WO2012085358A1

WO2012085358A1 - Method for preparing a spherical material having a hierarchized porosity and including metal particles trapped in a silicon matrix

Info

Publication number: WO2012085358A1
Application number: PCT/FR2011/000657
Authority: WO
Inventors: Pierre Et Marie Curie Universite; Alexandra Chaumonnot; Clément Sanchez; Cédric BOISSIERE; Frédéric COLBEAU-JUSTIN; Audrey Bonduelle
Original assignee: IFP Energies Nouvelles; Centre National De La Recherche Scientifique
Priority date: 2010-12-22
Filing date: 2011-12-15
Publication date: 2012-06-28
Also published as: FR2969514B1; FR2969514A1

Abstract

The invention relates to a method for preparing an inorganic material having a hierarchized porosity in the microporosity, mesoporosity, and macroporosity ranges, said material consisting of at least two basic spherical particles having a maximum diameter of 200 microns, each of said spherical particles including metal particles trapped in a silicon-oxide matrix, said method including the following steps: a) preparing a solution containing a structuring agent and a silicic precursor; b) mixing said metal particles or at least one metal precursor of said metal particles, a surfactant, and said solution obtained according to step a) into a solution, such that the ratio V(inorganic)/V(organic) is between 0.09 and 0.28; c) atomizing, by means of an aerosol, said solution obtained in step b) in order to form spherical droplets; d) drying said particles; and e) removing said structuring agent and said surfactant.

Description

PROCESS FOR THE PREPARATION OF A SPHERICAL MATERIAL HIERARCHISED POROSITY COMPRISING METALLIC PARTICLES PIEGEES IN A MATRIX BASED ON

SILICON

The present invention relates to the field of inorganic oxide materials containing transition metals and silicon, in particular metallosilicate materials and more specifically aluminosilicate materials, having a hierarchical porosity in the fields of microporosity, mesoporosity and macroporosity. It relates more specifically to the preparation of these materials which are obtained by the use of the so-called "aerosol" synthesis technique. The present invention also relates to the use of these materials after sulfurization as catalysts in various hydrocarbon charge conversion processes particularly relating to the hydrotreating and hydroconversion fields.

State of the art

The composition and use of the hydroconversion (HDC) and hydrotreatment (HDT) catalysts of hydrocarbon feedstocks are respectively described in "Hydrocracking Science and Technology", 1996, J. Scherzer, AJ Gruia, Marcel Dekker Inc. and in the article by B. S. Clausen, HT Topsoe, FE Massoth, from "Catalysis Science and Technology", 1996, Volume 1 1, Springer-Verlag. Thus, these catalysts are generally characterized by a hydro-dehydrogenating function provided by the presence of an active phase based on at least one Group VIB metal and / or at least one Group VB metal and optionally at least one metal of the group group VIII of the periodic table of elements. The most common formulations are cobalt-molybdenum (CoMo), nickel-molybdenum (NiMo) and nickel-tungsten (NiW). These catalysts can be in mass form or in the supported state then involving a porous solid. After preparation, at least one Group VIB metal and / or at least one Group VB metal and optionally at least one Group VIII metal present in the catalytic composition of said catalysts is often in oxide form. . Since the active and stable form for the HDC and HDT processes is the sulphurized form, these catalysts are subjected to a sulphurization step.

It is generally known to a person skilled in the art that good catalytic performances in the fields of application mentioned above are a function of 1) the nature of the hydrocarbon feed to be treated, 2) the process employed, 3) operating conditions. selected operating conditions and 4) of the catalyst used. In the latter case, it is also accepted that a catalyst having a high catalytic potential is characterized by 1) an optimized hydro-dehydrogenating function (associated active phase perfectly dispersed on the support surface and having a high metal content) and 2 ) in the particular case of processes involving hydroconversion reactions (HDC), by a good balance between said hydro-dehydrogenating function and the crisp function provided by the acid function of a support. It is also generally desired that, whatever the nature of the hydrocarbon feedstock to be treated, the catalyst has a satisfactory accessibility of the active sites with respect to the reagents and reaction products while developing a high active surface area. leads to specific constraints in terms of structure and texture specific to the oxide support present in said catalysts. This last point is particularly critical in the case of the treatment of "heavy" hydrocarbon feedstocks. The usual methods leading to the formation of the hydro-dehydrogenation phase of the HDC and HDT catalysts consist of a deposit of the molecular precursor (s) of at least one Group VIB metal and / or at least one Group VB metal and optionally at least one Group VIII metal on an oxide support by the technique known as "dry impregnation" followed by the steps of maturation, drying and calcination leading to the formation of the oxidized form of the said (s) metal (s) employee (s). The final sulphurization step that generates the hydro-dehydrogenating active phase is then carried out as mentioned above.

The catalytic performances of catalysts resulting from these conventional synthesis protocols have been extensively studied. In particular, it has been shown that, for relatively high metal contents, sulphurization refractory phases formed after the calcination step (sintering phenomenon) appear (BS Clausen, HT Topsoe, and FE Massoth, from the book "Catalysis Science and Technology", 1996, volume 1 1, Springer-Verlag). For example, in the case of catalysts of CoMo or NiMo type supported on a carrier of an aluminic nature, it is 1) crystallites of MoO ₃ , NiO, CoO, COOMO ₄ or CO ₃ O ₄ , of sufficient size to be detected in DX, and / or 2) type Al ₂ (MoO ₄ ) ₃ , CoAl ₂ 0 ₄ or NiAl ₂ 0 ₄ species. The three aforementioned species containing the aluminum element are well known to those skilled in the art. They result from the interaction between the aluminum support and the precursor salts in solution of the hydro-dehydrogenating active phase, which concretely results in a reaction between Al ³⁺ ions extracted from the aluminum matrix and said salts to form heteropolyanions. Anderson of formula [Al (OH) ₆ Mo ₆ 0 themselves precursors of refractory phases to sulphidation. The presence of all these species leads to a non-negligible indirect loss of the catalytic activity of the associated catalyst because all the elements belonging to at least one Group VIB metal and / or at least one Group VB metal and optionally at least one Group VIII metal is not used to its full potential since a part of it is immobilized in little or no active species. The catalytic performances of the conventional catalysts described above could therefore be improved, in particular by developing new methods for preparing these catalysts which would make it possible:

1) to ensure a good dispersion of the hydro-dehydrogenating phase, in particular for high metal contents (for example by controlling the size of the transition metal-based particles, maintaining the properties of these particles after heat treatment, etc.),

2) to limit the formation of refractory species for sulfurization (for example by obtaining a better synergy between the transition metals forming the active phase, control of the interactions between the hydro-dehydrogenating active phase (and / or its precursors ) and the porous support used, etc.),

3) to ensure a good diffusion of the reactants and the products of the reactions while maintaining high developed active surfaces (optimization of the chemical, textural and structural properties of the porous support).

To meet the needs expressed above, it has been developed hydroconversion and hydrotreatment catalysts whose precursors of the hydro-dehydrogenating active phase are formed of heteropolyanions (HPA), for example cobalt-based heteropolyanions. and molybdenum (CoMo systems), nickel and molybdenum (NiMo systems), nickel and tungsten (NiW), nickel, vanadium and molybdenum (NiMoV systems) or phosphorus and molybdenum (PMo). For example, patent application FR 2.843.050 discloses a hydrorefining and / or hydroconversion catalyst comprising at least one group VIII element and at least one of molybdenum and / or tungsten present at least partly in the form of heteropolyanions in the oxide precursor. In general, the heteropolyanions are impregnated on an oxide support. The oxide support plays a significant role in the development of efficient catalysts insofar as it will induce modifications of the hydro-dehydrogenating support / active phase interactions (and / or its precursors) and the treatment of hydrocarbon feedstocks more and more. heavy requires to ensure the maintenance of the accessibility of active sites reagents and products while maintaining the catalytic activity.

New synthesis strategies to obtain well-defined porosity materials in a very wide range, ranging from microporous materials to macroporous materials through materials with hierarchical porosity, that is to say having pores of several sizes. have been very widely developed in the scientific community since the mid-1990s (GJ AA Soler-Illia, C. Sanchez, B. Lebeau, J. Patarin, Chem Rev., 2002, 102, 4093).

The solids with well-defined porosity or hierarchical porosity in the fields of microporosity, mesoporosity and macroporosity are for example obtained according to the EISA (Evaporated Induced Sel-Assembly) method. According to this process, the cooperative self-assembly of a structuring agent with hydrolyzed and condensed inorganic precursors is carried out at various stages of progress by progressive evaporation of a solution of these reagents whose concentration of structuring agent is less than critical micellar concentration (c _mc ) well known to those skilled in the art. The EISA process has already been implemented for the formation of mesostructured films in the case of a deposit on a substrate ("dip-coating" technique, for example implemented in US Pat. No. 6,387,453), or for the formation of a mesostructured powder after atomization of the solution (aerosol technique).

Non-mesostructured solids with a hierarchical porosity in a range from micro to macroporosity have also already been prepared by the aerosol technique, according to the same EISA method, by involving the chemical phenomenon of spinodal decomposition, a phenomenon that is competitive with that of mesotreaturation. . Summary of the invention

The subject of the present invention is a method for preparing an inorganic material with hierarchical porosity in the fields of microporosity, mesoporosity and macroporosity, said material consisting of at least two elementary spherical particles having a maximum diameter of 200 microns, each of said spherical particles comprising metal particles containing at least one or more metals selected from vanadium, niobium, tantalum, molybdenum, tungsten, iron, copper, zinc, cobalt and nickel, said metal particles being present in a matrix based on silicon oxide, said method comprising at least the following steps:

a) the preparation of a solution containing at least one structuring agent and at least one silicic precursor, b) mixing in solution said metal particles or at least one metal precursor of said metal particles, at least one surfactant and at least said solution obtained according to a),

c) the aerosol atomization of said solution obtained in step b) to lead to the formation of spherical droplets,

d) drying said particles,

g) removing at least said structuring agent and at least said surfactant.

Said preparation process according to the invention comprising said steps a), b), c), d) and g) is called the main process according to the invention. The inorganic material prepared according to the main process according to the invention is an amorphous material: the matrix based on silicon oxide, each forming spherical particles of the material prepared according to the main process according to the invention, has amorphous walls consisting of protozeolithic, which are at the origin of the microporosity present within each of the spherical particles of said material. The microporosity is uniformly distributed within each of the spherical particles of said amorphous material.

