WO2001072635A9

WO2001072635A9 - Method for preparing mixed porous oxides, materials thus obtained and the uses thereof

Info

Publication number: WO2001072635A9
Application number: PCT/ES2001/000122
Authority: WO
Inventors: Del Toro Pedro Jose Amoros; Porter Aurelio Beltran; Porter Daniel Beltran; Medina Saul Cabrera; Haskouri Jamal El; Martinez M Dolores Marcos
Original assignee: Univ Valencia; Del Toro Pedro Jose Amoros; Porter Aurelio Beltran; Porter Daniel Beltran; Medina Saul Cabrera; Haskouri Jamal El; Martinez M Dolores Marcos
Priority date: 2000-03-28
Filing date: 2001-03-27
Publication date: 2001-11-22
Also published as: WO2001072635A1; ES2181528A1; ES2181528B1; AU4253501A

Abstract

Oxides, particularly compositionally homogenous porous silicometalates exhibiting high phase purity, are prepared using a method involving the following steps: 1) Preparing stable hydroalcoholic solutions of atrane complexes of the metals and/or metalloids included in the composition of the desired product; 2) Conducting chemically and/or thermally induced hydrolysis of the atrane complexes in the presence of a compound with template effect; 3) aging the product from the hydrolysis reaction and 4) obtaining the porous material by conducting pyrolysis of the aged product. The resulting porous materials have compositions I, II and III: (SiO2)1-x(AmOn) x/m (M2O)z (I); (SiO2)1-x((AmOn)1-y(A'm'On')my/m)x/m(M2O)z (II); (Al2O3)t-x((P2O5)1-y(A'm'On')2y/m')x/2(M2O)z (III), wherein 0 x 1; 0 < y < 1; z < x/2 (for I and II); z < (1-x) (for III); A and A' represent metals from subgroups (1, 2, 3, 4, 5)B or (3, 4, 5, 6, 7)A, or group 8 of the periodic table and M represents a monovalent element. The mesoporous silicotitanates obtained are used as oxidation catalysts.

Description

Procedure for preparing porous mixed oxides, materials thus obtained and their uses.

Technical field

• Compounds that have molecular sieve properties.

• Preparation of mixed oxides • Preparation of synthetic zeolites

• Preparation of silica, alumina, aluminosilicates and compounds type A1PO or SAPO, with or without doping elements, using organic agents with template effect

• Preparation of mesoporous products • Preparation of oxidation catalysts

• Use of these products as catalysts

Introduction

A wide variety of crystalline, microporous or mesoporous metal silicates, silicon dioxide compounds and / or one or more metal oxides is known. According to the definition of the IUPAC, micropores means pores with a diameter of less than 2 nm and mesopores with pores with a diameter between 2 and 50 nm. In what follows, we will apply this definition. Some crystalline metal silicates with micropores or regular mesopores are extremely effective catalysts in a wide range of chemical applications. In particular, the microporous materials of composition (SiO ^ (A _m O _n ) _{x / m} (in which atoms of a metal, such as titanium, aluminum or vanadium, replace some of the silicon atoms in the reticulum) have acquired a enormous importance

SUBSTITUTE SHEET (RULE 26) industrial as molecular sieves, catalysts or ion exchangers. Siliconotanates, in particular, are commercially useful in oxidation reactions. The structures of silicotitates differ from one another, depending on the starting reagents and the preparative conditions, and, in general, reproducibility and doping control are problematic. Thus, for example, the so-called titanium silicalite-1 (TS-1), titanium silicalite-2 (TS-2) and titanium beta-zeolite (Ti-beta), respectively, have the MFI, MEL ( Pat. US No. 4,410,501) and BEA. The known structural types of zeolites and silicalites are described in the Atlas of Zeolite Structure Types, by WM Meier and DH Holson, Edited by Butterworth-Heinemann in 1993.

Mesoporous silica materials in which titanium replaces silicon have a high interest, both academically and commercially because of its extraordinary potential as oxidation catalysts. The incorporation of titanium in a silicate lattice gives rise to isolated Ti centers that can easily modify their coordination and, in contact with H ₂ 0 ₂ or TBPH (terbutyl hydroperoxide), form an active titanium-peroxo complex. Said peroxocomplex is responsible for inducing the very remarkable selectivities observed in oxidation reactions of organic compounds. On the other hand, it is known that the catalytic efficacy of each type of metallic silicate depends greatly on its purity as a phase, on its morphology and, therefore, on the preparation conditions. For example, the catalytic activity of titanium silicalite decreases greatly with the increase in crystalline size and in the presence of other titanium phases, such as Ti0 ₂ ; see for example the works of B. Notari in (a) Catal. Today 18 (1993) page 163 and (b) Stud. Surf. Sci.CataL, 67 (1991), page 243. Undesirable contamination by Ti0 ₂

SUBSTITUTE SHEET (RULE 26) It depends critically on the preparative procedure and constitutes one of the key problems in the preparation of mesoporous silicotitates of catalytic interest.

The problem of replacing reticular silicon with other elements is general and the interest in solving it is manifested in the large number of scientific and technical publications dedicated to the preparation of this type of materials.

In general, the interest that the study of high surface solids, microporous zeolite crystals, ordered mesoporous or simply amorphous, has aroused in the scientific community during the last decades is due to the numerous applications they present in the industrial field as sorbents , molecular sieves and in a large number of catalytic processes, many of them associated with the petrochemical industry [J. M. Thomas, Angew. Chem. Int. Ed. Engl. 33 (1994), p. 913; J. M. Thomas and W. J. Thomas in Principies and Practice of Heterogeneous Catalysis, VCH Publishers Inc., 1996]. Most of these solids consist of silicon oxide, pure or partially substituted, or mixtures of oxides. The incorporation of elements that replace, isomorphically or not, silicon in the network of sñice (which we will call heteroatoms) constitutes a strategy that has been commonly used both in non-porous amorphous solids and in porous, micro and mesoporous compounds, in order to provide functionality to the silica surface. In addition to titanium, as previously mentioned, other transition elements such as vanadium, zirconium etc. have been incorporated into silica matrices for the interest of these substituted solids in catalytic oxidation reactions [J. Y. Ying, C. P. Mehnert, M. S. Wong Λngew. Chem. Int. Ed. Engl. 38 (1999), page 56]. Other elements, such as aluminum, molybdenum and tin as well

SUBSTITUTE SHEET (RULE 26) they have been substituted in silica matrices providing catalytic activity in acid-base, hydroxylation and polymerization processes, respectively [JY Ying, CP Mehnert, MS Wong Angew. Chem. Int. Ed. Engl. 38 (1999), page 56]. However, despite the enormous industrial interest of these solids, the incorporation of various elements in the silica network still presents serious preparatory problems due to the marked difference in reactivity between silicon and these elements. The result is a clear lack of uniformity in preparative chemistry, especially in the case of zeolites [Microporous and Mesoporous Materials, Special Issue: Verified Syntheses of Zeolitic Materials 22 (1998)] and also in that of mesoporous solids. In this context, a rational, reproducible and general procedure that guarantees an intimate mixture of the oxide-forming elements (for example silicon and heteroatoms) at an atomic scale represents an important progress and has an enormous industrial interest in itself. State of the art

Zeolites are the crystalline microporous reference materials, their structures are described in the Atlas of Zeolite Structural Types, edited by W. M. Meier and D. H. Olson, published in by the Structure Commission of the International zeolite Assotiation, Butterworth-Heinemann 1993.

Of the ordered regular mesoporous materials, among others, the MCM-41 and MCM-48 described by C. T. Kresge et al., In Nature, 359, (1992) p. 710. S. Behrens presented a review of the regular mesoporous structures in Angew. Chem. Int. Ed. Engl., 108 (5), (1996), page 561-564. The topology of mesoporous materials similar to the one presented

SUBSTITUTE SHEET (RULE 26) MCM-41 (originally described in US patents No. 5,098,684; No. 5,102, 643; No. 5,108,725) has been called "hexagonal type" and is associated with characteristic X-ray diffraction diagrams. Such diagrams present a very intense peak corresponding to spacing greater than 1.8 nm and, frequently, other additional low intensity peaks that are associated with reflections 100, 110, 200 and 210 of a hexagonal cell. The mentioned additional peaks may appear poorly defined or superimposed, which is associated with a loss of the perfect hexagonal packing in which the average number of neighboring channels to a given one is now less than six. Hexagonal type packing is clearly manifested in TEM micrographs.

The problem posed by incorporation of heteroatoms in both amorphous and microporous or mesoporous meshes has recently been reviewed by A. Tuel in Microporous and Mesoporous Materials 27, (1999), p. 151. The most relevant issues in this context are: the difficulties in increasing and controlling the amounts of heteroatom incorporated, the control of the coordination of the heteroatom in silica, the existence of unwanted segregated phases and, finally, the methodological dispersion of the Preparatory chemistry and lack of reproducibility of procedures. Porous metal silicates in general, and porous silicotitates in particular, are frequently prepared by hydrothermal synthesis. In a first step, a compound of the heteroatom and one of silicon, conventionally orthoalcoxocomplexes, react with water at controlled pH and condense in the form of a gel in the presence of an agent with a template effect, often a halide or hydroxide of a quaternary ammonium cation . The gel is subsequently crystallized under mild hydrothermal conditions, autogenous pressure and temperatures below 200 ° C. The

SUBSTITUTE SHEET (RULE 26) solid thus formed is filtered off, washed, dried and then calcined at temperatures above 300 ° C. It is said of a compound that has a template effect (structural director effect is also said) when its presence as a reagent is associated with the formation of materials with concrete topology and symmetry, this concept is very common in the preparative chemistry of zeolites and other microporous materials [ME Davis, R. Lobo in Chem. Mater. 4 (1992) p. 756] and has been extended to the preparation of mesoporous materials [JY Ying, CP Mehnert, MS Wong Angew. Chem. Int. Ed. Engl. 38 (1999), page 56]. Hereinafter, the qualification of the template effect or structural director effect will be used interchangeably to refer to the aforementioned effect of a compound in the specific topology and / or symmetry of the reaction products. Suitable chemical compounds for their proven structural directing effect are amines with one or more amino groups, amino alcohols or tetrasubstituted ammonium derivatives. Tetraalkylammonium compounds are very suitable in the form of hydroxide or halide; In the latter case, the pH is properly regulated with alkaline hydroxides. The nature of the alkyl groups in said tetraalkylammonium compounds influences the nature of the possible porosity induced by their structural directing effect. Thus, for example, in the preparation of microporous materials (zeolites) tetraalkylammonium compounds in which the alkyl groups are short chain, such as ethyl, propyl, butyl or n-propyl, are particularly suitable although the presence is sometimes sufficient of alkaline or alkaline earth hydroxides. On the other hand, for the preparation of mesoporous materials, long-chain tetraalkylammonium derivatives with tensioactive properties are usually used. In the case of the replacement of silicon with titanium, several have been described

SUBSTITUTE SHEET (RULE 26) Mesoporous silicotitates and various preparative pathways. EP543247 proposes a modification of the described methodology that involves the replacement of quaternary ammonium hydroxide with a salt of the same cation and the appropriate amount of ammonium hydroxide. According to US Patent 5,198,203, cetyltrimethylammonium hydroxide (CTAOH) can be used as a template agent, in the preparation of Ti-MCM-41, a mesoporous titanium silicate with structure type MCM-41. Various subsequent patents claim the preparation of porous silicas with significant titanium contents in the lattice. Thus, WO9429022 (US Patent 5,783,167) claims the preparation of a mesoporous silicotitanate with structure type MCM-41, containing a maximum of 10% by weight of Ti0 ₂ , after processing gels from component mixtures, in which the ratio molar Ti0 ₂ / Si0 ₂ is 0.2 maximum. The process is based on the fact that the hydrolysis of part of the silicon components is \. prior to that of the species that contribute titanium. RD-UV spectroscopy indicates that, at least in the porous solid materials obtained from solutions of relative molar contents Ti0 ₂ / Si0 ₂ of 0.17 and containing 2.3% Ti0 ₂ by weight after calcination, Ti (IV) is incorporated into the network in a tetrahedral environment. Such materials behave as oxidation catalysts for organic compounds. Another preparation of mesoporous silica with high titanium contents is described in US Patent 5,958,369. The molar Ti0 ₂ / Si0 ₂ ratio maximum in the precursor solutions of the gel is 0.27. In this case, the gel preparation is carried out in a non-aqueous medium to which water is added as a stoichiometric hydrolytic reagent. Mesoporous materials there described and claimed together with its production process are called MTM and containing a molar ratio Ti0 ₂ / Si0 ₂ Minimum and maximum 0.03 0.25.

SUBSTITUTE SHEET (RULE 26) It is indicated that, at least, the materials with a molar content of Ti0 ₂ with respect to Si0 ₂ of 14.73% do not contain crystalline anatase and that, calcined in air at 700 ° C, do not show in their X-ray diffractogram additional peaks to the characteristic of an interplanar spacing of 3.0 nm, typical of the mesoporous material. An alternative and general preparative methodology for various heteroatoms is that presented in US Patent 5,919,430 and is characterized by the use of pyrogenic oxides (simple, mixed or mixtures) as a source of silicon and other metals in the gel preparation process. The gel compositions are conditioned by that of mixed pyrogenic oxides, whose formulation includes the molar fraction (1-x) of Si0 ₂ and the molar fraction (x) of oxides of elements belonging to the set B, Al, Ga, In, Ge, Sn, Pb or subgroups 3 to 8 of the periodic system; in addition, x is a number between the values 0.0001 and 0.25, preferably between 0.001 and 0.2, but especially between 0.005 and 0.1. Most of the procedures described for obtaining mesoporous oxides involve, in practice, the formation of mesostructured intermediate materials. These can be considered as organic-inorganic composite materials with a structure similar to that of liquid crystals (composites, "composites" in English, are materials consisting of two or more intimately assembled solid phases). In such composite materials the organic phase is essentially constituted by the organic component with a template effect that very often has surface active properties. The formation of these intermediate materials can proceed in two different ways: either through the so-called liquid crystal templating mechanism (LCT) mechanism or through processes that involve the cooperative organization (self-assembly) of the corresponding portions

SUBSTITUTE SHEET (RULE 26) Organic and inorganic supramolecular. In the case of the LCT mechanism, the inorganic phase grows and occupies the intermicelar space of an ordered organic mesophase that has been previously formed and could thus be conceived as a supramolecular template. The other procedures are more related to conventional colloidal chemistry: regardless of the specific details of the corresponding mechanisms, cooperative self-assembly processes involve the formation of compound micelles (inorganic-organic). These compound micelles are those that are organized to form nuclei of particles that flocculate after a more or less prolonged growth phase. The essential practical difference between the LCT mechanism and those based on cooperative self-assembly processes lies in the concentration of the surfactant (surfactant) compound in the reaction medium. While the formation of authentic liquid crystals (LCT mechanism) requires very high surfactant concentrations, cooperative self-assembly processes take place in the presence of surfactant concentrations close to the so-called critical values (eme). Although the LCT method was an extraordinary advance in this field of activity, the main advances in the synthesis of mesoporous oxides have resulted from the development of the chemistry on which the processes of cooperative self-assembly at low concentrations of surfactant are based. As indicated, the preparative chemistry of ordered mesoporous solids is, in that case, closely related to colloidal chemistry; that is, it deals primarily with processes that involve micelles. However, the dissolution chemistry of inorganic precursors (usually constituted by a metal or metalloid element surrounded by several ligands) is an essential tool in the search for rational synthesis designs. This can

SUBSTITUTE SHEET (RULE 26) easily understood considering that the solvolysis and condensation processes that affect the precursor are those that generate the inorganic component of the composite micelles. Thus, in addition to the nature and relative concentration of the surfactant, other parameters (which affect both the thermodynamics and the kinetics of the solvolysis and condensation processes) that can be deliberately adjusted for the design of mesoporous materials are the chemical characteristics of the precursor and its concentration, as well as temperature and pH. The process as a whole can also be modulated by using a suitable cosol (additional solvent miscible with the solution).

