities are discharged into the atmosphere when the hydrocarbon i8 burned, creating a major source of pollution. They also tend to rapidly foul catalysts used for processing of the hydrocarbon or treat-ing the exhaust from combusted hydrocarbons. The removal o these undesirable impurities as early as possible in the processing of the hydrocarbonaceous materials is therefore highly desirable.
When metals such as nickel, iron and vanadium are present, they tend to deposit on the interior surface of the pores of hydroprocessing catalysts, tending to plug the pore mouths thereby reducing activity. It is desir-able, therefore, that a substantial volume of the pores have a pore mouth diameter greater than 200 Angstroms.
The majority of the pores should be preferably smaller than about a 1000 Angstroms because large pores tend to decrease the mechanical crush strength of the catalyst bodies, and also decrease surface to volume ratios.
Catalysts that effectively trea~ asphaltene containing fractions are desirable because many known crude oil reserves worldwide are high in asphaltenes.
Additionally, various synthetic fuel processes tend to create fractions high in asphaltenes.

~ ti8ZJ O

Catalysts containing clay materials have been suggested for hydroprocessing heavy hydrocarbon feeds.
05 For example, U.S. Patent No. 4,152,250 to Inooka suggests the use of a catalyst containing the mineral sepiolite (Meershaum), a fibrous magnesium silicate clay and transi-tion metals and/or Group II-B metals. Another clay which has been suggested is halloysite. Halloysite is an aluminum silicate clay that frequently occurs naturally in a rod like form. The basic formula is A12Si2O5(OH)4-In U.S. Patent No. 4,098,696, a synthesis of the plate form of halloysite is disclosed. In U.S. Patent No.
3,891,541 a demetalation catalyst is disclosed that is formed from halloysite and alumina. The pore structure contains pores with a diameter of between about 180 Angstroms to about 300 Angstroms. The pore diameters are said to be an artifact of the alumina.
SUMMARY OF THE INVENTION
This invention provides a method for the hydroprocessing of hydrocarbonaceous feedstocks containing asphaltenes. It also provides a catalyst and catalyst support useful, for example, in hydroprocessing hydrocarbonaceous feedstocks containing asphaltenes.
These and other objects are achieved in a porous composition of matter having dispersed rods of halloysite and from 0-15 percent by weight of a binder oxide. The weight percentage is based on the total weight of both the halloysite and the binder oxide.
In one embodiment of this invention a catalyst is prepared by (a) preparing a mix of halloysite and a fibrous second clay, halloysite having predominantly rods having a length within the range of 0.5-2 microns and a diameter within the range of 0.04-0.2 microns, and the fibrous second clay having predominantly rods having a length within the range of 1-5 microns and a diameter within the range of 50-100 Angstroms, (b) adding suffi-cient liquid to said mix to form a slurry of no more than 25 percent solid, and then vigorously agitating the slurry to substantially disperse the rods, tc) removing enoùgh ~8;~0 Ol -3-water from the slurry to form an easily shapable mass, shaping the mass, and (d) drying and calcining the shaped 05 body. It is preferred that attapulgite be used as the fibrous second clay.
In its composition of matter aspects, this invention comprises c~dispersed rods of halloysite and a fibrous second clay, halloysite composed predominantly of fibers with a length range of 0.5-2 microns and a diameter range of 0.04-0.2 microns and a fibrous second clay predominantly composed of fibers having a length range of 1-5 microns and a diameter range of 50-100 Angstroms.
Halloysite must be in the tubular form. A preferred second clay is fibrous attapulgite. It is preferred that the composition be at least 5 percent attapulgite. It is preferred that the binder oxide be alumina. It is preferred that the catalyst body have a total pore volume of at least 0.35 cc/g and at least 60 percent of the volume of the pores is present in pores having diameters of 200-700 Angstroms. This invention also comprises a method for hydroprocessing hydrocarbonaceous feedstocks comprising contacting the feedstocks with molecular hydrogen under hydroprocessing conditions in the presence of a catalyst having codispersed rods of halloysite having rods predominantly in the range of 0~.5-2 microns with a ; diameter range of 0.04-0.2 microns and a fibrous second clay having rods in the range of 1-~ microns and a diameter range of S0-100 Angstroms.
It is preferred that the composition include at least one catalytic transition metal preferably a metal selected from Group VI-B or VIII of the Periodic Table.
It is preferred that the composition have a pore volume of at least 0.35 cc/g of which at least 70 percent of the pore volume is present in pores having a diameter of 200-700 Angstroms and at least 70 percent of those pores have diameters of 300-700 Angstroms. Hydrocarbon feedstocks containing at least one percent by weight asphaltenes can be processed by contacting feedstocks with hydrogen under

