CA2068495A1 - Catalysts containing homogeneous layered clay/inorganic oxide - Google Patents

Abstract

"CATALYSTS CONTAINING HOMOGENEOUS
LAYERED CLAY/INORGANIC OXIDE"

ABSTRACT
This invention relates to a composition, a method of preparing the composition and a catalyst using the composition. The composition consists essentially of a layered clay homogeneously dispersed in an inorganic oxide matrix. The clay is dispersed in such a way that the clay layers are completely surrounded by the inorganic oxide matrix. The inorganic oxide is selected from the group consisting of alumina, titania, silica, zirconia, P2O5 and mixtures thereof. The clay can be a natural clay such as montmorillonite, a metal exchanged clay (Fe-3 exchanged) or a pillared clay such as aluminum chlorohydrate (ACH) pillared clay. The composition can be used as a catalyst foralkylation or hydrocracking or metals can be dispersed on it to provide a catalyst which is also useful for hydrocracking or alkylation.

Description

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"CATALYSTS CONTAINING HOMOGENEOUS
LAYERED CLAY/INORGANICQXIDE"

BA~KGROUND ~:)F THE INVENTION

Naturally occurring clays such as smectites, vermiculi~es and bentoni~es 5 are composed of semicrystalline aluminosilicate layers (lamellae) held toge~her by Van der Waals and ~lectrostatic forces. Anionic charges on the siliceous layers are neutralized by cations in the interlamellar spaces. These cations, usually Na+, Ca+2, can be ion exchanged with large inorganic cations such as Fe+3, Cr+3 or with metal hydroxy polymer cations such as [Al134(H)24(H~)12]
10 or [Zr(OH)2 4H2O]4~+. The polymeric cations act as pillars, propping the clay layers apart.
Pillared clays are known to catalyze numerous reactions such as alkyla-tion, cracking, ester formation, dimerization, oligomerization, etc. A review of the reactions catalyzed by pillared clays may be found in an article by J.M. Adams, 15 Applied Clay Science, ~, pp. 309-342 (1987). Of these reactions, alkylation has received considerable at~ention. For example, U.S. Patent No. 4,499,319 dis-closes layered clays such as montmorillonite which have been ion-exchanged with metal cations such as chromium and aluminum, which are used to alkylate aromatic compounds. Other examples include U.S. Patent No. 4,605,806 which 20 discloses a hydrogen ion-exchanged pillared clay; U.S. Patent No. 3,965,043 dis-closes a metallic cation exchanged trioctahedral 2:1 layer-lattice smectite-typeclay and U.S. Patent No. 3,979,331 which discloses a metallic cation exchanged synthetic hectorite-type clay useful for alkylating aromatic hydrocarbons.
Another reference is U.S. Patent No. 4,499,195 which discloses a co-gel of 25 a smectite clay with an inorganic metal oxide to produce a co-gel. The inorganic oxides include Group IV-B metal oxides and other oxides such as silicon, aluminum, thorium and uranium. However, since the metal oxide gel is stated to be formed before addition of the clay, it appears that the clay is not homogeneously dispersed in the metal oxide gel. A continuation-in-part of the 30 '195 reference (U.S. Patent No. 4,587,009) discloses the use of the co-gel for hydrogenation of hydrocarbons.
U.S. Patent No. 4,111,846 discloses a catalyst that contains a zeolite as the active material and a clay as a "weighting" agent. Apparently what is meant by a"weighting" agent is a filler which is used to increase the density of the catalyst.

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Finally, U.S. Patent No. 4,844,790 discloses a delaminated clay. The patentee, in passing, states that the catalyst may include a zeolite and/or a refractory oxide component as part of tha catalyst. The catalyst is prepared by spray drying.
In contrast ~o this prior art, a composition has now been prepared which 5 contains a clay (pillared or non-pillared) homogeneously dispersed in an inorganic oxide matrix. The inorganic oxides which may be used as the matrix material include alumina, titania, silica, zirconia, P205 and mixtures thereof. A
preferred method of preparing the cornposition involves dispersing the clay in asol of the element which is the precursor of the oxide, thereby providing a mixture 10 which can be formed into particles such as spheres by methods such as oil dropping, followed by calcination to form a metal oxide matrix with a clay dispersed therein. The composition has increased activity versus an untreated clay.
The inorganic oxide matrix completely surrounds the clay layers such that 15 they are delaminated and truly homogeneously dispersed, on a one micron scale, throughout the inorganic oxide matrix. It is the use of a hydrosol which gives rise to this homogeneity which cannot be obtained by extruding or spray drying physical mixtures of a clay and a metal oxide. In fact, it has been found that acomposition of the present invention containing an acid washed montmorillonite 2 o clay in an alumina matrix has better activity than a physical mixture of the clay and alumina.

