MXPA99010217A - Aluminosilicate compositions, preparation and use - Google Patents

Abstract

process for catalytic cracking of a hydrocarbon feed, comprising the steps of:providing an initial hydrocarbon fraction;providing a catalyst comprising an aluminosilicate composition having an aluminosilicate framework and containing at least one metal other than aluminum incorporated into said aluminosilicate framework;and exposing said hydrocarbon to said catalyst under catalytic cracking conditions so as to provide an upgraded hydrocarbon product.

Description

PREPARATION AND USE OF ALUMINOSILICATE COMPOSITIONS BACKGROUND OF THE INVENTION The history of zeolites begins with the discovery of the stylbita in 1756 by the mineralogist A. Cronsted. Zeolite means "stone that boils" and refers to the porous mass that can be obtained when the zeolite is fused in a jet plane. Volatile zeolitic water forms bubbles within the melt. The zeolites are crystalline aluminosilicates having as a fundamental unit a tetrahedral complex consisting of Si4 + and Al3 + in tetrahedral coordination with 4 oxygens. These tetrahedral units of [SiO and [A10] are linked together by shared oxygens and are thus forming three-dimensional networks.The construction of such networks produces channels and cavities of molecular dimensions.The water molecules and charged compensating cations are found within the channels and cavities of zeolitic networks, although there has been much knowledge about zeolites and their properties, it was until the middle of this century that commercial preparation and use of zeolites was possible. and modification of zeolitic materials.

The modification of the physical chemical properties of the zeolitic molecular sieve by the incorporation of other elements than silicon and aluminum can be obtained by one of the following ways: 1.- Incorporation through ion exchange 2. - Incorporation through impregnation 3 .- Incorporation in the synthesis gel. The most common and well known way to introduce different elements into the channels and cavities of zeolitic molecular sieves is through ion exchange. In this way, the compensating cation balances the negative charge of the lattice (usually sodium) which is replaced by a new cation after the ion exchange is performed. In this case, the new cation is located within the channels and cavities of the zeolite, but is not coordinated with the silicon atoms through the oxygen atoms. The incorporation of other chemical elements in the zeolitic molecular sieve through impregnation is another common way to modify the properties of zeolitic materials. For this case, most of the element incorporated in the zeolite is found on the surface of the crystallites of the zeolitic material. The incorporation in synthesis gel of other chemical elements to produce zeolitic molecular sieves allows an important advance in this research area. This variation has not only modified the physico-chemical properties of the zeolitic materials of known structures, but has also led to the production of unknown new structures in the aluminosilicate frameworks. The patent literature and the open literature have shown two important groups of zeolitic molecular sieves which incorporate other elements besides silicon and aluminum. These two main groups are the metalosilicates and the metalloaluminophosphates. The metalosilicatos are molecular sieves in which the aluminum is replaced by another element like gallium, iron, boron, titanium, zinc, etc. Metalloaluminophosphates are molecular sieves in which the aluminophosphate framework is modified by the incorporation of another element such as magnesium, iron, cobalt, zinc, etc. Because the present invention is more related to metallosilicates than to metalloaluminophosphates, the metalosilicates are discussed in greater detail. To choose an element to be incorporated within a molecular sieve framework, researchers have considered the possibility that the chosen element can acquire a tetrahedral coordination as well as the ionic radius ratio of that element. Table 1 shows the elements that can obtain a tetrahedral coordination as well as the radii of ionic proportion of such elements.

Some of the elements indicated in table 1 have been claimed or have been incorporated into molecular sieve structures of the metallosilicate type. Some examples are: iron silicates or ferrisilicates [patents of the U.S. Nos. 5,013,537; 5,077,026; 4,705,675; 4,851,602; 4,868,146 and 4,564,511], zincosilicates [patents of the US. Nos. 5,137,706; 4,670,617; 4,962,266; 4,329,328; 3,941,871 and 4,329,328], gallosilicates [US patents. Nos. 5,354,719; 5,365,002; 4,585,641; 5,064,793; 5,409,685; 4,968,650; 5,158,757; 5,133,951; 5,273,737; 5,466,432 and 5,035,868], zirconosilicates [Rakshe et al, Journal of Catalysis, 163: 501-505, 1996; Rakshe et al, Catalysis Letters, 45: 41-50, 1997; US patent 4,935,561 and 5,338,527], chromosilicates [patents of the U.S. 4,299,808; 4,405,502; 4,431,748; 4,363,718; and 4, 4534, 365], magnesosilicates [US patents. Nos. 4,623,530 and 4,732,747] and titanosilicates [US patents. Nos. 5,466,835; 5,374,747; 4,827,068; 5,354,875 and 4,828,812].

Table 1 Metal ions that can obtain tetrahedral coordination and their ionic crystal radii.

Ion metallic Radio (?) Ion metallic Radio (A) Al3 + 0.530 Mg2 + 0.710 As5 + 0.475 Mn2 + 0.800 B3 + 0.250 Mn4 + 0.530 Be2 + 0.410 Mn5 + 0.470 C? + 0.720 Mn6 + 0.395 Cr4 + 0.550 Ni2 + 0.620 Cr5 + 0.485 P5 + 0.310 Fe + 0.770 Si4 + 0.400 Fe3 + 0.630 Sn4 + 0.690 Ga3 + 0.610 Ti4 + 0.560 Ge4 + 0.530 Vs + 0.495 Hf4 + 0.720 Zn2 + 0.740 In3 + 0.760 Zr4 + 0.730 Conventional preparation of metallosilicates is successful only if a guide compound structure ("organic templates") is added to the synthesis mixture. In general, tetraalkylammonium compounds, tertiary and secondary amines, alcohols, ethers and heterocyclic compounds are used as organic templates. All of these known methods for producing metalosilicates have a number of serious disadvantages if it is desired to produce them on a commercial scale. For example, those organic templates that are used are toxic and easily flammable so that, since their synthesis must be carried out under hydrothermal conditions and at high pressure in autoclaves, an escape of these templates into the atmosphere can never be completely avoided. . In addition, the use of templates increases the cost of production of the material because the template is expansive and because the effluent from the production of the metallosilicate also contains toxic materials which require a costly and careful disposal in order to avoid contamination of the environment In addition to this, the obtained metallosilicate has an organic material within the channels and cavities so that, to be useful as a catalyst or adsorbent, this organic material must be removed from the network. The removal of the organic template is carried out by combustion at high temperatures. The removal of the template can cause damage to the lattice structure of the metalosilicate molecular sieve and thereby decrease its catalytic and adsorption properties. Metalloaluminosilicate is another group of zeolitic molecular sieves that can be prepared, however, research in this area is not as popular as with metalloaluminophosphates and metalosilicates. Despite this, in the patent literature it is possible to find some examples of this type of material. The preparation of iron-titano- and galloaluminosilicates can be found in US Pat. No. 5,176,817; US patent No. 5,098,687, US patent. No. 4,892,720; US patent No. 5,233,097; US patent No. 4,804,647; and US patent. No. 5,057,203. For these cases, the preparation of the material is through a post-synthesis treatment. An aluminosilicate zeolite is placed in contact with a suspension of a titanium fluoro salt and / or an iron or gallium salt and then part of the aluminum is replaced by titanium, iron or gallium. This methodology has certain disadvantages due to the additional steps necessary to produce the material. The ideal action that must be carried out must be to add the desired element in the synthesis gel and then through a hydrothermal process obtain the metalloaluminosilicate material. In the patent literature it is possible to find some examples of this type of procedure. The US patent No. 5, 648,558 describes the preparation and use of metalloaluminosilicates of the BEA topology with chromium, zinc, iron, cobalt, gallium, tin, nickel, lead, indium, copper and boron. The US patent No. 4,670,474 describes the preparation of ferrimetalosilicates with aluminum, titanium and manganese. The US patent No. 4,994,250 describes the preparation of a galloaluminosilicate material having the topology OFF. The US patents Nos. 4,761,511; 5,456,822; 5,281,566; 5,336,393; 4,994,254 describe the preparation of galloaluminosilicates of the MFI topology. The US patent No. 5,354,719 describes the preparation of metalloaluminosilicates of the MFI topology with gallium and chromium. These examples of metalloaluminosilicates require the use of organic templates or seeding procedures so that these methods of preparing metalloaluminosilicates have problems similar to those described above for the methods of preparing the metalosilicate.