Despite the undoubted advances that have occurred in a short period of time in the synthesis of mesoporous materials from ideas such as the previous ones (essentially involving the use of inorganic precursors that include alkoxy ligands), there is something that continues to result Obviously: obtaining ordered mesoporous non-siliceous materials (and also that of highly substituted or "highly doped" siliceous) through the preparation of a mesostructured intermediate (inorganic-organic) composite is not easy a priori. There are many competitive factors that must be harmonized in the search for a suitable precursor. Thus, it is first necessary that the polymerization kinetics of the alkoxy-complex (unstable against hydrolysis) can be controlled (relative inertia) so that the corresponding inorganic solutes condense on the ionic terminal groups of the surfactant; The formation of nuclei of particles of pure oxide with the critical size should be avoided in any case. However, the inherent reactivity of alkoxides is opposed to this methodological requirement that hydrolysis take place in the presence of the surfactant when dilutions are relatively high. Moreover, the

SUBSTITUTE SHEET (RULE 26) The nature of the precursor itself must not prevent hydrolysis processes from being completed and, when thinking about material precursors that include two or more oxidizing elements, it will be necessary to harmonize the reactivity of the different precursors in order to guarantee chemical homogeneity of the product. In fact, the various approaches mentioned above have the common purpose of overcoming the most important difficulty in the synthesis of silicomethalates (mixed silicon metal oxides) in general and silicotitates in particular: the formation of composition domains caused by the difference in reactivity of the silicon source compounds and those of other elements, in general, and, in particular, by the high lability of the metal alkoxides against hydrolysis. The methods used to compensate for differences in the rates of hydrolysis and condensation are based, for this reason, already on the formation of mixed complexes of alkoxides and chelating ligands or the modification of those, already in the prior hydrolysis of silicon generating compounds or, finally, in the use of concrete mixed precursors alternative to alkoxides. The sol-gel chemistry of alkoxides has been developed extensively for preparative purposes of simple and mixed oxides. On the other hand, metal alkoxides are prepared by well known procedures and typically by reaction of a metal or its halide with the respective aliphatic or aromatic alcohol or its salts, frequently in the presence of a catalyst. The knowledge of the exchange reactions in which a system formed by a metal alkoxide (OR) _x M and an alcohol HOR 'is also part of the public chemical pool evolves into a balance in which the possible alcohols coexist with mixed alkoxides ( OR) _and (OR ') _z M. Los

SUBSTITUTE SHEET (RULE 26) Alkoxides are thermodynamically unstable and, in general, kinetically labile with respect to the formation of oxohydroxy species when reacting with water, decreasing their lability with increasing metal electronegativity and the complexity of the alkoxy group. There are many relatively stable metal alkoxides due to the presence of other functional groups, such as amines or carboxylate groups, in the molecule. In particular there is a family of molecular compounds, commonly called metalatrans or atranocomplexes, in which the metal coordinates to aminotrialcoxo ligands of type N (ORjOR ₂ OR ₃ ) ^{3 "} , where the R, R ₂ , R ₃ moieties represent organic groups , same or different, containing carbon and hydrogen, saturated, unsaturated or aromatic, and preferably linear aliphatic chains. In particular, the simplest compounds of this family come from 2,2 ', 2 "-nitrilotrietanol (commercially called triethanolamine and of acronym TEA), in which the nitrogen has a remarkable basic character. The preparation of atranocomplexes of a wide variety of elements, such as B (IH), Al (ffl), Fe (III), Bi (III), Sm (III), Si (IV), Ge () is described in scientific publications IV) and Ti (IV), Zr (IV), V (V). The chemistry of silicon attractants, or silatrans, was highly developed by MO Voronkov, who reviewed it in Mashed Appl. Chem., 13 (1966) p. 35. The general chemistry of atrans has also recently been reviewed by JO See also in Acc Chem. Res., 26 (1993), p. 483. Attrants are commonly prepared from the alkoxides (for example isopropoxides) of the element by displacement of the alcohol by the aminotrialcoxo, and, particularly, by the ASD. The reaction usually takes place in benzene, chloroform or other dry organic solvent solution and under an argon or nitrogen atmosphere, using standardized inert atmosphere and Schlenk techniques. The

SUBSTITUTE SHEET (RULE 26) preparation of alumatran (aluminum atrane) by transesterification of aluminum alkoxides with triethanolamine, in the presence or absence of an organic solvent, and always in anhydrous medium and inert atmosphere [J. Pinkas et al. Inorg Chem., 32 (1993), p. 2711]. Frye [OL Frye et al. , J. Am. Chem. Soc. 93 (25) (1971), p. 6805] describes various reactions of silatran formation and, in particular, the direct conversion of silica into a polymer silatran by reaction with TEA at more than 200 ° CRM Laine, in US Patent 5,418,298, describes the formation of polymetaloxanes containing silatrane by reaction of silica with ethylene glycol as solvent and TEA as catalyst under nitrogen atmosphere; The aforementioned patent declares the use of TEA and extends its claims to the preparation of ceramic precursor polymers containing Si, Ge, Sn, Al, Ga, Ti, Zr or Hf and alkaline or alkaline earth elements. According to the scientific literature and related patents, it is known that ASD forms atranocomplexes (simple or mixed with other ligands) of many chemical elements and that the preparation of such attractants is carried out under reaction conditions in which prevents the presence of oxygen and water. In general, metalatrans are described as unstable against hydrolysis. Although in the case of silatrans a clear inertia has been detected against hydrolysis [OL Frye et al., J. Am. Chem. Soc. 93 (25) (1971), p. 6805], such property does not appear to have been used in the preparation of zeolites, zeotypes or ordered porous materials. In addition, the reactions of known metalatrans with water as a function of pH do not appear to have been studied and the possibility of using controlled hydrolysis of mixed aqueous or hydroalcoholic solutions of silatrans and other metalatrans as the metal mind for preparation of pure or mixed porous, ordered or mixed silicomethalates or oxides

SUBSTITUTE SHEET (RULE 26) do not.

Object of the present invention

In accordance with all of the above, it is the object of the present invention to provide mixed oxides or oxides, in particular silicomethalates, ordered porous of great compositional homogeneity, high phase purity and, possibly, of great catalytic activity. Another object of the present invention is to provide a suitable process not only for the preparation of products based on (Si0 ₂ ) ₁ _ _x (Tiθ ₂ ) _x but also for the preparation of products in which silicon, titanium or both are replaced, partially or totally, by one or more different elements in the solid lattice. Porous silicas, with pores of diameter greater than 1 nm, in which silicon is partially substituted by titanium, will eventually be catalysts for the oxidation of organic molecules with an effective dynamic diameter greater than 0.65 nm. The presence of aluminum in such mesoporous silicotitates can modify its acidity and extend its functionality. The preparation of simple or mixed mesoporous oxides and, in particular, that of ordered mesoporous metal silicates, comprises obtaining a mesostructured material precursor to the final mesoporous material. An aspect of the present invention is the preparation and control of both the composition of the inorganic part of mesostructured materials (compounds) capable of being possible precursors of mesoporous materials and of the properties of such mesostructured precursors and the final mesoporous. The precursor mesostructured material precipitates from aqueous or alkaline hydroalcoholic solutions in the presence of ions of the NRjR ₂ R ₃ R ₄ ^{+ type} with activity

SUBSTITUTE SHEET (RULE 26) surfactant and after the addition of a homogeneous hydroalcoholic solution containing, as a source of the elements involved in the formulation, oxides, oxohydroxides, oxoacids, halides and / or simple or mixed polyalkoxo derivatives of such elements. The precipitation of the mesostructured material is eventually induced by a heat treatment. The mesostructured material is characterized by having a well-defined metal or metalloid composition and a characteristic X-ray diffraction diagram and an image of TEM, as well as a thermal evolution of its mass with well-defined stages. When the amines used do not have surfactant activity and / or in the presence of an excess of alkaline or organic hydroxide of the ROH type, microporous or amorphous materials can be prepared depending on the synthesis conditions.

Brief Description of the Invention

The process of obtaining the precursor mesostructured materials of the corresponding mesoporous materials object of the present invention is carried out using an operative process comprising the reaction of hydrolysis and condensation in solution of an intimate mixture of source compounds or mixed source compounds of metals or / and metalloids in the presence of an agent with template effect and where the so-called source compounds are atranocomplexes of the metals and / or metalloids involved. Hydrolysis and condensation may involve the use of hydrothermal conditions under autogenous pressure. The generator of the aforementioned atranocomplexes can be any organic compound among the so-called attractants, but especially 2,2 ', 2 "nitrilotriethanol. The template effect agent

SUBSTITUTE SHEET RULE 26 suitable for the purposes of the present invention can be any. The preparative methodology of the aforementioned atranocomplexes in the present invention is advantageous with respect to those known because it is general and because it can reduce costs with respect to other known processes, thereby improving its possible commercial use.

Each mesoporous material object of the present invention is obtained by calcination, under conditions suitable for the elimination of the organic components, of the corresponding mesostructured material, prepared by the process described herein. Each mesoporous material, obtained from its mesostructured precursor, is characterized by having a characteristic X-ray diffraction diagram and an image of TEM and also a high compositional homogeneity, a unimodal pore distribution, a high specific surface area and, in addition, high thermal stability Porous silicotitates prepared by the process described herein could act as catalysts for the selective oxidation of molecules of interest in the field of organic chemistry. Other porous silicomethalates synthesized by the same procedure can act as acid, hydroxylation and polymerization catalysts. In other fields, silicoalúmines are active as catalysts in cracking and hydrocracking processes, porous silicovanadates, such as siliciotonates, have catalytic activity in epoxidation processes, siliconcirconates in various processes of oxidation of organic compounds etc.

Another aspect of the invention is the preparation of microporous materials of the zeolite type by a process identical to that used by the present invention for the preparation of mesostructured materials except that, in the case of microporous materials, the use of so-called

SUBSTITUTE SHEET (RULE 26) surfactants or surfactants as agents with template effect, although other organic compounds, mainly amines, can be used as such template agents.

Another aspect of the present invention is the preparation, by simple modifications of the preparative process claimed, of amorphous mixed oxides and, in particular, of amorphous silicomethalates. Many such amorphous silicomethalates are characterized in that the metal or metals that accompany the silicon have an average coordination environment of less than six.

Detailed description of the invention

In the process object of the present invention, the sources of metal, metals and / or metalloids are hydroalcoholic solutions of metallatran compounds, which are subjected to a hydrolysis reaction in the presence of one or more agents with template effect, necessarily comprising the following stages:

1) Preparation of stable hydroalcoholic solutions of metal and / or metalloid attractant complexes included in the composition of the desired product, consisting of starting from a hydroalcoolic solution containing the metallatran compounds or the reagents necessary to prepare these, that is, an attractant and compound of the metals and / or metalloids involved in the composition of the final product. Optionally it also contains alkali metal and / or quaternary ammonium hydroxides or halides, other alcohols, polyalcohols, carboxypolyalcohols, aminoalcohols, aminopolyalcohols or mixtures thereof, amines or polyamines, which will act as template agents. This

SUBSTITUTE SHEET (RULE 26) Initial solution, fractions with a boiling point below 190 ° C are removed by distillation.

2) Hydrolysis induced chemically and / or thermally atrane complexes in the presence of a compound with template effect, namely that the solution obtained in stage I ^to the agent is now added, should not be done at that stage, template. It is mixed, under stirring and at temperatures between 5 and 100 ° C, with a certain amount of water, preferably demineralized; the molar ratio of water to the total metal and / or metalloid content should be greater than 10 and, preferably, be between the limits 25 and 175. Optionally, the pH of the mixture can be increased, to favor the hydrolysis reaction, by addition of a hydroxide or an amine. This step provides, as a reaction product, a solution, a gel or a suspension of a solid. 3) Aging the product of the hydrolysis reaction, consisting of the product obtained in step 2 is subjected to a heat treatment at a temperature exceeding 220 ° C in an open container at reflux and atmospheric pressure or hydrothermal reactor closed (autoclave) under pressure in general autogenous, for a minimum period of 5 minutes and a maximum of 15 days. This heat aging treatment provides a solid precipitate; The solid is filtered or centrifuged, washed with water, preferably demineralized, and subsequently dried, preferably at a temperature between 18 and 25 ° C in a desiccator containing calcium chloride or other agent with a drying capacity similar to that of the latter. 4) Obtaining the porous product by pyrolysis of the aged product, consisting in that the solid isolated in step 3 ^a , is subjected to the elimination of the organic and aqueous fraction that it may contain,

SUBSTITUTE SHEET (RULE 26) by successive heat treatment or treatments at temperatures between 300 ° C and 600 ° C in an atmosphere of preferably dynamic air, oxygen or nitrogen, for a minimum time of 5 hours and a maximum of 7 days, thus obtaining the final porous material.

The present invention is based on the fact that the aminotrialcoxo type ligands and, in particular, the TEA ligand (2,2 ', 2 "- nitrilotriethanol), meet all the requirements necessary to generate suitable precursors (which must be simultaneously unstable and inert in aqueous solution in neutral or basic medium) for the preparation of oxides in the form of mesostructured, mesoporous and microporous materials by the process object of this invention in the case of a wide set of elements, thus, in accordance with the present invention, atranocomplexes are precursors suitable for the synthesis of mesostructured and mesoporous materials both in the case of silica and many other simple oxides.In addition, mixtures of attractants or mixed attractants are precursors suitable for the synthesis of microporous, mesostructured and mesoporous materials of mixed siliceous and many non-siliceous oxidic systems In what follows it is used indiscriminately the name of atrane, metallatran or atranocomplex to refer to compounds foimados by an organic component of aminotrialcoxo type and a metal or metalloid.