According to a first preferred embodiment of the process according to the invention, following said step d) is carried out a step e) consisting in autoclaving the particles resulting from said step d) and then proceeding to a step f ) of practicing the drying of said particles obtained at the end of said e). Said step f) is then followed by the implementation of said step g) of eliminating said structuring agent and said surfactant. Said first embodiment of the method of the invention comprising said steps a), b), c), d), e), f) and g) is called secondary process according to the invention. The autoclaving step e) performs the transformation of the proto-zeolite entities formed during said step a) of said secondary process into crystallized zeolite entities. The inorganic material prepared according to the secondary process according to the invention is a crystallized material: the matrix based on silicon oxide each forming spherical particles of the material prepared according to the secondary process according to the invention has crystallized walls consisting of zeolites, which are at the origin of the microporosity present within each of the spherical particles of the material according to the invention. The microporosity is uniformly distributed within each of the spherical particles of said crystallized material.

We will speak of the method according to the invention to designate indifferently the main process according to the invention, the secondary process according to the invention and the different embodiments of the method described later in the present description.

According to the invention, the matrix based on silicon oxide forming each of the elementary spherical particles of the inorganic material obtained according to the process of the invention is constituted either entirely of proto-zeolitic entities or integrally of zeolitic entities. Said matrix based on silicon oxide is either entirely silicic or it comprises, besides silicon, at least one element Y chosen from among aluminum, iron, boron, indium and gallium, preferably aluminum.

The microporosity induced by the respectively crystalline amorphous walls of the material obtained according to the method of the invention is consecutive not only to the use of a solution containing the elements precursors of the proto-zeolite entities according to step a) of the process according to the invention respectively to the implementation of an autoclaving of the particles according to step e) of the secondary process according to the invention but also to the aerosol atomization of the solution according to step c) of the process according to the invention. The mesoporosity and the macroporosity of the material prepared according to the method of the invention are consecutive to the nonorganization of the organic phase generated by the presence of the surfactant associated with the hydrolysis and condensation reactions of the precursors of the inorganic phase resulting from the solutions containing the metal particles or their precursors and the precursor elements of the proto-zeolitic entities according to step a) of the preparation process of the invention, this macroporous and mesoporous porosity not organized being also induced by the aerosol technique in accordance with step c) of the process according to the invention.

Interest of the invention

The preparation method proposed by the present invention is a simple method and operating continuously. It makes it possible to obtain, by aerosol, an inorganic material with hierarchical porosity in the fields of microporosity, mesoporosity and macroporosity, formed of elementary spherical particles in which metal particles are trapped in a mixed matrix. micro / meso / macroporous based on silicon oxide.

The material obtained according to the preparation process according to the invention is an advantageous catalytic precursor. It is advantageously used, after sulfurization, as a catalyst in applications relating to hydrotreating and hydroconversion of hydrocarbon feeds. In particular, the metal particles are precursor species of the active sulphide phase present in the catalyst derived from the material prepared according to the method of the invention. The preparation method according to the invention makes it possible to obtain a material which simultaneously has the properties specific to the presence of metal particles based on elements chosen from vanadium, niobium, tantalum, molybdenum, tungsten and iron. copper, zinc, cobalt and nickel, in particular metal particles in the form of heteropolyanions (better dispersion of the active phase, better synergy between the metallic species, reduction of the phases which are refractory to sulphurisation, etc.) and textural properties of silicon-based microporous materials, silicon-based mesoporous materials, and macroporous silicon-based materials.

Preferably, said matrix based on silicon oxide each forming elementary spherical particles of the material prepared according to the process of the invention comprises, in addition to silicon, at least one element Y chosen from aluminum, iron and boron. indium and gallium, preferably aluminum so as to form an aluminosilicate material. The material prepared according to the process of the invention then has, when Y is aluminum, acid-base properties superior to the acid-base properties presented by the previous aluminosilicate materials, prepared in the absence of precursors of entities. proto-zeolitic and according to synthetic protocols well known to those skilled in the art using inorganic precursors of silica and alumina. In addition, the material prepared according to the method of the invention consists of spherical elementary particles of controlled size, namely having a maximum diameter equal to 200 μπι, preferably less than 100 μπι, advantageously varying from 50 nm to 50 μιη, very advantageously from 50 nm to 30 μιη and even more advantageously from 50 nm to 10 μιτι. The limited size of these particles and their homogeneous spherical shape allows a better diffusion of the reagents and reaction products when using a catalyst whose material prepared according to the process of the invention is a precursor, in applications industrial potential compared to materials known in the state of the art, obtained off-air and in the form of elementary particles of non-homogeneous shape, that is to say irregular, and much larger than 500 nm .

The trapping of said metal particles within the micro / meso / macroporous mixed oxide matrix generates favorable additional technical effects such as controlling the size of said metal particles, increasing the thermal stability of said metal particles, developing particle interactions. metallic / original support, etc. Said metal particles are, for example, in the form of polyoxometalates, preferably in the form of heteropolyanions (HP A).

On the other hand, the aerosol preparation method according to the invention makes it possible to elaborate sulphurized catalyst precursors in a simple manner with a limited number of steps. The aerosol preparation method according to the invention makes it possible to conserve the stoichiometry of the non-volatile species present in the initial solution according to said step b) in the material obtained according to the process of the invention, and thus to ensure the expected properties of the final material in terms of chemical composition, unlike other processes involving filtration and washing steps often causing a loss of elements initially present in the solution for the preparation of the final material . Presentation of the invention

a) the preparation of a solution containing at least one structuring agent and at least one silicic precursor,

b) mixing in solution said metal particles or at least one metal precursor of said metal particles, at least one surfactant and at least said solution obtained according to a),

d) drying said particles,

g) removing at least said structuring agent and at least said surfactant. Said preparation process according to the invention comprising said steps a), b), c), d) and g) is called the main process according to the invention. The inorganic material prepared according to the main process according to the invention is an amorphous material: the matrix based on silicon oxide, each forming spherical particles of the material prepared according to the main process according to the invention, has amorphous walls consisting of protozeolithic, which are at the origin of the microporosity present within each of the spherical particles of said material. The protozeolitic entities are species prepared from reagents used for the synthesis of zeolites according to said step a) of the process according to the invention, the preparation of said species not having been carried out up to the stage of the formation of crystallized zeolites. As a result, said small protozeolithic entities are not detected when characterized by wide-angle X-ray diffraction. More precisely and in accordance with the invention, the proto-zeolitic entities constituting the amorphous microporous walls of the matrix of each of the spherical particles of said material prepared according to the main process according to the invention are species which can serve as a primer for the synthesis of any zeolite known to those skilled in the art and in particular, but not exhaustively, to the synthesis of zeolites listed in Atlas of zeolite framework types, 6 ^th revised Edition, 2007, C. Baerlocher, LB McCusker, DH Oison The protozeolitic entities constituting the amorphous walls of the matrix of each of the particles of said material prepared according to the main process according to the invention and at the origin of the microporosity thereof are preferably species for the primer. at least one zeolite selected from zeolites IZM-2, ZSM-5, ZSM-12, ZSM-48, ZSM-22, ZSM-23, ZBM-30, EU-2, EU-1 1, silicalite, beta , zeolite A, fa ujasite, Y, USY, VUSY, SDUSY, mordenite, NU-10, NU-87, NU-88, NU-86, NU-85, IM-5, IM-12, IM-16, ferrierite and EU-1. Very preferably, said proto-zeolitic entities constituting the amorphous walls of the matrix of each of the particles of said material are species for the primer of at least one zeolite chosen from zeolites of structural type MFI, BEA, FAU and LTA. .

According to a first preferred embodiment of the process according to the invention, following said step d) is carried out a step e) consisting in autoclaving the particles resulting from said step d) and then proceeding to a step f ) of practicing the drying of said particles obtained at the end of said e). Said step f) is then followed by the implementation of said step g) of removing at least said structuring agent and at least said surfactant. Said first embodiment of the method of the invention comprising said steps a), b), c), d), e), f) and g) is called secondary process according to the invention.

The inorganic material prepared according to the secondary process according to the invention is a crystallized material: the matrix based on silicon oxide each forming spherical particles of the material prepared according to the secondary process according to the invention has crystallized walls consisting of zeolites, which are at the origin of the microporosity present within each of the spherical particles of the material according to the invention. Said zeolite entities are derived from said proto-zeolite entities described above. In particular, said zeolite entities constituting the crystallized walls of the matrix of each of the particles of the material prepared according to the secondary process according to the invention and at the origin of the microporosity thereof preferably comprise at least one zeolite chosen from the zeolites IZM-2, ZSM-5, ZSM-12, ZSM-48, ZSM-22, ZSM-23, ZBM-30, EU-2, EU-1, silicalite, beta, zeolite A, faujasite, Y, USY , VUSY, SDUSY, mordenite, NU-10, NU-87, NU-88, NU-86, NU-85, IM-5, IM-12, IM-16, ferrierite and EU-1. Very preferably, said zeolite entities constituting the crystallized walls of the matrix of each of the particles of said material comprise at least one zeolite chosen from zeolites of structural type MFI, BEA, FAU and LTA.

The material prepared according to the process of the invention is a hierarchically porous material. For the purposes of the present invention, the term "material with hierarchical porosity" is intended to mean a material in which each of the spherical particles has a triple porosity: a macroporosity characterized by a macroporous mercury volume ranging from 0.05 to 2 ml / g and from preferably in a range of from 0.1 to 0.4 ml / g, a mesoporosity characterized by a mesoporous volume measured by volumetric nitrogen ranging from 0.01 to 1 ml / g and preferably in a range from 0.01 to 1 ml / g. ranging from 0.1 to 0.6 ml / g and a microporosity induced by the amorphous or crystallized walls, the characteristics of the microporosity being a function of the proto-zeolitic entities or zeolitic entities constituting the respectively amorphous or crystallized walls of the matrix of each of the spherical particles of the material obtained according to the method of the invention. The microporosity is characterized by a microporous volume measured by nitrogen volumetry of between 0.01 and 0.4 ml / g. The porosity at the mesoporous scale is unorganized, that is to say that the material obtained does not present a response signal after X-ray analysis at low angles, a standard characterization technique of the skilled person making it possible to highlight an organized mesoporosity associated with a so-called mesostructured solid. The mesoporosity of the material obtained according to the process of the invention is characterized by the presence of mesoporous domains ranging from 2 to 50 nm and preferably in a range varying from 4 to 50 nm, said ranges being assimilated to the mesoporous diameter. obtained from the nitrogen adsorption isotherm as described later in the present description. The macroporosity is itself characterized by the presence of macroporous domains of size greater than or equal to 50 nm, generally between 50 nm and 10 microns and preferably between 50 and 300 nm. It can be intraparticular or interparticular in nature. It should be noted that porosity of a microporous nature may also result from the interlaying of the surfactant, used during the preparation of the material according to the process of the invention, with the inorganic wall at the level of the developed organic-inorganic interface. during the preparation of said material according to the method of the invention.