BRIEF DESCRIPTION OF THE INVENTION The invention presents a new method for obtaining a new family of aluminosilicate and metalloaluminosilicate materials of MFI topology, and their use in the FCC area. The synthetic metalloaluminosilicates produced with this method of invention have physical and chemical characteristics which make them clearly differentiated from other products. The methodology does not use organic templates or planting procedures. The preparation method developed in the invention allows incorporation into the synthesis gel of other elements of the periodic table and these interact with the silicon source in an acid medium. In this way, the elements are incorporated into the prepared material and these elements are not ionically interchangeable when the final material is obtained. The elements that can be incorporated into the aluminosilicate framework of the present invention include those elements of the groups HA, 11IB, IVB, VB, VIB, VIIB, VIII, IB, IIB, IIIA, IVA, and VA (using the nomenclature of the CAS version) of the periodic table. The amount of such elements present in the aluminosilicate framework of the present invention may vary based on the required amount of such element in the material. In addition, it is possible to mix more than two elements in a given material of the present invention. However, for all the compositions of the present invention, it is a feature that at least part of the incorporated elements are not ionically interchangeable by conventional techniques and that they are present in the aluminosilicate material. The new compositions show X-ray diffraction patterns which contain certain definable minimum lattice distances. In addition, new metalloaluminosilicate materials show specific absorption bands in the infrared spectrum. In addition, the new materials show specific bands in the NMR spectrum analysis. The method developed for preparing metalloaluminosilicate materials can also be used to prepare aluminosilicate material such as ST5 (U.S. Patent No. ,254,327) and other materials of type MFI or of higher proportions of Si / Al given the correct conditions. The materials of the present invention have a composition which can be expressed according to one of the formulas given below in terms of molar ratios of oxides: 1. - a (M2 / nO): b (Al203): c (E203): d (YES02): e (H20) 2. - a (M2 / nO): b (Al203): c (F02): d (YES02): e (H20) 3. - a (M2 / n0): b (Al203): c (GO): d (YES02): e (H20) 4. - a (M2 / n0): b (Al203): c (H205): d (Si02): e (HaO) wherein M is at least one interchangeable cation of ions having a valence of n; E is an element with a valence 3+ which has not become ionically interchangeable by conventional means; F is an element with valence 4+ which is not ionically interchangeable by conventional means, - G is an element with a valence 2+ which is not ionically interchangeable by conventional means; H is an element with valence 5+ which is not ionically interchangeable by conventional means; a / b > 0; c / b > 0; d / b > 0; d / c > 0; e / b > 0; a / (b + c) > 0; d / (b + c) > 0; a is from > 0 to 6, b is equal to l, c-li is from > 0 to 10, d is from 10 to 80 and e is from 0 to 100. The invention is not limited to such wet materials or oxide forms, but rather its composition may be present in terms of oxides and on a wet basis (as in the above formulas) in order to provide a means to identify part of the novel compositions. In addition, the compositions of the present invention can also incorporate more than one element which is not ion exchangeable and which have different valences (mixtures of E, F, G and H). Other formulas can be written by those familiar in the art to identify particular subsets or embodiments of the present invention which comprise porous crystalline metalloaluminosilicates. The metalloaluminosilicates of the present invention have useful properties including catalytic activity. These novel compositions can be used advantageously in known processes which currently use aluminosilicate zeolites. The aluminosilicate compositions of the present invention can be advantageously incorporated with binders, clays, aluminas, silicas or other materials that are well known in the art. They can also be modified with one or more elements or compounds by deposition, occlusion, ion exchange or other techniques known to those familiar in the art to improve, supplement or alter the properties or usefulness of the aluminosilicate compositions of the present invention. The metalloaluminosilicates of the present invention can be used as an additive in the FCC area. The metalloaluminosilicates of the present invention are prepared by hydrothermal methods and, therefore, the elements incorporated in the aluminosilicate compositions are not ion exchangeable and form part of the structure of the crystalline aluminosilicate composition. According to the invention, there is provided a method for preparing a metalloaluminosilicate which includes the steps of: providing a solution containing a source of silica, -providing a solution containing an alumina source, -providing an aqueous acid solution which contains a metal other than silicon or aluminum; mix the source solution with an aqueous acid solution so that a mixture containing silica metal source is formed, - mix the mixture containing metal and silica source with the alumina source solution so as to provide a gel mixture; and hydrothermally crystallizing the gel mixture so as to provide a metalloaluminosilicate material having an aluminosilicate framework and having the metal incorporated within the aluminosilicate framework. In further accordance with the invention, there is provided a method for preparing aluminosilicate comprising the steps of: providing a solution containing a silica source, -providing a solution containing an alumina source, -mixing the silica source solution with the aqueous acid solution so that a silica-acid source mixture is formed, - mixing the silica source-acid mixture with the alumina source solution so as to provide a gel mixture; and hydrothermally crystallizing the gel mixture so as to provide a composition having an aluminosilicate framework, in which the composition is formed without the organic additives. A composition is also provided which comprises a metalloaluminosilicate composition comprising an aluminosilicate composition having an aluminosilicate framework and containing at least one metal incorporated within the aluminosilicate framework.

BRIEF DESCRIPTION OF THE DRAWINGS A detailed description of preferred embodiments of the invention follows with reference to the accompanying drawings, in which: Figure 1 is a Mossbauer spectrum of Example 3. Figure 2 is a 29S NMR spectrum of a silicalite sample. Silicalite is a silicate material with the topology of MFI. In this material there is no aluminum or other element in the structure of the material, only silicon. Figure 3 is a 29 Si NMR spectrum of a sample of aluminosilicate material with the MFI topology. The 5 molar ratio of silica to SiO2 / Al203 alumina of this material is 54. Figure 4 is a 29Si NMR spectrum of the ferrialuminosilicate product of Example 4. Figure 5 is a 9S NMR spectrum of the ferrialuminosilicate product. of Example 5. Figure 6 is a 29S-NMR spectrum of the zincoaluminosilicate product of Example 8. Figure 7 is a 29Si NMR spectrum of the product of galloaluminosilicate of Example 15. Figure 8 is a 9S NMR spectrum of the product of magnesoaluminosilicate of Example 20. Figure 9 is an infrared spectrum of the region 400-1500 cm "1 of the silicalite sample, Figure 10 is an infrared spectrum of the region 400-1500 cm" 1 of the aluminosilicate material of MFI of Si02 / Al203 in a ratio of 54. Figure 11 is an infrared spectrum of the region 400-1500 cm "1 of the ferrialuminosilicate product of example 4. Figure 12 is an infrared spectrum of the region 400-1500 cm "1 of the ferrialuminosilicate product of example 5.

Figure 13 is an infrared spectrum of the region 400-1500 cm "1 of the zincoaluminosilicate product of example 7. Figure 14 is an infrared spectrum of the region 400-1500 cm "1 of the zincoaluminosilicate product of example 8.