2~0 01 _4_ hydroprocessing conditions in the presence of a catalyst composition comprising dispersed rods of halloysite and S between 0-15 weight percent of a binder oxide.
DETAILED DESCRIPTION
The catalyst composition of the present inven-tion involves the rod form of halloysite processed alone or in combination with a fibrous clay so that the rods are dispersed. "Dispersed rods" are defined herein to mean - rods of halloysite which have been substantially complete-ly disassociated from one another and are substantially randomly oriented with respect to one another.
The tubular or rod form of halloysite is readily available from natural deposits. It frequently comprises bundles of tubular rods or needles consolidated or bonded together in a weakly parallel orientation. It has been discovered that if these bundles of rods are broken up by mechanical means and re-oriented in a substantially random orientation with respect to one another, a catalyst sup-port with superior asphaltene hydroconversion properties results. Halloysite occurs naturally in tubular rods that are approximately 1 micron long and 0.1 micron in diameter with a centrally located hole penetrating the rod from about 100 Angstroms to about 300 Angstroms in diameter resulting in a scroll-like rod, in contrast to fibrous - clays like attapulgite and sepiolite which are non-tubular. The exact dimensions vary from rod to rod and are not critical. It is critical that the rod form, rather than the platy form, of halloysite be used.
When halloysite rods or other rods of similar dimensions are agitated in a fluid such as water to disperse the rods, the dispersion can be shaped, dried and calcined to provide a porous body having a large pore volume present as 200-700 Angstroms diameter pores. When the shaping is by extrusion, however, it has been found that mixtures of dispersed clay rods of the halloysite type, do not extrude well. The rods on the surface of the extruded bodies tend to realign, destroying the desirable pore structure at the surface of the catalyst. This is ~8210 01 _5_ defined herein as a "skin effect". It has been discov-ered, however, that if a fibrous second clay with longer, oS narrower and presumably more flexible, fibers is codis-persed with the halloysite-type clay, the resulting composition is easily extrudible, and there is no signi-ficant skin effect. "Codispersed~ is defined herein as having rod- or tube-like clay particles of at least two distinct types substantially randomly oriented to one another.
The second fibrous clay should have long slender fibers typically about 1-5 microns in length with a diameter range of about 50-100 Angstroms. Clays for use as the second component include attapulgite, crysotile', immogolite, palygorskite, sepiolite and the like.
In addition to the'halloysite component and the second fibrous clay component of the present catalyst, an inorganic binder oxide may be added to increase crush strength. Inorganic binder oxides are defined as refractory inorganic oxide such as, silica and oxides of elements in Group 2a, 3b and 3a of the Periodic Table as defined in Handbook of Chemistry and Physics, 45th Edition. Preferable binder oxides include: silica, alumina, magnesia, zirconia, titania, boria and the like. An especially preferred binder oxide is alumina.
It has been discovered that the amount of asphaltene adsorbed onto a catalyst support of dispersed rods of halloysite is related to the amount of binder oxide used. When the amount of binder oxide exceeds about 15 percent of the total weight of halloysite and binder oxide, the amount of asphaltenes adsorbed is severely reduced. It has been found that an especially preferable amount of binder oxide is about 5 percent. As more binder oxide is added to the catalyst support, the pore sizes tend to cluster around smaller distributions. A catalyst support with 25 percent alumina has substantially all of its pores less than 100 Angstroms in diameter.
If an inorganic oxide component is to be present into the composition of the present invention, codispersal 8Z~O
Ol -6-of the rods of the fibrous clay is preferably carried out in the presence of an aqueous hydrogel or the sol precur-sor of the inorganic oxide gel component. The preferred inorganic oxide is alumina. Mixtures of two or more inorganic oxides are ~;uitable for the present invention for example, silica and alumina.
A function of the inorganic oxide gel component is to act as a bonding agent for holding or bonding the clay rods in a rigid, three-dimensional matrix. The resulting rigid skeletal framework provides a catalyst body with high crush strength and attrition resistance.
A catalyst support made from halloysite alone or in combination with a fibrous clay can contain any catalytic reactive transition metal. The catalytic metal component can be added during any stage of preparation.
Catalytic metals can be added as powdered salts or oxides during the agitation stage or by impregnation of the catalyst body by adding a metal containing solution after the catalyst bodies have been formed. Preferred catalytic metals are those of Groups VI-B and VIII of the Periodic Table. When preparing hydroprocessing catalysts, it is preferable that the composition include at least one metal of the group of chromium, molybdenum, tungsten and vanadium, and at least one metal of the group of iron, nickel and cobalt, such as cobalt-molybdenum, nickel-tungsten or nickel-molybdenum.
The metal component can be added to the catalyst composition at any stage of the catalyst preparation by any conventional metal addition step. For example, metals or metal compounds can be added to the slurry as solids or in solution, preferably before dispersion of the clay rods. Alternatively, an aqueous solution of metal can impregnate the dried or calcined bodies. The metals can be present in reduced form or as one or more metal compounds such as oxides or sulfides. One preferred method is impregnating the calcined catalyst bodies with a solution of phosphomolybdic acid and nickel nitrate.

