CN1035600C - Catalysts Containing Uniformly Layered Clay/Inorganic Oxide - Google Patents

Abstract

The present invention relates to a composition, a process for preparing the composition and a catalyst for use in the composition. The composition consists essentially of a layered clay uniformly dispersed in an inorganic oxide matrix. The clay is dispersed in such a manner that the clay layers are completely encapsulated by the inorganic oxide matrix. The inorganic oxide is selected from the group consisting of aluminum oxide, titanium dioxide, silicon dioxide, zirconium dioxide, phosphorus pentoxide, and mixtures thereof. The clay may be natural clay such as montmorillonite, metal ion-exchanged clay (Fe)⁺³Ion exchanged) or pillared clays such as Aluminum Chlorohydrate (ACH) pillared clays. The composition may be used as an alkylation or hydrocracking catalyst, or the metal may be dispersed on the composition to form a catalyst effective for hydrocracking or alkylation reactions.

Description

Catalysts Containing Uniformly Layered Clay/Inorganic Oxide

Naturally occurring clays such as montmorillonite, vermiculite, and bentonite are composed of semicrystalline aluminosilicate flakes, the layers held together by van der Waals forces or electrostatic attraction. The anionic charge of the siliceous layer is neutralized by cations in the interlayer space, usually Na ⁺ Ca ⁺² , which can polymerize with large inorganic cations such as Fe ⁺³ , Cr ⁺³ or with metal hydroxyls cations such as [Al ₁₃ O ₄ (OH) ₂₄ (H ₂ O) ₁₂ ] ⁺⁷ , [Zr(OH) ₂ ·4H ₂ O] ₄ ⁺⁸ for ion exchange. These polymeric cations act like pillars to support the clay layers.

Pillar clays are known to catalyze many reactions such as alkylation, cracking, ester synthesis, dimerization, and oligomerization. A review of reactions catalyzed by propped clays can be found in J.M. Adams, Chapter 2, Applied Clay Science, pp. 309-342 (1987). Among these reactions, alkylation has received great attention. For example, US Patent 4,499,319 discloses layered clays such as montmorillonite ion-exchanged with metal cations such as chromium and aluminum for the alkylation of aromatic compounds. Other examples include U.S. Patent 4,605,806, which discloses hydrogen ion exchange pillar clays; U.S. Patent 3,965,043, which discloses metal cation-exchanged three octahedral 2:1 layered smectite clays; and U.S. Patent 3,979,331, which discloses a Synthetic hectorite-like clays for metal cation exchange, which are suitable for the alkylation of aromatic hydrocarbons.

Another reference is US Patent No. 4,499,195, which discloses a cogel composed of a smectite clay and an inorganic metal oxide. Inorganic oxides include Group IV-B metals and other oxides such as silicon, aluminum, thorium and uranium. However, since the metal oxide colloid is formed before the clay is added, there occurs a phenomenon that the clay cannot be uniformly dispersed in the metal oxide colloid. 195 reference (US Pat. No. 4,587,009), in which such cogels are used for hydrocarbon hydrogenation, is described in continuation.

US Patent 4,111,846 discloses a catalyst using zeolite as the active material and clay as the "weighting" agent. Apparently the "weighting" agent is a filler used to increase the density of the catalyst. Finally, US Patent No. 4,844,790 discloses a lamellar clay and the patentee incidentally mentions that the catalyst may consist of zeolite and/or refractory oxide components as part of the catalyst. The catalyst is prepared by spray drying.

In contrast to the prior art, we have prepared a composition comprising a clay (pillared or non-pillared) uniformly dispersed in a matrix of inorganic oxides. Inorganic oxides that can be used as substrates can be alumina, titania, silica, zirconia, P ₂ O ₅ and mixtures thereof. The preferred method of preparing such a composition involves dispersing the clay into a sol containing the elements which are precursors to oxides, thus passing through the oil droplets to form the mixture into spherical particles, which are then calcined to form a clay With the metal oxide matrix dispersed therein, the composition is more reactive than untreated clay.