The most prominent feature of atranocomplexes, with respect to the present invention, is their surprising chemical inertia against hydrolysis. In fact, in many cases, once an atranocomplex has been obtained in the absence of water, the addition of this does not result in the immediate formation of any precipitate. In practice, the resulting solutions remain unchanged for long periods of time, which can reach several

SUBSTITUTE SHEET (RULE 26) weeks for a given ligand and metal. Although in the case of silicon such inertia has been described [Frye C, Vicent G., Finzel W., J. Am. Chem. Soc. 93 (1971) p. 6805] and it is not surprising, since it is common with that of its orthoalkoxides, however it is unexpected in other elements (such as Al, Ti, Sn, among others) whose orthoalkoxides are extremely labile against hydrolysis. The authors of the present invention have proven the surprising inertia of the aqueous solutions of the TEA derivatives of B, Al, Si, and Ti, among other elements. The detection of the species in solution by means of spectroscopic techniques (Nuclear Magnetic Resonance, NMR) or analytical (Mass Spectrometry after Bombardment by Ultrafast Ions, MS-FAB) allows to test the inertia against the hydrolysis of metalatrans, which is the foundation chemical of its application in the present invention. In anhydrous solution, the dominant species depend on the charge and acidity of the cation involved. In the case of trivalent elements, the majority species present in anhydrous medium are of the type

[N (CH ₂ CH ₂ 0) ₃ M] _n (n = 2-4, M = Al; n = 1, M = B)

Tetravalent elements (M = Si, Ti, Zr) form species of the type

[N (CH ₂ CH ₂ 0) ₃ M-OR] (Type

I)

In the reaction of orthoalkoxides with ASD the OR groups come from the starting alkoxide or from another molecule of ASD. In the case of Ti, the formation of oligomers consisting of Type I species has been detected.

SUBSTITUTE SHEET (RULE 26) concatenated However, the majority species in the case of Si are

[N (CH ₂ CH ₂ 0) ₃ Yes] _(3. _x) [N {(CH ₂ CH ₂ 0) _(3. _λ) (CH ₂ CH ₂ OH) _x }]

(Type II)

The presence of NaOH in anhydrous medium, not only modifies the system generating alkoxy ions of the type

[N {(CH ₂ CH ₂ 0) _(3. _x) (CH ₂ CH ₂ OH) _x ] ^ -

but also originating anions annoying as

[N (CH ₂ CH ₂ 0) ₃ SiN {(CH ₂ CH ₂ 0) ₂ (CH ₂ CH ₂ OH)}] ^' .

Similarly, in the case of trivalent elements, such as Al, the dominant ammonium species are atranocomplexes of type

[N (CH ₂ CH ₂ 0) ₃ AlN {(CH ₂ CH ₂ 0) _{(1 + x)} (CH ₂ CH ₂ OH) _(2. _X) }] (l + x) -

Most likely, all these ammonium species are stabilized in anhydrous medium incorporating Na ⁺ cations. In fact, mass spectrometry results indicate the presence of mixed sodium-silicon or sodium-aluminum attractants in significant amounts. The behavior of the attrains against the addition of water depends on the characteristics of the element involved (acidity and preferential coordination), being particularly sensitive to the characteristics of the coordination sphere of the element in the starting complex.

SUBSTITUTE SHEET (RULE 26) The atrano-complexes of elements such as B, Al, Si, and Ti are inert against hydrolysis and their inertia is controllable as a function of pH. Such behavior is not exclusive to these elements and the atrano-derived metals such as Zr, V, Mo, Fe, Co, Ni, and Zn behave similarly. The preparative procedure described below is based on inertia against the hydrolysis of metallatrans and their control, which allows simultaneous hydrolysis and condensation of several elements, and in particular silicon and one or more additional metals or metalloids.

The process for obtaining the precursor materials of porous materials, object of the present invention, can be carried out using the operating process described below and comprising the steps a, b, c, d, e, f, g, h . Stage i, applied to the microstructured, mesostructured or amorphous precursor material obtained after the previous stages, respectively provides the microporous, mesoporous or fine amorphous material. The steps are described below: a) A hydroalcoholic solution is prepared A. Solution A may contain , in addition to water and an attractant compound, an alkaline or quaternary ammonium hydroxide, alcohols, polyalcohols, carboxypolyalcohols, aminoalcohols, aminopolyalcohols or mixtures thereof and, eventually, amines or polyamines; All these organic compounds can be straight or branched chain, varying the number of carbon atoms of each chain between 1 and 6 and, in addition, they must be miscible with each other and with water in the proportions and conditions in which it is defined and used Solution A for the purpose of preparing the materials object of the invention.

SUBSTITUTE SHEET (RULE 26) b) In a sufficient portion of solution A, the source reagents of the metals and / or metalloids involved in the formulation are dissolved. The maximum total molar concentration in metals and / or metalloids is that of the attractant compound. The liquid thus prepared is called Bl. c) The liquid Bl is distilled and all boiling point fractions below 190 ° C at 1 atm (101.3 kPa) are removed. The residual solution is called Cl. D) To the rest of the solution A is added, optionally, salts of alkaline monovalent cations M ⁺ , preferably sodium, or quaternary ammonium NR _j R ^ R ^, where R ₂ , R ₃ and R ₄ may be the same or different and represent organic groups with a chain length between 1 and 6 carbon atoms, the preferred composition being that in which R ₂ = R ₃ = R ₄ = CH ₃ ; R _! represents an organic group containing carbon and hydrogen, saturated or unsaturated, preferably a linear or branched aliphatic chain; the number of C atoms in this chain can vary between 2 and 36 and those organic groups containing between 10 and 18 carbon atoms are preferred; As examples of this template agent, not process limitation, the following cations can be cited: hexadecyltrimethylammonium, dodecyltrimethylammonium, benzyltrimethylammonium, dimethyldidodecylammonium, hexadecylpyridinium or hexamethyltrimethylphosphonium. The solution thus prepared is called solution B2. e) Liquid B2 is distilled and all boiling point fractions below 190 ° C at 1 atm (101.3 kPa) are removed. The residual solution is called C2. f) Cl and C2 solutions are mixed under gentle agitation and

SUBSTITUTE SHEET (RULE 26) temperatures between 10 and 150 ° C. The solution thus prepared is called solution C. g) Solution C is mixed, with stirring and at temperatures between 5 and 100 ° C, with a certain amount of demineralized water. The molar ratio of water to the total metal content should be between limits 25 and 175. This step provides as a reaction product a solution, a gel or, possibly, a suspension of a solid. The product of this stage is called D. h) Product D is subjected to a thermal aging process at temperatures between 20 and 190 ° C in an open reflux vessel or in an autogenous pressure hydrothermal reactor (autoclave) during a period of minimum time of 5 minutes and maximum of 15 days. This thermal process provides a solid precipitate. This solid is filtered or centrifuged, washed with demineralized water and subsequently dried at 25 ° C in a desiccator preferably containing calcium chloride. The resulting solid is called M. i) The final porous material is obtained from solid M, by elimination of the organic and aqueous fraction that it may contain, by successive treatment or heat treatments at temperatures between 300 ° C and 600 ° C in a dynamic atmosphere of synthetic air or oxygen and for a minimum of 5 hours and a maximum of 7 days.

The described process provides ordered porous oxides with molecular sieve structure, in general, and, in particular, provides mesoporous silicas in which silicon ions have been substituted,

SUBSTITUTE SHEET (RULE 26) isomorphically or not and in a controlled manner, by ions of other elements, both representative and transitional, in significant proportions. If, in step d of the described process, quaternary ammonium salts with surfactant properties are not used, the continuation of the procedure leads, after step g, to a G gel. The subsequent application to G of the type of aging process described in step h it provides, depending on the type of heat treatment, zeolite-type crystalline microporous materials, or, frequently, amorphous heteromethalic materials. They are eventually subjected to a treatment of the type described in step i in order to eliminate the organic components. The surfactant preferably used is cetyltrimethylammonium bromide (CTAB) and the pH is adjusted to the appropriate range for the formation of inorganic polyanions, which depends on the nature of the elements involved. Reaction parameters such as temperature, time and reagent concentrations should be optimized depending on the system studied. In any case, to obtain most of the materials described in the present invention, molar proportions close to the following defined by the values are used:

Element involved 2 ASD 7

Surfactant 0.6

Water 100-300

Description of the materials obtained according to the present invention.

The porous materials obtained by the process object of the present invention respond, in their anhydrous form, to the compositional formulas I,

SUBSTITUTE SHEET (RULE 26) Il and HI:

(Si0 ₂ ) ₁ . _x (A _m O _n ) _{x / m} (M ₂ 0) _z (D

(Si0 ₂ ) _] . _x ((A _m O _n ) _1. _y (A ' _m , O _n ,) _{my / m} .) _{x / m} (M ₂ 0) _z αD

(A ^ O ^^ CP ^^ A'Λ ^ ^ CM _a ), (III)

In formulas I, II and / or III, x, y, z represent molar fractions that define the empirical composition of the anhydrous porous material and take actual values defined by the following conditions:

• x is a number between 0 and 1; • y is a number greater than 0 and less than 1;

• z is a number less than x / 2 in the case of the compositions of formulas I and II; in the case of formula III, z is less than (1-x).

In formulas I, II and / or III, A and A 'represent metals of Valencian p and p', equal or different from each other, chosen from among those of the following groups: • Any belonging to group 3B preferably B and Al.

• Anyone belonging to group 3 A preferably Se, Y, La and the lanthanides.

• Anyone belonging to group 4B_ preferably Ge, Sn and Pb.

• Anyone belonging to group 5B_ preferably P and Bi. • Anyone belonging to group 4A_ preferably Ti and Zr.

• Anyone belonging to group 5 A preferably V.

• Anyone belonging to group 6A_preferably Mo.

• Anyone belonging to group 7A preferably Mn.

• Anyone belonging to the group 8_ preferably Fe, Co and Ni. • Anyone belonging to the group lB_ preferably Cu.

• Anyone belonging to group 2B_ preferably Zn.

In the formulas of compounds I, II and III, the subscripts m, m ', n and n'

SUBSTITUTE SHEET (RULE 26) they represent numbers of atoms per formula that satisfy the relations: mp = 2n m'ρ '= 2n'. M represents one or more monovalent elements, preferably Na.

The porous materials of this invention have a composition, in anhydrous form, which is expressed by the respective empirical formulas, which are: • For mesoporous silicotitates (SiO ^ TiO,), (M ₂ 0) _z O≤x≤l; z <0.01 especially

0.005 <x <0.40; z <0.01 and specifically x = 1.00; z≤0.01

• For porous silicoaluminatos (SiO ^ Al) ^ (M ₂ 0) _z O≤x≤l; z≤x / 2 especially

0.001 <x ≤ 0.485; z <0.02 and specifically x = 1.00; z≤0.01

• For other quaternary porous silicomethalates (Si0 ₂ ) ₁ . _x (A _m O _n ) _{x / m} (M ₂ 0) ₂ If A = B: 0.01 <x <0.10; z <x / 2 and especially

0.01 <x <0.065; z <0.01

SUBSTITUTE SHEET (RULE 26) If A = Sn:

0.01 ≤x <0.25; z <0.01 and especially

0.01 ≤x <0.165; z <0.01 If A = Zr:

0.01 ≤x <1; z≤0.01 and especially

0.01 ≤ x <0.77; z ≤ 0.01 If A = V: 0.01 ≤ x <0.25; z ≤ 0.01 and especially

0.01 ≤ x <0.20; z ≤ 0.01 If A = Mo:

0.01 <x <0.20; z <0.01 and especially

0.01 ≤x <0.15; z <0.01 If A = Mn:

0.01 <x <0.30; z ≤ 0.01 and especially 0.01 ≤ x <0.25; z ≤ 0.01

If A = Faith:

0.01 ≤x <0.15; z≤0.01 and especially

0.01 ≤x <0.10; z≤0.01 If A = Co:

0.01 ≤x <0.15; z≤O.Ol

SUBSTITUTE SHEET (RULE 26) and especially

0.01 ≤x <0.05; z≤0.01 If A = Ni:

0.01 ≤x <0.15; z≤0.01 and especially

0.01 ≤x <0.10; z≤0.01 If A = Cu:

0.01 ≤x <0.10; z≤0.01 and especially 0.01 ≤ x <0.05; z <0.01

If A = Zn:

0.01 ≤ x <0.20; z ≤ 0.01 and especially

0.01 ≤x <0.15; z≤0.01 • For porous sicotitanoaluminatos

(SiO ^ CAl) ^ (TiO ^ (M ₂ 0) _z 0.001 <x <0.455;O≤y≤l; z≤x (ly) / 2 • For other quinary porous silicomethalates

(Si0 ₂ ) _l4 (i0 ₂ ) ₁ ^ (Zt0 ₂ ) _y ) _x (M2θ) _z 0.005 <x <0.50; O≤y≤ 1; z <0.01

(SiO ^ ZrO ^ (V ₂ 0 ₅ ) _{y / 2} ) _x (M ₂ 0) _z

0.001 ≤x≤0.485; 0≤y <0.15; z≤0.01

(SiO ^^ íCZnO ^ CNiO ^ d ^ O),

0.001 ≤ x <0.15; 0 ≤ and ≤ 0.15; z ≤ 0.01 (SiO ^^ ÍCM O ^^ iO ^ CMaO),

0.001 ≤ x ≤ 0.15; 0 ≤ and ≤ 0.13; z ≤ 0.01

SUBSTITUTE SHEET (RULE 26) • For porous aluminophosphates

(At ₂ 0 ₃ ) _I. _x ((P ₂ 0 ₅ ) _1. _y (A ' _m O _n> ) _{2y / m} ,) _x (M ₂ 0) _z 0.001 ≤ x ≤ 0.80; O≤y≤l; z ≤ (lx) / 2 especially if y = 0 (ALPOs)

0.15 ≤x <0.50 z≤0.01

If A '= Ti

0.15 ≤x <0.50; O≤y≤ 0.2; z≤0.01 and especially 0.15 ≤x <0.40; 0≤y≤0, l; z≤0.01

Yes A '= Yes (SAPOs)

0.15 ≤x <0.80; O≤y≤ 0.8; z≤0.01 and especially

0.15 ≤x <0.65; 0≤y≤O, 65; z≤0.01

In addition to their chemical composition, other distinguishing features of all mesoporous materials of the compositions described above are:

• Present X-ray diffraction diagrams in which at least one peak corresponds to a reticular spacing value greater than 1.8 nm. • Have a unimodal pore distribution, with a mean diameter, d _BJH , greater than 1 nm, typically close to 2.5 nm and generally less than 4 nm. Additionally, the distribution of the pore diameter in each single phase material does not exceed 20% of the average pore diameter value. • Have a hexagonal packing structure, typical of porous materials type MCM-41, for relatively small values of x, but also for gradually losing the aforementioned

SUBSTITUTE SHEET (RULE 26) Hexagonal topology and get to acquire the so-called commonly worm type ("wormhole-lü e") by increasing the values of x and / or y. The hexagonal type topology and the worm type topology can be distinguished by TEM micrographs • The silicotitanatos and the porous silicotitanoaluminatos, in addition to the above characteristics, have an RD-UV spectrum in which an absorption band centered at 220 + 10 nm is observed and, eventually, a second band centered at 270 + 10 nm. These bands indicate the incorporation of titanium in the reticulum; the first indicates the presence of titanium with less than six oxygen coordination and the second is indicative of the presence of hexacoordinated oxygen to titanium. The presence of penta or tetracoordinated titanium in the lattice of these materials is also inferred from the increase in intensity of the localized absorption band to 960 + 5 cm ^" ¹ in its IR spectra with the increase in the proportion of titanium in its compositions.