SUMMARY OF THE INVENTION

This invention relates to a composition, a method of preparing the composition, a catalyst using the composition, and a process using the 25 composition. Accordingly, one embodiment of the invention is a composition comprising a layered clay homogeneously dispersed in an inorganic oxide matrix where the clay laycrs are completely surrounded by the inorganic oxide matrix, where the inorganic oxide selected from the group consisting of alumina, titania, silica, zirconia, P2O5 and mixtures thereof and where the clay is present in a 3 o combination of from 5 to 80 wt.% of the composition.
Another embodiment of the invention is a catalyst comprising a support having dispersed thereon a metal selected from the group consisting of Group IIIA, IIIB, IVB, Vlll metals, molybdenum, tungsten and mixtures thereof, the support comprising a layered clay homogeneously dispersed in an inorganic 3 ~0~8~9~

oxide ma~rix where the clay layers are completely surrounded by the inorganic oxide matrix and where the inorganic oxide selected from the group consisting ofalumina, titania, silica, zirconia, P205 and mixtures thereof.
Yet another embodiment of the invention is a method of preparing a 5 composltion comprising a layered clay homogeneously dispersed in an inorganic oxide matrix, the method comprising mixing a layered clay with a hydrosol of a precursor of the inorganic oxide, forming spherical particles froms said clay containing hydrosol and calcining said particles to form a composition consisting essentially of a layered clay homogeneously dispersed in an inorganic oxide o matrix, such that the clay layers are completely surrounded by the inorganic oxide matrix.

BRIEF DESCRIPTION OF THE DRAWINGS

Figure 1a is a scanning electron microscope (SEM) photograph showing the silicon distribution of a cross-section of an extrudate containing a physical 15 mixture of alumina and an acid washed montmorillonite clay.
Figure 1b is a SEM photograph showing the aluminum distribution of the extrudate sample of Figure 1a.
Figure 2a is a SEM photograph showing the silicon distribution of a cross-section of a sphere containing alumina and an acid washed montmorillonite clay 2 o prepared according to the instant invention.
Figure 2b is a SEM photograph showing the aluminum distribution of the sphere sample of Figure 2a.

DETAILED DESCRIPTION OF THE INVENTION
This invention relates to a composition, a method of preparing the 25 composition, a catalyst using the composition, and a process using the com-position. One necessary component of the composition of this invention is a clay.
Both natural and synthetic clays may be used including but not limited to ben-tonite, sepiolite, LaponiteTM, vermiculite, montmorillonite, kaolin, palygorskite (attapulgus), hectorite, chlorite, beidellite, saponite and nontronite. Of the above 30 clays LaponiteTM is a synthetic hectorite clay manufactured by LaPorte Co. and having the chemical formula Na0 58Si8Mg5 42Lio 58F2 5(0H)1 .520 (Laponite-B) or Nao46sisMgss4Lio46(oH)4o2o(Laponite-RD)- Montmorillonite, hectorite, beidellite 206~9~