According to the invention, said metal particles are homogeneously and uniformly trapped in the matrix contained in each of said spherical particles of the material prepared according to the method of the invention. They advantageously contain at least one or more metals chosen from vanadium, niobium, tantalum, molybdenum and tungsten. In particular, said metal particles are characterized by Raman spectroscopy and have at least one wave number band of between 750 and 1050 cm ^-1 . Raman spectroscopy is a technique well known to those skilled in the art. More specifically, said metal particles have at least one wave number band between 750 and 950 cm ^-1 or between 950 and 1050 cm ^-1 . The wave number band between 750 and 950 cm ^-1 is attributable to the asymmetric stretching (MOM) or symmetric stretching bonds (-0-M-0). The wave number band between 950 and 1050 cm ^-1 is attributable to the stretching modes of the terminal bonds M = 0. The element M present in the MOM bonds, -OMO- and M = 0 is preferably chosen from vanadium, niobium, tantalum, molybdenum, tungsten and the mixture of these metals. The Raman apparatus used for the demonstration of said metal particles is described later in the present description. Said metal particles have an average size of between 0.3 and 3 nm, preferably between 0.3 and 2 nm, and even more preferably it is greater than or equal to 0.3 nm and strictly less than 1 nm. The size of said metal particles is advantageously measured by transmission electron microscopy (TEM). The absence of MET metal particle detection means that said metal particles have a size less than 1 nm. Said metal particles are preferably chosen from metal particles in the form of polyoxometalate of the formula (X _x M _m O _y H _h) ^{q 'and} the metal particles in the form of oxide nanoparticles, the definitions of this type of metallic particles are given below.

Preferably, said metallic particles are in the form of a polyoxometalate of the formula (X _x M _m O _y H _h) ^{q "(I)} where H is hydrogen, O is an oxygen atom, X is a member selected from phosphorus, silicon, boron, nickel and cobalt and M is one or more elements selected from vanadium, niobium, tantalum, molybdenum, tungsten, iron, copper, zinc, cobalt and nickel, where x is 0, 1, 2 or 4, where m is 5, 6, 7, 8, 9, 10, 11, 12 and 18, y being between 17 and 72, h being between 0 and 12 and q being between 1 and 20 (y, h and q being integers) .For the definition of this formula, it is understood, within the meaning of the present invention, that the elements H, X, M and O are present in the structure of the polyoxometalates, said metal particles in the form of polyoxometalate of formula (I) are characterized by the presence of at least one wave number band between 750 and 1050 cm ^-1 in Raman spectroscopy. Said metal particles in the form of polyoxometalate of formula (I) have an average size of between 0.6 and 3 nm, preferably between 0.6 and 2 nm, and even more preferably it is greater than or equal to 0.6 nm and strictly less than 1 nm. Said metal particles in the form of polyoxometalate of the formula (X _x M _m O _y H _h) ^{q ",} trapped in the matrix included in each of said spherical particles of the material prepared according to the method of the invention advantageously have atoms which M the degree of oxidation is equal to + IV, + V and / or + VI, where M is preferentially chosen from vanadium, niobium, tantalum, molybdenum, tungsten and the mixture of these metals. the polyoxometallate form are uniformly and uniformly trapped in the matrix.

According to the invention, said metal particles in the polyoxometallate form of formula (I) are chosen from isopolyanions and heteropolyanions (HPA). They are characterized by the presence of at least one wave number band varying between 750 and 1050 cm ^-1 in Raman spectroscopy.

The isopolyanions and heteropolyanions entrapped in the matrix included in each of said spherical particles of the material prepared according to the process of the invention are fully described in the book Heteropoly and Isopoly Oxometallates, Pope, Ed Springer-Verlag, 1983. Preferably, said metal particles of formula (I) are heteropolyanions. Said metal particles of formula (I), preferably as heteroplyanions, are negatively charged salts q compensated by positively charged counterions of the same or different nature. Counterions are advantageously provided by metal cations, in particular Group VIII metal cations such as Co ²⁺ , Ni ²⁺ , H ⁺ protons and / or NH ⁺ ammonium cations. When all the counter-ions are H ⁺ protons, it is commonly referred to as heteropoly acid to designate the form in which are found said metal particles of formula (I). Such a heteropoly acid is for example phosphomolybdic acid (3H ⁺ , PM012O40 ^{3 "} ) or phosphotungstite acid (3H ⁺ , PW ₁₂ 0 ₄ o ^3" ) -

According to a first embodiment of the material prepared according to the process of the invention consisting in trapping metal particles in the form of isopolyanions in each of said silicon oxide matrices, the element X in the general formula ( I) above is absent and x = 0. The element M is one or more elements advantageously chosen from vanadium, niobium, tantalum, molybdenum, tungsten, cobalt and nickel. More preferably, the element M is one or more elements chosen from vanadium, niobium, tantalum, molybdenum and tungsten. Cobalt and / or nickel as element M present in said general formula (I) is / are advantageously in a mixture with one or more elements M chosen from vanadium, niobium, tantalum, molybdenum and tungsten (partial substitution of one or more elements M = V, Nb, Ta, Mo and W by Ni and / or Co). Preferably, the m atoms of elements M present in the general formula (I) are all exclusively either Mo atoms or W atoms, or a mixture of Mo and W atoms, or a mixture of W and Nb atoms, a mixture of Mo and V atoms, a mixture of W and V atoms, or a mixture of Mo and Co atoms, or a mixture of atoms of Mo and Ni, a mixture of W and Ni atoms. According to said first embodiment, m is equal to 5, 6, 7, 8, 9, 10, 11, 12 and 18. Even more preferably, m is equal to 6, 7 and 12. In the particular case where the element M is molybdenum (Mo), the value of m is preferably 7. In another particular case where the element M is tungsten (W), the value of m is preferably equal to 12. In the general formula ( I), O denotes the oxygen element with 17 <y <48. q denotes the isopolyanion charge, with 3 <q <12 and H is the hydrogen element with h = 0 to 12. A preferred isopolyanion according to said first embodiment has the formula H ₂ W ₁₂ O ₄₀ ^{6 "} (h = 2, m = 12, y = 40, q = 6) or the formula Mo ₇ 0 ₂ 4 ^6" (h = 0, m = 7, y = 24, q = 6).

According to a second embodiment of the material prepared according to the method of the invention consisting in trapping metal particles in the form of heteropolyanions (denoted HP A) in each of said silicon oxide-based matrices, the element X is the central atom in the structure of the heteropolyanion and is selected from P, Si, B, Ni and Co with x = 1 or 2. The element M is a metal atom advantageously systematically in octahedral coordination in the structure of the heteropolyanion. The element M is one or more elements advantageously chosen from vanadium, niobium, tantalum, molybdenum, tungsten, cobalt and nickel. More preferably, the element M is one or more elements chosen from vanadium, niobium, tantalum, molybdenum and tungsten. Cobalt and / or nickel as element M present in said general formula (I) is / are advantageously in admixture with one or more elements M chosen from vanadium, niobium, tantalum, molybdenum and tungsten ( partial substitution of one or more elements M = V, Nb, Ta, Mo and W by Ni and / or Co). Preferably, the m atoms M present in the general formula (I) are all exclusively either Mo or W atoms, or a mixture of Mo and W atoms, either a mixture of W and Nb atoms, or a mixture of Mo and V atoms, or a mixture of W and V atoms, or a mixture of Mo and Co atoms, a mixture of Mo and Ni atoms, or a mixture of W and Ni atoms. According to said second embodiment, m is equal to 5, 6, 7, 8, 9, 10, 1 1, 12 and 18 and preferably equal to 5, 6, 9, 10, 1 1, 12, 18. In the general formula (I), O denotes the oxygen element with between 17 and 72, preferably between 23 and 42, q denotes the charge of the heteropolyanion with 1 <q <20, preferably 3 <q <12 , and H is the hydrogen element with h = 0 to 12.