~ti82~0 01 _7_ Preparation of the catalyst with dispersed rods is accomplished by creating a mi~ture of tubular halloy-05 site a fibrous second clay and if desired, binder oxideand enough water to form a slurry of about 20 weight percent solid content~ As the mixture is violently agitated the slurry i5 observed to thicken. Agitation is continued until the slurry stops thickening with continued agitation. This takes about l0 minutes of agitation.
This thickening is indicative of dispersal of the rods.
Excess water in the slurry is removed by evaporation until a moldable plastic mass is formed. The bodies are then shaped by spheridizing, pelletizing and similar procedures and then calcined. It has been observed that a catalyst body made e~clusively of dispersed rods of halloysite tends not to extrude well. The rods tend to realign on the surface of the extruded mass, and this skin effect decreases the average pore diameter at the surface of the extruded mass. Alternatively, the halloysite mass can be dried and calcined; and the calcined mass broken up to produce cataly~t bodies. The final product is a catalyst body with the characteristics of dispersed rods of halloysite. It is preferable that the binder oxide be added to the halloysite as the gel or the sol precursor to the gel at the agitation stage of the slurry.
Referring to Table I, the pore size distribution for unprocessed halloysite and pore size distribution for halloysite with dispersed rods are compared. It will be noted that in unprocessed halloysite most of the pore size is in the 200-400 Angstrom range. On the other hand, halloysite with dispersed rods has most of its pores distributed from 400-600 Angstroms. In halloysite with dispersed rods there is a substantial amount of pore volume provided by pores having diameters in the range of l00-300 Angstroms. It is believed that these pores are from the central hole present in halloysite rods. The presence of these smaller pores is not a gauge of the thoroughness of dispersion of the rods.

o TABLE I
Pore Size Distribution 05(Expressed as percentage of Total Pore Volume) With Pore Size DiameterUnprocessedDispersed Rods >600 Angstroms 4% < 1~
500-600 Angstroms 2% 22%
400-500 Angstroms 13% 29%
300-400 Angstroms 19% 18%
200-300 Angstroms 44% 14 <200 Angstroms 17% 17%

Total Pore Volume .26 cc/g .39 cc/g It will also be noted that the halloysite with dispersed rods has a substantially greater total pore volume than the natural halloysite.
It is believed that the pores in the range of 200 Angstroms to about 700 Angstroms impart especially 2 good deasphalting properties to the catalyst support. One explanation is that demetalation and desulfurization reactions tend to be fast, therefore, pores significantly larger than the molecules tend to allow rapid diffusion into and out of the pores. Large pores are preferable in demetalation catalysts since the metals removed from the feedstocks tend to deposit on the surface of the catalyst support, thereby rapidly plugging the mouths of the smaller pores. Since there is no substantial amount of pore volume in pores greater than 1000 Angstroms, there is less problem with mechanically weak catalyst bodies and attendant attrition.
The catalyst support and catalyst of this inven-tion are versatile and can be u~ed for conversion of a variety of hydrocarbonaceous feeds. This catalyst is especially useful in hydroprocessing of heavy fractions ~t~32~(~