and saponite have syntheti~ analogs. As stated, these clays are composed of semicrystalline aluminosilica layers held together by Van der Waals and electrostatic forces. The elays (both natural and synthetic analogs) may b~ usedas they oc~ur (or as synthesized) or th~y may be modified by exchanging with 5 metals or introducing pillars between the layers to give pillared clays. Any of the clays, including all the ones ~numerated above, may be exchanged with on~ or more metals selected from the group consisting of Fe+3, Cr+3, Al+3, Ti+4 and Zr+4: The clays into which pillars may be introduced are the smectite clays (natural and synthetic) which are he~orite, beidelGte, nontronite, saponite and lO montmorillonite. The pillars are selected from aluminum chlorohydrate (ACH) and rare earth ACH.
Aluminum chlorohydrate (also known as aluminum chlorohydroxide) is a polymeric metal complex having the empirical formula A12+ n(H)2nC16 15 where n has a value of 4 to 12. The preparation of this aluminum polymer is generally known to those skilled in the art. See, for example: Tsuitida and Kobayashi, J. Chem. Soc. Japan (Pure Chem. Sect.), 64, 1268 (1943). Inoue, Osugi and Kanaji, J. Chem. Soc. Japan (Ind. Chem. Sec.), 61, 407 (1958).
A rare earth ACH is an ACH as described above which is modKied to in-20 clude one or more rare earth elements sùch as cerium, lanthanum, neodymium,europ.ium, etc. The ACH polymer is modified with the rare earth by adding a sol-uble rare earth salt, preferably a water soluble rare earth salt. Examples of rare earth salts are the nitrates, halides, sulfates and acetates. Preferred rare earth el-ements are cerium and lanthanum with cerium nitrate and lanthanum nitrate being 25 the preferred salts. The rare earth is introduced into the polymer or oligomer structure by mixing the rare earth salt either in solution (water preferred) or as a solid with the ACH. The mixture is refluxed at a temperature of 105 to 145C for a time of 24 to 100 hours. The weight ratio of rare earth (expressed as oxide, e.g., CeO2) to alumina (Al2O3) in the solution prior to refluxing is from about 1:52 to 30 1:1.
When these pillars are introduced into the clays, the clays are referred to as ACH clays and rare earth ACH, e.g., CeACH, clays. The ACH or rare earth ACH clays are prepared by means well known in the art such as adding the de-sired clay to an ACH or rare earth ACH solution, stirring, filtering, redispersing 2~6~5 with water (one or more times), isolating, drying and calcining at 500 tc 800Cfor a time sufficient to fix the structure (prefefably about 16 hours). Any and all mixtures of the clays enumerated above can be used in the invention.
A second necessary component of the composition of this invention is an inorganic oxide matrix. ~he irlorganic oxide may be selected from the group con-sisting of aiumina, titania, silica, zirconia, P205 and mixtures thereof with alumina being preferred. The clay will be present in the inorganic oxide matrix in a con-centration from 5 to 80 weight percent of the composition and preferably from 3 to 70 weight percent of the composition.
0 In addition to the composition containing a clay and an inorganic oxide matrix, it is necessary that the clay be homogeneously disperssd throughout the inorganic oxide matrix. By homogeneously dispersed is meant that the composi-tion is homogeneous on a one micron scale, that is, if one looks at a one squaremicron area one will find a uniform distribution of matrix and clay components, i.e., there are no large, segregated, areas of one or the other component.
One can obtain such a homogeneous dispersion by using a sol of the ele-ment which is the precursor of the inorganic oxide. A sol or hydrosol is a solution which, when placed in a glass vessel be~Neen one's line of vision and a strong light source, shows a bluish cast. This is known as the Tyndall effect. By using a 20 sol, the clay layers become totally surrounded by the sol such that upon further processing one obtains clay layers that ara totally or completely surrounded by the inorganic oxide matrix. That is, one obtains a layered clay homogeneously dispersed in an inorganic oxide matrix.
A preferred mathod of obtaining such a dispersion involves modifying the 25 well known oil drop method which is taught in U.S. Patent No. 2,620,314 and which is incorporated by reference. For example, when alumina is the desired in-organic oxide, the modified oil drop method comprises forming an aluminum hy-drosol by any of the techniques taught in the art and preferably by reacting alu-minum metal with hydrochloric acid; adding the desired clay to the aluminum hy-3 0 drosol; combining the resulting hydrosol mixture with a suitable gelling agent; anddropping the resultant mixture into an oil bath maintained at elevated tempera-tures. The droplets of the mixture remain in the oil bath until they set and form hydrogel spheres. The spheres are then continuously withdrawn from the oil bath and typically subJected to specific aging and drying treatments in oil and ammoni-35 acal solution to further improve their physical characteristics. The resulting agedand gelled spheres are then washed and dried at a relatively low temperature of 2 ~