Figure 15 is an infrared spectrum of the region 400-1500 cm "1 of the nickel aluminosilicate product of example 12. Figure 16 is an infrared spectrum of the region 400-1500 cm" 1 of the product of galloaluminosilicate of example 15. 10 Figure 17 is an infrared spectrum of the region 400-1500 cm "1 of the product of galloaluminosilicate of example 16. Figure 18 is an infrared spectrum of the region 400-1500 cm" 1 of the product of chromoaluminosilicate of example 18. Figure 19 is an infrared spectrum of region 15 400 -1500 cm "1 of the magnesium aluminosilicate product of example 20. Figure 20 is an X-ray diffraction diagram of the ferrialuminosilicate product of example 4. Figure 21 is an X-ray diffraction diagram of the zincoaluminosilicate product of the example 7. Figure 22 is an X-ray diffraction diagram of the phosphorus aluminosilicate product of Example 9. Figure 23 is an X-ray diffraction diagram of the nickel aluminosilicate product of Example 10.

Figure 24 is an X-ray diffraction diagram of the cobalt aluminosilicate product of Example 13. Figure 25 is an X-ray diffraction diagram of the product of galloaluminosilicate of Example 15. Figure 26 is an X-ray diffraction diagram of the chromoaluminosilicate product of example 17. Figure 27 is an X-ray diffraction diagram of the magnesoaluminosilicate product of example 20. Figure 28 is an XPS spectrum of the Mg2p region of the aluminosilicate magnesium product of example 20.

DETAILED DESCRIPTION OF THE INVENTION The invention relates to a method for obtaining a new family of metalloaluminosilicate material of MFI topology, and its use in the FCC area. The materials are produced with a simple and advantageously inorganic, alkaline and aqueous reaction mixture under mild hydrothermal conditions. The invention also relates to a metalloaluminosilicate of the ST-5 type and to a method for preparing the same. According to the invention, the metalloaluminosilicate is advantageously prepared without the need for tempering agents and / or seeding processes. further, the method of the present invention advantageously results in a desired material which is located in the crystalline structure or framework of the aluminosilicate material. The compositions are prepared from a synthesis gel which is provided in a sequential manner. The preparation of the synthesis gel is carried out by mixing three solutions: an acid solution of the salt of the element to be incorporated, a solution of the silica source and an alumina source solution. The salts of the elements to be incorporated preferably are nitrates, chlorides, sulfates, bromides and the like. The acidification of the solution can be carried out with one or more of sulfuric acid, nitric acid, hydrochloric acid and the like. Preferred sources of silica are sodium silicate, sodium metasilicate, colloidal silica and the like. The preferred sources of alumina are sodium aluminate, aluminum nitrate, aluminum sulfate and so on. The solution of the element to be incorporated is preferably prepared by dissolving a weight of the salt in a volume of a diluted acid solution. The silica source solution is prepared by diluting or dissolving an amount of a soluble silica source in a volume of water.

The solution of the alumina source is prepared by dissolving a weight of the aluminum salt in an amount of water. The metal to be incorporated in the metalloaluminosilicate according to the invention can suitably be a ore or metals of the groups HA, IIIB, IVB, VB, VIB, VIIB, VIII, IB, IIB, IIIA, HA, VAT, and VA (CAS), more preferably iron, zinc, zirconium, chromium, nickel, cobalt, magnesium, phosphorus, gallium and mixtures thereof. Particularly suitable metals are iron, zinc, and mixtures thereof. According to the invention, the mixing is carried out in a sequential manner. The preferred sequence of mixing is, first, slowly adding a silica solution under vigorous stirring to the acid solution of the element to be incorporated. After homogenization of the formed mixture, the alumina solution is added under vigorous stirring. The final mixture is allowed to homogenize for a given period of time. The gel composition for preparing these metalloaluminosilicate materials is given in the form of molar proportions of the elements as follows: Si02 / Al203 from 5 to 80, Si02 / DOx from 10 to 1500, Si02 / (A1203 + DOJ from 5 to 70, Na20 / Si02 from 0.22 to 2.20, OH / Si02 from: 0.01 to 2.00.

OH / Si02 from 14 to 40, where D is the element or elements incorporated in the gel. After homogenization is complete, the gel is transferred to an autoclave where hydrothermal crystallization is preferably carried out. The temperature of the crystallization is preferably in the range of 150 ° C to 220 ° C with a more preferred range of 165 ° C to 185 ° C. The stirring during crystallization is carried out with a speed that preferably varies between 40 rpm and 400 rpm, the preferred range is from 80 rpm to 300 rpm. The crystallization time preferably ranges from 24 hours to 120 hours, with a more preferred range between 36 hours and 76 hours. The crystallization is carried out at autogenous pressure. After the crystallization time has ended, the aluminosilicate composition is filtered and washed with water preferably to a pH close to 7. The filtered and washed material is then placed to dry at a temperature which is preferably in the range from 80 ° C to 140 ° C for a period of about 12 hours.

The metalloaluminosilicate materials obtained according to the invention preferably have a chemical composition which can be described in molar proportions using one of the following formulas: 1. - a (M2 / nO): b (Al203): c (E203): d (YES02): e (H20) 2. - a (M2 / nO): b (Al203): c (F02): d (Si02): e (H20) 3. - a (M2 / n0): b (Al203): C (GO): d (YES02): e (H20) 4. - a (M2 / n0): b (Al203): c (H205): d (S02): e (H20) wherein M is at least one ion exchangeable cation having a valence of n, the preferred alkali cation is sodium, however, other alkali cations may be used (lithium, potassium and the like), - E is an element with valence 3+ which is not ionically interchangeable by conventional means, suitable examples include iron, gallium, chromium, boron, indium and the like; F is an element with valence 4+ which is not ionically interchangeable by conventional means, suitable examples include titanium, zirconium, germanium and the like; G is an element with a valence 2+ which is not ionically interchangeable by conventional means, suitable examples include nickel, zinc, cobalt, magnesium, beryllium and the like; H is an element with valence 5+ which is not ionically interchangeable by conventional means, suitable examples include phosphorus, vanadium and the like, - a is from > 0 to 6; b is equal 1, c is from > 0 to 10; d is from 10 to 80; d / c is from 10 to 1500; e is from 0 to 100; a / (b + c) is from > 0 to 5; and d / (b + c) is from 10 to 70. The invention is not limited to such wet materials or such forms of oxide, rather its composition may be present in terms of oxides and in a wet base (as in the above formulas) in order to provide a means to identify part of the novel compositions. In addition, the compositions of the present invention may also incorporate more than one element which is not ion exchangeable and which has different valences (mixtures of E, F, G and H). Other formulas can be written by those familiar with the art to identify particular subsets or embodiments of the present invention which comprise porous crystalline metalloaluminosilicates. The present invention advantageously provides a metalloaluminosilicate composition in which the metal is incorporated into the aluminosilicate framework of the composition. As used herein, the term "incorporated" means that the metal can not be removed through an ion exchange process.

Together with the above chemical composition, the metalloaluminosilicates produced with the methodology of the present invention show an X-ray diffraction diagram which contains at least the lattice distances that are included in table 2 below.