01 _9_ which contain more than one percent by weight asphal-tenes. Asphaltenes are defined herein to mean any hydro-05 carbon fraction that is insoluble in n-heptane whether or not it is soluble in benzene. Any feedstock containing asphaltenes can be treated by use of this catalyst whether or not the asphaltenes have been previously separated from the remainder of the feedstock.
10The feedstocks with more than about 10 percent asphaltenes are especially suitable for upgrading by use of the present invention. Suitable feedstocks include those oils that have an API gravity below about 25 or a Conradson carbon residue of at least 7 percent. Particu-larly suitable are those feedstocks that boil at greaterthan 550C. Suitable feedstocks include: crude petro-leum, vacuum and atmospherlc residua from petroleum, coal-liquids, shale oil, topped crudes and the like.
The present invention is especially suitable for any of the numerous hydroconversion processes that use molecular hydrogen. The generic conditions are exposing the feedstock to hydrogen at a partial pressure ranging from 0 to 200 atmospheres at between 200C and 540C, and hydrogen to oil feed ratio of from zero to 9,000 standard cubic liters per liter of oil and an hourly liquid space velocity from about 0.1 to about 25 reciprocal hours.
Among the specific uses for which this catalyst is suit-able are hydrocracking, hydrodesulfurization, hydrode-nitrification, hydrodemetalation, and hydroconversion of asphaltenes. The present catalyst is especially suitable for hydrodemetalation and hydrocracking of asphaltenes.
The following examples are for illustrative purposes only and should not be considered to be limiting.
Example I
35This example illustrates the preparation of a catalyst support containing only halloysite without a binder oxide or catalytic metals.
Naturally occurring halloysite from Dragon Iron Mine, Utah, #13 powder is placed in a blender with enough water to make a slurry of about 20 weight percent solid content. The slurry is vigorously agitated in a Waring blender until it reaches a constant thickness. After 05 removal from the blender, the clay containing slurry is dried and calcined and shaped into catalytic bodies.
Example II
-This example illustrates preparation of a catalyst support containing halloysite and a binder oxide. Dragon Halloysite ~13 powder is placed in a blender. Enough 5 percent alumina by weight alumina hydrogel is added to form a mixture that is 5 percent by dry weight alumina. The alumina hydrogel is prepared conventionally, as by peptizing a commercially available alumina by a vigorous agitation with a peptizing agent such as nitric acid or formic acid, or by precipitation of the hydrogel from an aluminum nitrate solution with a base such as ammonium hydroxide. Enough water is then added to make a slurry that is no more than about 20 percent solid content. The mixture is then vigorously agitated in a Waring blender until the ~lurry no longer visibly thickens. Once the halloysite rods are adequately disper-sed, the slurry will not get any thicker. Normally this takes about 10 minutes of agitation. Excess water is evaporated from the slurry to form a plastic, workable mass. The mixture is heated to 500C for three hours and the calcined ~ass is broken up into catalyst particles.
Example III
A mixture of 50 9 of halloysite #13 from the Dragon Iron Mine, Utah, 10 9 of attapulgite from Gadsden City, Florida, and 25 g of alumina sol (20 percent Catapal*
alumina by weight) in 500 ml of water was agitated in a Waring blender for 10 minutes. At this point the slurry mixture had stopped visibly thickening. The slurry was slowly evaporated dry at 110C to a thick paste which could be easily extruded. The paste was extruded, and dried and calcined at 500C.

* Trade mark 1~i8~0 Example IV
This example illustrates the deasphaltening 05 properties of a catalyst support made from dispersed rods of halloysite.
A calcined catalyst support prepared by the general method illustrated in Example I was impregnated by a solution of phosphomolybdic acid and cobalt nitrate.
The impregnated catalyst contained 2 percent by weight of cobalt and 6 percent by weight of molybdenum. The support was employed for hydrodemetalizing a feedstock comprising Arabian Atmospheric Residue in a microreactor. The temperature was 382C, the pressure of hydrogen was 112 atmospheres, the hydrogen flow was 90 standard liters per liter of feed and the liquid hourly space velocity was 0.86 reciprocal hours. The concentration of impurities in the feedstock was reduced after hydrogen processing the feedstock in the presence of the catalyst. Table II shows the concentrations of the impurities in the feedstock before and after hydrodemetalation.