These inorganic oxide matrices envelop the clay layers such that they are layered and uniformly dispersed throughout the inorganic oxide matrix at a size per micron. Uniformity is obtained by using hydrosols, which cannot be obtained by extrusion and spray drying of physical mixtures of clay and metal oxides. In fact, the alumina-matrix-coated acid-washed montmorillonite compositions of the present invention are more active than physical mixtures of clay and alumina.

The present invention relates to a composition, a method of preparing the composition, a catalyst using the composition and a method of using the composition. Accordingly, one embodiment of the present invention is a composition of uniformly dispersed layered clays in a matrix of inorganic oxides, the clay layers being completely surrounded by said matrix of inorganic oxides selected from the group consisting of aluminum oxide , titanium dioxide, silicon dioxide, zirconium dioxide, P ₂ O ₅ and their mixtures, and the clay content in the composition accounts for 5-80% (percentage by weight) of the whole.

Another embodiment of the present invention is a catalyst comprising metal elements dispersed on a carrier, the metal is selected from Group IIIA, IIIB, IVB, VIII metals, molybdenum, tungsten and their mixtures, and the carrier is uniformly dispersed on an inorganic oxide Layered clay within a matrix, wherein the clay layer is completely surrounded by a matrix of these inorganic oxides selected from the group consisting of alumina, titania, _silica , zirconia, _P2O5 and mixtures thereof .

Yet another embodiment of the present invention is a method of preparing the composition comprising uniformly dispersing the layered clay in an inorganic oxide matrix, the method further comprising mixing the layered clay with an aqueous sol of these inorganic oxide precursors Mixing, forming spherical particles from the hydrosol-containing clay, and calcining said particles forms a composition consisting essentially of layered clay uniformly dispersed in an inorganic oxide matrix, the clay layers being entirely surrounded by the inorganic oxide matrix.

Figure 1a is an electron microscope (SEM) photograph of silicon distribution in a cross-section of an extrudate of a physical mixture containing alumina and acid-washed montmorillonite clay.

Figure 1b is a SEM photograph of aluminum distribution in the extruded sample of Figure 1a.

Fig. 2a is a SEM photo of silicon distribution in the cross-section of a sphere composed of Al2O3 and acid-washed montmorillonite clay prepared by the method of the present invention.

Figure 2b is an SEM image of the aluminum distribution in the sphere sample of Figure 2a.

The present invention relates to a composition, a method of preparing the composition, a catalyst using the composition and a method of using the composition. An essential component of the compositions of the present invention is clay. Both natural and synthetic clays can be used, including but not limited to bentonite, sepiolite, Laponite ^™ , vermiculite, montmorillonite, kaolin, montmorillonite active ingredient, hectorite, chlorite, beidellite, Talc and nontronite. Laponite ^TM in the clay above is a synthetic hectorite manufactured by LaPorte Corporation with the chemical formula: Na _0.58 Si ₈ Mg _5.42 Li _0.58 F _2.5 (OH) _1.5 O ₂₀ (Laponite-B) or Na _0.45 Si ₈ Mg _5.54 Li _0.45 (OH) ₄ O ₂₀ (Laponite-RD). Montmorillonite, hectorite, beidellite, and talc have synthetic analogs. As mentioned earlier, these clays are composed of aluminosilicate semi-crystalline layers held together by van der Waals forces or electrostatic attraction. These clays (including natural and synthetic analogues) can be used directly in the existing form (or synthetic form), and can also be improved by metal exchange or by introducing a column structure between layers to become a pillar-type structural clay. reuse. Any clay including each of the above listed ones can be exchanged with one or more of Fe ⁺³ , Cr ⁺³ , Al ⁺³ , Ti ⁺⁴ and Zr ⁺⁴ . Clays that can be introduced into pillared structures are smectites (natural and synthetic), which are hectorite, beidellite, nontronite, talc and montmorillonite. Its pillars are selected from aluminum chlorohydrate (ACH) and rare earth ACH.