TABLE 2 Interplanar separation Relative intensity 11. 2 ± 0.4 strong 10.0 ± 0.4 strong 6.01 ± 0.2 weak 5.72 ± 0.2 weak 5.58 ± 0.2 weak 4.38 ± 0.1 weak 3.86 ± 0.1 very strong 3.73 ± 0.1 strong 3.65 ± 0.1 strong 3.49 ± 0.1 weak 3.23 ± 0.1 weak 3.06 ± 0.06 weak 3.00 ± 0.06 weak 2.00 ± 0.04 weak In addition to the chemical composition and the above reticle distances included in table 2, the metalloaluminosilicates produced according to this invention have absorption bands in the infrared spectrum and NMR spectra which make them different from other materials. Other techniques that can be used in certain specific cases such as Mossbauer spectroscopy for iron, XPS for magnesium, etc. Infrared spectroscopy is a simple but powerful technique that can provide information regarding the structural details of zeolitic materials. The region of 400 to 1500 cm "1 is important because in that region different sets of infrared vibrations related to zeolitic materials can be observed, for example, tetrahedral and external internal junctions.The infrared spectrum can be classified into two groups of vibrations: 1.- internal vibrations of the T04 framework, which are insensitive to structural vibrations, and 2.- vibrations related to the external union of the T04 units in the structure.The latter are sensitive to structural variations.This technique has been used To identify the incorporation of the framework of other elements, the modifications and displacement in the asymmetric and symmetric vibrations have been observed with the successful incorporation of such new elements in the framework of the zeolitic material, for this reason, this is an important characterization of the materials of metalloaluminosilicate of the present invention. important n of the metalloaluminosilicates of the present invention is 29 Si NMR spectroscopy. In silicate systems, the unit Q is used to indicate the different silicate atoms in a system. However, this annotation is not sufficient to describe the basic construction units in the zeolite or aluminosilicate frameworks. In zeolite systems, the Q units are always Q4, where each silicate is surrounded by four silicate or aluminate units. Therefore in the zeolites, there are five possibilities, described by Q4 (nAl, (4-n) Si), where n = 0, 1, 2, 3, and 4. Generally, these are noted as Si (nAl) o Si ((4-n) Si), which indicates that each silicon atom is bound by means of oxygen to aluminum and 4-n neighboring silicones. Therefore, silicon with 4 neighboring alumins can be indicated by Si (4Al). When one or more Si atoms in the position of unit Q4 are replaced by Al atoms, a displacement occurs in the chemical shift of 29 Si. In the case of the metalloaluminosilicate of the present invention, in addition to the Al atoms there are other atoms incorporated in the structure of the material, so that the displacement in the chemical displacements are due to them, because for a material with a Given the silicon molar with respect to aluminum, the displacements due to aluminum are fixed, so that the modification in the chemical shift by NMR 29 Si is caused by the other element incorporated in the structure which joins the silicon through the atoms of oxygen . Mossbauer spectroscopy is used to confirm the incorporation of iron into the aluminosilicate framework of the ferrimetaloaluminosilicate material of Example 3 below. The Mossbauer spectra of this material show a broad singlet at room temperature indicative of iron in tetrahedral coordination with oxygen. X-ray photoelectron spectroscopy is a technique that has been used in the characterization of magnesium incorporation in the magnesium aluminophosphate framework (Zeolites 15: 583-590, nineteen ninety five). When magnesium is tetrahedrally coordinated with four oxygens, in the case of magnesoaluminophosphate, the value of the binding energy for the Mg2p signal is approximately 50.1 eV. For example 20 below, this technique is used and the value of the binding energy of the Mg 2p signal is 49.8, which is close to the value found for magnesium in the magnesium aluminophosphate. The compositions of the present invention can be converted to proton form, for example by ion exchange, with the aid of a mineral acid, an ammonium compound or other proton suppliers, or with other cations. An important aspect of the invention is that the elements incorporated in the framework of the material are not interchangeable ionically and therefore are not lost when an ion exchange is carried out. The modified materials can be used in catalytic reactions as pure materials or in combination with other materials such as clays, silicas, aluminas and other well-known fillers. The metalloaluminosilicates of the present invention have useful properties including catalytic activity. These novel compositions can be used advantageously in known processes which currently use aluminosilicate zeolites. The aluminosilicate compositions of the present invention can advantageously be incorporated with binders, clays, aluminas, silicas or other materials which are well known in the art. They can also be modified with one or more elements or compounds by deposition, occlusion, ion exchange or other techniques known to those familiar in the art to improve, supplement or alter the properties or utility of the aluminosilicate compositions of the present invention. The metalloaluminosilicates of the present invention can be used as additives in the FCC area. The metalloaluminosilicate compositions of the present invention are prepared by hydrothermal methods so that the elements incorporated in the aluminosilicate compositions are not ion exchangeable and form part of the structure of the crystalline aluminosilicate compositions. In accordance with the present invention, there is provided a method which is advantageous for preparing metalloaluminosilicate compositions, and which is also advantageous for preparing aluminosilicate compositions themselves. In the preparation of aluminosilicate compositions, a composition such as that identified as ST5 aluminosilicate can be prepared (U.S. Patent No. 5,254,327) by sequential mixing of three solutions as described above. In order to prepare an aluminosilicate composition, a first solution containing a silica source composition is prepared. A second solution containing a source of alumina is prepared and a third aqueous acid solution is prepared. The silica source is then mixed with the aqueous acid solution so as to form a mixture of silica-acid source and the silica-acid source mixture is then preferably mixed with the alumina source solution so as to provide a mixture of gel which can be hydrothermally crystallized so as to provide an aluminosilicate composition having an aluminosilicate framework. This composition is advantageously formed without the need for stenter or other organic additives, and provides an aluminosilicate composition similar to ST5 which can be advantageously used for various catalytic applications. In this method, as with the method for preparing metalloaluminosilicates as discussed above, the sequence of first mixing a solution of silica source with an acid or with a metal solution of acid, followed by mixing with an alumina source solution to provide the desired gel mixture, advantageously provides the formation of the desired aluminosilicate framework structure without the need for seeding or template agent, in the case of metalloaluminosilicates, which advantageously incorporate the desired metal within the aluminosilicate framework. The new materials and their methods of preparation will be better understood with reference to the following examples. The raw materials used in the examples are: commercial sodium silicate GLASSVEN (28.60% by weight of SiO2, 10.76% by weight of Na20, 60.64% by weight of H2O), commercial sodium silicate VENESIL (28.88% by weight of SiO2, 8.85% by weight of Na20, 62.27% by weight of H20), Fisher's or Aldrich's sulfuric acid (98% by weight, d = 1.836), Aldrich's phosphoric acid (85% by weight), LaPINE sodium aluminate (49.1% by weight of A1203), 27.2% by weight of Na20, 23.7% by weight of H2O), the salts of the different elements to be incorporated are reactive grade ACS or analytical grade of Aldrich.

The first two examples are to demonstrate the use of the method of the present invention for the preparation of the MFI topology aluminosilicates without seeding or templates. The rest of the examples demonstrate the preparation and use of the metalloaluminosilicate of the present invention. In relation to the examples, a comparative reference can be made to figures 2, 3, 9 and 10. Figures 2 and 9 are 29Si NMR spectra and an infrared spectrum (400-1500 cm "1) of silicalite, which it has a silicon structure only, Figures 3 and 10 are a 29Si NMR spectrum (400-1500 cm "1) of an aluminosilicate material.

EXAMPLE 1 The preparation of an aluminosilicate material of the ST5 type (proportion of Si02 / Al203 of 20) is illustrated. The reaction batch consists of the following solutions which are prepared according to the method of the present invention described above: • Sulfuric acid solution: 6.4 ml of concentrated H2SO4 and 40 ml of distilled water. Sodium silicate solution: 85 g of sodium silicate and 38 ml of distilled water. Sodium aluminate solution: 4.2 g of sodium aluminate and 20 ml of distilled water.

The gel composition in the form of molar proportions of oxides are given below: Si02 / Al203 H20 / Si02 0H / Si02 Na / Si02 Na20 / Si02 20. 18 20. 67 0. 10 0. 68 0. 3. 4 The hydrothermal crystallization is carried out in a stirred 300 ml autoclave at a reaction temperature of 170 ° C for a period of 48 hours. The dry material consists of a pure aluminosilicate phase with an X-ray diffraction spectrum with at least the d values that are included in Table 2 above. The chemical composition of the product, expressed in molar proportions is: 1.1 of Na20: A1203: 20.6 of Si02: 7 of H20. The white material obtained in this way is similar to the aluminosilicate ST5 (U.S. Patent 5,254,327).

EXAMPLE 2 The preparation of an aluminosilicate material of the MFI type with an SiO2 / Al203 ratio of 50 is illustrated. A reaction batch consisting of the following solutions is prepared according to the invention described above: Sulfuric acid solution: 6.1 ml of Concentrated H2S04 and 40 ml of distilled water.