TABLE II
V,ppm N,ppm % S% Asphaltene Feed 83 22 4.4 7.2 Product 57 18 3.9 5.3 Table III shows the concentrations of impurities in the asphaltene fraction of the feedstocks when the heptane insoluble asphaltenes are separated and analyzed separately ~~ iO

TABLE III

05 V,ppm N,ppm % S

Asphaltenes From Feed 1030 300 10.5 Asphaltenes From 10Product 760 250 8 . 8 It will be appreciated that the asphaltene left behind was cleaner than the asphaltene in the initial feedstock.
Analysis of the catalyst particles revealed that the metals deposited on the catalyst support tended to be evenly distributed throughout the particles, rather than on the surface only.
Example V
A series of catalysts were made according to the general method of Example II except that varying amounts of alumina were used in each preparation. The catalysts were then placed in toluene solutions of asphaltenes and the absorbance at 550 nm is monitored with respect to time according to the method of Saint-Just (Ind. Eng. Chem.
Prod. R Div . 1980, 19, 71). 550 nm is chosen because the absorbance of this wavelength of light has been corre-lated to the concentration of vanadium, which in turn has been correlated to the concentration of asphaltenes.
Table IV shows the absorbance of light at 550 nm at varying time intervals for various halloysite catalysts - that have varying amounts of alumina. As the catalyst adsorbs asphaltenes, the solution becomes progressively more clear, therefore, absorbing less light. Therefore, the better catalyst compositions for deasphaltening action will have lower final light absorbances.

;8'!~0 TABLE IV

05 Time (Minutes) Halloysite with 1.0 0.280.14 0.0~ 0.06 0.04 0~ alumina Halloysite with 1.0 0.220.01 0.05 0.04 0.03 5% alumina Halloysite with 1.0 0.670.56 0.49 0.43 0.36 10% alumina Halloysite with 1.0 1.0 1.0 1.0 1.0 1.0 25% alumina Halloyqite with 5% alumina ~extruded) 1.0 0.92 0.850.82 0.79 0.73 It can be seen that the best asphaltene absorb-ance is for the catalyst composition with 0-5 percent alumina content, and asphaltenes are absorbed progres-sively more poorly for the catalyst supports with higher amounts of alumina. The extruded halloysite shows decreased light absorbance with time, indicating that asphaltene absorption onto the catalyst support is taking place, but it is considerably inferior to the 5 percent alumina catalyst that has been shaped by alternate means. This is apparently due to a skin effect on the extruded catalyst body that tends to realign the dispersed rods during extrusion. The results of this absorbance test can be roughly correlated to the pore size distribution of the catalyst support, which should be large enough to adsorb molecules the size of asphaltene molecules. It will also be noted that there is no decrease in light adsorbance in the 25 percent alumina catalyst. It is thought that the pore sizes are too small to allow the catalyst body to preferentially adsorb asphaltenes. The light absorbance characteristics of this series of dispersed rod catalysts indicate that dispersed rods of halloysite can be superior catalyst supports for hydroprocessing if the catalyst support contains no more 05 than about 15 percent binder oxide.
Example VI
The catalyst of Example III is tested for absorbance. The absorbance of 550 nanometers (nm) of a solution of asphaltenes dissolved in toluene is followed with time according to the method of Saint-Just (Ind. Eng.
Chem. Prod. Res. Div., 1980, _ , '71). The wave length of light chosen has been correlated to concentration of vanadium in solution, which has in turn been correlated to asphaltene concentration. Various catalysts are added. A
reduction in the absorbance means that the catalyst preferentially adsorbs asphaltene materials from the toluene solution. The results are tabulated in Table V.
It can be appreciated that the extruded halloysite/
attapulgite mixture adsorbs asphaltenes much better than the extruded halloysite. It has been shown that good demetalation catalysts will always show a marked decrease in the absorbance of the toluene solution when tested in this manner.

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Claims

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

1. A porous composition of matter comprising dispersed rods of halloysite, and 0-15 percent by weight of a binder oxide, based on the tot-al weight of said halloysite and binder oxide having a pore volume of at least 0.35 cc/gm of which at least 70 percent of the pore volume is present as pores having a diameter of between 200-700 Angstroms and at least 70 percent of said pores have a diameter of 300-700 Angstroms.