Aluminum chlorohydrate (also known as basic aluminum chloride) is a polymeric metal complex with the following empirical formula:

Al _2+n (OH) _2n Cl ₆ n is a value from 4 to 12. The preparation of such aluminum polymers is well known to those skilled in the art, eg 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).

Rare earth ACH is improved by introducing one or more of the following rare earth elements into ACH as described above, which are: cerium, lanthanum, neodymium, europium, etc. This modification of ACH polymers with rare earths is accomplished by adding soluble rare earth salts, preferably water soluble rare earth salts. Examples of rare earth salts are nitrates, halides, sulfates and acetates. Preferred rare earth elements are cerium and lanthanum, and preferred rare earth salts are cerium nitrate and lanthanum nitrate. Rare earths are introduced into the polymeric or oligomer structure by mixing a rare earth salt solution (preferably an aqueous solution) or a solid rare earth salt with ACH. The mixture was refluxed at 105°-145°C for 24-100 hours. The weight ratio of rare earth elements (expressed by oxides, such as CeO ₂ ) to aluminum oxide in the solution before reflux is 1:52 to 1:1.

When a pillar-type structure is introduced into the clay, the clay is expressed as ACH clay and rare earth ACH clay, such as CeACH, clay. ACH clay or rare earth ACH clay is prepared by methods known in the literature, such as adding the required clay to ACH or rare earth ACH solution, stirring, filtering, redispersing with water (once or several times), isolating, drying and drying at 500 ° C to Calcination at 800°C for a certain time is sufficient to fix its structure (preferably about 16 hours). Any and all clay mixtures listed above may be used in the present invention.

The second essential component in the present invention is the inorganic oxide matrix. These inorganic oxides are selected from alumina, titania, silica, zirconia, P ₂ O ₅ and mixtures thereof, preferably alumina. The clay concentration in the inorganic oxide matrix is 5-80% of the composition, preferably 30-70% by weight.

In addition, the composition contains a clay and an inorganic oxide matrix, and the clay must be uniformly dispersed in the inorganic oxide matrix. Uniform dispersion means that it is uniformly dispersed in each micron, that is to say, if you check the area per square micron, you will find that the distribution of matrix components and clay components is uniform, that is to say, the degree of separation of each component will not be too large .

Uniform dispersion can be achieved by utilizing the elemental sol as an inorganic oxide precursor. The sol or hydrosol solution is contained in a glass container, and when it is placed between the strong light and the observation line of sight, it appears as a light blue tube, which is the Tyndall effect. By using a sol, the clay layer is completely covered by the sol so that by further processing it is possible to obtain a clay layer completely or partly covered by the inorganic oxidizing matrix. That is, it is possible to obtain a layered clay uniformly dispersed in an inorganic oxide matrix.

A preferred method for obtaining such dispersions involves modifying the well known oil drop method given in US Patent 2,620,314. For example, when aluminum oxide is used as the specified inorganic oxide, the improved oil drop method includes making an aluminum hydrosol by means of any technique given in the above-mentioned documents, and the preferred solution is to react with metal aluminum and hydrochloric acid; the selected The clay is added to the aluminum hydrosol; a suitable gelling agent is used to combine with the resulting hydrosol mixture, and the resulting mixture is dropped into an oil bath kept at a high temperature. The mixture drops were kept in an oil bath until they coagulated into hydrosol spheres. These spheres are then successively extracted from the oil bath, typically subjected to specialized aging in oil, drying, and ammonia solution to further improve their physical properties. The aged and gelled spheres are washed and dried at a low temperature of 80°-150°C, and then calcined at 455°-705°C for 1-20 hours. The aforementioned treatments affect the conversion of the hydrogel into a corresponding crystalline gamma-alumina matrix in which the layered clay is uniformly dispersed.

Another method for uniformly dispersing clay in an inorganic oxide matrix is to form a precursor sol or a mixture of precursor salt solution and clay, then spray-dry the mixture to form particles containing uniformly dispersed clay, and finally calcinate these particles to make the sol Or the salt is converted into the desired inorganic oxide.