Sodium silicate solution: 79 g of sodium silicate and 40 ml of distilled water. Sodium aluminate solution: 1.5 g of sodium aluminate and 20 ml of distilled water. The gel composition in the form of molar proportions of oxides is given below: Si02 / Al203 H20 / Si02 0H / Si02 Na / Si02 Na20 / Si02 52. 06 21.89 0.13 0.76 0.38 The hydrothermal crystallization is carried out in a stirred 300 ml autoclave at a reaction temperature of 170 CC for a period of 36 hours. The dry material consists of a pure aluminosilicate phase with an X-ray diffraction spectrum with at least the d values that are included in Table 2 above. The chemical composition of the product, expressed in molar proportions is: 1.0 of Na20: Al203: 50.2 of Si02: 16 of H20.

EXAMPLE 3 The preparation of an aluminosilicate iron material of the MFI type is illustrated. A reaction batch is prepared consisting of the following solutions, according to the present invention.- Acid solution of iron (III) nitrate: 12 g of Fe (N03) 3.9H20, 38 ml of concentrated H2SO4 and 200 ml of distilled water. Sodium silicate solution: 528 g of 5-sodium silicate and 187 ml of distilled water. Sodium aluminate solution: 23 g of sodium aluminate and 123 ml of distilled water. The gel composition in the form of molar proportions of oxides is given below: SiO2 / Al203 H20 / SiO2 OH / SiO2 Na / SiO2 NaO2 / SiO2 22.69 20.67 0.13 0.81 0.40 Si02 / Fe203 Si / Fe 15 169.16 84.58 The hydrothermal crystallization is carried out in a stirred autoclave, of 2 liters, up to a reaction temperature of 170 ° C for a period of 54 hours. The dry material consists of a pure phase of ferroaluminosilicate with an X-ray diffraction spectrum with at least the d values that are included in table 2 above. The chemical composition of the white product, expressed in molar proportions is: 1.21 of Na20: A1203: 0.14Fe203: 25.6 of Si02: 10.2 of H20. Figure 1 5 shows the Mossbauer spectrum of this material. This type of spectrum is typical of iron (III) in tetrahedral coordination.

EXAMPLE 4 Preparation of an aluminosilicate iron material of the MFI type. A reaction batch is prepared consisting of the following solutions, according to the procedure described above: • Acid solution of iron (III) nitrate: 7 g of Fe (N03) 3.9H20, 6 ml of concentrated H2SO4 and 40 ml of distilled water. Sodium silicate solution: 85 g of sodium silicate and 38 ml of distilled water. Sodium aluminate solution: 1.7 g of sodium aluminate and 20 ml of distilled water. The gel composition in the form of molar proportions of oxides is given below: Si02 / Al203 H20 / Si02 OH / Si02 Na / Si02 Na20 / Si02 49.42 20.58 0.18 0.89 0.445 Si02 / Fe203 Si / Fe 46.68 23.34 The hydrothermal crystallization is carried out in a stirred autoclave of 300 ml up to a reaction temperature of 170 ° C for a period of 72 hours. The dry material consists of a pure phase of ferrialuminosilicate with an X-ray diffraction spectrum with at least the d values that are included in table 2 above. The chemical composition of the white product, expressed in molar proportions is: 3.73 Na20: A1203: 1.59 of Fe203: 74.4 of Si02: 15.7 of H20. In Figure 4 the 29Si NMR spectrum of this product is shown. The molar ratio of Si02 / Al203 of this material is 74.4. It is clear that the iron is coordinated with the silicon and therefore the spectrum is different from a simple silicate or aluminosilicate material of MFI topology. In figure 11 the infrared spectrum of this material is shown. The molar ratio of Si02 / Al203 of this material is 74.4. It is clear that the iron is coordinated with the silicon and therefore the different spectrum of a simple silicate or aluminosilicate material of MFI topology. Figure 20 shows the X-ray diagram of this material.

EXAMPLE 5 The preparation of a ferrialuminosilicate material of the MFI type is illustrated. A reaction batch consisting of the following solutions is prepared according to the procedure described above: Acid solution of iron (III) nitrate: 4 g of Fe (N03) 3.9H20, 6 ml of concentrated H2SO4 and 40 ml of distilled water. • Sodium silicate solution: 85 g of sodium silicate and 38 ml of distilled water. Sodium aluminate solution: 3.0 g of sodium aluminate and 20 ml of distilled water. The gel composition in the form of molar proportions of oxides is given below: Si02 / Al203 H20 / Si02 0H / Si02 Na / Si02 Na20 / Si02 28. 00 20.62 0.15 0.84 0.42 Si02 / Fe203 Si / Fe 81. 70 40. 85 The hydrothermal crystallization is carried out in a stirred autoclave of 300 ml, up to a reaction temperature of 170 ° C for a period of 54 hours. The dry material consists of a pure phase of ferrialuminosilicate with an X-ray diffraction spectrum with at least the d values that are included in table 2 above. The chemical composition of the white product, expressed in molar proportions is: 1.77 Na20: A1203: 0.35 Fe203: 28.7 Si02: 15.3 H20. Figure 5 shows the S9Si NMR spectrum of this product. The molar ratio of Si02 / Al203 of this material is 28.7. It is clear that the iron is coordinated with the silicon and therefore the spectrum is different from a simple silicate or aluminosilicate material of MFI topology. Figure 12 shows the infrared spectrum of this material. The molar ratio of Si02 / Al203 of this material is 28.66. It is clear that the iron is coordinated with the silicon and therefore the spectrum is different from a simple silicate or aluminosilicate material of MFI topology.

EXAMPLE 6 The preparation of a zincoaluminosilicate material of the MFI type is illustrated. A reaction batch consisting of the following solutions is prepared according to the procedure described above: Acid solution of zinc nitrate (II): 1.2 g of Zn (N03) 3.6H20, 6.1 ml of concentrated H2SO4 and 33 ml of distilled water. Sodium silicate solution: 79.2 g of sodium silicate and 40 ml of distilled water. Sodium aluminate solution: 3.9 g of sodium aluminate, 0.5 g of NaOH and 24 ml of distilled water.

The gel composition in the form of molar proportions of oxides is given below: SiO2 / Al203 H20 / SiO2 OH / SiO2 Na / SiO2 Na2? / SiO2 20. 07 21. 50 0. 14 0. 85 0. 43 Si02 / ZnO Si / Zn 93 .43 93 .43 The hydrothermal crystallization is carried out in a stirred autoclave, 300 ml, up to a reaction temperature of 170 ° C for a period of 36 hours. The dry material consists of a pure zincoaluminosilicate phase with an X-ray diffraction spectrum with at least the d values included in table 2 above. The chemical composition of the white product, expressed in molar proportions is: 1.13 of Na20: A1203: 0.21 of ZnO: 22.7 of Si02: 6.7 of H20.

EXAMPLE 7 The preparation of a zincoaluminosilicate material of the MFI type is illustrated. A reaction batch is prepared consisting of the following solutions, according to the procedure described above: Acid solution of zinc nitrate (II): 3.0 g of Zn (N03) 3.6H20, 6.0 ml of concentrated H2S04 and 38 ml of distilled water. Sodium silicate solution: 79.2 g of sodium silicate and 40 ml of distilled water. Sodium aluminate solution: 2.5 g of sodium aluminate, 1.0 g of NaOH and 19 ml of distilled water. The gel composition in the form of molar proportions of oxides is given below: Si02 / Al203 H20 / Si02 0H / Si02 Na / Si02 Na20 / Si02 31.31 21.44 0.15 0.85 0.43 Si02 / ZnO Si / Zn 37.37 37.37 The hydrothermal crystallization is carried out in a stirred autoclave of 300 ml, up to a reaction temperature of 170 ° C for a period of 72 hours. The dry material consists of a pure zincoaluminosilicate phase with an X-ray diffraction spectrum with at least the d values included in table 2 above. The chemical composition of the white product, expressed in molar proportions is: 1.40 Na20: A1203: 0.86 ZnO: 33.9 Si02: 21.4 H20. Figure 13 shows the infrared spectrum of this material. The molar ratio of Si02 / Al203 of this material is 33.9. It is clear that zinc is coordinated with silicon and therefore the spectrum is different from a simple silicate or aluminosilicate material of MFI topology. Figure 21 shows the X-ray diagram of this material.