80-150C and subjected to a calcination procedure at a temperature of 455-705C for a period of 1 to 20 hours. The treatment effects conversion of the hy-drogel to the corresponding crystalline gamma-alumina matrix having the layered clay homogeneously dispersed therein.
Another method of homogeneously dispersing the clay in the inorganic oxide matrix is to form a mixture of a precursor sol or a precursor salt solution and a clay followed by spray drying the mixture to give particles containing homo-geneously dispersed clay and finaily calcining the particles to convert the sol or salt into the deslred inor~anic oxide.
The homogeneous dispersion described above cannot be obtained by spray drying (see U.S. Patent 4,~44,790~ or extruding physical mixtures of the in-organic oxide and layered clay. When a slurry or dough is formed of the two components, one is using powders of the two components, whose particle sizes can range from 5 microns to 30 microns. Therefore, there will be 5 to 30 micron particles of one component separating particles of the other component.
Althoùgh the final produd will look homogeneous on a macroscopic scale, it will not be homogeneous on a microscopic scale as derined above. Additionally, since'there is no sol to surround and separate the clay layers and keep them separated, upon calcining the clay layers are not completely surrounded by the 2 o inorganic oxide matrix.
It is believed that it is the homogeneous dispersion of the clay in the oxide matrix which leads to the observed increase in activity. The homogeneous dis-persion is illustrated by the SEM photographs presented in Figures 1 and 2.
Figure 1 presents two SEM cross-sectional photographs of an extrudate prepared 25 as in Example 2, namely a physical mixture of Filtrol ~24 and alumina. The bright spots in Figure la indicate the presence of silicon, while the bright spots in Figure 1b indicate the presence of aluminum. Figure 2 presents two SEM cross-sec-tional photographs of a sphere prepared according to this invention and as de-scribed in Example 1. The clay used in this sample was Filtrol #24 and the matrix 3 o oxide was alumina. Figure 2a is a silicon (bright areas) spot map, while Figure 2b is an aluminum spot map of the cross-sectional area of a sphere. Since silicon is only found in the clay the more homogeneous the silicon spot map the greater theextent of the dispersion of the clay in the alumina matrix.
Looking at Figure 1a one observes regions which are very intense and 35 other regions which are less intense. This is evidence of inhomogeneous disper 2~684~

sion of the clay. The same pattern is observed for the aluminum distribution (Fig.
2b); that is, some areas are more intense than others. It is also observed that there are large voids probably formed by the packing of the two components.
Further, certain areas that have intense aluminum spots do not have intense sili-5 con spots and vice versa. Clearly this sample is not homogeneous.
In contrast to Figures ~a and lb, Figures 2a and 2b are extremely homo-geneous. For example the silicon spot map of Figure 2a shows that the intensity of the spots is uniform throughout the whole area photographed. The aluminum spo~ map of Figure 2b similarly shows that the int~nsity of the aluminum spots is o uniform throughout the area photographed. Additionally, there is a correspon-dence of silicon intensity with aiuminum intensity and whatever voids are present are uniformly distributed throughout the sample area. The homogeneity of this sample, prepared according to the instant invention, is therefore verified.
Without wishing to be bound by any particular theory, it is believed that the 15 fact that the clay layers are surrounded by the inorganic oxide matrix leads to synergistic interaction between the clay and the inorganic oxide matrix, e.g., alumina. This synergistic effect gives rise to an increase in activity.
The composition which is derived from this invention is useful as a catalyst or as a support for metals which are themselves catalysts. Thus, without any fur-20 ther modifications, the composition of this invention can be used to catalyzehydrocarbon conversion reactions by contacting hydrocarbons with such composition at hydrocarbon conversion conditions such as are used in alkylation,cracking, oligomerization, isomerization and transalkylation. Additionally, a metal component (either as the metal or as the metal oxide) may be deposited on the 25 composition to provide additional or different catalytic properties. The metal which makes up the metal component may be selected from the group consisting of the ~3roup IIIA, IIIB, IVB, Vlll metals, molybdenum, tungsten and mixtures thereof.
The metal component may be deposited on the composition, which acts 30 as a support, in any suitable manner known in the art. One method involves im-pregnating the support with an aqueous solution of a decomposable compound of the metal or metals. By decomposable is meant that upon heating the metal compound is converted to the metal or metal oxide and the release of byprod-ucts. Illustrative of the decomposable compounds of said metals are cobalt chlo-35 ride, cobalt nitrate, cobalt acetate, cobalt sulfat0, iron chloride, iron nitrate, ironacetate, iron sulfate, nickel chloride, nickel nitrats, nickel acetate, nickel sulfate, ~068~