• Mesoporous silicotitates, in particular, in addition to the above characteristics, have, for the entire range of detailed x, a surface area of specific area greater than 590 m ² g ^_1 , which is greater than 950 m ² g ^"1 when these materials they have compositions corresponding to values of x less than 0.05.

• The mesoporous silicotitates referred to in the present invention constitute materials that catalyze the selective oxidation of organic products. • All mentioned mesoporous silicomethalates retain their characteristics and are stable after heat treatments at temperatures below or equal to 600 ° C in an air atmosphere for at least 24

SUBSTITUTE SHEET (RULE 26) hours.

Zeolites, microporous materials, typically have molar ratios (Si0 ₂ / Al ₂ 0 ₃ ) greater than 2, or (SiO ^ TiO _j ) greater than 65 and uniform pores of diameter between 4 to 15 Angstroms; In addition to Al or Ti, other heteroatoms such as V, Zr, B have an interest as silicon reticular substituents for the catalytic properties that confer zeolite. The process of this invention leads to the simultaneous hydrolysis of silicon and heteroatoms, which provides coordination environments of less than six e for the latter; that is, it facilitates and optimizes the incorporation of the heteroatom into the siliceous reticulum. The preparatory potential is enormous and virtually the synthesis of many zeolites is approachable. In general, the use of low molecular weight organic compounds with a template effect, in particular the short chain quaternary alkylammonium hydroxides in the preparative process, leads to microporous materials.

Use of the materials obtained according to the present invention

The present invention provides porosity materials controlled on the one hand, and on the other of excellent homogeneity of composition regardless of its microstructure, topology or porosity. The properties derived from porosity and its order refer, for example, to its use as adsorbers and / or molecular sieves. On the other hand, the uses as catalysts depend a lot on the nature, distribution and geometry of the active elements or groups in the material. The compositional homogeneity of the materials, promoted by the preparative methodology proposed here, is particularly

SUBSTITUTE SHEET (RULE 26) suitable for use in various catalytic reactions. In particular, the porous silicomethalates prepared by the claimed process, in which the metal that accompanies the silicon is Ti, Zr, V or Mo, are active and selective catalysts in concrete oxidation reactions of

5 organic compounds In particular, the application of the process of this invention to the preparation of a mesoporous silicotitanate when the ratio between the molar fractions of the tetraalkylammonium template agent with surfactant activity and of the total metals is between 0.3 and 1.0; additionally when the hydroalcoholic solution of metalatrans is prepared or contacted with an alkali hydroxide so that the ratio between the molar fractions of the alkaline element and of the total metals is between 10 ^"6 and 5.10 ^{" 1} , leads to a material suitable for use in the selective oxidation of organic products. Said material comprises an ordered mesoporous phase characterized by

15 have at least one diffraction peak at a spacing d greater than 1.8 nm, with pores with a diameter greater than 1.0 nm and less than 20 nm and whose reticulum is composed of silicon and titanium oxides; In addition, the material has an intense spectral band in the infrared at 960 ± 5 cm ^'1 and others in the ultraviolet spectral range close to 220 ± 10 nm and, eventually, at

20 270 + 10 nm, indicating the presence of reticular titanium; In addition, the material has a composition according to the stoichiometric formulation:

(ZO ^^ Al ^^ iO ^ La (M ₂ 0) _z where Z0 ₂ is an oxide in which Z represents one or more cations with valence 4, always Si ⁴⁺ and, optionally, Ge ⁴⁺ , Sn ⁺ o Pb ⁴⁺ ; 25 where M ₂ 0 is an oxide in which M represents one or more cations interchangeable by ions from the set H ⁺ , Na ⁺ and K ⁺ ; and where the stoichiometric coefficients x, y, z can take values

SUBSTITUTE SHEET (RULE 26) limited by the following conditions

0.001 <x ≤ 0.485; (1-y) ≤ 10 ^"4 ; z ≤ 0.01

Description of the figures Figure 1.

Variation of the ₁₀₀ x-ray diffraction peak (white circles) and the BET surface (black circles) of the mesoporous silicoaluminations of Examples 4 and 5 with the Al / Si molar ratio in the final mesoporous solid.

Figure 2. TEM images of mesoporous silicoaluminatos with Si / Al = ratios

13.9 in image a (product of example 4), Si / Al = 1.45 in image b, and

Si / Al = 1.06 in image c (product of example 5).

Figure 3

Variation of the d-ray diffraction peak d ₁₀₀ (white circles) and the BET surface (black circles) of the mesoporous silicotitates of Examples 6 and 7 with the Ti / Si molar ratio in the final mesoporous solid.

Figure 4

TEM images of pure silicas from example 1 with topologies: laminar

(image a), ordered hexagon (image b) and disordered hexagonal (image c). The boxes show an enlargement (x 2) of selected areas.

Figure 5

X-ray diffraction spectra (CuK radiation) of pure mesostructured silicas obtained with values of x = 0 in the diffractogram a, x = 1.0 in the diffractogram b, x = 1.5 in the diffractogram c, x = 3 , 0 in the diffractogram dyx = 4.5 in the diffractogram e. The diffractograms a, b and e correspond to the products of example 1.

SUBSTITUTE SHEET (RULE 26) Figure 6

TEM images of mesoporous aluminas. Image a: product with a pore diameter of 3.3 nm (corresponding to the solid described in example 2). Image b: product with pore diameter of 6.9 nm. Figure 7. Nitrogen adsorption-desorption isotherms of mesoporous aluminas.

Curve a: product with a pore diameter of 3.3 nm (corresponding to the solid described in example 2). Curve b: product with a pore diameter of 6.9 nm. Figure 8

Variation of the pore size (line a) and the X-ray diffraction peak d ₁₀₀ (line b) of mesoporous aluminas described in Example 2 with the ratio H ₂ 0 / TEA in the reaction medium.

Figure 9. Nitrogen adsorption-desorption isotherm of mesoporous titanium oxide of Example 3. The pore size distribution is shown in the box.

Figure 10

X-ray diffraction spectra (CuKα radiation) (at low and high angles) of the mesoporous titanium oxide of example 3 calcined at 350 ° C

(diffractograms a), and at 500 ° C (diffractograms b). At high angles (24 to 28 degrees) a characteristic wide peak of anatase microdomains is observed

(diffractograms a) that increases in intensity and definition when the material is calcined at 500 ° C (diffractograms b). Figure ll.

X-ray diffraction spectra (CuKα radiation) of mesoporous silicoaluminatos with molar ratios Si / Al = 13.9 (diffractogram a)

SUBSTITUTE SHEET (RULE 26) (product of example 4) (diffractogram b); If Al = 8.17 (diffractogram c); Si / Al = 4.51 (diffractogram d); Si / Al = 1.45 (diffractogram e); and Si / Al = 1.06 (product of example 5) (diffractogram f). Figure 12. Nitrogen adsorption-desorption isotherms of mesoporous silicoaluminates with molar ratios Si / Al = ∞ (curve a); Si / Al = 13.9 (product of example 4) (curve b); Si / Al = 4.51 (curve c); Si / Al = 1.06 (product of example 5) (curve d). Figure 13. X-ray diffraction spectra (CuKα radiation) of mesoporous silicotitates with molar ratios Si / Ti = 50.0 (diffractogram a) (product of example 6); Si / Ti = 34.9 (diffractogram b); Si / Ti = 19.0 (diffractogram c); Si / Ti = 8.0 (diffractogram d): Si / Ti = 3.2 (diffractogram e); Si / Ti = 1.9 (product of example 7) (diffractogram f). Figure 14

Nitrogen adsorption-desorption isotherms of mesoporous silicotitates with molar ratios Si / Ti = 50.0 (curve a) (product of example 6); Si / Ti = 34.9 (curve b); Si / Ti = 19.0 (curve c); Si / Ti = 8.0 (curve d); Si / Ti = 1.9 (product of example 7) (curve e). Figure 15

TEM images of mesoporous silicotitates with "worm" type topology and Si / Ti molar ratios = 34.9 (image a); Si / Ti = 19.0 (image b); Si / Ti = 1.9 (product of example 7) (image c). Figure 16. Diffuse refractive spectra in the visible ultraviolet zone (RD-UV) of mesoporous silicotitates with Si / Ti molar ratios = 50.0 (product of example 6) (spectrum a); Si / Ti = 34.9 (spectrum b); Si / Ti = 19.0

SUBSTITUTE SHEET (RULE 26) (spectrum c); Si / Ti = 8.0 (spectrum d); Si / Ti = 1.9 (product of example 7)

(spectrum e).

Figure 17

X-ray diffraction spectra (CuKα radiation) of mesoporous silicocirconate with different Si / Zr molar ratios. Specifically, the spectra labeled Si / Zr = 10 and Si / Zr = 3 correspond to the products of examples 8 and 9, respectively.

Figure 18

TEM images of mesoporous silicocirconate with Si / Zr ratios = 10.0 (product of example 8) (image a); Si / Zr = 5.0 (image b); Yes / Zr =

3.3 (product of example 9) (image c).

Figure 19

Nitrogen adsorption-desorption isotherms of mesoporsal silicocirconate with molar ratios Si / Zr = 10.0 (product of example 8) (curve a); Si / Zr = 3.3 (product of example 9) (curve b).

Figure 20

X-ray diffraction spectra (CuKα radiation) of mesoporous silicovanadates with different Si / V molar ratios. Specifically, the spectra labeled Si / V = 30 and Si / V = 5 correspond to the products of examples 10 and 11, respectively.

Figure 21

TEM images of mesoporous silicovanadates with Si / V = ratios

30.0 (product of example 10) (image a); Si / V = 9.0 (image b); Yes / V =

5.0 (product of example 11) (image c). Figure 22

Nitrogen adsorption-desorption isotherms of mesoporsal silicovanadates with molar ratios Si / V = 30.0 (product of example 10) (graph a);

SUBSTITUTE SHEET (RULE 26) Si / V = 5.0 (product of example 11) (graph b).

Figure 23

X-ray diffraction spectra (CuKα radiation) of mesoporous siliconiquelates with different Si / Ni molar ratios. Specifically, the spectra labeled Si / Ni = 29 and Si / Ni = 12 correspond to the products of examples 12 and 13, respectively.

Figure 24

TEM images of mesoporous siliconiquelates with Si / Ni ratios =

29.0 (product of example 12) (image a); Si / Ni = 25.0 (image b); Si / Ni = 12.0 (product of example 13) (image c).

Figure 25

Nitrogen adsorption-desorption isotherms of mesoporous siliconiquelates with molar ratios Si / Ni = 29.0 (product of example 12) (graph a);

Si / Ni = 12.0 (product of example 13) (graph b). Figure 26

X-ray diffraction spectra (CuKα radiation) of silicoaluminotitanate molar ratio Si / Ti = 2.7, Si / Al = 5 (product of example 14) mesostructured (diffractogram a) and mesoporous (diffractogram b).

X-ray diffraction spectra of another mesostructured solid (diffractogram c) and mesoporous (diffractogram d) with molar ratio Si / Ti =

5.5 and Si / Al = 3.9.

Figure 27

Nitrogen adsorption-desorption isotherms and pore size distribution of mesoporous silicoalummotitanatos with molar ratios Si / Ti = 2.7 and Si / Al = 5 (product of example 14) (curves a); Si / Ti = 5.5 and Si / Al =

3.9 (curves b).

SUBSTITUTE SHEET (RULE 26 Figure 28

X-ray diffraction spectrum (CuKα radiation) of the mesoporous silicotitanocirconate of example 15. Figure 29. Nitrogen adsorption-desorption isotherm and pore size distribution of the mesoporous silicotitanocirconate of example 15. Figure 30.

TEM images of porous aluminophosphates with molar ratio P / Al = 0.74 (product of example 16) (image a); P / Al = 0.17 (image b). Figure 31

X-ray diffraction spectra (CuKα radiation) of porous aluminophosphates with molar ratio P / Al = 0.74 (product of example 16) (diffractogram a); P / Al = 0.55 (diffractogram b); P / Al = 0.17 (diffractogram c). Figure 32

X-ray diffraction spectra (CuKα radiation) of the mesoporous silicoaluminophosphate of Example 17 (diffractogram a) and another mixed mesoporous aluminum and titanium phosphate synthesized by the same procedure (diffractogram b). Figure 33

Nitrogen adsorption-desorption isotherms and pore size distribution of the mesoporous silicoaluminophosphate of example 17 (graph a) and another mixed mesoporous aluminum and titanium phosphate synthesized by the same procedure (graph b). Figure 34

X-ray diffraction spectrum (CuKα radiation) of the product of Example 18.

SUBSTITUTE SHEET (RULE 26) Examples

Example 1 demonstrates the influence of the preparative conditions both in the topology of the precursor mesostructured materials and in the properties of the corresponding final mesoporous materials. In general, obtaining highly ordered mesoporous silicas with high thermal stability requires treatments and / or post hydrothermal treatments (T <180 ° C and autogenous pressure). The process object of the present invention allows to obtain highly ordered silica with high thermal stability without the need for hydrothermal treatments. Preventing the formation of laminar aluminas constitutes a challenge in the preparation chemistry of mesoporous aluminas [Inoue M., Kondo Y .., Inui T., Inorg. Chem. 27 (1988) p. 215; Yada M., Machinda M., Kijima T., Chem. Commun. (1996) p. 769]. Such a tendency is manifested, when conventional preparative methodologies are used, probably due to the stabilization in the course of the anisotropic particle process that are precursors of phases analogous to the bohemite [Brinker C, Scherér G., Sol Gel Science: The physics and chemistry of sol-gel processing, Academic Press, New York, 1990, p. 108; Livage J., Henry M., Sánchez C, Prog. Solid. St. Chem. 18 (1988) p. 259]. Some published information suggests that the preparation of mesoporous alumina in aqueous medium is not favorable and advises to work in non-aqueous media [Vaudry P., Khodábandeh S., Davis M., Chem. Mater. 8 (1996) p. 1451; Bagshaw S., Pinnavaia T., Angew. Chem. Int. Ed. Engl. 35 (1996) p. 1102]. In contrast, the technique of the present invention allows to isolate thermally stable mesoporous alumina with a controlled pore diameter between 3 and 7 nm, as shown in example 2.