A first preferred category of heteropolyanions (second embodiment of the material prepared according to the process of the invention) advantageously trapped in the matrix included in each of said spherical particles of the material prepared according to the process of the invention is such that said heteropolyanions present the formula XM ₆ 0 ₂ 4H _h ^{q "} (with x = 1, m = 6, y = 24, q = 3 to 12 and h = 0 to 12) and / or the formula X ₂ M, o0 ₃₈ H _h ^{q "} (with x = 2, m = 10, y = 38, q = 3 to 12 and h = 0 to 12) with H, X, M, O, h, x, m, y and q having the same definitions as those given in the general formula (I) above. Such heteropolyanions are known as Anderson heteropolyanions (Nature, 1937, 150, 850). They comprise 7 octahedra located in the same plane and interconnected by the edges: 6 octahedra surround the central octahedron containing the hetero element X. The heteropolyanions CoMo ₆ 0 ₂ 4H ₆ ^{3 "} and NiMo ₆ 0 ₂ 4H ₆ ^4" are good examples of Anderson heteropolyanions entrapped in each of said matrices, wherein Co and Ni are the X-heteroelements of the HPA structure, respectively. Such Anderson heteropolyanions of formula CoMo ₆ 0 ₂ 4H ₆ ^{3 "} and ΝίΜο ₆ 0 ₂₄ Η ₆ ^4" have the advantage when in the form of cobalt or nickel salts (i.e. when cobalt or nickel are present as cations to compensate for the negative charge of HP A), to reach an atomic ratio [(promoter = Co and / or Ni) / Mo] of between 0.4 and 0.6 , that is to say close to or equal to the optimum ratio known to those skilled in the art and between 0.4 and 0.6 to maximize the performance of hydrotreatment catalysts, Co and / or Ni taken in account for the calculation of this atomic ratio being Co and / or Ni present both as counterions and heteroelements X of the HPA structure. By way of example, the cobalt or nickel salts of the monomeric ion 6-molybdocobaltate (of formula CoMo ₆ 0 ₂₄ H ₆ ^{3 "} , 3 / 2Co ⁺ , or CoMo ₆ 0 ₂₄ H ₆ ^3" , 3 / 2Ni ²⁺ ) and the cobalt or nickel salts of the dimeric decamolybdocobaltate ion (of the formula Co ₂ Moio0 ₃₈ H4 ^{6 "} , 3Co ²⁺ or Co ₂ Moio0 ₃ gH ₄ ^6" , 3Ni ²⁺ ) are characterized by Atomic ratios [(promoters = Co and / or Ni) / Mo] respectively of 0.41 and 0.5. Similarly, by way of example, the cobalt or nickel salts of the monomeric ion 6-molybdonickellate (of formula NiMo ₆ 0 ₂₄ H ₆ ^{4 "} , 2Co ²⁺ and NiMo ₆ 0 ₂₄ H ₆ ^4" , 2Ni ^{2 +} ) and the cobalt or nickel salts of the dimeric decamolybdonickellate ion (of formula Ni ₂ Moio0 ₃₈ H4 ^{8 "} , 4Co ²⁺ and Νί ₂ Μθιοθ3 ₈ Η4 ^8" , 4Ni ²⁺ ) are characterized by atomic ratios [ (promoters = Co and / or Ni) / Mo] respectively of 0.5 and 0.6, the Co and / or the Ni taken into account for the calculation of this atomic ratio being the Co and / or the Ni present at the both as counterions and heteroelements X of the HPA structure. In the case where ΓΗΡΑ contains within its structure cobalt (X = Co) and molybdenum (M = Mo), it is preferably dimeric. A mixture of the two monomeric and dimeric forms of said HPA may also be used. In the case where ΗΡΑ contains within its structure nickel (X = Ni) and molybdenum (M = Mo), it is preferably monomeric. A mixture of the two monomeric and dimeric forms of said HPA may also be used. Very preferably, Anderson used to obtain the material prepared according to the process of the invention is a dimeric HPA containing cobalt and molybdenum within of its structure and the counter ion of the HPA salt can be cobalt Co ^II 3 [Co " ^I 2Moio038H ₄ ] or nickel Ni" 3 [Co ^n, ₂ Mo ₁₀ O38H4].

A second preferred category of heteropolyanions (second embodiment of the material prepared according to the process of the invention) advantageously trapped in the matrix included in each of said spherical particles of the material prepared according to the process of the invention is such that said heteropolyanions present the formula XM _l2 O ₄₀ H _h ^{q "} (x = 1, m = 12, y = 40, h = 0 to 12, q = 3 to 12) and / or the formula XM ₁₁ 0 ₃ 9H _h ^q" (x = 1, m = 1 1, y = 39, h = 0 to 12, q = 3 to 12) with H, X, M, O, h, x, m, y and q having the same definitions as those given in the general formula (I) above. Heteropolyanions of formula XMi ₂ 0 ₄ oH _h ^{q "are} heteropolyanion having a Eggin structure and heteropolyanions of formula XM _u 0 ₃₉ H _h ^{q 'are} heteropolyanion having a lacunary Keggin structure. Keggin structure of the heteropolyanion are obtained, for variable pH ranges, according to the routes of production described in the publication by A. Griboval, P. Blanchard, E. Payen, M. Fournier, JL Dubois, Chem Lett, 1997, 12, 1259. Keggin structure of heteropolyanions are also known as the substituted forms in which a metal element of group VIII, preferentially cobalt or nickel, is in substitution of the metal M in formula XM ₁₂ O ₄₀ h _h ^{q ':} of such substituted Keggin species are, for example, the heteropolyanions PNiMo _u O ₄₀ H ^{6 "} or PCoMo _n O ₄₀ H ^6" (a Mo atom substituted respectively by a Ni atom or by a Co atom) PCoMo species _u O ₄₀ H ^{6 '} is for example prepared according to the protocol described in the publication of LGA van de Water et al. J. Phys. Chem. B, 2005, 109, 14513. Other substituted Keggin species, advantageously trapped in the matrix included in each of said spherical particles of the material prepared according to the method of the invention, are the PVMonO species ₄₀ ^{4 "} , PV ₂ Moi ₀ O ₄₀ ^{5 "} , PV ₃ Mo ₉ O ₄₀ ^6" or also PV Mo ₈ O ₀ ^{7 "} (1 or more V atoms substituted for 1 or more Mo atoms as M element): these species and their method of preparation are described in the publication by D. Soogund, et al. Appl. Catal. B, 2010, 98, 1, 39. Other substituted species of Keggin heteropolyanions are PMo ₃ W ₉ O ₄₀ ^{3 "} , PMo ₆ W ₆ O ₄₀ ^3" , PMo ₉ W ₃ O ₄ o ^{3 "} Still other substituted species of Keggin heteropolyanions and their method of preparation are described in patent application FR 2.764.21 1: said species have the formula Z _w XM _n 0 ₄₀ Z'C _(Z _2w) Z is cobalt and / or nickel, X is phosphorus, silicon or boron and M is molybdenum and / or tungsten, Z 'is an atom substituted for an atom of element M and is selected from cobalt, iron, nickel, copper or zinc and C is an H ⁺ ion or an alkylammonium cation, C acting as a counter ion as Z, w is 0 to 4.5, z a value between 7 and 9. Heteropolycomposés (heteropolyanions + counterions) particularly suitable for the implementation of the material prepared according to the process of the invention and corresponding to this formula are for example ple the PCoMo species _n O ₄₀ H (NH ₄₎ ₆ PNiMouO ₄₀ M (NH ₄₎ ₆ SiCoMonO ₄₀ H ₂ (NH ₄₎ ₆ CO ₃ PCoMo _n 0 ₄ oH, Co ₃ PNiMo _M O ₄₀ H whose preparation is precisely described in the application FR 2.764.21 1. The heteropolyanions described in the patent application FR 2.764.21 1 are advantageous because they have an atomic ratio between the group VIII element and group VI up to 0.5.

Keggin heteropolyanions of formula XMi ₂ O ₄₀ ^{q '} where X is selected from phosphorus, silicon and boron and M is selected from molybdenum and / or tungsten with cobalt and / or nickel as counter ions have been described in US Patent 2,547,380 and FR 2,749,778. In particular, US Pat. No. 2,547,380 teaches the beneficial use in hydrotreatment processes of heteropoly acid salts of Group VIII metals such as cobalt or nickel salts of phosphomolybdic, silicomolybdic, phosphotungstic or silicotungstic acids for hydrotreatment applications. By way of example, it is possible to use nickel phosphotungstate of formula 3 / 2Ni ²⁺ PWi ₂ O ₄₀ ^{3 "} with a Ni / W ratio of 0.125 and cobalt phosphomolybdate of formula 3 / 2Co ²⁺ _, PMo _I2 O ₄₀ ^{3 "} . A method of preparation is particularly described in the patent application FR 2749778 for the specific preparation of heteropoly C07 / 2PM012O40, C04S1M012O ₄ 0, C07 2S1M012O40 and Co PMo ₆ _I2 0 ₄ o, which are particularly suitable as the metallic particles trapped in the matrix included in each of the spherical particles of the material prepared according to the method of the invention. The heteropoly compounds disclosed in the patent application FR 2,749,778 have the advantage, in particular compared with those disclosed in US Pat. No. 2,547,380, of presenting atomic ratios (Group VIII element / Group VI element) higher than those of US Pat. thus lead to more efficient catalysts. This increase in the ratio is obtained by reducing the HPA. Thus, the presence of at least a portion of the molybdenum or tungsten is at a valence lower than its normal value of 6 as resulting from the composition, for example, phosphomolybdic, phosphotungstic, silicomolybdic or silicotungstic acid.

Heteropolyanions having a gap Keggin structure and particularly suitable for the preparation of the material according to the process of the invention are described in the patent application FR 2 935 139. They have the formula _{Ni +} y ₂ Wu. _Y 0 ₃₉ .5 / 2y, bH ₂ 0 wherein Ni is nickel, X is selected from phosphorus, silicon and boron, W is tungsten, O is the oxygen, y = 0 or 2, a = 3.5 if X is phosphorus, a = 4 if X is silicon, a = 4.5 if X is boron and b is a number between 0 and 36. Said heteropolyanions do not have any nickel atom in substitution for a tungsten atom in their structure, said nickel atoms being placed in the counter-ion position in the structure of said heteropolyanion. These heteropolyanion salts are advantageous because of their high solubility. Preferred heteropolyanions according to the teaching of the patent application FR 2 935 139 for the preparation of the material according to the process of the invention have the formula NUSiWnC ^ and Ni _7/2 PW _n 0 ₃ 9.

A third preferred category of heteropolyanions (third embodiment of the material prepared according to the process of the invention) advantageously trapped in the matrix included in each of said spherical particles of the material prepared according to the process of the invention is such that said heteropolyanions present the formula P ₂ Mo ₅ 0 ₂ 3H _h ^{(6'h) "} , with h = 0, 1 or 2. Such heteropolyanions are called Strandberg heteropolyanions The preparation of Strandberg HPAs is described in the WC article. Cheng et al J. Catal., 1988, 109, 163. It has thus been shown by JA Bergwerff, et al, Journal of the American Chemical Society 2004, 126, 44, 14548, that the use of the heteropolyanion P ₂ Mo ₅ 0 ₂₃ h _h ^{(6 "h)"} was particularly advantageous for hydrotreating applications.

Advantageously, the elementary spherical particles constituting said inorganic material prepared according to the process of the invention comprise metal particles in the form of heteropolyanions chosen from the first, second and / or third category described above. In particular, said metal particles may be formed of a mixture of HPA of different formulas belonging to the same category or a mixture of HPA belonging to different categories. For example, it is advantageous to use alone or in combination HPA type with HPA Keggin type ΡΜθ | ₂ 0 ₄ ο ^{3 "} , PCoMon0 ₄ oH ^6" and P2M05O23H2 ^{4 '} goods known to those skilled in the art.