2. The composition of claim 1 further comprising a catalytic trans-ition metal.

3. The composition of claim 2 further comprising at least one metal selected from Group VI-B and Group VIII of the Periodic Table.

4, The composition of claims 1, 2 or 3 wherein said binder oxide is alumina.

5. A method of hydroprocessing a hydrocarbonaceous feedstock con-taining at least one percent by weight asphaltenes comprising: contacting said feedstock under hydroprocessing conditions with a catalyst composition comprising dispersed rods of halloysite, and 0-15 percent by weight of a binder oxide, based on the total weight of said halloysite and binder oxide having a pore volume of at least 0.35 cc/gm of which at least 70 percent of the pore volume is present as pores having a diameter of between 200-700 Angstroms and at least 70 percent of said pores have a diameter of 300-700 Angstroms.

6. The method of hydroprocessing of claim 5 wherein said catalyst includes catalytic transition metals.

7. The composition of claim 6 further comprising at least one metal selected from Group VI-B or Group VIII of the Period Table.

8. The method of hydroprocessing of claim 5, 6 or 7 wherein said binder oxide is alumina.

9. A porous composition of matter comprising codispersed rods of halloysite and a fibrous second clay, said halloysite having predominantly rods with the length range of 0.5-2 microns and a diameter range of 0.04-0.2 microns and said fibrous second clay having predominately rods with a length range of 1-5 microns and a diameter range of 50-100 Angstroms.

10. The composition of claim 9 wherein the composition contains at least 5 weight percent of said fibrous second clay based on the total weight of said composition.

11. The composition of claim 9 including up to 15 weight percent of a refractory inorganic oxide based on the total weight of said composition.

12. The composition of claim 11 wherein said refractory inorganic oxide is alumina.

13. The composition of claim 9 wherein at least 60 percent of the vol-ume of the pores is present in pores having diameters of 200-700 Angstroms.

14. The composition of claim 9 further comprising at least one metal selected from the transition metals group.

15. A method for preparing a porous composition of matter comprising preparing a mixture of a halloysite and a fibrous second clay, said halloy-site having predominately rods with a length range of 0.5-2 microns and a diameter range of 0.04-0.2 microns, and said fibrous second clay predomin-antly having rods with a length range of 1-5 microns and a diameter range of 50-100 Angstroms; adding sufficient water to create a slurry of no more than 25 weight percent solid content; vigorously agitating the slurry until the slurry ceases to thicken; drying the slurry to create a dry mass; and shaping the dried mass; and calcining the shaped mass.

16. The method of claim 15 wherein said mixture contains up to 15 dry weight percentage of a refractory inorganic oxide bond on total weight of the composition.

17. The method of claim 16 wherein the refractory inorganic oxide is alumina.

18. The method of claim 16 wherein said composition has at least 60 percent of the volume of the pores is present in pores having diameters of 200-700 Angstroms.

19. A method for producing a composition of matter comprising preparing a mixture of tubular halloysite and fibrous attapulgite; adding enough water to create a slurry of no more than 25 weight percent water content; vigor-ously agitating the slurry until the thickening of the slurry ceases; drying the mass, shaping the mass, and calcining the shaped mass.

20. The method of claim 19 wherein the mixture contains up to 15 dry weight percent of a refractory inorganic oxide based on total weight of the composition.

21. The method of claim 19 wherein the refractory inorganic oxide is alumina.

22. The method of claim 19 wherein the mixture contains between 0.1 and 10 weight percent of a catalytic transition metal based on total weight of the composition.

23. The method of claim 19 wherein the calcined mass has at least 60 percent of the pore volume present as pores having diameters between 200 and 700 Angstroms.

24. A method for hydroprocessing of hydrocarbonaceous feedstocks com-prising: contacting the feedstocks with molecular hydrogen under hydropro-cessing conditions in the presence of a porous catalyst having codispersed halloysite rods and attapulgite rods.

25. The method of claim 24 wherein the catalyst includes up to 15 weight percent of a refractory inorganic oxide based on total weight of the composition.

26. The method of claim 25 wherein said refractory inorganic oxide is alumina.

27. The method of claim 24 wherein said porous catalyst has at least 60 percent of the volume of the pores is present in pores having diameters of 200-700 Angstroms.

28. The method of claim 24 wherein the catalyst further comprises at least one metal selected from the transition metals.