SUBSTITUTE SHEET (RULE 26) In scientific publications, references to procedures for the preparation of ordered mesoporous titania are scarce and, on the other hand, the materials that have been obtained incorporate phosphorus impurities in significant quantities [Antonelli D., Ying J. Angew. Chem. Int. Ed. England 34, (1995), p. 2014; Putman R., et al Chem. Mater. 9, (1997), p. 2690]. The failure in the synthesis has no doubt origin in the thermodynamic instability of the source compounds of titanium, halides or alkoxides, against hydrolysis. In fact they are even more labile than similar aluminum compounds. The preparation of pure, mesoporous and ordered Ti0 ₂ materials, however, is possible using the process of this invention, as shown in example 3.

After the discovery of the mesoporous materials rich in silica type MCM-41, the control of the replacement of the reticular silicon, isomorphically or not, by other elements in significant quantities has been an objective of general interest. In particular, aluminum is a typical element of isomorphic and omnipresent substitution in the chemistry of zeolites. Substitution in significant quantities over ordered mesoporous is not, however, trivial and only two procedures have been described in which the theoretical substitution limit is approximated (Si / Al = 1) [Jannicke M. T., et al Chem. Mater. 11, (1999), p. 1342; Cabrera S., The Haskouri J., Mendioroz S., Guillem C, Latorre J., Beltrán A., Beltrán D., Marcos M. D., Amorós P., Chem. Commun. (1999) p. 1679].

By means of the present invention, which allows the hydrolysis rate of the aluminum precursor to be adapted to that of silicon, the Si / Al ratio can be modulated (example 4) above a minimum Si / At least 1.06 value to the theoretical limit. The surface area of mesoporous materials synthesized by the

SUBSTITUTE SHEET (RULE 26) The method of this invention is high, although it decreases as the content of Al increases. The mesoporous silicoaluminates obtained are chemically homogeneous and, by means of MAS NMR spectroscopy of ²⁷ Al, only Al is detected therein in tetrahedral coordination. This last result proves that the methodology of the procedure allows an isomorphic substitution of aluminum instead of reticular silicon. The regular evolution of both the position of the intense diffraction peak observed at low angles and the BET surface with the Al / Si molar ratio is consistent with the isomorphic substitution of silicon for aluminum proven by NMR. However, the analysis of the X-ray diffraction spectra, together with the TEM images [Figure 1; Figure 2] differentiates two ranges of composition. One, for Si / Al values> 14.15, in which the hexagonal topology is maintained, and another, for Si / Al values <14.15, in which the topology can be described as a "worm" type. As in the case of Al, the incorporation of Ti into the framework of silica-rich mesoporous materials implies a progressive decrease in the hexagonal order typical of MCM-41 silicas. Unlike the replacement of reticular silicon with aluminum, in which the evolution of the structural characteristics and physical properties of the material is smooth and progressive, the incorporation of titanium in the position of the silicon manifests two regimes [Figure 3], as shown in examples 6 and 7. For Ti / Si molar ratios of less than 0.02, the pore system topology of the material is hexagonal and most of the titanium atoms have a tetra or pentacoordinated environment typical of an isomorphic substitution. of silicon. The surface area remains close to 1100 m ² / g and the reticular spacing grows rapidly from 3.7 to 4.2 nm. For Ti / Si molar ratios greater than 0.02 and up to 0.52, the pore system topology of the material

SUBSTITUTE SHEET (RULE 26) It is a "worm" type and the proportion of titanium with an octahedral environment increases with the titanium content. There is an abrupt decrease in surface area for the 0.02 molar ratio and the reticular spacing changes its tendency and decreases with increasing titanium content. This behavior shows that mesoporous silicotitates prepared according to the process of this invention can be classified, by the whole of their physical properties, into two families: hexagonal, low titanium content, Ti / Si <0.02, which possibly are of the type MCM-41 and, on the other hand, those rich in titanium, Ti / Si> 0.02, of porosity type "worm".

The process object of the present invention allows to prepare a great variety of substituted mesoporous silicas with relatively low content in dopants and with hexagonal symmetry and others, with high M / Si ratio, which have "worm" type topology, as shown in the examples 8 to 13. The process allows silicomethalates to be prepared with a wide variety of metals and metalloids, as indicated in the detailed description of the invention. In all cases it is possible to extend the silicon replacement range. Below are some selected examples in which silicon is replaced by Zr, V and Ni. In the case of silicocirconatos, the maximum replacement values previously reached corresponded to molar ratios Zr / Si = 0.2. The process object of the present invention has allowed to extend this range significantly to porous materials with Zr / Si ratios = 3.3, in which the zirconium is the largest itary metal. In the case of silicovanadates, the compositional range has been extended to molar ratios V / Si = 0.25, compared to the maximum values of 0.05 mentioned in the literature. In the case of silicomethalates, maximum substitutions corresponding to

SUBSTITUTE SHEET (RULE 26) Molar ratios Ni / Si = 0.08, compared to the maximum values of 0.04 mentioned in the literature.

The process object of the present invention has demonstrated its validity and versatility in the preparation of quaternary systems containing three different metals and / or metalloids. The precursor solutions of mixtures of atranes allow a synchronized hydrolysis and condensation around the surfactant molecules, which allows to prepare quaternary materials with a high compositional homogeneity (Examples 14 and 16). The present invention also applies successfully to the preparation of ALPOs and SAPOs, using phosphoric acid as a source of phosphate groups as starting precursors, together with the corresponding attractants. The compositional range studied extends from pure alumina to systems whose ratio (P + Si) / Al is equal to 1. The procedure allows to incorporate practically the same P / Al or Si / All molar proportions present in the final solid. initial mix Thus, for example, mesoporous worm-type ALPOs with the ratio P / Al = 1 have been prepared for the first time. In ALPOs, the average pore diameter varies inversely to the phosphate content in the material and this effect is all the stronger when higher is the pH. In fact, even for a fixed molar ratio P / Al 0.35 it is possible to modulate the pore size and surface area from 33 Á / 300 m ² g ^_1 to 15 Á / 500 πrY (Examples 16 to 18).

Finally, example 19 shows a practical application of these solids in a catalytic oxidation reaction. Example 1. Mesoporous silica: SiO _z (M ₂ 0) _z (x = 0; z = 0). Three identical hydroalcoholic solutions containing 34.46 g of 2.2 ', 2 "-nitrilotriethanol (TEA), 10 g of ethyl alcohol and less than 1 g of water are prepared. These solutions are made alkaline by the addition of hydroxide

SUBSTITUTE SHEET (RULE 26) solid sodium The resulting transparent solutions (solutions A) have the compositions corresponding to the TEA molar ratios: 1

NaOH: x (x = 0.0, 0.14, 0.65, respectively) Ethanol: 0.91

H ₂ 0 0.24

One third by weight of each solution A is mixed with 14.02 g of tetraethyl orthosilicate (TEOS) under gentle stirring for 5 minutes at 20 ° C. The three resulting Bl liquids have the following molar compositions: Si0 ₂ : 2

ASD: 7

NaOH: x (x = 0.0, 1.0, 4.5, respectively)

Ethanol: 14.36

H ₂ 0 1.66 The remaining portion of each solution A is mixed with 6.60 g of CTAB. The three B2 solutions are thus obtained.

From the liquids Bl and B2, respectively, the extract solutions Cl and C2 are obtained by fractional distillation, strictly following the protocols described respectively in steps c and e of the general procedure.

Solutions C are obtained by mixing the corresponding Cl and C2 under gentle stirring at 30 ° C. To each solution C, 198 g of demineralized water are added under gentle stirring at 5 ° C. The resulting solutions are kept under stirring, at a temperature close to 20 ° C, for a time between 15 minutes and 1 hour. After the addition of water, the overall composition of the three resulting D products corresponds to the molar ratios.

SUBSTITUTE SHEET (RULE 26) Si0 ₂ : 2

ASD: 7

CTAB: 0.60

NaOH: x (x = 0.0, 1.0, 4.5) H ₂ 0 333.33

The aging of each product D is carried out according to the protocol described in step h, and the conditions are: continuous stirring for 72 hours at a temperature of 45 ° C under a total pressure of 1 atm (101.3 kPa). In all cases, aging leads to a suspension of a solid in a solution. The solid is filtered off, washed three times with demineralized water and twice with ethanol (94%) and then kept in a desiccator over calcium chloride for 12 hours. The nature of the mesostructured material thus isolated, M, is a function of the pH of product D, which in turn depends on the value of the molar fraction x of NaOH it contains.

When the molar fraction of NaOH in D is x = 0.0, its pH is 9.5 and the mesostructured material M is of the "disorganized hexagonal" type [Figure 4 (image c); Figure 5 (diffractogram a)].

When the molar fraction of NaOH in D is x = 1.0, its pH is 10.1 and the mesostructured material M is of the "ordered hexagonal" type [Figure 4 (image b); Figure 5 (diffractogram b)].

When the molar fraction of NaOH in D is x = 4.5, its pH is 12.6 and the mesostructured material M is of the laminar type [Figure 4 (image a); Figure 5 (diffractogram c)]. The calcination process for this type of materials, corresponding to stage i of the general procedure, regardless of the value of x, is carried out under the following conditions:

SUBSTITUTE SHEET (RULE 26) static atmosphere of synthetic air at latm (101.3 kPa) and 500 ° C for 5 hours.

In the case of x = 0.0, the material obtained after stage i is a sodium-free mesoporous silica, with a disordered hexagonal topology, and has a characteristic TEM image. Both this porous material and its mesostructured precursor have, in their X-ray diffraction diagrams at low angles, a single peak of high intensity at 4.19 or 4.26 nm, respectively. The mesoporous material has a surface area S _BET = 941 m ² / g and a pore diameter d _BJH = 2.75 nm. The adsorption-desorption curve is of type IV and indicates that the material is of high textural porosity. In the case of x = 1.0, the material obtained after stage i is a sodium-free mesoporous silica with an ordered hexagonal topology. Both this porous material and its mesostructured precursor present, in their X-ray diffraction diagrams at low angles, four peaks, corresponding to reflections 100; 110; 200 and 210. The most intense peak (associated with reflection 100) appears at 3.74 or 4.08 nm, respectively, for the porous material and its mesostructured precursor. The mesoporous material has a surface area S _BET = 1136 m ² / g and a pore diameter d _BJH = 2.90 nm. With regard to mesoporous silicas, in addition to the characteristics described, the process of this invention allows the preparation of mesostructured precursor materials without the need for hydrothermal treatments. In the case of x = 4.5, the material obtained after stage i is a sodium-free amorphous silica.

Simple procedure modifications allow varying the pore topology and the symmetry of the material. Specifically the preparation of mesoporous

SUBSTITUTE SHEET (RULE 26) Cubic type MCM-48 is possible under the following conditions: i. The composition of solution Bl is described by the following molar ratios Si0 ₂ : 2 TEA: 7

NaOH: 1.0

Ethanol: 14.36

H ₂ 0 1.66 ii. Solution B2 is prepared with a CTAB / Si molar ratio = 0.75. iii. the amount of water added to solution C is 60 g iv. The aging of product D is carried out by hydrothermal treatment at autogenous pressure and 100 ° C for 72 hours. v. the rest of the conditions of all the stages involved that give rise to the mesoporous material through the mesostructured

M be those described above. Under these conditions, both the porous material and its mesostructured precursor possess cubic symmetry. These are materials of type MCM-48 and have, in their X-ray diffraction diagrams at low angles, a peak of high intensity at 3.32 and 3.91 nm, respectively, together with at least eight additional peaks very well resolved that allow to determine the group of symmetry Ia3d. The mesoporous material has a surface area S _BET = 1013 m ² / g and a pore diameter d _BJH = 2.43 nm. The adsorption-desorption curve is type IV. Example 2. Mesoporous aluminas: Al ₂ 0 ₃ . (M _z O) _z (x = l; z <0.01).

A hydroalcoholic solution containing 44.96 g of 2.2 ', 2 "-nitrilotriethanol (TEA), 10 g of secbutyl alcohol and less than 1 g of water is prepared.

SUBSTITUTE SHEET (RULE 26) This solution is made alkaline by adding 0.40 g of solid sodium hydroxide. The resulting transparent solution, A, has the composition corresponding to the molar ratios

TEA: 1 NaOH 0.03: secbutanol: 8.92

H ₂ 0 ≤ 0.18

Half by volume of solution A is mixed with 10.68 g of sec-butyl ortho aluminate under gentle stirring for 15 minutes at 10 ° C. The resulting liquid Bl has the following molar composition:

A1 ₂ 0 ₃ : 1

ASD: 7.20

NaOH: 0.24 secbutanol: 8.92 H ₂ 0 ≤ 1.28

The remaining volume half of solution A is mixed with 7.28 g of CTAB. The solution B2 is thus obtained.

Solution C is obtained by mixing Cl and C2 under gentle stirring at 20 ° C. Subsequently, under gentle agitation at 5 ° C, 40 g of demineralized water are added. The resulting solution is kept under stirring, at a temperature close to 20 ° C, for a time of 1 hour. After the addition of water, the overall composition of the resulting product D corresponds to the molar ratios.

SUBSTITUTE SHEET (RULE 26) A1 ₂ 0 ₃ : 1

ASD: 7.20

CTAB: 0.52

NaOH: 0.24

H ₂ 0 106

The aging of the product D is carried out according to the protocol described in step h and specifically: the product D is introduced into a Teflon container in an autoclave for 72 hours at a temperature of 120 ° C and autogenous pressure. Aging leads to a suspension of a solid in a solution. The solid is separated by centrifugation, washed three times with demineralized water and twice with ethanol (94%) and then kept in a desiccator over calcium chloride for 12 hours. The mesostructured material thus isolated, M, has a "worm" type topology and a single, intense peak at 7.5 nm in its X-ray diffractogram.