arnmonium chloroplatinate, chloroplatinic acid, bromoplatinic acid, dinitrodiamino platinum, sodium tetranitroplatinate, rhodium trichloride, hexaarnminerhodium chloride, rhodium carbonylchloride, sodium hexanitrorhodate, chloropalladic acid, palladium chloride, palladium nitrate, diamminepalladium hydroxide, tetraam-5 minepalladium chloride, hexachloroiridate (IV) acid, hexachloroiridate (Ill) acid,ammonium hexachloroiridate (Ill), ammonium aquohexachloroiridate (IV), ruthe-nium tetrachloride, hexachlororuthenate, hexaammineruthenium chloride, os-mium trichloride, ammonium osmium chloride, ammonium paramolybdate, am-monium tungstate, aluminum chloride, aluminum nitrate, boric acid, gallium ni-10 trate, gallium trichloride, indium chloride, indium nitrate, thallium acetate, scan-dium nitrate, lanthanum chloride, lanthanum nitrate, yttrium chloride, yttrium ni-trate, titanium trichloride, zirconium tetrachloride, zirconium suifate, and hafnium chloriçie.
When more than one metal is desired, ths metals can be in a common 15 aqueous solution or in separate aqueous solutions. When separate aqueous so-lutions are used, impregnation of ~he support can be performed sequentially in any order. Although the concentration of metal component can vary substantially it is desirable that the catalyst contain a concentration of the metal component as the metal from 0.1 to 30 weight percent of the support and preferably from 1 to 15 20 weight percent.
A preferred impregnation procedure involves the use of a steam1acketed rotary dryer. The support is immersed in the impregnating solution containing the desired metal compound contained in the dryer and the support is tumbled therein by the rotating motion of the dryer. Evaporation of the solution in contact 25 with the tumbling support is expedited by applying steam to the dryer jacket. The resultant composite is allowed to dry under ambient temperature conditions, or dried at a temperature of 80 to 110C, followed by calcination at a temperatureof 400 to 650C for a time of 1 to 4 hours, thereby converting the metal compound to the metal or metal oxide.
The composition of this inv0ntion with or without an additional metal component can be used as an alkylation catalyst. The conditions necessary to carry out alkylation of aromatic compounds are well known and are disclosed, forexample, in U.S. Patent Nos. 3,965,043 and 3,979,331 which are incorporated by reference. Generally the process can be carried out in a batch type or a 35 continuous type operation. In a batch type process, the catalyst, aromatic compound and alkyiating agent are placed in an autoclave and the pressure 9 20~8~

increased, if necessary, in order to effect the reaction in the liquid phase. Anexcess amount of aromatic compound should be present, preferably in a range of 2:1 to 20:1 moles of aromatic compound per mole of alkyla~ing agent. The reaction is carried out at an elevated temperature since the rate of alkylation is 5 undesirably low at room temperature. Preferably the temperature is in the range of 40 to 200C. The process is carried out for a time of about 0.5 to about 4 hours, after which the product is separated from the starting materials by conventional rneans.
If it is desired to carry out the process in a continuous manner, the catalyst 10 is placed in a reactor which is hea~ed to the desired operating temperature and the pressure increased above atmospheric, if necessary. The aromatic com-pound and alkylating agent are flowed over the catalyst bed at a predetermined liquid hourly space velocity sufficient to effect alkylation. The effluent is continu-ously withdrawn and conventional separation means used to isolate the desired 15 product.
Additionally, the composltion of this invention with or wlthout additional catalytic metals or other catalytic materials such as Y zeolite may be used as ahydrocracking catalyst. Typically, hydrocracking conditions include a tempera-ture in the range of 400~ to 1200F (204-649C), preferably between 600 and 20 950F (316-510C). Reaction pressures are in the range of atmospheric (101.3 kPa) to 3,500 psig (24235 kPa), preferably between 200 an~ 3000 psig (482 -20788 kPa). Contact times usually correspond to liquid hourly space velocities (LHSV) in the range of 0.1 hr~~ to 15 hr~1, preferably between 0.2 and 3 hr~l.
Hydrogen circulation rates are in the range of 1,000 to 50,000 standard cubic feet 25 (scf) per barrel of charge (189-8,888 std. m3/m3), preferably between 2,000 and 30,000 scf per barrel of charge (355-5333 std. m3/m3).