The uniform dispersion described above cannot be achieved by spray drying (see US Patent No. 4,844,790) or extrusion of physical mixtures of inorganic oxides and layered clays. When forming a two-component slurry or dough, a two-component powder is used with a particle size between 5 and 30 microns. Thus, there will be particles of one component ranging from 5 to 30 microns dispersed among the particles of the other component. While the final product is homogeneous on a macroscopic scale, it is not homogeneous on a microscopic scale as defined above. In addition, since there is no sol to wrap and separate the clay layers to keep them in a separate state, the calcination of the clay layer cannot completely wrap the clay layer with the inorganic oxide matrix.

It is entirely plausible that a uniform dispersion of clay in an oxide matrix can significantly increase its activity. The uniform dispersion results can be proved by the SEM photos in Figure 1 and Figure 2. Figure 1 represents two SEM cross-sectional photographs of an extrudate prepared as in Example 2, a physical mixture of Filtrol #24 and alumina. The bright spots on Figure 1a indicate the presence of silicon, and the bright spots on Figure 1b indicate the presence of aluminum. Fig. 2 represents the SEM photos of two cross-sections of spheres, which are prepared according to the method of the present invention in Example 1. The clay sample is Filtrol #24 and the oxide matrix is alumina. Figure 2a is a spot diagram for silicon (bright areas) and Figure 2b is a spot diagram for aluminum on a cross-section of a sphere. Since silicon exists only in clay, the more uniform the distribution of the dot diagram of silicon, the greater the degree of dispersion of clay in the alumina matrix.

From Fig. 1a, it can be observed that one area is very strong and other areas are weaker, which is obviously caused by clay inhomogeneity. Aluminum has the same profile (Fig. 1b); that is, some areas are stronger than others, and large voids, possibly caused by accumulation of the two components, can also be seen. Furthermore, a certain region with strong Al dots does not have strong Si dots, and vice versa. It is clear that the sample is not homogeneous.

Figures 2a and 2b are particularly homogeneous compared to Figures 1a and 1b. For example, the silicon dot map of Figure 2a shows strong spots that are evenly distributed over the entire photograph. The Al dot map of Figure 2b also shows that the Al dot intensity is evenly distributed over the entire photograph. In addition, the strength of silicon and the strength of aluminum are blank spots, which are uniformly distributed throughout the sample. The homogeneity of the samples prepared by the method of the invention was thus verified.

Without wishing to be bound by any particular theory, it is believed that the fact that the clay layer is surrounded by the inorganic oxide matrix causes a synergistic interaction between the clay and the inorganic oxide matrix (such as aluminum oxide). The synergistic effect results in increased activity.

The resulting composition of the present invention is an effective catalyst or support for the metal itself as a catalyst. Accordingly, without further modification, the compositions of the present invention are useful in catalyzing hydrocarbon conversion reactions by contacting hydrocarbons under hydrocarbon conversion reaction conditions. For example for alkylation, cracking, oligomerization, isomerization and transalkylation reactions. Additionally, the metal component (whether metal or oxide thereof) deposited on the composition may provide additional or different catalytic properties. Metals constituting the metal component may be selected from group IIIA, IIIB, IVB and VIII metals, molybdenum, tungsten and mixtures thereof.

The metal component can be deposited on the composition by suitable methods known in the literature, the composition serving as a support. One method is to impregnate the support in an aqueous solution of one or more metal compounds which are decomposable. Decomposable means that metal compounds can be converted to metals or metal oxides by heating and release by-products. Examples of said decomposable metal compounds are cobalt chloride, cobalt nitrate, cobalt acetate, cobalt sulfate, ferric chloride, ferric nitrate, ferric acetate, ferric sulfate, nickel chloride, nickel nitrate, nickel acetate, nickel sulfate, platinum chloride Ammonium acid, chloroplatinic acid, bromoplatinic acid, dinitrodiamidoplatinum, sodium tetranitroplatinate, rhodium trichloride, hexaammine rhodium chloride, carbonyl rhodium chloride, sodium hexanitrorhodate, chlorine Palladium acid, palladium chloride, palladium nitrate, diammine palladium hydroxide, tetraammine palladium chloride, hexachloroiridium(IV) acid, hexachloroiridium(III) acid, hexachloroiridium(III) acid ammonium, hydrated Ammonium hexachloroiridium(IV), ruthenium tetrachloride, ruthenium hexachloride, ruthenium hexaamine chloride, osmium trichloride, osmium ammonium chloride, ammonium paramolybdate, ammonium tungstate, aluminum chloride, aluminum nitrate , boric acid, gallium nitrate, gallium trichloride, indium chloride, indium nitrate, thallium acetate, scandium nitrate, lanthanum chloride, lanthanum nitrate, yttrium chloride, yttrium nitrate, titanium trichloride, zirconium tetrachloride, zirconium sulfate and hafnium chloride.