The calcination process for this type of materials, corresponding to stage i of the general procedure, is carried out under the following conditions: static atmosphere of synthetic air at latm (101.3 kPa) and 500 ° C for 5 hours. The material obtained after stage i is a "worm" mesoporous alumina [Figure 6 (image a)] containing a molar ratio A1 ₂ 0 ₃ : 1

Na ₂ 0. 0.01

This porous material has, in its X-ray diffraction diagram at low angles, a single peak of high intensity at 6.90 nm, has a surface area S _BET = 340 m ² / g and an average pore diameter d _H = 3 , 30 nm [Figure 7 (curve a)]. It also maintains its topological characteristics after

SUBSTITUTE SHEET (RULE 26) heat treatments in air at 900 ° C for 1 hour. By a minimal modification of the procedure, which implies simply and only the variation of the molar ratio H ₂ 0: ASD in step g, it is possible to modify the pore size of the alumina [Figure 8]. Thus the variation of the molar ratio H ₂ 0: ASD between 7.4 and 48.8 leads to mesoporous aluminas of "worm" type topology and average pore diameter between 3.3 [Figure 6 (image a); Figure 7 (curve a)] and 6.9 nm [Figure 6 (image b); Figure 7 (curve b)].

Example 3. Mesoporous titania: Ti0 ₂ (M ₂ 0) _z (x = l; z <0.01). A hydroalcoholic solution containing 33.72 g of 2.2 ', 2 "-nitrilotriethanol (TEA), 15 g of propanol and less than 1 g of water is prepared. This solution is made alkaline by adding 0.80 g of hydroxide solid sodium The resulting clear solution, A, has the composition corresponding to the TEA molar ratios: 1

NaOH: 0.09 propanol: 1.11

H ₂ 0 ≤ 0.24

One third by volume of solution A is mixed with 17.06 g of propyl orthotitanate under gentle stirring at 5 ° C for 15 minutes. The resulting liquid Bl has the following molar composition: Ti0 ₂ : 2

ASD: 7.50

NaOH: 0.66 Propanol: 16.30

H ₂ 0 ≤ 1.83

The remaining two thirds by volume of solution A is mixed with 6.56

SUBSTITUTE SHEET (RULE 26) g of CTAB. The solution B2 is thus obtained.

From the liquids Bl and B2, respectively, the extract solutions Cl and C2 are obtained by fractional distillation, strictly following the protocols described respectively in steps c and e of the general procedure. Solution C is obtained by mixing Cl and C2 under gentle stirring at 20 ° C. Subsequently, 180 g of demineralized water is added slowly under vigorous stirring at 5 ° C. The resulting solution has a pH = 10 and eventually evolves into a suspension by increasing the temperature to 40 ° C and maintaining it for 15 m. After the addition of water, the overall composition of the resulting product D corresponds to the molar ratios.

Ti0 ₂ : 2

ASD: 7.50 CTAB: 0.66

NaOH: 0.66

H ₂ 0 333.33

The aging of product D is carried out according to the protocol described in step h, and specifically: the suspension is kept under vigorous stirring, at a temperature close to 20 ° C, and 1 atmosphere (101.3 kPa) depression, for a time 40 hours

Aging leads to a suspension of a solid in a solution. The solid is filtered off, washed three times with demineralized water and twice with ethanol (94%) and then kept in a desiccator over calcium chloride for 12 hours. The mesostructured material thus isolated, M, has a "worm" type topology and a unique and intense peak at 3.85 nm in its

SUBSTITUTE SHEET (RULE 26) X-ray diffractogram.

The calcination process for this type of material, corresponding to stage i of the general procedure, is carried out under the following conditions: the material is calcined in a dynamic atmosphere of argon to latm (101.3 kPa) and 120 ° C for 2 hours , followed by a second treatment in the same atmosphere at 350 ° C for 5 hours, and a third treatment in a dynamic atmosphere of oxygen at a pressure of latm (101.3 kPa) and 350 ° C for 120 hours. The material obtained after stage i is a pure mesoporous titania, with "worm" type pore topology.

This porous material has, in its X-ray diffraction diagram at low angles, a single peak of high intensity at 5.60 nm, has a surface area S _BET = 610 m ² / g [Figure 9] and a pore diameter mean d _BJH = 3.51 nm (inside box of Figure 9). On the other hand, X-ray diffraction shows the presence of anatase crystalline microdomains in the material [Figure 10]. Example 4. Mesoporous silicoaluminatos of hexagonal topology porosity: (SiO,) ^ (Al ₂ 0 ₃ ) _{x / 2} (M ₂ 0) _z (x <0.066; z <0.01). A hydroalcoholic solution containing 33.72 g of 2.2 ', 2 "-nitrilotriethanol (TEA), 10 g of s-butyl alcohol and less than 1 g of water is prepared. This solution is made alkaline by the addition of 1.32 g of solid sodium hydroxide The resulting clear solution, A, has the composition corresponding to the TEA molar ratios: 1

NaOH: 0.13 secbutanol: 0.54

SUBSTITUTE SHEET (RULE 26) H ₂ 0 <0.24

One third by volume of solution A is mixed with 0.74 g of secbuule orthoaluminate and 13.12 g of ethyl orthosilicate (TEOS) under gentle stirring at 15 ° C for 15 minutes. The resulting liquid Bl has the following molar composition:

Si0 ₂ : 2

A1 ₂ 0 ₃ : 0.048

ASD: 7.17

NaOH: 0.95 secbutanol: 4.16 ethanol: 8.00

H ₂ 0 <1.75

The remaining two thirds by volume of solution A is mixed with 6.50 g of CTAB. The solution B2 is thus obtained. From the liquids Bl and B2, respectively, the extract solutions Cl and C2 are obtained by fractional distillation, strictly following the protocols described respectively in steps c and e of the general procedure.

Solution C is obtained by mixing Cl and C2 under gentle stirring at 30 ° C. To each solution C, 180 g of demineralized water are added under gentle stirring at 5 ° C. The resulting solution is kept under stirring, at a temperature close to 20 ° C, for a time of 15 minutes. After the addition of water, the overall composition of the resulting product D corresponds to the Si0 ₂ : 2 molar ratios.

A1 ₂ 0 ₃ : 0.048

ASD: 7.17

SUBSTITUTE SHEET (RULE 26) CTAB: 0.57

NaOH: 0.95

H ₂ 0 317.46

The aging of the product D is carried out according to the protocol described in step h and specifically: it is applied to the product D continuous agitation for 72 hours at 45 ° C temperature and latm (101.3 kPa) synthetic air depression. Aging leads to a suspension of a solid in a solution. The solid is filtered off, washed three times with demineralized water and twice with ethanol (94%) and then kept in a desiccator over calcium chloride for 12 hours. The mesostructured material thus isolated, M, has a "hexagonal" type topology and an intense peak at 3.51 nm in its X-ray diffractogram.

The calcination process for this material, corresponding to stage i of the general procedure, is carried out under the following conditions: the material is calcined in a static atmosphere of synthetic air at latm (101.3 kPa) and 500 ° C for 5 hours.

The material obtained after step i is a "hexagonal" mesoporous silicoaluminate [Figure 2 (image a); Figure 11 (diffractogram a)] containing a certain amount of sodium, in the Si0 ₂ : 1 molar ratio

A1 ₂ 0 ₃ : 0.036

Na ₂ 0 ≤ 0.01

This porous material has a surface area S _BET = 985 m ² / g [Figure 12 (curve b)], an average pore diameter d _{B] H} = 2.50 nm and an intense peak at 3.85 nm in its diffractogram X-ray. It also maintains its topological characteristics after heat treatments in air at 750 ° C during

SUBSTITUTE SHEET (RULE 26) 12 hours.

This preparatory protocol is applicable to all header compositions, that is (x <0.066; z <0.01).

Example 5. Mesoporous porosity silicoaluminatos of "worm" type topology:

(Si0 ₂ ) ₁ . _x (Al ₂ 0 ₃ ) _{x / 2} (M _z O) _z (0.066 _<X <0.455; z <0.07). The procedure is identical for all the header compositions and here it is specifically described for the composition x = 0.485, z = 0.062. A hydroalcoholic solution is prepared containing 33.72 g of 2.2 ', 2 "- nitrilotriethanol (TEA), 10 g of secbutyl alcohol and less than 1 of water. This solution is made alkaline by the addition of 1.32 g of hydroxide solid sodium The resulting clear solution, A, has the composition corresponding to the TEA molar ratios: 1

NaOH: 0.13

-? t? cbutanol: 0.54

H ₂ 0 <0.24

One third by volume of solution A is mixed with 8.06 g of sec-butyl orthoaluminate and 6.72 g of ethyl orthosilicate (TEOS) under gentle stirring at 10 ° C for 15 minutes. The resulting liquid Bl has the following molar composition:

Si0 ₂ : 1

A1 ₂ 0 ₃ : 0.5 ASD: 6.85

NaOH: 0.91 secbutanol: 6.70

SUBSTITUTE SHEET (RULE 26) ethanol: 4.00

H ₂ 0 <1.66

The remaining two thirds by volume of solution A is mixed with 6.50 g of CTAB. The solution B2 is thus obtained. 5 From the liquids Bl and B2, respectively, the extract solutions Cl and C2 are obtained by fractional distillation, strictly following the protocols described respectively in steps c and e of the general procedure.

Solution C is obtained by mixing Cl and C2 under gentle stirring at 10-30 ° C. To the solution C, 180 g of demineralized water are added under gentle stirring at 5 ° C. The resulting solution is kept under stirring, at a temperature close to 20 ° C, for a time of 15 minutes. After the addition of water, the overall composition of the resulting product D corresponds to the molar ratios 15 Si0 ₂ : 1

A1 ₂ 0 ₃ : 0.50

CTAB: 0.54

ASD: 6.85

NaOH: 0.91

20 H ₂ 0 303.33

The aging of product D is carried out according to the protocol described in step h and specifically: product D is subjected to continuous stirring for 24 hours at a temperature of 45 ° C and latm (101.3 kPa) depression of synthetic air. Aging leads to a suspension of a solid in a solution. The solid is filtered off, washed three times with demineralized water and twice with ethanol (94%) and then kept in a desiccator over chloride

SUBSTITUTE SHEET (RULE 26) Calcium for 12 hours. The mesostructured material thus isolated, M, has a "worm" type topology and an intense peak at 3.70 nm in its X-ray diffractogram.

The material obtained after step i is a "worm" mesoporous silicoaluminate [Figure 2 (image c); Figure 11 (diffractogram f)] containing a certain amount of sodium, in the Si0 ₂ : 1 molar ratio

A1 ₂ 0 ₃ : 0.47

Na ₂ 0 0.12

This porous material has a surface area S _BET = 430 m ² / g [Figure 12 (curve d)], an average pore diameter d _BJH = 2.00 nm and an intense peak at 4.18 nm in its ray diffractogram X. It also maintains its topological characteristics after heat treatments in air at 750 ° C for 12 hours.

Example 6. Mesoporous hexotonal silicotitates:

(M ₂ 0) _z (x <0.02; z ≤0.01).

The procedure is identical for all the header compositions and here it is specifically described for the composition x— 0.02, z = 0.

A hydroalcoholic solution containing 33.72 g of 2.2 ', 2 "-nitrilotriethanol (TEA), 10 g of propyl alcohol and less than 1 g of water is prepared.

This solution is made alkaline by the addition of 0.80 g of solid sodium hydroxide. The resulting clear solution, A, has the composition

SUBSTITUTE SHEET (RULE 26) corresponding to molar relationships ASD: 1

NaOH: 0.09 isopropanol: 0.73 mol H ₂ 0 <0.24

One third by volume of solution A is mixed with 0.37 g of isopropyl orthotitanate and 13.48 g of ethyl orthosilicate (TEOS) under gentle stirring at 10 ° C for 15 minutes. The resulting liquid Bl has the following molar composition: Si0 ₂ : 2

Ti0 ₂ : 0.04

ASD: 6.99

NaOH: 0.62 isopropanol: 6.74 ethanol: 8.00

H ₂ 0 <1.70

The remaining two thirds by volume of solution A is mixed with 4.23 g of CTAB. The solution B2 is thus obtained.

From the liquids Bl and B2, respectively, extract solutions Cl and C2 are obtained by fractional distillation, strictly following the protocols described respectively in steps c and e of the general procedure.

Solution C is obtained by mixing Cl and C2 under gentle stirring at 30 ° C. To the solution C, 180 g of demineralized water are added, with gentle stirring at 60 ° C. The resulting solution is kept under stirring, at a temperature close to 20 ° C, for a time of 15 minutes. After the addition of water, the overall composition of the resulting product D corresponds

SUBSTITUTE SHEET (RULE 26) to molar relationships.

Si0 ₂ : 1

Ti0 ₂ : 0.02

CTAB: 0.20 ASD: 3.50

NaOH: 0.31

H ₂ 0 154.6

The aging of product D is carried out according to the protocol described in step h and specifically: product D is subjected to continuous stirring for 24 hours at 25 ° C temperature and latm (101.3 kPa) synthetic air depression. Aging leads to a suspension of a solid in a solution. The solid is filtered off, washed three times with demineralized water and twice with ethanol (94%) and then kept in a desiccator over calcium chloride for 12 hours. The mesostructured material thus isolated, M, has a hexagonal topology and an intense peak at 3.71 nm in its X-ray diffractogram.

The calcination process for this material, corresponding to stage i of the general procedure, is carried out under the following conditions: the material is calcined in a sealed atmosphere of synthetic air at latm (101.3 kPa) and 550 ° C for 5 hours.

The material obtained after step i is a mesoporous silicotitanato hexagonal type [Figure 13 (diffractogram)] with molar ratio Si0 _2: 1 Ti0 ₂ 0.02

This porous material has a surface area S _BET = 1110 m ² / g [Figure 14 (curve a)], an average pore diameter d _BJH = 2.80 nm and an intense peak at

SUBSTITUTE SHEET (RULE 26) 4.00 nm in its X-ray diffractogram. It also maintains its topological characteristics after thermal treatments in air at 650 ° C during

12 hours.

Example 7. "Worm" mesoporous silicotitates: (Si0 ₂ ) ₁ . _x (Ti0 ₂ ) _x (M ₂ 0) _z (0.02 <x <0.34; z <0.01).

The preparation of this family strictly follows the preparative protocol of example 6, with the appropriate modification of the Ti / Si molar ratio.

In particular, for a Ti / Si value = 0.53, 3.61 g of isopropyl orthotitanate and 10.62 g of tetraethyl orthosilicate are used. The material obtained after stage i is a "worm" mesoporous silicotitanate [Figure 13

(diffractogram f); Figure 15 (image c)] with the Si0 ₂ : 1 molar ratio

Ti0 ₂ 0.53

This porous material has a surface area S _BET = 595 m ² / g [Figure 14 (curve e)], an average pore diameter d _BJH = 2.01 nm and an intense peak

3.52 nm in its X-ray diffractogram. It also maintains its topological characteristics after thermal treatments in air at 650 ° C during

12 hours.