EX~MPLE 1 Spheres containing a clay and an alumina matrix were prepar~d as follows.
An aluminum hydrosol was prepared by reacting aluminum metal with hydrochlo-30 ric acid to give a sol containing 12-13.5 weight percent aluminum and an Al to Cl ratio of 1.19. Filtrol #24 clay (an acid washed or activated montmorillonite clay obtained from Engelhard Corp.) was added to the sol to give 50% clay by weight (and 50% alumina) in the finished spheres. The clay was added to the hydrosol 20~9~

with vigorous mixing and then further mixed by using a ball mill. Hexamethylene tetrammine (HMT) was added ~o the mixture to gel the mix~ure into spheres when dropped through a tower of oil maintained at 95C. The amount of HMT which was added was ab~ut 130% of the amount required to neutralize the acid in the 5 aluminum sol.
After the spheres were removed from the hot oil, they were pressure aged at 140C for 2 hours and then washed with 10 liters of a dilute ammonium hy-droxide solution (1 weight percent NH40H) dried at 110C and calcined at 650C
for 2 hours. These spheres were designated sample A. After calcination, the 10 cracking activity of the spheres was measured using the 1-heptene microreactor test described in Example 10. The results of this test are presented in Table 1.

A catalyst was prepared by forming a doughy paste from a powder con-taining 80% Filtrol #24 and 20% alumina and water. The paste was extruded 15 through a die to form 1/1~" extrudates which were than calcined in an air atmo-sphere containing 10% steam for 2 hours at 600C. This catalyst was designated sample B and was also tested according to Example 10 and the results presented in Table 1.

Synthetic saponite was prepared by hydrothermal synthesis as described in U.S. Patent No. 4,749,676 which is incorporated by reference. Magnesium sulfate, sodium aluminate and waterglass were used as the sources of the Mg, Al and Si respectively. The atomic ratio of (Na-AI): Mg+Si+3/2AI) in the gel was 0.34 which corresponds to a Si/AI ratio of 5.6 in the tetrahedral sheet. The gel pH
25 was adJusted to 9 by adding NaOH and Na2CO3 and then the gel was placed in a Parr Bomb heated to 20~C undcr autogenous pressure for 6 hours to crystallize the saponite. The product was recovered by filtration washed with deionized wa-ter and dried at 110C for 4 hours. The dried product was ground to a fine pow-der.

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The saponite powder prepared in Example 3 was exchanged with alu-minum chlorohydrate as follows. The saponite powder (clay) was suspended in a solution consisting of water and a!uminum chlorohydrate. The aluminum chloro-5 hydrate was obtained from Reh0is as a 50% aqueous solution. After 30 minutes,the saponite clay was collected by filtration and washed with water until the wash water was free of chloride. The clay was dried at 110C for 2 hours and then cal-cined at 450C for 3 hours. This sample was desi~nated sample C and was tested in the 1-heptene cracking test of Example 10 and the results are presented 10 in Table 1.

This example presents the preparation of spheres using the aluminum chlorohydrate exchanged saponite of Example 4. The procedure detailed in Example 1 was used to prepare the spheres except that the saponite of Example 15 4 was used in place of the Filtrol #24 clay. These spheres were designated sam-ple D. After calcination, these spheres were tested using the 1-hsptene crackingtest of Example 10 and the results are presented in Table 1.

E)CAMPLE 6 Filtrol #24 was obtained from Engelhard Corp. as 40-60 mesh granules.
20 This sample was designated sample E and tested according to Example 10. The results are presented in Table 1.

Alumina spheres were prepared according to the procedure of Example 1 except that no clay was added to the alumina sol. These spheres were desig-25 nated sample F and tested according to Example 10. These results are pre-sented in Table 1.

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~ ceriurn-aluminum chlorohydrate pillared montmorillonite was prepared according to the procedure set forth in International Patent No. WO 88/06488.
After drying, the pillared clay was steamed at 650C for 3 hours. This sample was 5 designated sample G and was tested in the 1-heptene cracking test of Example 10. The resuits are presented in Table 1.

This example presents the preparation of spheres using the Ce-aluminurn chlorohydrate pillared clay of Example 8. The procedure detailed in Example 1 10 was used to prepare the spheres except that the pillared clay of Example 8 was used in place of the Filtrol #24 c~ay. These spheres were designated sample H.
After calcination, these spheres were tested using the 1-heptene cracking test of Example 10 and the results are presented in Table 1.