If more than one metal is desired, the metals can be in a common aqueous solution or in separate aqueous solutions. When separate aqueous solutions are used, the supports may be impregnated successively in any order. Although the concentration of the metal component can vary considerably, it is desirable that the concentration of the metal component in the catalyst is 0.1 to 30% by weight of the support, preferably 1 to 15% by weight.

A preferred impregnation procedure involves the use of a rotary steam jacket drier. The carrier is immersed in the impregnation solution containing the predetermined metal compound in the drier, and the carrier is rolled by the rotary motion of the drier. The use of water vapor in the jacket of the dryer accelerates the evaporation of the solution in contact with the rolling carrier. The resulting composite material is dried at ambient temperature, or at 80°-110°C, and then calcined at 400°-650°C for 1-4 hours, so that the metal compound is converted into metal or metal oxide thing.

Compositions of the present invention with or without a metal component can be used as catalysts for alkylation. The conditions necessary to achieve alkylation of aromatic compounds are well known and disclosed in U.S. Patent 3,965,043 or 3,979,331, incorporated herein by reference. This process can generally be accomplished by batch operation or continuous operation. In a batch operation, the catalyst, aromatic compound and alkylating agent are placed in an autoclave and, when necessary, pressurized to affect the progress of the reaction in the liquid phase. The aromatic compound should be present in excess, preferably in the range of 2:1 to 20:1 moles of aromatic compound to moles of alkylating agent. This reaction is achieved at high temperature because the rate of alkylation is very low at room temperature. The preferred temperature range is 40° to 200°C and the time required to carry out the process is about 0.5 to 4 hours, after which the product is separated from the starting material by conventional means.

If it is desired to carry out the process in a continuous manner, the catalyst is placed in the reactor and heated to the desired operating temperature and, if necessary, the pressure is raised above atmospheric pressure. The aromatic compound and alkylating agent flow through the catalyst bed at a predetermined liquid hourly space velocity effective for alkylation. The fluid is discharged continuously, and the desired product is separated by conventional separation methods.

Additionally, the compositions of the present invention, with or without the addition of catalytic metals or other catalytic materials such as Y zeolite, can be used as hydrocracking catalysts. Typical hydrocracking conditions include temperatures from 400° to 1200°F (204 to 649°C), preferably 600° to 950°F (316 to 510°C), and reaction pressures from atmospheric pressure (101.3KPa) to 3500 lbs/ ^hour2 (24235KPa), preferably 200-3000 lb/ ^h2 (482-20788KPa). The contact time generally corresponds to the liquid hourly space velocity (LHSV) in the range of 0.1 hr ^-1 to 15 hr ^-1 , preferably 0.2 to 3 hr ^-1 . The hydrogen circulation rate is 1000-50000 standard cubic feet (scf) per barrel (189-8888 standard m ³ /m ³ ), preferably 2000-30000 scf per barrel (355-5333 standard m ³ /m ³ ).