Figure 16 also shows that for Ti / Si values <0.02 [spectrum b], almost all of titanium is in tetrahedral coordination

(an absorption band centered at 220 + 10 nm).

Example 8. Hexagonal mesoporous silicocirconate type: (SiO ^^ ζ¿rO ^) _x

(M ₂ O) _z (x <0, l; z <0.01).

The preparation of this family strictly follows the preparative protocol of example 6, with the appropriate modification of the Zr / Si molar ratio.

In particular, for a value x = 0.09, 1.45 g of isopropyl orthocirconate and 12.83 g of tetraethyl orthosilicate are used. The material

SUBSTITUTE SHEET (RULE 26) Mesostructured obtained after stage h has an intense peak in its X-ray diffractogram at 3.94 nm. The material obtained after stage i is a hexoponal mesoporous silicocirconate [Figure 17, spectrum corresponding to the Si / Zr = 10 ratio; Figure 18 (image a)] with the molar relationship

Si0 ₂ : 1

Zr0 ₂ 0.10

This porous material has a surface area S _BET = 997 m ² / g [Figure 19 (graph a)], an average pore diameter d _BJH = 2.20 nm and an intense peak at 3.21 nm in its ray diffractogram X. In addition, it maintains its topological characteristics after heat treatments in air at 7510 ° C for 12 hours.

Example 9. Mesoporous "worm" type silicocirconate: (SiO ^^ (r, 0 ^ _x (M ₂ 0) _z (0.1 <x <0.77; z <0.01). Preparation of this family follows strictly the preparative protocol of example 6, with the appropriate modification of the Zr / Si molar ratio. Specifically, for a value x = 0.25, 4.85 g of isopropyl orthocirconate and 10.67 g of tetraethyl orthosilicate are used The mesostructured material obtained after stage h has an intense peak in its X-ray diffractogram at 4.60 nm The material obtained after stage i is a "worm" mesoporous silicocirconate [Figure 17, spectrum corresponding to the Si / Zr = 3 ratio; Figure 18 (image c)] with the molar ratio

Si0 ₂ : 1 Zr0 ₂ 0.30

This porous material has a surface area S _BET = 382 m ² / g [Figure 19 (graph b)], an average pore diameter d _BJH = 1.90 nm and an intense peak at 3.15 nm in its X-ray diffractogram. In addition, it maintains its topological characteristics after heat treatments in air at 750 ° C for 12 hours.

Example 10. Hexagonal mesoporous silicovananates:

(V ₂ 0 ₅ ) _{x / 2} (M ₂ 0) _z (x <0.07; z <0.01).

The preparation of this family strictly follows the preparative protocol of example 6, with the appropriate modification of the V / Si molar ratio. In particular, for a value V / Si = 0.033, 0.36 g of isopropyl orthovananate and 9.25 g of tetraethyl orthosilicate are used. The material obtained after step h is a hexagonal mesostructured silicovanadate that shows in its X-ray diffraction spectrum an intense peak at 3.84 nm and three other peaks of less intensity. The material obtained after stage i is a hexagonal mesoporous silicovanadate [Figure 20, spectrum corresponding to the Si / V = 30 ratio; Figure 21 (image a)] with the molar relationship

Si0 ₂ : 1

V ₂ 0 ₅ 0.016

This porous material has a surface area S _BET = 1107 m ² / g [Figure 22 (graph a)], an average pore diameter d _BJH = 2.69 nm and an intense peak at 3.51 nm in its ray diffractogram X. In addition, it maintains its topological characteristics after heat treatments in air at 750 ° C for 12 hours.

Example 11. "Worm" mesoporous silicovanadates:

(V ₂ 0 ₅ ) _{x / 2} (M _z O) _z (0.07 <x <0.20; z <0.01).

The preparation of this family strictly follows the preparative protocol of example 6, with the appropriate modification of the V / Si molar ratio.

SUBSTITUTE SHEET (RULE 26) In particular, for a value V / Si = 0.2, 2.70 g of isopropyl orthovanadate and 4.58 of tetraethyl orthosilicate are used. The mesostructured material obtained after step h exhibits an intense peak in its X-ray diffractogram at 4.01 nm. The material obtained after step i is a "worm" mesoporous silicovanadate [Figure 20, spectrum corresponding to the Si / V = 5 ratio; Figure 21 (image c)] with the Si0 ₂ : 1 molar ratio

V ₂ O _s 0.10

This porous material has a surface area S _BET = 433 m ² / g [Figure 22 (graph b)], an average pore diameter d _BJH = 2.69 nm and an intense peak at 3.91 nm in its ray diffractogram X. In addition, it maintains its topological characteristics after heat treatments in air at 750 ° C for 12 hours. Example 12. Hexagonal mesoporous siliconiclate type:

(NiO) _x (M ₂ 0) _z (x <0.05; z <0.01).

The preparation of this family strictly follows the preparative protocol of example 6, with the appropriate modification of the Ni / Si molar ratio. Specifically, for a Ni / Si value = 0.034, 0.35 g of ₂ '6H ₂ 0 NiCl is used. The mesostructured material obtained after step h has an intense peak in its X-ray diffractogram at 4.10 nm and three other peaks of less intensity. The material obtained after step i is a hexagonal mesoporous siliconiquelate [Figure 23, spectrum corresponding to the Si / Ni ratio = 29; Figure 24 (image a)] with Si0 ₂ molar ratio: 1 ₂ 0.034 NI0

This porous material has a surface area S _BET = 894 m / g [Figure 25 (graph a)], an average pore diameter d _BJH = 2.87 nm and an intense peak at

SUBSTITUTE SHEET (RULE 26) 3.50 nm in its X-ray diffractogram. In addition, it maintains its topological characteristics after thermal treatments in air at 650 ° C for 12 hours.

Example 13. "Worm" mesoporous siliconiclates: (SiOJ ^ (NiO) _x 5 (M ₂ 0) _z (0.05 <x <0.10; z <0.01). The preparation of this family strictly follows the preparative protocol of example 6, with the appropriate modification of the Ni / Si molar ratio. Specifically, for a Ni / Si value = 0.083 1.05 g of Ni0 ₂ 6H ₂ 0 are used. The mesostructured material obtained after step h it has an intense peak 0 in its X-ray diffractogram at 4.75 The material obtained after stage i is a "worm" mesoporous siliconiquelate [Figure 23, spectrum corresponding to the Si / Ni-12 ratio; Figure 24 (image c)] with the molar relationship

Si0 ₂ : 1

15 Ni0 ₂ 0.083

This porous material has a surface area S _BET = 831 m ² / g [Figure 25 (graph b)], an average pore diameter d ^ = 2.72 nm and an intense peak at 4.41 nm in its ray diffractogram X. In addition, it maintains its topological characteristics after thermal treatments in air at 650 ° C for 20 12 hours.

Example 14. "Worm" mesoporous silicoaluminotitanatos: (SiO JtA J ^ CπOJ ^ _M (M ₂ 0) _z (0.001 <x <0.485; 0 <and <1; z <0.01).

The preparation of this family strictly follows the preparative protocol 25 of Example 6, using three metal alkoxides in suitable molar proportions. Specifically, for a value of Ti / Si = 0.37 and Al / Si = 0.2, 9.17 g of

SUBSTITUTE SHEET (RULE 26) ethyl orthosilicate, 4.12 g of isopropyl orthotitanate and 1.79 g of sec-butyl orthoaluminate. The mesostructured material obtained after step h has a single diffraction peak _. X-ray with a spacing value of 3.8 nm [Figure 26 (diffractograrna a)]. The material obtained after step i is a "worm" mesoporous silicoaluminotitanate [Figure 26 (diffractogram b)] with the Si0 ₂ : 1 molar ratio

Ti0 ₂ : 0.37

A1 ₂ 0 ₃ 0.10 This porous material has a surface area S _BET = 707 m ² / g [Figure 27 (curves a)], a mean pore diameter d ^ = 2.15 nm and an intense peak at 4, 40 nm in its X-ray diffractogram. In addition, it maintains its topological characteristics after heat treatments in air at 750 ° C for 12 hours. Following the same procedure, other ternary oxides with different composition can be prepared. For example, a silicoaluminotitanate with composition Ti / Si = 0.182 and Al / Si = 0.256 [Figure 26 (cyd diffractograms); Figure 27 (curves b)]. Example 15. Mesoporous "worm" mesotorous silicone

(0.005 <x <0.50; 0 <y <1, z <0.01). The preparation of this family strictly follows the preparative protocol of Example 6, using three metal alkoxides in suitable molar proportions. In particular, for a Ti / Si value = 0.025 and Zr / Si-0.16, 9.25 g of ethyl orthosilicate, 0.108 g of isopropyl orthotitanate and 1.46 g of isopropyl orthocirconate are used. The mesostructured material obtained after step h has a single X-ray diffraction peak at a value of

SUBSTITUTE SHEET (RULE 26) 3.20 nm spacing. The material obtained after stage i is a "worm" mesoporous silicotitanocirconate [Figure 28] with the molar ratio

Si0 ₂ : 1 Ti0 ₂ : 0.025

Zr0 ₂ 0.16

This porous material has a surface area S _BET = 848 m ² / g [Figure 29], a mean pore diameter d _BJH = 2.70 nm and an intense peak at 3.50 nm in its X-ray diffractogram. In addition, maintains its topological characteristics after heat treatments in air at 700 ° C for 12 hours.

Example 16. Mesoporous "worm" aluminum phosphates: (Al ₂ 0 ₃ ) _x (P ₂ 0 ^ _x (M ₂ 0) _z (0.001 <x <0.80; z <0.01).

The procedure is identical for all header compositions and here it is specifically described for the composition x— 0.43, z = 0.

A hydroalcoholic solution is prepared containing 11.24 g of 2.2 ', 2 "- nitrilotriethanol (TEA), 5 g of secbuturic alcohol and less than lg of water. The resulting transparent solution, A, has the composition corresponding to the ratios TEA molars: 1 secbutanol: 0.90

H ₂ 0 <0.74 moles

One third by volume of solution A is mixed with 4.90 g of sec-butyl orthoaluminate under gentle stirring at 10 ° C for 15 minutes. The resulting liquid Bl has the following molar composition: A1 ₂ 0 ₃ : 1

ASD: 7.5

SUBSTITUTE SHEET RULE 26 secbutanol: 12.75

H ₂ 0 <5.50

The remaining two thirds by volume of solution A is mixed with 2.10 g of CTAB. The solution B2 is thus obtained. From the liquids Bl and B2, respectively, the extract solutions Cl and C2 are obtained by fractional distillation, strictly following the protocols described respectively in the steps c and of the general procedure. Solution C is obtained by mixing Cl and C2 under gentle stirring at 30 ° C. To the solution C, 43 g of demineralized water are added, with gentle stirring at 30 ° C. The resulting solution is kept under stirring, at a temperature close to 20 ° C, for a time of 10 minutes. After the addition of water, 10 ml of a solution containing 0.55 moles of H ₃ P0 ₄ are added under vigorous stirring. The precipitation of a white solid is observed. The overall composition of the resulting product D corresponds to the molar ratios A1 ₂ 0 ₃ : 1

ASD: 7.5

H ₃ P0 ₄ : 55 H ₂ 0 55

The aging of product D is carried out according to the protocol described in step h, and specifically: product D is subjected to continuous stirring for 24 hours at 25 ° C temperature and latm (101.3 kPa) synthetic air depression. The solid is filtered off, washed three times with demineralized water and twice with ethanol (94%) and then kept in a desiccator over calcium chloride for 12 hours. The mesostructured material thus isolated, M, has

SUBSTITUTE SHEET RULE a "worm" type topology and an intense peak at 4.1 nm in its X-ray diffractogram.

The calcination process for this material, corresponding to stage i of the general procedure, is carried out under the following conditions: the material is calcined in a dynamic atmosphere of synthetic air at latm (101.3 kPa) and 300 ° C for 2 hours, followed by a second treatment in the same atmosphere at 400 ° C for 2 hours, and a third treatment at 500 ° C for 5 hours.

The material obtained after step i is a "worm" mesoporous aluminophosphate [Figure 30 (image a); Figure 31 (diffractogram c)] with molar relationship

A1 ₂ 0 ₃ : 1

P ₂ 0 ₅ 0.74

This porous material has a surface area S _BET = 480 m ² / g, an average pore diameter d ^ = 1.30 nm and an intense peak at 2.80 nm in its X-ray diffractogram.

The variation in the amount of phosphoric acid (Al: m H ₃ P0 ₄ , 0.12 m <1.5) introduced after water in the process object of this invention allows to modulate the pore size from the micro (1.3 nm) [Figure 30 (image a); Figure 31 (diffractogram c)] to the mesopores (3.7 nm) [Figure 30 (image b); Figure 31 (diffractogram a)]. Example 17. "Worm" mesoporous silicoaluminophosphates: (A OJ _t P.OJ ^ SiOJ ^ MO), (0.15 <x <0.80; 0 <y <0.80, z <0.01). The preparation of this family strictly follows the preparative protocol of Example 16 using two metal alkoxides in suitable molar proportions.

SUBSTITUTE SHEET RULE 2 The procedure is identical for all the header compositions and here specifically described for the composition x = 0.68, and -0.39, z = 0. 1.48 g of ethyl orthosilicate and 3.18 g of isopropyl orthoaluminate. The mesostructured material obtained after step h has a single X-ray diffraction peak at a spacing value of 3.8 nm. The material obtained after stage i is a "worm" mesoporous silicoaluminophosphate [Figure 32 (diffractogram a)] with the molar ratio

A1 ₂ 0 ₃ : 1 Si0 ₂ : 0.86

PA 0.66

This porous material has a surface area S _BET = 640 m ² / g, an average pore diameter d _BJH = 1.81 nm [Figure 33 (curves a)] and an intense peak at 3.33 nm in its ray diffractogram X. Following the same procedure, mixed aluminum and titanium phosphates can be prepared. For example, Figures 32 (diffractogram b) and 33 (curves b) show, respectively, the X-ray diffraction spectrum and the nitrogen adsorption curve of a solid having the following composition referring to molar compositions: P / Al = 0.60 and Ti / Al = 0.13.

Example 18. Preparation of Na _x jIf ₄₈ _ _x A _x 0 ₉₆ j.l6H ₂ O with analcime crystal structure.