Heptene Cracking Test The following test procedure was used to evaluate the materials prepared in Examples 1-5. The heptene cracking test or the microreactor cracking test uses an electrically heated reactor which is loaded with 125 mg of 40-60 mesh (420-250 microns) particles of the catalyst to be tested. Each catalyst was dried 20 in situ for 30 minutes at 200C using flowing hydrogen, and then subjected to a reduction treatment of 425C in flowing hydrogen for one hour. The temperature of the reactor was then adjusted to 425C (inlet). The feed stream used to test the catalyst consists of hydrogen gas which is saturated with 1-heptene at 0C
and atmospheric pressure. The feed stream was flowed over the catalyst at a 25 flow rate of 125 cc/min. The effluent gas stream was analyzed using a gas chro-matograph. What is reported in the examples that follow is the total conversion of 1-heptene to cracked products. The results from all the tests is presented in Table 1.

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Table 1 Sample !.D. Crackiny (% Conv.) A (50% Filtrol #24/50% Al2O3 prepared 20 by oil dropping) B (80% Filtrol #24/20% Al2O3 as 7 extrudates) C (100% Saponite) 56 D (30% saponite/70% Al23 25 by oil dropping) E (Filtrol #24,100%) 25 F (Al2O3 spheres) 3 G (CeACH montmorillonite) 2 H (CeACH clay/AI2O3 spheres) 13 The data show several important features. First, the activity of sample A
which was prepared by oil dropping a mixture of Filtrol #24 clay and alumina is greater than would be expected from a physical mixture of clay and alumina.
Indeed, an extruded sample of 80% Filtrol ~24 and 20% alumina (sample B) shows much poorer activity than the oil dropped sample.
Second, a comparison of the results for samples C, D and F shows that an intimate mixture of a saponite clay (30/O) and alumina (70/O) has greater activity than would be expected from a physical mixture of the saponite and alumina.
Finally, samples G and H show the same effect, that is, when a CeACH clay is tested alone (sample G) very little activity is observed, whereas when the clay is 25 dispersed in an alumina matrix, a significant increase in activity is observed.

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Therefore, dispersing a clay in an aiumina matrix gives rise to synergistic effects which increases the activity of the composition versus a physical mixture of theclay and alumina.

Claims (8)

1. A composition comprising a layered clay homogeneously dispersed in an inorganic oxide matrix where the clay layers are completely surrounded by theinorganic oxide matrix, where the inorganic oxide is selected from the group consisting of alumina, titania, silica, zirconia, P2O5 and mixtures thereof and where the clay is present in a concentration from 5 to 80 weight percent of the composition.

2. The composition of Claim 1 where the clay is selected from the group consisting of bentonite, vermiculite, montmorillonite, kaolin, sepiolite, palygorskite, hectorite, chlorite, beidellite, saponite, nontronite and mixtures thereof.

3. The composition of Claim 1 where the clay is a pillared clay selected from the group consisting of aluminum chlorohydrate (ACH) clay and rare earth ACH clay and where the clay selected from the group consisting of hectorite, beidellite, nontronite, saponite, montmorillonite and mixtures thereof.

4. A catalyst comprising the composition of Claim 1, 2 or 3 having dispersed thereon a metal component selected from the group consisting of a Group IIIA, IIIB, IVB, VIII metal, molybdenum, tungsten and mixtures thereof.

5. The catalyst of Claim 4 where the metal component is present on the support in an amount from 1 to 30 weight percent (as the metal) of the support.

6. The catalyst of Claim 4 or 5 where the metal component is a mixture of nickel and tungsten.

7. A method of preparing the composition of Claim 1, 2 or 3 comprising mixing a clay with a hydrosol of a precursor of the inorganic oxide, forming spherical particles from said clay containing hydrosol and calcining said particles to form a composition comprising a clay homogeneously dispersed in an inorganic oxide matrix, such that the clay layers are completely surrounded by the inorganic oxide matrix.

8. A method of converging hydrocarbons comprising contacting the hydrocarbons with the compositions of Claim 1, 2 or 3 or the catalyst of Claims 4, 5 or 6 at hydrocarbon conversion conditions.