According to another embodiment of the material prepared according to the method of the invention, the metal particles trapped in the silicon oxide-based matrix included in each of said spherical particles are oxide nanoparticles characterized by the presence of at least one A wave number band varying between 750 and 1050 cm ^-1 in Raman spectroscopy, said nanoparticle oxides comprise at least one metal selected from vanadium, niobium, tantalum, molybdenum, tungsten and the mixture of these metals. Very preferably, said oxide nanoparticles comprise at least one metal chosen from molybdenum and tungsten and the mixture of these two metals, said metal chosen from vanadium, niobium, tantalum, molybdenum and tungsten, and their mixture. , preferentially molybdenum or tungsten, are in an oxygenated environment, said nanoparticles oxides being for example these monomolybdiques, monotungstiques of species, species or polymolybdiques polytungstic species. Such species, in particular polymolybdate species, are described by SB Umbarkar et al., Journal of Molecular Catalysis A: Chemical, 310, 2009, 152. Said oxide nanoparticles have a size of less than or equal to 3 nm, preferentially strictly less than 1 nm and greater than or equal to 0.3 nm. Said metal nanoparticles are prepared using monometallic precursors such as those described hereinafter in the disclosure of the invention. According to step a) of the preparation process according to the invention, at least one structuring agent and at least one silicic precursor are mixed so as to prepare a solution containing the precursor elements of proton entities. zeolite. The silicic precursor used for the implementation of said step a) for the preparation of said proto-zeolite entities is chosen from the precursors of silicon oxide well known to those skilled in the art. In particular, a silicic precursor chosen from the silica precursors normally used in the synthesis of zeolites is advantageously used, for example solid powdered silica, silicic acid, colloidal silica, dissolved silica or an alkoxide type silicic precursor of formula Si (OR) ₄ . _is R _'where R = H, methyl, ethyl and R' is an alkyl chain or a functionalized alkyl chain, a is between 0 and 4 such as tetraethoxysilane also known as tetraethylorthosilicate (TEOS). Preferably, the silicic precursor is TEOS. The structuring agent used for the implementation of said step a) for the preparation of said proto-zeolite entities may be ionic or neutral depending on the nature of the zeolite obtained from said proto-zeolite entities. It is common to use the organic structuring agents of the following non-exhaustive list: nitrogenous organic cations such as tetrapropylammonium (TPA), ethercouronnes, diamines and any other organic structuring agent well known to those skilled in the art for zeolite synthesis. Preferably, said organic structuring agent is tetrapropylammonium hydroxide TPAOH.

Said step a) is advantageously carried out in the presence of at least one precursor of at least one Y element chosen from aluminum, iron, boron, indium and gallium. Said precursor of the element Y advantageously used for the implementation of said step a) for the preparation of said protozeolithic entities may be any compound comprising the element Y and able to release this element in solution, especially in aqueous or aquo-organic solution, in reactive form. In the preferred case where Y is aluminum, the aluminum precursor is advantageously an inorganic aluminum salt of formula A1Z ₃ , Z being a halogen, a nitrate or a hydroxide. Preferably, Z is chlorine. The aluminum precursor may also be an aluminum sulphate of formula A1 ₂ (SO ₄ ) 3. The aluminic precursor can also be an organometallic precursor of formula Al (OR) ₃ or R = ethyl, isopropyl, n-butyl, s-butyl (Al (O ^s C ₄ H ₉ ) ₃ ) or t-butyl or a chelated precursor such as aluminum acetylacetonate (A1 (C ₅ H ₈ O 2) 3). Preferably, R is s-butyl. The aluminum precursor may also be ammonium aluminate or alumina proper in one of its crystalline phases known to those skilled in the art (alpha, delta, teta, gamma), preferably in hydrated form. or that can be hydrated. It is also possible to use mixtures of the precursors mentioned above. Some or all of the aluminic and silicic precursors may optionally be added in the form of a single compound comprising both aluminum atoms and silicon atoms, for example an amorphous alumina silica.

The solution containing the precursor elements of said proto-zeolite entities according to step a) of the preparation process according to the invention is generally obtained by preparing a reaction mixture containing at least one silicic precursor, optionally at least one precursor of at least one Y element chosen from aluminum, iron, boron, indium and gallium, preferably at least one aluminic precursor, and at least one structuring agent, preferably of organic nature. The reaction mixture is either aqueous or aqueous-organic, for example a water-alcohol mixture. The reaction mixture may be placed under hydrothermal conditions under autogenous pressure, optionally adding a gas, for example nitrogen. Said step a) is preferably carried out at a temperature between room temperature and 200 ° C, preferably between room temperature and 170 ° C and still more preferably at a temperature that does not exceed 120 ° C and even more preferred at a temperature which does not exceed 60 ° C until the formation of a solution containing the proto-zeolite entities constituting the microporous walls of the matrix of each of the spherical particles of the material obtained according to the method of the invention. According to a preferred procedure, the reaction mixture containing at least said structuring agent, at least said silicic precursor and advantageously at least said precursor of at least one Y element chosen from aluminum, iron, boron, indium and the gallium is cured at room temperature so as to obtain a solution containing the proto-zeolite entities constituting the microporous walls of the matrix of each of the spherical particles of the material obtained according to the method of the invention. Said proto-zeolite entities are capable of generating the formation of crystallized zeolite entities during the e) autoclaving step of the secondary process according to the invention.

According to said step a) of the preparation process according to the invention, it is preferred to work in a basic reaction medium in order to promote the development of the proto-zeolite entities constituting the microporous walls of the matrix of each of the particles of the material obtained according to the process of the invention. The basicity of the solution is advantageously ensured by the basicity of the structuring agent used.

According to step a) of the preparation process according to the invention, the solution containing the precursor elements of protozeolitic entities is produced from operating protocols known to those skilled in the art. For example, for a material obtained according to the process of the invention, in particular according to the process main invention according to the invention respectively according to the secondary method according to the invention, the matrix of each spherical particle consists of proto-zeolitic entities respectively zeolitic entities of beta type, a solution containing precursor elements of proton entities. zeolitic beta type is carried out from the operating protocol described by P. Prokesova, S. Mintova, J. Cejka, T. Bein et al., Micropor. Mesopor. Mater., 2003, 64, 165. For a material obtained according to the process of the invention, in particular according to the main process according to the invention respectively according to the secondary process according to the invention, in which the matrix of each spherical particle is constituted. of proto-zeolitic entities respectively of FAU-type zeolite entities, a solution containing precursor elements of proto-zeolitic FAU-type entities is produced from the operating protocols described by Y. Liu, Zhang WZ, TJ Pinnavaia et al. J. Am. Chem. Soc., 2000, 122, 8791 and. R. Kloetstra, HW Zandbergen, JC Jansen, H. VanBekkum, Microporous Mater., 1996, 6, 287. For a material obtained according to the process of the invention, in particular according to the main process according to the invention respectively according to the process secondary, according to the invention, whose matrix of each spherical particle is made up of proto-zeolite entities respectively zeolitic entities of ZSM-5 type, a solution containing precursor elements of proto-zeolitic entities of ZSM-5 type is made from the operating protocol described by AE Persson, BJ Schoeman, J. Sterte, J.-E. Otterstedt, Zeolites, 1995, 15, 61 1. For a material obtained according to the process of the invention, in particular according to the main process according to the invention respectively according to the secondary process according to the invention, the matrix of each spherical particle consists of proto-zeolitic entities respectively of zeolitic entities of silicalite type, a solution containing precursor elements of proto-zeolitic entities of silicalite type is made from the operating protocol described AE Persson, BJ Schoeman, J. Sterte, I. Otterstedt, Zeolites, 1994, 14, 557.

The proto-zeolitic entities obtained by the implementation of said step a) of the process according to the invention, in particular by the implementation of said step a) of the secondary process according to the invention, are intermediate species at formation zeolite entities and in particular to zeolite nanocrystals. The transformation of the proto-zeolitic entities constituting the amorphous microporous walls of the material obtained at the end of step d) of the secondary process according to the invention is the result of the autoclaving step e) of said secondary process according to the invention which leads to the formation of crystallized microporous walls consisting entirely of zeolite entities as described above. The transformation of protozeolitic entities into zeolitic entities is followed by the analysis method known to those skilled in the art of X-ray diffraction at large angles (no response for amorphous microporous inorganic materials obtained according to the main preparation method according to the invention and detection of signals corresponding to at least the smallest detectable crystalline entities for the crystallized microporous inorganic materials obtained according to the secondary method according to the invention). According to step b) of the preparation process according to the invention, said metal particles or their precursors are mixed with at least one surfactant and at least said solution obtained according to said step a) in a medium that is preferably aqueous or aquo-organic. According to step b) of the preparation process according to the invention, the surfactant used is an ionic or nonionic surfactant or a mixture of both. Preferably, the ionic surfactant is chosen from anionic surfactants such as sulphates, for example sodium dodecyl sulphate (SDS). Preferably, the nonionic surfactant may be any copolymer having at least two parts of different polarities conferring properties of amphiphilic macromolecules. These copolymers advantageously belong to one of the following families of polymers: fluorinated copolymers (- [CH ₂ -CH ₂ -CH ₂ -CH ₂ -O-CO-R 1 with R 1 = C ₄ F ₉ , C ₈ F ₁₇ , etc.), biological copolymers such as polyamino acids (poly-lysine, alginates, etc.), dendrimers, block copolymers consisting of poly (alkylene oxide) chains. Any other amphiphilic copolymer known to a person skilled in the art may be used if it makes it possible to obtain a stable solution (ie not leading to the formation of a precipitate in the time preceding the atomization) in step b) of the preparation process according to the invention, such as poly (styrene-b-acrylamide) for example (S. Fôrster, M. Antionnetti, Adv.Mater, 1998, 10, 195-217; Forster, T. Plantenberg, Angew Chem Ed, 2002, 41, 688-714, H. Colfen, Macromol Rapid Rapid, 2001, 22, 219-252). In the context of the present invention, a block copolymer consisting of poly (alkylene oxide) chains is preferably used. Said block copolymer is preferably a block copolymer having two, three or four blocks, each block consisting of a poly (alkylene oxide) chain. For a two-block copolymer, one of the blocks consists of a poly (alkylene oxide) chain of hydrophilic nature and the other block consists of a poly (alkylene oxide) chain of a nature hydrophobic. For a copolymer with three blocks, at least one of the blocks consists of a chain of poly (alkylene oxide) hydrophilic nature while at least one of the other blocks consists of a poly ( alkylene oxide) of hydrophobic nature. Preferably, in the case of a three-block copolymer, the hydrophilic poly (alkylene oxide) chains are poly (ethylene oxide) chains denoted (PEO) _x and (PEO) _z and the Poly (alkylene oxide) chains of hydrophobic nature are chains of poly (propylene oxide) denoted (PPO) _y , poly (butylene oxide) chains, or mixed chains, each chain of which is a mixture of several alkylene oxide monomers. Very preferably, in the case of a three-block copolymer, a compound consisting of two poly (ethylene oxide) chains and a poly (propylene oxide) chain is used. More specifically, use is made of a compound of formula (PEO) _x - (PPO) _y - (PEO) _z where x is between 5 and 300 and y is between 33 and 300 and z is between 5 and 300. Preferably , the values of x and z are identical. A compound is advantageously used in which x = 20, y = 70 and z = 20 (P123) and a compound in which x = 106, y = 70 and z = 106 (F127). Commercial nonionic surfactants known as Pluronic (BASF), Tetronic (BASF), Triton (Sigma), Tergitol (Union Carbide), Brij (Aldrich) are useful as nonionic surfactants in step b ) of the preparation process of the invention. For a four-block copolymer, two of the blocks consist of a poly (alkylene oxide) chain of hydrophilic nature and the other two blocks consist of a chain of poly (alkylene oxide) hydrophobic nature. Any blowing agent which makes it possible to modify the size of the micelles may advantageously be added with the surfactant. For example, said blowing agent is polypropylene glycol.