A hydroalcoholic solution containing 10.44 g of 2,2 ', 2 "-nitrilotriethanol (TEA), 5 g of secbutyl alcohol and less than 1 g of water is prepared. This solution is made alkaline by the addition of 3.6 g of solid sodium hydroxide The resulting clear solution, A, has the composition corresponding to the molar ratios

RE SUBSTITUTE SHEET ASD: 1

NaOH: 1.29 secbutanol: 1.19

H ₂ 0 <0.79 Solution A is mixed with 10.44 g of sec-butyl orthoaluminate and 9.37 g of ethyl orthosilicate (TEOS) under gentle stirring at 15 ° C for 15 minutes. The resulting liquid Bl has the following molar composition: Si0 ₂ : 1

A1 ₂ 0 ₃ : 0.50 ASD: 1.55

NaOH: 2.00 secbutanol: 29.40 ethanol: 4.00

H ₂ 0 <1.22 From liquid Bl, the Cl extract solution is obtained by fractional distillation, strictly following the protocols described in the general procedure.

Solution C (which in this case is identical to Cl) is kept under gentle agitation at 20 ° C. To the solution C, 63 g of demineralized water is added under gentle stirring at 5 ° C. The resulting solution is kept under stirring, at a temperature close to 20 ° C, for a time of 2 minutes. After this time the overall composition of the resulting gel D corresponds to the molar ratios Si0 ₂ : 1 A1 ₂ 0 ₃ : 0.50

ASD: 1.55

NaOH: 2.00

SUBSTITUTE SHEET H ₂ 0 77.77

The aging of the gel D is carried out according to the protocol described in step h and specifically: an autoclave hydrothermal treatment is applied to the product D for 8 days at 18QPC of autogenous temperature and pressure. Aging leads to a suspension of a solid in a solution. The solid is filtered off, washed three times with demineralized water, two with ethanol (94%) and then kept in a desiccator over calcium chloride for 12 hours. The material thus obtained has a typical X-ray diffractogram of the analcime [Figure 34]. The resulting molar composition is:

Si0 ₂ : 1

A1 ₂ 0 ₃ : 0.47

Na ₂ 0. 0.47 This preparatory protocol is applicable to other zeolites. If an organic template agent is required, it can be added in stage d of the general procedure.

Example 19. Use of mesoporous silicotitates in the catalytic oxidation of cyclohexene. 2.274 g of cyclohexene, 1.041 g of terbutylhydroperoxide, and 0.15 g of catalyst with a Si / Ti molar ratio = 49.9, obtained as described in example 7, were introduced into a glass reactor. stirring at the reaction temperature of 70 ° C. After 5 hours the conversion with respect to the oxidant was 97%, the epoxide selectivity being 98%.

The solids obtained in example 7, with titanium contents in the range 8.0 <Si / Ti ≤ 49.9, show similar values of

SUBSTITUTE SHEET (RULE 26) Conversion and selectivity

fifty

35

40

SUBSTITUTE SHEET (RULE 26)

Claims

1. Procedure for preparing crystalline, mesoporous or porous amorphous microporous products, formed by simple or mixed oxides or mixtures of metal and / or metalloid oxides, in which the sources of meta], metals and / or metalloids are liidroalcoholic solutions of Metallatran compounds, which undergo a hydrolysis reaction in the presence of one or more agents with a template effect, comprising the following steps:

1) pi-eparation of stable hydroalcoholic solutions of metal complexes and / or metalloids included in the composition of the desired product, from a hydroalcoholic solution containing the metallatran compounds or containing the reagents necessary to prepare said metallatran compounds, said reagents comprising a formant of airanes and compounds of the metals and / or metalloids involved in the composition of the final product, and said hydroalcoholic solution comprising, optionally, one or more agents with a template effect selected from hydroxides or alkali and / or ammonium halides quaternary, other alcohols, polyalcohols, carboxypolyalcohols, amino alcohols, aminopolyalcohols or mixtures thereof, amines or polyamines; by distillation of said hydroalcoholic solution and elimination of fractions with a boiling point below 190 ° C;

2) chemical and / or thermally induced hydrolysis of the backward complexes in the presence of one or more agents with a template effect, the addition was measured, if not done in step 1) of said agent or agents with a template effect to the solution resulting from the stage

one); the addition to said solution, and mixing, with stirring, at temperatures between 5 and 100 ° C, of water, preferably demineralized, in a molar ratio of water to the total content of metals and / or metalloids greater than 10, preferably, comprised between

25 and 175; and, optionally, the addition of a hydroxide or an amine in order to increase the pH of the mixture, to favor the hydrolysis reaction; obtaining as solution of the reaction a solution, a gel or a suspension of a solid;

3) aging of the product of the hydrolysis reaction of stage 2), by heat treatment of the product obtained in stage 2) at a temperature equal to or less than

SUBSTITUTE SHEET (RULE 26) 220 ° C in open vessel at reflux and ambient pressure or in closed hydrothermal reactor (autoclave) under pressure, in general, autogenous, for a minimum period of 5 minutes and a maximum of 15 days, to obtain a solid precipitate; said solid is filtered or centrifuged, washed with water, preferably demineralized, and subsequently dried, preferably at a temperature between 18 and 25 ° C in a desiccator containing calcium chloride or other agent of desiccant capacity similar to that thereof; Y

4) obtaining the porous product by pyrolysis of the aged product resulting from stage 3), consisting in that the solid isolated in stage 3) is subjected to the elimination of the organic and aqueous fraction that it may contain, by successive treatment or therapeutic treatments at temperatures between 300 ° C and 600 ° C in an atmosphere of air, oxygen or nitrogen, preferably dynamic, for a maximum period of 5 hours and a maximum of 7 days, thus obtaining the final porous material.

2. Process for preparing crystalline, mesoporous or porous amorphous microporous products, formed by simple or mixed oxides or mixtures of metal and / or metalloid oxides, according to claim 1, characterized in that the attractant compound is an N ^ OH aminotrialcoho R ₂ OHR ₃ OH, in which R _: R ₂ and R ₃ represent the same or different organic groups, preferably hydrocarbons and particularly aliphatic chains of chain length less than four and especially 2.2 ', 2 "nitrilotriethanol or 2, 2 ', 2 "nitrilotripropanol.

3. Process for preparing crystalline, mesoporous or porous amorphous icroporous products, formed by simple or mixed oxides or mixtures of metal oxides and / or metalloids, according to claims 1 and 2, characterized in that the reagents containing the metals and / or Metalloids to form the complexes are alkoxides derived from aliphatic alcohols with a number of carbon atoms per chain of less than 4, or are the respective balides, oxides, oxyhydroxides υ oxyacids.

4. Process for preparing crystalline, mesoporous or porous amorphous microporous products, formed by simple or mixed oxides or mixtures of metal and / or metalloid oxides, according to claims 1 to 3, characterized in that the dissolution

SUBSTITUTE SHEET (RULE 26) hydroalcoholic metalalranos is prepared or is contacted with an alkali hydroxide so that the ratio of the molar fractions of the alkali metal element and total metals is between lO ^"6 and 0.5.

5. Process for preparing crystalline microporous products, fused by simple or mixed oxides or mixtures of metal oxides and / or metalloids, according to claims 1 to 4, characterized in that the agent or agents with template effect are alkaline or alkaline earth hydroxides, amines containing one or more amino groups, or stainless alcohols, or quaternary ammonium hydroxides or halides without lensoactive activity, of the NR¡R ₂ R ₃ R type, where the R, R ₂ R ₃ and R _A moieties are linear or branched alkyl chains, fencing the number of carbon atoms in each chain between 1 and 6.

6. Procedure for preparing ordered mesoporous products, formed by simple or mixed oxides or mixtures of metal and / or metalloid oxides, according to claims 1 to 4, characterized by the use of agents with a template effect with surfactant activity, in particular hydroxides or tetraalkylammonium halides NR ^ R ^ R, the preferred composition being that in which R ₂ = R ₃ = R ₄ = CH ₃ and R _j is an organic group containing

10 and 18 carbon atoms.

7. Method for preparing ordered mesoporous products according to claim 6, characterized in that the ratio between the molar fractions of the tetraalkylammonium-effecting agent with tensoacuva activity and of the total metals is between 0.3 and 1.0; additionally, because the ratio between the molar fractions of the alkaline element and the total metals is between 10 ^" " and 0.5, and because it gives rise to mesoporous materials of the "worm" type structure, or MCM-41, or MCM-48 .

8. Process for preparing amorphous products, formed by simple or mixed oxides or mixtures of metal and / or metalloid oxides, according to claims 1 to A, characterized in that in step 3) of claim 1 short reaction times are used and / or low temperatures to avoid the crystallization of material is my crop, preferably times less than 3 days and temperatures below 150 ° C.

SUBSTITUTE SHEET (RULE 26)

9. Porous materials obtainable according to claims 1 to 8, characterized in that, in their anhydrous form, they respond to the formulas I, II and ID:

(SiO ^. AA ^ M), (I) (SiO ₂ ) _] . _λ ((A _m O _n ) _] ,, (A ' _n , O _{n my / m} - ( ₂ O) ₂ (II) (Al ₂ O ₃ ), _-λ ((P ₂ O ₅ ) _μy (A' _m , O _n UM ₂ O) ₂ (lü)

where in formulas I, II and III, x, y, z represent molar fractions that define the empirical composition of the anhydrous porous material and take actual values defined by the following conditions: x is a number between 0 and 1, and is a number greater than 0 and less than 1, z is a lower number ax / 2 in the case of the compositions of the fonnulas I and II; or less than (1-x) in the case of the formula UJ,

where in formulas I, π and III, A and A 'represent metals and / or metalloids of valence p and p', equal or different enü-e yes, chosen from among the following groups: any belonging to group 3B and in particular B and Al, anyone belonging to group 3 A and in particular Se, Y, La and the lanlanids, anyone belonging to group 4B and in particular Ge, Sn and Pb, anyone belonging to group 5B and specifically P and Bi, any belonging to group 4A and in particular Ti and Zr, any belonging to group 5 A and in particular V, any belonging to group 6A and in particular Mo, any belonging to group 7A and in particular n, any belonging to group 8 and in in particular Fe, Co and Ni, anyone belonging to group IB and in particular Cu, and anyone belonging to group 2B and in particular Zn,

where in the formulas 1, II and III the subscripts, m \ n and n 'represent numbers of atoms per formula that satisfy the relations:

SUBSTITUTE SHEET (RULE 26) nr p = 2 n; m 'p' = 2 n '; Y

M represents one or more monovalent elements, preferably Na.

10. Mesoporous materials, obtainable according to the procedure of any of claims 1 to 4, 6 or 7, characterized in that, in their anhydrous form, they respond to formulas bounded between the following values:

- for systems containing up to two metals and / or metalloids, of the type: (SiO ^ CAA) ^ the values of x in the range if A = Ti O≤x≤l if A = Al O≤x≤l if A = B 0.01 ≤x ≤ 0.10 if A = Sn 0.01 ≤ x ≤ 0.25 if A = Zr 0.01 <x <1 if A = V 0.01 ≤x≤ 0.25 if A = Mo 0.01 ≤x≤ 0.20 if A = Mn 0.01 ≤x≤ 0.30 if A = Fe 0.01 ≤x≤ 0.15 if A = Co 0.01 ≤x≤ 0.15 yes A = Ni 0.01 ≤x≤ 0.15 if A = Cu 0.01 ≤x≤ 0.10 if A = Zn 0.01 ≤x≤ 0.20

- for systems containing up to three metals and / or metalloids, of the type:

the values of x and y in the ranges 0.001 ≤x≤ 0.485; O≤y≤ l (Si0 ₂ ), _.x ((Ti0 ₂ ) ₁ ,, (Zr0 ₂ ) _y ) _x the values of x and y in the intervals 0.005 ≤x≤ 0.50; O≤y≤ l (Si0 ₂ (ZrO ₂ ) ,. _y (V ₂ O ₅ ) _{y / 2} ) _x the values of x and y in the intervals 0.001 ≤x≤ 0.485; 0 ≤ and ≤ 0.15

SUBSTITUTE SHEET (RULE 26) (Si0 ₂ ) ₁ . _λ ((ZnO) _] ,, (NiO) _y ) _λ os values of x and y in the intervals 0.001 ≤ x ≤ 0.15; O ≤ and ≤ 0.15

(SiO ^ flMoO ^ iO) ^ os values of x and y in the range 0.001 ≤ x ≤ 0.15; O ≤ y ≤ 0.13 ( ^At A ^ ^P ^ ^A ^ λ the values of x and y in the intervals 0.001 ≤ x ≤ 0.80; O ≤ and ≤ l if y = 0 (ALPO) especially the values of x and y included in the intervals 0.15 ≤ x ≤ 0.50; O ≤ y ≤ l if A '= Ti the values of x and y in the intervals 0.15 ≤ x ≤ 0.50; 0 ≤ y ≤ 0.2 if A '= Yes (SAPO) the values of x and y in the intervals 0.15 ≤ x ≤ 0.80; 0 ≤ and ≤ 0.8

11. Mesoporous materials obtainable according to the procedure of any of claims 1 to 4, 6 or 7, characterized in that they have hexagonal pore topology and compositions comprised in those of claim 10.

12. Mesoporous materials obtainable according to the procedure of any one of claims 1 to 4, 6 or 7, characterized in that they have "worm" type topology and compositions comprised in those of claim 10.

13. Use of the materials obtainable according to the process of any of claims 1 to 8, containing silicon and one or more elements selected from Ti, Zr, V and Mo, co or catalysts in the selective oxidation of organic products.

14. Use of the materials of claims 11 and 12, containing silicon and one or more elements selected from Ti, Zr, V and Mo, as catalysts in the selective oxidation of organic products.

15. Use of a material obtainable according to the method of claim 7, wherein said material is an optionally doped silicotitanate, comprising an ordered mesoporous phase characterized by having at least one diffraction peak at a spacing.

SUBSTITUTE SHEET (RULE 26) d greater than 1.8 nm, with pores with a diameter greater than 1.0 nm and less than 20 nm and whose cross-link is composed of silicon and titanium oxides; said material having, in addition, an intense spectral band in the infrared infrared at 960 ± 5 cm ^"1 and others in the ultraviolet spectral range close to 220 ± 10 nm 5 ', possibly, at 270 ± 10 nm, indicating the presence of reticular titanium; said material also containing a composition in accordance with the stoichiometric formulation:

where

ZO ₂ is an oxide in which Z represents one or more cations with valence 4, always Si ^4-1 and, optionally, Ge ^{4 "1} , Sn ⁴⁺ or Pb ⁴⁺ ;

M ₂ O is an oxide in which M represents one or more ion exchangeable cations from the set H ⁺ , Na ⁺ and K ⁴ ; and stoichiometric coefficients x, y, z may take values limited by the following conditions

0.001 ≤ x ≤ 0.485; (1-y) ≤ 10 ^"4 ; z ≤ 0.01

in the selective oxidation of organic products.

SUBSTITUTE SHEET (RULE 26)