Example 1

Spheres containing clay and alumina were prepared in the following manner. The aluminum hydrosol is produced by the reaction of metal aluminum and hydrochloric acid, the weight percentage of aluminum in the sol is 12-13.5%, and the ratio of aluminum and chlorine is 1.19. Filtrol#24 clay (an acid-washed or activated montmorillonite clay manufactured by Engelhard) was added to the sol so that the weight percent of clay in the fine spheres was 50% (50% for Al2O3). The clay was added to the hydrosol by intensive mixing and further mixing using a ball mill. Hexamethylenetetramine (HMT) was added to the mixture to gel the mixture into spheres as it dripped through an oil tower maintained at a temperature of 95°C. The amount of HMT added was about 130% of the amount required to neutralize the acid in the aluminum sol.

After removal from the hot oil, the spheres were aged under pressure at 140°C for 2 hours, washed with 10 liters of dilute ammonium hydroxide solution (1% by weight _NH4OH ), dried at 110°C and calcined at 650°C for 2 hours. These spheres were identified as Sample A. After calcination, the cleavage activity of the spheres was determined using the 1-heptene microreactor test described in Example 10, the results of which are reported in Table 1. Example 2

The catalyst was a dough-like paste made with 80% Filtrol #24 and 20% aluminum oxide powder and water. This paste is extruded into 1/16 " extrudate through die, in 600 ℃ of calcining 2 hours in 10% water vapor air. This catalyst is marked as sample B and measures with the method for embodiment 10, and the result is listed in the table 1. Example 3

Synthetic talcum powder was prepared by hydrothermal synthesis as described in US Pat. No. 4,749,676, which is incorporated by reference, and can be exemplified by reference. Magnesium sulfate, sodium aluminate and water glass were used as sources of Mg, Al and Si, respectively. The atomic number ratio of (Na-Al):(Mg+Si+3/2Al) in the sol is 0.34, corresponding to the Si/Al ratio of the tetrahedral sheet being 5.6. Adjust the pH of the gel to 9 with NaOH and _Na2CO3 , then place the gel in a Parr Bomb and heat it to 200° _C under autogenous pressure for 6 hours to crystallize the talc powder come out. The product was recovered by filtration, washed with deionized water and dried at 110°C for 4 hours. The dried product is ground to a fine powder. Example 4

The talc powder prepared in Example 3 was exchanged with aluminum chlorohydrate in the following manner, talc powder (clay) was suspended in a solution consisting of water and aluminum chlorohydrate. Aluminum chlorohydrate was obtained from Reheis as a 50% aqueous solution. After 30 minutes, the talc clay was collected by filtration and washed with water until the washed water was free of chlorides. The clay was dried at 110°C for 2 hours and then calcined at 450°C for 3 hours. This sample is designated as sample C, carries out 1-heptene cracking test with the method for embodiment 10, and its result is listed in table 1. Example 5

This example describes the preparation of spheres using the aluminum chlorohydrate-exchanged talc powder of Example 4. The talcum powder obtained in Example 4 was used instead of Filtrol #24 clay, and the spheres were prepared according to the detailed steps in Example 1. This sphere was designated Sample D. After calcination, the spheres were tested in the heptene cracking test of Example 10, and the results are listed in Table 1. Example 6

Filtrol#24 was obtained from Engelhard Company, the particle size was 40-60 mesh, this sample was designated as sample E, and tested by the method of Example 10, the results are listed in Table 1. Example 7

Alumina spheres were prepared according to the method in Example 1, but no clay was added to the alumina sol. This sphere was designated Sample F and tested as in Example 10. The results are listed in Table 1. Example 8

Cerium chloride-aluminum hydrate pillar-type montmorillonite was prepared according to the method of international patent WO88/06488. After drying, the pillar-type clay was steamed and baked at 650° C. for 3 hours. This sample was designated as sample G and used 1- Heptene cracking test test, the results are listed in Table 1. Example 9

This example describes the preparation of spheres from the cerium chloride-aluminum hydrate pillar clay prepared in Example 8. Spheres were prepared using the procedure detailed in Example 1, except that the pillar clay of Example 8 was used in place of the Filtrol #24 clay. These spheres were designated Sample H. After calcination, the spheres were tested in the 1-heptene cracking test of Example 10, and the results are listed in Table 1. Example 10