EXAMPLE 8 The preparation of a zincoaluminosilicate material of the MFI type is illustrated. A reaction batch is prepared consisting of the following solutions, according to the procedure described above: • Acid solution of zinc nitrate (II): 3.0 g of Zn (N03) 2 -6H20, 6.0 ml of concentrated H2S04 and 38 ml of distilled water. • Sodium silicate solution: 79.2 g of sodium silicate and 40 ml of distilled water. • Sodium aluminate solution: 1.6 g of sodium aluminate, 0.8 g of NaOH and 19 ml of distilled water.

The gel composition in the form of molar proportions of oxides is given below: The hydrothermal crystallization is carried out in a stirred autoclave of 300 ml up to a reaction temperature of 170 ° C for a period of 120 hours. The dry material consists of pure aluminosilicate base with an X-ray diffraction spectrum with at least the d values that are included in table 2, above. The chemical composition of the white product, expressed in molar proportions, is: 1.68 Na20: A1203: 1.37 ZnO: 52.9 Si02: 32.1 H20. The 29S NMR spectrum of this product is shown in Figure 6. The molar ratio of SiO2 / Al203 of this material is 52.9. It is clear that zinc is coordinated with silicon and therefore the spectrum is different from a simple silicate or aluminosilicate material of MFI topology. Figure 14 shows the infrared spectrum of this material. The molar ratio of Si02 / Al203 of this material is 52.9. It is clear that zinc is coordinated with silicon and therefore the spectrum is different from a simple silicate or aluminosilicate material of MFI topology.

EXAMPLE 9 The preparation of a phosphoroaluminosilicate material of the MFI type is illustrated. A reaction batch is prepared consisting of the following solutions, according to the procedure described above: Acid solution of phosphoric acid: 0.82 g of H3P04, 5.5 ml of concentrated H2SO4 and 40 ml of distilled water. Sodium silicate solution: 79.2 g of sodium silicate and 33 ml of distilled water. Sodium aluminate solution: 3.9 g of sodium aluminate and 19 ml of distilled water.

The gel composition in the form of molar proportions of oxides is given below: The hydrothermal crystallization is carried out in a given autoclave of 300 ml up to a reaction temperature of 170 ° C for a period of 72 hours. The dry material consists of a pure phase of phosphorus aluminosilicate with an X-ray diffraction spectrum with at least the d values included in Table 2, above. The composition of the white product, expressed in molar proportions, is: 1.07 Na20: A1203: 0.25 P20s: 24.3 Si02: 3.3 H20. The X-ray diagram of this material is shown in Figure 22.

EXAMPLE 10 The preparation of a niquelaluminosilicate material of the MFI type is illustrated. A reaction batch is prepared consisting of the following solutions, according to the procedure described above: • Acid solution of nickel nitrate (II): 180 g of Ni (N03) 2 -6H20, 1000 ml of concentrated H2SO4 and 600 ml of distilled water. • Sodium silicate solution: 14400 g of sodium silicate and 6000 ml of distilled water. • Sodium aluminate solution: 695 g of sodium aluminate and 4800 ml of distilled water.

The gel composition is then given in the form of molar proportions of the oxides: The hydrothermal crystallization is carried out in a stirred 40 liter autoclave at a reaction temperature of 170 ° C for a period of 54 hours. The dry material consists of a pure phase of niquelaluminosilicato with an X-ray diffraction spectrum with at least the d values that are included in table 2, above. The chemical composition of the white to pale green product, expressed in molar proportions, is: 1.03 Na20: A1203: 0.18 NiO: 23.5 Si02: 9.2 H20. Figure 23 shows the X-ray diagram of this material.

EXAMPLE 11 The preparation of a niquelaluminosilicate material of the MFI type is illustrated. A reaction batch is prepared consisting of the following solutions, according to the procedure described above: Acid solution of nickel (II) nitrate: 16 g of Ni (N03) 2 -6H20, 36 ml of concentrated H2SO4 and 240 ml of distilled water.

• Sodium silicate solution: 576 g of sodium silicate and 240 ml of distilled water. • Sodium aluminate solution: 27.8 g of sodium aluminate and 192 ml of distilled water.

The composition of the gel in the form of molar proportions of the oxides is given below: The hydrothermal crystallization is carried out in a stirred 40 liter autoclave at a reaction temperature of 170 ° C for a period of 54 hours. The dry material consists of a pure phase of niquelaluminosilicato with an X-ray diffraction spectrum with at least the d values that are included in table 2, above. The chemical composition of the white to pale green product, expressed in molar proportions, is: 1.24 Na20: A1203: 0.43 NiO: 23.2 Si02: 10.1 H20.

EXAMPLE 12 The preparation of the niquelaluminosilicate material of the MFI type is illustrated. A reaction batch is prepared consisting of the following solutions, according to the procedure described above.

Acid solution of nickel nitrate (II): 3.6 g of Ni (N03) 2 -6H20, 6 ml of concentrated H2SO4 and 40 ml of distilled water. Sodium silicate solution: 85 g of sodium silicate and 38 ml of distilled water. Sodium aluminate solution: 2.0 g of sodium aluminate, 0.4 g of NaOH and 20 ml of distilled water.

The gel composition is then given in the form of molar proportions of the oxides: The hydrothermal crystallization is carried out in a stirred autoclave of 300 ml up to a reaction temperature of 170 ° C for a period of 84 hours. The dry material consists of a pure phase of niquelaluminosilicato with an X-ray diffraction spectrum with at least the values d that are included in table 2, previous. The chemical composition of the white to pale green product, expressed in molar proportions, is: 1.66 Na20: A1203: 1.59 NiO: 53.7 Si02: 38.6 H20. Figure 15 shows the infrared spectrum of this material. The molar ratio of Si02 / Al203 of this material is 53.7. it is clear that the nickel is coordinated with the silicon and therefore the spectrum is different from a simple silicate or aluminosilicate material of MFI topology.

EXAMPLE 13 The preparation of a cobalt aluminosilicate material of the MFI type is illustrated. A reaction batch is prepared consisting of the following solutions, with the procedure described above: • Acid solution of cobalt nitrate (II): 1.2 g of Co (N03) 2 -6H20, 6.1 ml of concentrated H2S04 and 40 ml of distilled water.

• Sodium silicate solution: 79.2 g of sodium silicate and 33 ml of distilled water. • Sodium aluminate solution: 3.8 g of sodium aluminate and 19 ml of distilled water.

The gel composition is then given in the form of molar proportions of the oxides: The hydrothermal crystallization is carried out in a stirred 300 ml autoclave at a reaction temperature of 170 ° C for a period of 54 hours. The dry material consists of a pure phase of cobalt-aluminosilicate with an X-ray diffraction spectrum with at least the d-values that are included in Table 2, above. The chemical composition of the product white to pale pink, expressed in molar proportions, is: 1.15 Na20: A1203: 0.21 CoO: 27.6 Si02: 15.4 H20. Figure 24 shows the X-ray diagram of this material.

EXAMPLE 14 The preparation of a zirconoaluminosilicate material of the MFI type is illustrated. A reaction batch is prepared consisting of the following solutions, according to the procedure described above: Acid solution of zirconyl chloride: 1.2 g of ZrOCl2 -8H20, 6 ml of concentrated H2SO4 and 40 ml of distilled water. Sodium silicate solution: 79.4 g of sodium silicate and 33 ml of distilled water. Sodium aluminate solution: 3.8 g of sodium aluminate and 19 ml of distilled water.