According to said step b) of the preparation process according to the invention, said metal particles or at least one metal precursor of said metal particles are introduced into said mixture. Said metal particles are chosen from metal particles in the form of polyoxometalate of formula (X _x M _m O _y H _h) ^{q "(I),} particularly isopolyanions or heteropolyanions as described above in the present description, and oxide nanoparticles as described above in the present description. Said particles metal are prepared according to synthetic methods known to those skilled in the art or commercially available.

Said metal particles are easily prepared by dissolving, prior to said step b), the metal precursor (es) necessary to obtain them, in a solvent, said solution being then introduced into the mixing according to said step b). Preferably, the solvent used for the dissolution of the precursor (s) is aqueous. The solution obtained after the solution (es) precursor (s) metal (s), prior to step b), containing said precursors, is clear and neutral pH or acid, preferably acid. Said metal particles may also be advantageously prepared by directly introducing the metal precursor (s) necessary (s) to obtain them in the mixture according to said step b).

In a general manner and in a manner known to those skilled in the art, the isopolyanions are formed by reaction oxoanions type M0 ₄ ^{n "} (the value of n depending on the nature of the metal M: n being preferably equal to 2 when M = Mo or W and preferably equal to 3 when M = V, Nb, Ta) between them where M is one or more elements chosen from vanadium, niobium, tantalum, molybdenum, tungsten, cobalt and nickel. example, molybdic compounds are well known for this kind of reactions, since according to the pH, molybdic compound solution may be in the form _4n Mo0 ^{2 'or} in the form of a isopolyanion Mo ₇ 0 ₂ 4 ^{6 "obtained} according to the reaction: 7 MoO ₄ ^{2 "} + 8H ⁺ → Mo ₇ 0 ₂ 4 ^6" + 4H ₂ 0. Concerning the tungsten-based compounds, the potential acidification of the reaction medium can lead to the generation of Γα-metatungstate, 12 times condensed: 12 W0 ₄ ^{2 '} + 18 H ⁺ → H ₂ Wi ₂ 0 ₄ o ^{6 "} + 8 H ₂ 0. These esp Isopolyanion species, in particular species Mo ₇ 0 ₂₄ ^{6 '} and H ₂ W ₁₂ O ₀ ^{6 "} are advantageously employed as metal particles in the preparation process according to the invention. The preparation of isopolyanions is amply described in Heteropoly and Isopoly Oxometallates, Pope, Ed Springer-Verlag, 1983 (Chapter II, pages 15 and 16).

In a general manner and in a manner known to those skilled in the art, the heteropolyanions are obtained by polycondensation of oxoanions of M0 ₄ ^{n "type} (the value of n depending on the nature of the metal M: n being preferably equal to 2 when M = Mo or W and preferentially equal to 3 when M = V, Nb, Ta) around one (or more) oxoanion (s) of the type X0 ₄ ^{q "} , (the value of q depending on the nature of M, the charge q being dictated by the byte rule and the nature of X), M being one or more elements selected from vanadium, niobium, tantalum, molybdenum, tungsten, cobalt and nickel and X being a element selected from P, Si, B, Ni and Co. There is then removal of water molecules and creation of oxo bridges between the X and M atoms. These condensation reactions are governed by various experimental factors such as pH, concentration of the species in solution, the nature of the solvent, and the ratio of the number of atoms M / X. The preparation of heteropolyanions is amply described in Heteropoly and Isopoly Oxometallates, Pope, Ed Springer-Verlag, 1983 (Chapter II, pages 15 and 16).

Particular modes of preparation of heteropolyanions which can advantageously be used for the synthesis of the metal particles used in said step b) of the preparation process according to the invention are described in patent applications FR 2.935.139, FR 2.764.21 1, FR 2.749.778 and FR 2.843.050. Other particular methods of preparation of heteropolyanions as metal particles used in the preparation method according to the invention are described in the various publications indicated above for the description of the different categories of HPA.

For example, for the implementation of said step b) of the process according to the invention, the metal particles in the form of polyoxometallate of formula (I), preferentially in the form of heteropolyanions, are easily prepared from the metal precursors necessary to obtain them, which are either put in solution, prior to the implementation of said step b), in a solvent before being introduced into said mixture according to step b) are introduced directly into said mixture according to step b). In the case where said metal precursors are dissolved in a solvent, preferably aqueous, prior to the implementation of said step a), the solution obtained is clear and of neutral or acidic pH, preferably acidic. Said metal particles, preferably heteroplyanions, can also be used in solid and isolated form, and can be introduced directly into the mixture according to said step b) of the preparation process according to the invention or be dissolved in a preferably aqueous solvent before to be introduced into said mixture according to said step b).

According to the embodiment consisting in dissolving the metal precursors of the polyoxometalates of formula (I) prior to the implementation of said step b), it is advantageous to add to the solution, containing said precursors, at least one agent complexing said metal precursors to facilitate obtaining in step b) an atomizable mixture for the implementation of said step c) of the preparation process according to the invention. Said complexing agent may be any compound known to those skilled in the art for its possible complexation with metal precursors of the HPA type. For example, said complexing agent is urea, thiourea or acetylacetonate.

According to the particular embodiment in which said metal particles are oxide nanoparticles as described above in the present description, the preparation of said nanoparticles is carried out by dissolving, prior to said step b), the precursor (es) ( s) metal (s) necessary (s) to obtain them in a solvent, said solution then being introduced into the mixture according to said step b). Preferably, the solvent used for the dissolution of the precursor (s) is aqueous. The precursors employed are monometallic precursors. According to this embodiment, at least a first monometallic precursor based on a metal chosen from vanadium, niobium, tantalum, molybdenum and tungsten, is put in solution prior to the implementation of said step b ). Preferably, said first monometallic precursor is based on molybdenum or tungsten. It is advantageous to use at least two metal precursors, each of said precursors being based on a different metal chosen from vanadium, niobium, tantalum, molybdenum and tungsten. Thus, a mesostructured inorganic material is obtained in which nanoparticles based on a metal chosen from vanadium, niobium, tantalum, molybdenum and tungsten and other nanoparticles based on another metal chosen from vanadium. , niobium, tantalum, molybdenum and tungsten are trapped in the matrix based on silicon oxide. For example, a molybdenum precursor and a tungsten precursor are advantageously used. in order to trap molybdenum-based nanoparticles and nanoparticles based on tungsten in the matrix based on silicon oxide.

In the preferred case where said nanoparticles comprise tungsten and / or molybdenum, the monometallic precursors formed from the following species are advantageously used in the process according to the invention: the alkoxide or phenolate type species (WO bond, Mo-O bond) , the amide-type species (W-NR ₂ bond, Mo-NR ₂ bond), the halide species (W-Cl bond, Mo-Cl bond for example), the imido-type species (W = NR bond, Mo = NR bond), the oxo type species (W = 0 bond, Mo bond = 0), the hydride type species (WH bond, Mo-H bond). Advantageously, said first monometallic precursor is chosen from the following species: (NH ₄ ) ₂ M0 ₄ (M = Mo, W), Na ₂ M0 ₄ (M = Mo, W), H ₂ MoO ₄ , (NH ₄ ₂ MS ₄ (M = Mo, W), MoO ₂ Cl ₂ , MoCl ₄ , MoCl ₅ , W (OEt) ₅ , W (Et) ₆ , WCl ₆ , WCl ₄ , WCl ₂ , WPhCl ₃ . Advantageously, a first monometallic precursor based on molybdenum, for example MoCl _{5, is used} . However any monometallic precursor well known to those skilled in the art can be used. Said metal particles or their precursors are introduced into the mixture according to said step b) in an amount such that the mass content of vanadium, niobium, tantalum, molybdenum, tungsten and their mixtures is between 1 and 40% expressed in% by weight of oxide with respect to the mass of the final inorganic material in oxide form, preferably between 4 and 35% by weight, preferably between 4 and 30% by weight and even more preferably between 4 and 20% by weight and such that the mass content Group VIII metal total, in particular cobalt and nickel, is between 0 and 15% expressed in% by weight of oxide relative to the weight of the final inorganic material in oxide form, preferably between 0.5 and 10% by weight and even more preferably between 1 and 8% by weight.