Heptene cracking test

The following test procedures were used to evaluate the materials prepared in Examples 1-5. Heptene pyrolysis test or microreactor pyrolysis test uses an electronically heated reactor, which contains 125 mg of 40-60 mesh (420-250 micron) granular catalyst to be tested. Each catalyst was dried in situ with flowing hydrogen at 200°C for 30 minutes. It was then subjected to reduction treatment at 425°C for 1 hour in flowing hydrogen. The reactor was set to 425°C (inlet). The feed stream for the determination of the catalyst consisted of hydrogen saturated with 1-heptene at 0°C and atmospheric pressure. The flow rate of the feed stream over the catalyst was 125 cc/min. The effluent gas was analyzed by gas chromatography. The examples reported are total conversions of 1-heptene cracking products. All test results are listed in Table 1.

Table 1 Sample I.D. Cracking rate (conversion %) A (50% Filtrol#24/

50% Al ₂ O ₃ , prepared by the oil drop method) 20B (80% Filtrol#24/

20% _Al2O3 extrudate) 7C (100% talc ₎ 56D (30% talc/70%

Al ₂ O ₃ prepared by oil drop method) 25E (Filtrol#24, 100%) 25F (Al ₂ O ₃ spheres) 3G (CeACH montmorillonite) 2H (CeACH clay/Al ₂ O ₃ spheres) 13

These data reveal an important feature. First of all, the sample A prepared by the mixture of Filtrol#24 clay and aluminum oxide by the oil drop method has higher activity than the physical mixture of clay and aluminum oxide. The 80% Filtrol #24 and 20% alumina extruded sample (Sample B) showed much lower activity than the oil drop method sample.

Second, a comparison of the results for Samples C, D and F shows that an intimate mixture of talc clay (30%) and alumina (70%) is more active than a physical mixture of talc and alumina. Finally, samples G and H showed the same effect, namely the very low activity observed when the CeACH clay was measured alone (sample G), while the activity was significantly increased when the clay was dispersed in the alumina matrix. Thus, the dispersion of the clay in the alumina matrix acts synergistically to increase the activity of the composition relative to a physical mixture of clay and alumina.

Claims (7)

1. A composition comprising layered clay uniformly dispersed in an inorganic oxide matrix, characterized in that the clay layer is completely wrapped by the inorganic oxide matrix, and the inorganic oxide is selected from the group consisting of aluminum oxide, titanium dioxide, titanium dioxide Silicon, zirconium dioxide, phosphorus pentoxide and mixtures thereof, and the clay concentration is 5-80% (wt) of the composition. 2. composition as claimed in claim 1 is characterized in that clay is selected from bentonite, vermiculite, montmorillonite, kaolin, sepiolite, montmorillonite active ingredient, hectorite, chlorite, Beide stone, talc, nontronite and mixtures thereof. 3. The composition of claim 1, wherein the clay is a pillar clay selected from aluminum chlorohydrate (ACH) clays and rare earth ACH clays and the clay is selected from hectorite, beidellite, Talc, montmorillonite and mixtures thereof. 4. A catalyst comprising a carrier and a metal component loaded thereon, and the carrier comprises a composition as claimed in claim 1, 2 or 3, the metal component being selected from IIIA, IIIB, IVB, VIII Group metals, molybdenum, tungsten and their mixtures, and the metal component on the carrier is 1-30% (wt) (calculated as metal) of the weight of the carrier. 5. A catalyst as claimed in claim 4, characterized in that the metal component is a mixture of nickel and tungsten. 6. A method for preparing a composition as claimed in claim 1, 2 or 3, characterized in that the clay and the hydrosol of the inorganic oxide precursor are mixed, the clay containing the hydrosol is made into spherical particles, and the calcined Spherical particles make the clay uniformly dispersed in the inorganic oxide matrix to form a composition in which the clay layer is completely covered by the inorganic oxide matrix. 7. A process for the conversion of hydrocarbons, characterized in that the hydrocarbons are contacted with a composition as claimed in claim 1, 2 or 3 or a catalyst as claimed in claim 4 or 5 under hydrocarbon conversion conditions.

Images