The gel composition is then given in the form of molar proportions of the oxides: The hydrothermal crystallization is carried out in a stirred 300 ml autoclave at a reaction temperature of 170 ° C for a period of 96 hours. The dry material consists of a pure phase of zirconoaluminosilicato with an X-ray diffraction spectrum with at least the d values that are included in Table 2, above. The chemical composition of the white product, expressed in molar proportions, is: 1.32 Na20: A1203: 0.26 Zr02: 23.9 Si02: 17.2 H20.

EXAMPLE 15 The preparation of a galloaluminosilicate material of the MFI type is illustrated. A reaction batch is prepared consisting of the following solutions, according to the procedure described above: • Acid suspension of gallium oxide (III): 2 g of Ga203, 6.5 ml of concentrated H2SO4 and 40 ml of distilled water.

• Sodium silicate solution: 85 g of sodium silicate and 38 ml of distilled water. • Sodium aluminate solution: 1.5 g of sodium aluminate, 0.6 g of NaOH and 20 ml of distilled water.

The gel composition is then given in the form of molar proportions of the oxides: The hydrothermal crystallization is carried out in a stirred autoclave of 300 ml up to a reaction temperature of 170 ° C for a period of 72 hours. The dry material consists of a pure phase of galloaluminosilicate with an X-ray diffraction spectrum with at least the values d that are included in Table 2, above. The chemical composition of the white product, expressed in molar proportions, is: 3.11 Na20: A1203: 0.77 Ga203: 81.1 Si02: 55.4 H20. Figure 7 shows the 29 Si NMR spectrum of this product. The molar ratio of Si02 / Al203 of this material is 81.1. it is clear that gallium is coordinated with silicon and therefore the spectrum is different from a simple silicate or aluminosilicate material of MFI topology. Figure 16 shows the infrared spectrum of this material. The molar ratio of Si02 / Al203 of this material is 81.1. it is clear that the gallium is coordinated with the silicon and therefore the spectrum is different from a simple silicate or aluminosilicate material of MFI topology.

Figure 25 shows the X-ray diagram of this material.

EXAMPLE 16 The preparation of a galloaluminosilicate material of the MFI type is illustrated. A reaction batch is prepared consisting of the following solutions, according to the procedure described above: • Acid suspension of gallium (III) oxide: 2.8 g of Ga203, 6.5 ml of concentrated H2SO4 and 40 ml of distilled water. • Sodium silicate solution: 85 g of sodium silicate and 38 ml of distilled water. • Sodium aluminate solution: 1.5 g of sodium aluminate and 20 ml of distilled water.

The gel composition is then given in the form of molar proportions of the oxides: The hydrothermal crystallization is carried out in a stirred 300 ml autoclave at a reaction temperature of 170 ° C for a period of 96 hours. The dry material consists of a pure phase of galloaluminosilicate with an X-ray diffraction spectrum with at least the values d that are included in Table 2, above. The chemical composition of the white product, expressed in molar proportions, is: 3.41 Na20 : A1203: 2.26 Ga203: 84.1 Si02: 41.3 H20. Figure 17 shows the infrared spectrum of this material. The molar ratio of Si02 / Al203 of this material is 84.1. it is clear that the gallium is coordinated with the silicon and therefore the spectrum is different from a simple silicate or aluminosilicate material of MFI topology.

EXAMPLE 17 The preparation of a chrome aluminosilicate material of the MFI type is illustrated. A reaction batch is prepared consisting of the following solutions, according to the procedure described above: • Acid solution of chromium (III) nitrate: 12 g of Cr (N03) 3 -9H20, 38 ml of concentrated H2S04 and 287 ml of distilled water.

• Sodium silicate solution: 528 g of sodium silicate and 200 ml of distilled water. • Sodium aluminate solution: 23 g of sodium aluminate and 123 ml of distilled water.

The gel composition is then given in the form of molar proportions of the oxides: The hydrothermal crystallization is carried out in a stirred 300 ml autoclave at a reaction temperature of 170 ° C for a period of 72 hours. The dry material consists of a pure phase of chromoaluminosilicate with an X-ray diffraction spectrum with at least the d values that are included in Table 2, above. The chemical composition of the pale green product, expressed in molar proportions, is: 1.21 Na20: A1203: 0.07 Cr203: 24.6 Si02: 6.8 H20. Figure 26 shows the X-ray diagram of this material.

EXAMPLE 18 The preparation of a chromium aluminosilicate material of the MFI type is illustrated. A reaction batch is prepared consisting of the following solutions, according to the procedure described above: Acid solution of chromium nitrate (III): 5 g of Cr (N03) 3 -9H20, 6 ml of concentrated H2SO4 and 40 ml of distilled water. Sodium silicate solution: 85 g of sodium silicate and 38 ml of distilled water. Sodium aluminate solution: 1.7 g of sodium aluminate, 1.6 g of NaOH and 20 ml of distilled water.

The gel composition is then given in the form of molar proportions of the oxides: The hydrothermal crystallization is carried out in a stirred 300 ml autoclave at a reaction temperature of 170 ° C for a period of 96 hours. The dry material consists of a pure phase of chromoaluminosilicate with an X-ray diffraction spectrum with at least the d values that are included in Table 2, above. The chemical composition of the pale green product, expressed in molar proportions, is: 2.40 Na20: A1203: 0.82 Cr203: 53.7 Si02: 35.6 H20. Figure 18 shows the infrared spectrum of this material. The molar ratio of Si02 / Al203 of this material is 53.7. It is clear that chromium is coordinated with silicon and therefore the spectrum is different from a silicate or aluminosilicate material of MFI topology.

EXAMPLE 19 The preparation of a magnesium aluminosilicate material of the MFI type is illustrated. A reaction batch is prepared consisting of the following solutions, according to the procedure described above: • Acid solution of magnesium nitrate (III): 1.2 g of Mg (N03) 2 -6H20, 6.1 ml of concentrated H2S04 and 40 ml of distilled water.

• Sodium silicate solution: 79.6 g of sodium silicate and 33 ml of distilled water. • Sodium aluminate solution: 3.8 g of sodium aluminate and 19 ml of distilled water.

The gel composition is then given in the form of molar proportions of the oxides: The hydrothermal crystallization is carried out in a stirred 300 ml autoclave at a reaction temperature of 170 ° C for a period of 96 hours. The dry material consists of a pure phase of magnesoaluminosilicate with an X-ray diffraction spectrum with at least the d values that are included in table 2, above. The chemical composition of the white product, expressed in molar proportions, is: 1.11 Na20: A1203: 0.30 MgO: 22.1 Si02: 10.6 H20.

EXAMPLE 20 The preparation of a magnesium aluminosilicate material of the MFI type is illustrated. A reaction batch is prepared consisting of the following solutions, according to the procedure described above: Acid solution of magnesium nitrate (III): 3.0 g of Mg (N03) 2 -6H20, 6.1 ml of concentrated H2SO4 and 40 ml of distilled water. Sodium silicate solution: 79.2 g of sodium silicate and 38 ml of distilled water. Sodium aluminate solution: 2.0 g of sodium aluminate and 19 ml of distilled water.