The solution obtained at the end of step b) of the preparation process according to the invention may be acidic, neutral or basic. Preferably, said solution is neutral, slightly acidic or slightly basic, that is to say that it preferably has a pH of between 5 and 9. The solution obtained at the end of step b) can be aqueous or may be a water-organic solvent mixture, the organic solvent preferably being a polar solvent, especially an alcohol, preferably ethanol. The amount of organic compounds, that is to say in surfactant and structuring agent, present in the mixture obtained at the end of the implementation of said step b) of the preparation process according to the invention is defined with respect to the amount of inorganic material present in said mixture. The amount of inorganic material corresponds to the quantity of material of the metallic elements introduced by means of the metal precursors defined above or by means of the metal particles themselves, to the amount of silicon material introduced by means of said silicic precursor and to that of of the element Y introduced by means of said precursor of the element Y when it is present. The volume ratio V _inorgan _that j / V j _organ _in the mixture obtained after the implementation of step b) is such that the organic-inorganic binary system formed during the atomizing step c) of method Preparation according to the invention leads to an unorganized porosity on the scale of mesoporosity via nonorganization of the organic phase generated by the presence of the surfactant together with the hydrolysis / condensation reactions of the various inorganic precursors. Said volume ratio

_i / ft _"gold gi) / Σ _j _(RGJ mo / _org p _j) with i varying from 1 to the total number of the inorganic precursors and j varying from 1 to the total number of surfactants and structuring agents and wherein m _inorg is the mass of the oxide associated with the inorganic precursor i condensed in the solid elementary particle obtained by atomization, m _{org j} is the mass of the surfactant or nonvolatile structuring agent found in the solid elementary particle obtained by atomization and p _org j and p _{inorg j} are the densities respectively associated with each of the nonvolatile and inorganic organic compounds i. The density of the oxide associated with the inorganic precursor i is equal to the density of the corresponding crystalline oxide decreased by 15%. In the context of the invention, Σj (m _inorg / p _inorg j) generally corresponds to the sum of the mass ratios of the oxides of at least one element selected from vanadium, niobium, tantalum, molybdenum, tungsten, iron, copper, zinc, cobalt and nickel supplemented with the masses of SiO ₂ and the oxide of element Y, preferably of Al ₂ O ₃ , on their respective densities. Similarly, Σ _j (m _{org j} / p _{org j} ) generally corresponds to the sum of the ratios of the mass of the structuring agent, for example TPAOH, added with the mass of the surfactant, for example the surfactant PI 23 on their density. respectively. The possible use of a complexing agent for metal precursors of polyoxometalates is also taken into account in the calculΣ _j (m _0, _BJ / w _{org j)} - The polar solvent preferably ethanol and water n ' are not taken into account in the calculation of said _inorganic V / _organic V ratio. The species comprising an element Y, preferably the alumina species, optionally introduced at a stage subsequent to said step b) of the preparation process according to the invention, as described later in the present description, are not taken into account. for calculating the volume ratio V r _in0 aiiique _g / organic defined above.

Conversely, if inorganic precursors other than those mentioned above are present in the mixture at the end of step b) of the preparation process, the mass of the associated oxides is to be taken into account in the calculation of V _inorg .

According to the invention, the amount of organic matter and the amount of inorganic material in the mixture after the implementation of step b) are such that the ratio Vi _"organ _that i / V _organiquc ranges between 0.09 and 0.28 and preferably between 0.15 and 0.28.

According to step b) of the process according to the invention, the initial concentration of surfactant, introduced into the mixture, defined by c ₀ is such that c ₀ is less than or equal to c _mc , the parameter c _mc representing the micellar concentration criticism well known to those skilled in the art, that is to say the limit concentration beyond which occurs the phenomenon of self-arrangement of surfactant molecules in the solution. Before atomization, the concentration of surfactant molecules in the solution defined by step b) of the preparation process according to the invention therefore does not lead to the formation of particular micellar phases. In a preferred implementation of the method according to the invention, concentration c ₀ is less than c _mc, the ratio Vinorganique / _year _or g j _that is such that the composition of the binary system verifies the composition conditions for which the porosity is not organized on the scale of the mesoporosity via a non-organization of the organic phase generated by the presence of the surfactant in conjunction with the hydrolysis / condensation reactions of various inorganic precursors (Vj _Norgan ic / V _organ _qiie i is 0, 09 and 0.28 and preferably between 0.15 and 0.28) and said solution referred to in step b) of the preparation process according to the invention is a water-alcohol mixture.

In the case where the solution referred to in step b) of the preparation process according to the invention is a water-organic solvent mixture, it is essential during step b) of the preparation process according to the invention that the the concentration of surfactant is less than the critical micelle concentration and the organic organic ratio is between 0.09 and 0.28 and preferably between 0.15 and 0.28 so that the evaporation of said aqueous-organic solution, during step c) of the preparation process according to the invention by the aerosol technique induces an unorganized porosity on the scale of the mesoporosity via nonorganization of the organic phase generated by the presence of the surfactant together with the hydrolysis / condensation reactions of the various inorganic precursors. The observation of the unorganized porosity is consecutive to a progressive concentration, within each droplet, of the metal precursor (s) or metal particles themselves, of the silicic precursor, optionally of the precursor of the element Y, preferably of the precursor aluminum and surfactant resulting from evaporation of the aqueous-organic solution, to a concentration of reagents sufficient to cause said phenomenon of non-organization described above in the present description.

The step of atomizing the mixture according to step c) of the preparation process according to the invention produces spherical droplets. The size distribution of these droplets is lognormal. The aerosol generator used here is a commercial model 9306A device provided by TSI having a 6-jet atomizer. The atomization of the solution is carried out in a chamber in which a carrier gas, a 0 ₂ / N ₂ (dry air) mixture, is sent at a pressure P equal to 1.5 bar. The diameter of the droplets varies depending on the aerosol apparatus employed. In general, the droplet diameter is between 150 nm and 600 microns. According to step d) of the preparation process according to the invention, said droplets are dried using the aerosol tool. This drying is carried out by transporting said droplets via the carrier gas, the O ₂ / N ₂ mixture, in PVC tubes, which leads to the gradual evaporation of the solution, for example from the aquo-organic solution obtained in FIG. during step b) of the preparation process according to the invention, and thus to obtain spherical elementary particles. This drying is perfect by a passage of said particles in an oven whose temperature can be adjusted, the usual range of temperature ranging from 50 to 600 ° C and preferably from 80 to 400 ° C, the residence time of these particles in the oven being of the order of the second. The particles are then harvested on a filter. A pump placed at the end of the circuit promotes the routing of species in the aerosol experimental device. The drying of the droplets according to step d) of the process according to the invention is advantageously followed by a passage in an oven at a temperature between 50 and 1 0 ° C.

According to step g) of the preparation process according to the invention, the elimination of at least said structuring agent and at least said surfactant, in order to obtain the hierarchically porous inorganic material, is advantageously carried out by chemical extraction or by heat treatment and preferably by calcination under air in a temperature range of 300 to 1000 ° C and more precisely in a range of 400 to 600 ° C for a period of 1 to 24 hours and preferably for a period of 2 to 12 hours.

According to the preparation method according to the invention, at least one precursor of at least one Y element chosen from aluminum, iron, boron, indium and gallium, preferably aluminum, is advantageously introduced at one or more stages subsequent to said step a) of the preparation process. According to a first embodiment, at least one precursor of at least one element Y is introduced for the implementation of said step b) of the preparation method of the invention. Thus, the solution mixture of at least one surfactant, at least said solution obtained according to step a) and at least said metal particles or their precursors is produced in the presence of at least one precursor of said element Y chosen from the precursors of said element Y cited above, preferably from the aluminum precursors, described above in the present description for the implementation of said step a) of the preparation process of the invention. According to said first embodiment, the preparation of the solution according to step a) of the process of the invention is carried out either in the presence or in the absence of at least one precursor of at least one element Y. According to a second embodiment at least one precursor of at least one element Y is introduced subsequently to the implementation of said step d) and / or subsequent to the implementation of said step g) of the method of the invention, in order to produce a surface modification of the material obtained according to the preparation method of the invention. According to said second embodiment, said precursor of at least one element Y, preferably an aluminic precursor, is introduced subsequently to the implementation of said step d) and / or in a manner subsequent to the implementation of said step g) the method of the invention by any surface modification technique well known to those skilled in the art such as the grafting of at least one precursor of at least one Y element, the dry impregnation of at least one a precursor of at least one element Y and the impregnation in excess of at least one precursor of at least one element Y. Said precursor of at least one element Y, preferably an aluminic precursor, introduced according to said second mode by a surface modification technique, is chosen from the precursors of said element Y, preferably from the aluminum precursors, described above in the present description, together with the sodium aluminate precursor, for the m implementation of said step a) of the method of the invention. According to said second embodiment, step a) of the process of the invention is carried out in the presence or in the absence of at least one precursor of at least one Y element, preferably an aluminum precursor, and step b ) of the process of the invention is carried out in the presence or in the absence of at least one precursor of at least one element Y, preferably an aluminum precursor.

According to the preparation method according to the invention, said first mode and said second mode of introduction of at least one precursor of at least one element Y are only optional variants of the preparation method according to the invention. Also, when the matrix based on silicon oxide present in each of the spherical particles of the material obtained according to the preparation process of the invention comprises an element Y, preferably aluminum, said element Y is introduced either during of said step a) of the preparation method of the invention, either during said step b) in accordance with said first mode or again after the implementation of said step d) and / or subsequent to the implementation implementation of said step g) of the preparation process according to the invention according to said second mode. The element Y, preferably aluminum, can also advantageously be introduced, several times, at different stages according to all the possible combinations of the modes described above. In particular, it is advantageous to introduce the aluminum during said step a) and said step b) or during said step a) and so subsequent to the implementation of said step d) and / or subsequent to the implementation of said step g).

In the particular case where the element Y is aluminum, the aluminosilicate obtained according to the preparation method according to the invention then has a Si / Al molar ratio defined from the amount of silicon element introduced during the step a) the preparation method according to the invention and the total amount of aluminum element introduced into the step (s) of the preparation process of the invention according to the various modes described above. Under these conditions and preferably, the value of the Si / Al molar ratio is at least 0.02, preferably between 0.1 and 1000 and very preferably between 1 and 100.