The gel composition is then given in the form of molar proportions of the oxides: The hydrothermal crystallization is carried out in a stirred 300 ml autoclave at a reaction temperature of 170 ° C for a period of 96 hours. The dry material consists of a pure phase of magnesoaluminosilicate with an X-ray diffraction spectrum with at least the d values that are included in table 2, above. The chemical composition of the white product, expressed in molar proportions, is: 2.56 Na20 : A1203: 1.77 MgO: 25.2 Si02: 25.1 H20. In Figure 8 the 29Si NMR spectrum of this product is shown. The molar ratio of Si02 / Al203 of this material is 52.2. It is clear that magnesium is coordinated with silicon and therefore the spectrum is different from a simple silicate or aluminosilicate material of MFI topology. In figure 19 the infrared spectrum of this material is shown. The molar ratio of Si02 / Al203 of this material is 52.2. It is clear that magnesium is coordinated with silicon and therefore the spectrum is different from a simple silicate or aluminosilicate material of MFI topology. Figure 27 shows the X-ray diagram of this material. Figure 28 shows the XPS spectrum of the Mg 2p region of this product. This invention can be incorporated in other forms or it can be carried out in other ways without departing from the spirit or essential characteristics thereof. Therefore, the present embodiment is considered in all its illustrative and non-limiting aspects, the scope of the invention is indicated by the appended claims, and all changes which are within the meaning and scope of equivalence are intended to be encompassed for the same.

Claims (24)

1. A method for preparing a metalloaluminosilicate, comprising the steps of: providing a solution containing a source of silica; provide a solution containing a source of alumina; provide an aqueous solution containing a metal other than silicon or aluminum; mix the silicon source solution with the aqueous acid solution so that a mixture containing silicon-metal source is formed; mixing the mixture containing the silicon-metal source with the alumina source solution so that a gel mixture is provided; and hydrothermally crystallizing the gel mixture so as to provide a metalloaluminosilicate material having an aluminosilicate framework and having the metal incorporated within the aluminosilicate framework.

2. The method as recited in claim 1, wherein the metal comprises at least one metal which is selected from the group consisting of iron, zinc, zirconium, chromium, nickel, cobalt, magnesium, phosphorus, gallium and mixtures thereof. same.

3. The method as described in claim 1, wherein the metal is selected from the group consisting of iron, zinc and mixtures thereof.

4. The method as described in claim 1, wherein the gel mixture has a composition in molar proportions as follows: Si02 / Al203 from 5 to 80, Si02 / DOx from 10 to 1500, SiO2 / (A1203 + DOx) from 5 to 70, Na20 / Si02 from 0.22 to 2.20, OH / SiO2 from 0.01 to 2.00, H20 / SiO2 from 14 to 40, where D is the metal.

5. The method as described in claim 1, wherein the metalloaluminosilicate has a composition, expressed in molar ratios of oxides according to an equation that is selected from the following: 1.- a (M2 / n0): b (Al203 ): c (E203): d (YES02): e (H20) 2.- a (M2 / nO): b (Al203): c (F02): d (YES02): e (H20) 3.- a ( M2 / n0): b (Al203): C (GO): d (Si02): e (H20) 4. - a (M2 / nO): b (Al203): c (H205): d (Si02): e (H20) where M is at least one ion exchangeable cation having a valence of n, - E is an element with valence 3+, - F is an element with valence 4 +, - G is an element with valence 2+; H is an element with valence 5+; a is from > 0 to 6; b is equal to l; c is from > 0 to 10; d is from 10 to 80; d / c is from 10 to 1500; e from 0 to 100; a / (b + c) is from > 0 to 5; and d / (b + c) is from 10 to 70.

6. The method as recited in claim 1, wherein the hydrothermally crystallizing step is carried out at a temperature of between about 150 ° C and about 220 ° C under autogenous pressure for a period of at least about 24 hours.

7. The method as recited in claim 1, wherein the hydrothermal crystallization step is carried out at a temperature between about 165 ° C and about 185 ° C under autogenous pressure for a period of at least about 24 hours.

8. The method as recited in claim 1, wherein the hydrothermally crystallizing step further comprises the steps of filtering and washing the metalloaluminosilicate material to provide a separate metalloaluminosilicate and drying the separated metalloaluminosilicate to provide a metalloaluminosilicate product.

9. The method as described in claim 8, wherein the drying step is carried out at a temperature between about 80 ° C and about 140 ° C.

10. The method as described in claim 1, wherein the step of providing the silica source solution comprises dissolving sodium silicate in distilled water.

11. The method as recited in claim 1, wherein the step of providing the alumina source solution comprises dissolving sodium aluminate in distilled water.

12. The method as recited in claim 1, wherein the step of providing the aqueous acid solution comprises the steps of providing an acid solution and dissolving the metal salt in the acid solution.

13. The method as recited in claim 12, wherein the acid solution comprises an aqueous solution of an acid which is selected from the group consisting of sulfuric acid, nitric acid, hydrochloric acid and mixture thereof.

14. The method as described in claim 1, further comprising the step of mixing the gel mixture so as to provide a substantially homogenous gel mixture, and hydrothermally crystallizing the substantially homogeneous gel mixture.

15. The method as recited in claim 1, wherein the step of mixing the silica source solution with the aqueous acid solution is carried out under continuous mixing so as to provide a mixture containing substantially homogeneous silica-metal source. and wherein the step of mixing the mixture containing the silica-metal source is carried out under continuous mixing for a period of time sufficient to provide a substantially homogeneous gel mixture.

16. The method as described in claim 1, further comprising the step of converting the metalloaluminosilicate material to proton form.

17. The method as described in claim 16, wherein the conversion step is an ion exchange step.

18. A method for preparing an aluminosilicate composition, comprising the steps of: providing a solution containing a silica source; provide a solution containing a source of alumina; mixing the silica source solution with the aqueous acid solution so that an acid mixture of silica source is formed; mixing the acid mixture of silica source with the alumina source solution so that a gel mixture is provided; and hydrothermally crystallizing the gel mixture so as to provide a metalloaluminosilicate composition having an aluminosilicate composition having an aluminosilicate framework, wherein the composition is formed without organic additives.

19. A method for preparing an aluminosilicate composition, consisting essentially of the steps of: providing a solution containing a source of silica; provide a solution containing a source of alumina; mixing the silica source solution with the aqueous acid solution so that an acid mixture of silica source is formed; mixing the acid mixture of silica source with the alumina source solution so that a gel mixture is provided; and hydrothermally crystallizing the gel mixture so as to provide a metalloaluminosilicate composition having an aluminosilicate framework, wherein the composition is formed without organic additives.

20. A metalloaluminosilicate composition comprising an aluminosilicate composition having an aluminosilicate framework and containing at least one metal incorporated in the aluminosilicate framework.

21. The composition as described in claim 20, wherein the metal comprises at least one metal that is selected from the group consisting of iron, zinc, zirconium, chromium, nickel, cobalt, magnesium, phosphorus, gallium and mixtures thereof. same.

22. The composition as described in claim 20, wherein the metal comprises at least one metal that is selected from the group consisting of iron, zinc, and mixtures thereof.

23. The composition as described in claim 20, which is prepared from a gel mixture having the following molar ratios: Si02 / Al203 from 5 to 80, Si02 / DOx from 10 to 1500, SiO2 / (A1203 + DOx ) from 5 to 70, Na20 / Si02 from 0.22 to 2.20, OH / Si02 from 0.01 to 2.00, H20 / Si02 from 14 to 40, where D is the metal.

24. A composition as described in claim 20, wherein the composition has molar ratios of oxides according to an equation that is selected from the following: 1.- a (M2 / nO): b (Al203) c (E203) : d (YES02): e (H20) 2.- a (M2 / nO): b (Al203) c (F02): d (YES02): e (H20) 3.- a (M2 / nO): b ( Al203) C (GO): d (S02): e (H20) 4.- a (M2 / n0): b (Al203) c (H205): d (Si02): e (H20) where M is at minus an ion exchangeable cation that has a valence of n; E is an element with valence 3+; F is an element with valence 4 +, - G is an element with valence 2+; H is an element with valence 5+; a is from > 0 to 6; b is equal to l; c is from > 0 to 10; d is from 10 to 80; d / c is from 10 to 1500; e from 0 to 100; a / (b + c) is from > 0 to 5; and d / (b + c) is from 10 to 70.