When said first mode is applied (Y introduced for the implementation of said step b), the amounts of organic and inorganic material to be introduced for the implementation of step b) are to be adjusted according to the amount of material additional element Y, preferably aluminum, introduced during said step b), so that the total amount of organic and inorganic material introduced into the preparation process according to the invention allows to define an _inorganic V ratio / V _organiqu . between 0.09 and 0.28 and preferably between 0.15 and 0.28.

According to said first preferred embodiment of the process according to the invention, called secondary process according to the invention, one proceeds following said step d) to a step e) of practicing the autoclaving of the particles resulting from said step d ) then proceed to a step f) of practicing the drying of said particles obtained at the end of said e). Said step f) is then followed by the implementation of said step g) of removing at least said structuring agent and at least said surfactant. Step e) consists of placing said particles from said step d) in a closed chamber in the presence of a solvent at a given temperature so as to work with autogenous pressure inherent to the operating conditions chosen. The solvent used is advantageously a protic polar solvent. Preferably the solvent used is water. The volume of solvent introduced is defined relative to the volume of the autoclave selected, the mass of dry powder introduced and the treatment temperature. Thus, the volume of solvent introduced is in a range of 0.01 to 20% relative to the volume of the autoclave chosen, preferably in a range of 0.05 to 5% and more preferably in a range of 0. , 05 to 1%. The autoclaving temperature is between 50 and 200 ° C, preferably between 60 and 170 ° C and more preferably between 60 and 120 ° C so as to allow the growth of zeolite entities in the walls of the matrix of each of the particles of the crystallized material obtained by the secondary method of the invention. Autoclaving is maintained for a period of 1 to 96 hours and preferably for a period of 10 to 72 hours. According to step f) of said secondary process according to the invention, the drying of the particles after autoclaving of step e) is advantageously carried out by placing in an oven at a temperature of between 50 and 150 ° C.

In the preferred case where said metal particles, trapped in the matrix included in each of said spherical particles of the material prepared according to the process of the invention, are in the form of polyoxometalate of formula (X _x M _m O _y H _h ) ^{q "} (I), preferentially in the form of heteropolyanions, the preparation process according to the invention advantageously comprises, following the implementation of said step g), a step h) of regenerating said metal particles as polyoxometallate optionally decomposed in step g). Said regeneration step h) is preferably carried out by washing the solid resulting from said step g) with a polar solvent using a Soxhlet extractor. The operation of this type of extractor is well known to those skilled in the art. Preferably, the extraction solvent is an alcohol, acetonitrile, water, preferably an alcohol and very preferably methanol. Said step h) is carried out for a period of 1 to 24 hours, preferably 1 to 8 hours. Said regeneration step h) is carried out when said metal particles in the form of polyoxometalate are decomposed during said step g). The decomposition of said metal particles is demonstrated by Raman spectroscopy which makes it possible to detect the presence or absence of said metal particles in the form of polyoxometalates, preferably in the form of heteropolyanions, as a function of the bands appearing on the Raman spectrum. The decomposition of said metal particles, following the implementation of said step g), may be partial or total. Said step h) is a step of partial or total regeneration of said polyoxometalates. Said step h) is followed by a drying step i) which is advantageously carried out at a temperature between 40 and 100 ° C and very advantageously between 40 and 85 ° C. Said step i) is carried out for a period of between 12 and 48 hours. Said step i) is preferably implemented only when the preparation method according to the invention comprises the implementation of said step h). The process according to the invention advantageously comprises at least one shaping step preferably carried out following said step d) or said step g) in the case where the inorganic material is prepared according to the main process according to the invention or still following said step f) or said step g) in the case where the inorganic material is prepared according to the secondary method according to the invention. The shaping operation of the inorganic material resulting from one of the steps d) or g) if it is prepared according to said main process according to the invention or resulting from one of the steps f) or g) s' it is prepared according to the secondary process according to the invention consists in mixing said material with at least one porous oxide material having the role of binder. Said porous oxide material is preferably a porous oxide material chosen from the group formed by alumina, silica, silica-alumina, magnesia, clays, titanium oxide, zirconium oxide, lanthanum, cerium oxide, aluminum phosphates, boron phosphates and a mixture of at least two of the oxides mentioned above. Said porous oxide material may also be chosen from mixtures of alumina-boron oxide, alumina-titanium oxide, alumina-zirconia and titanium-zirconia oxide. Aluminates, for example aluminates of magnesium, calcium, barium, manganese, iron, cobalt, nickel, copper and zinc, as well as mixed aluminates, for example those containing at least two of the metals mentioned above, are advantageously used as porous oxide material. It is also possible to use titanates, for example titanates of zinc, nickel or cobalt. It is also advantageous to use mixtures of alumina and silica and mixtures of alumina with other compounds such as group VIB elements, phosphorus, fluorine or boron. It is still possible to use simple, synthetic or natural clays of 2: 1 dioctahedral phyllosilicate or 3: 1 trioctahedral phyllosilicate such as kaolinite, antigorite, chrysotile, montmorillonite, beidellite, vermiculite, talc. , hectorite, saponite, laponite. These clays can be optionally delaminated. It is also advantageous to use mixtures of alumina and clay and mixtures of silica-alumina and clay. Similarly, it may be envisaged to use as binder at least one compound selected from the group formed by the family of crystallized aluminosilicate molecular sieves and natural and synthetic zeolites such as zeolite Y, fluorinated zeolite Y, zeolite Y containing rare earths, zeolite X, zeolite L, zeolite beta, small pore mordenite, large pore mordenite, omega zeolites, NU-10, ZSM-22, NU-86, NU-87, NU-88, and zeolite ZSM-5. Among the zeolites, it is usually preferred to employ zeolites whose ratio of silicon / aluminum framework atom (Si / Al) is greater than about 3/1. Zeolites of faujasite structure and in particular stabilized and ultrastabilized Y zeolites (USY) are advantageously employed either in the form at least partly exchanged with metal cations, for example alkaline earth metal cations and / or earth metal cations. rare atomic number 57 to 71 inclusive, or in hydrogen form (Atlas of zeolite framework types, 6 ^th revised Edition, 2007, Ch. Baerlocher, LB McCusker, DH Oison). Finally, at least one compound chosen from the group formed by the family of uncrystallized aluminosilicate molecular sieves such as mesoporous silicas, silicalite, silicoaluminophosphates, aluminophosphates, ferrosilicates, silicoaluminates of aluminum, can be used as porous oxide material. titanium, borosilicates, chromosilicates and aluminophosphates of transition metals (including cobalt). The various mixtures using at least two of the compounds mentioned above are also suitable for acting as binder.

The inorganic material obtained at the end of the shaping operation is advantageously in the form of powder, beads, pellets, granules, or extrudates (hollow or non-hollow rolls, multilobed rolls of 2, 3, 4 or 5 lobes for example, twisted cylinders), rings, etc., these shaping operations being performed by conventional techniques known to those skilled in the art. Preferably, the inorganic material obtained according to the process of the invention is in powder form, which consists of elementary spherical particles having a maximum diameter of 200 μιη.

According to a second preferred embodiment of the preparation method according to the invention, independent or not of said first embodiment and the different variants described above, one or more additional element (s) is (are) introduced ( s) in the mixture according to said step b) of the preparation process according to the invention, and / or by impregnation of the material resulting from said g) with a solution containing at least said additional element and / or by impregnation of the material resulting from said i) with a solution containing at least said additional element and / or by impregnation of the inorganic material, prepared and shaped according to the method of the invention, with a solution containing at least said additional element. Said additional element is chosen from metals of group VIII of the periodic table of elements, organic agents and doping species belonging to the list of doping elements constituted by phosphorus, fluorine, silicon and boron and their mixture. According to said second embodiment of the preparation method according to the invention, one or more additional element (s) as defined above is (are) introduced during the implementation of the method of preparation according to the invention in one or more steps. In the case where said additional element is introduced by impregnation, the dry impregnation method is preferred. Each impregnation step is advantageously followed by a drying step, for example carried out at a temperature of between 90 and 200 ° C., said drying step being preferably followed by a step calcination under air, optionally enriched with oxygen, for example carried out at a temperature between 200 and 600 ° C, preferably between 300 and 500 ° C, for a period of between 1 and 12 hours, preferably between 2 and 6 hours. Impregnation techniques, especially dry impregnation, of a solid material with a liquid solution are well known to those skilled in the art. The doping species chosen from phosphorus, fluorine, silicon and boron do not, in themselves, have any catalytic character but make it possible to increase the catalytic activity of the metal (s) present in said metal particles, especially when the material is in sulphide form.

The sources of Group VIII metals used as precursors of said additional element based on at least one Group VIII metal are well known to those skilled in the art. Of the Group VIII metals, cobalt and nickel are preferred. For example, nitrates such as cobalt nitrate and nickel nitrate, sulphates, hydroxides such as cobalt hydroxides and nickel hydroxides, phosphates, halides (for example, chlorides, bromides and fluorides) will be used. ) and carboxylates (eg acetates and carbonates). According to the particular embodiment in which said metal particles are oxide nanoparticles, said group VIII metal source is used as second monometallic precursor in said step b) of the preparation process according to the invention. More particularly, at least said first metal precursor, preferably at least said first monometallic precursor, based on a metal selected from vanadium, niobium, tantalum, molybdenum and tungsten and at least said second monometallic precursor based on a metal of group VIII preferably selected from nickel and cobalt are dissolved prior to the implementation of said step b), said solution being then introduced into the mixture according to said step b) of the preparation process according to the 'invention. Advantageously, using a first monometallic precursor based on molybdenum, for example MoCl ₅ , or tungsten, for example WC1 ₄ , and a second monometallic precursor based on nickel or cobalt, for example Ni (OH) ₂ or Co (OH) ₂ .

The boron source used as a precursor of said boron dopant species is preferably selected from boron-containing acids, for example orthoboric acid H ₃ B0 ₃ , ammonium biborate, ammonium pentaborate , boron oxide and boric esters. When the metal particles are in the form of heteropolyanions as described above in the present description, the boron may also be introduced at the same time as one or more of the elements M chosen from the list given above (M = vanadium). , niobium, tantalum, molybdenum, tungsten, iron, copper, zinc, cobalt and / or nickel) in the form of heteropolyanions (X = boron in the formula X _x M _m O _y H _h ^{q "} ), especially Keggin heteropolyanions, lacunary eggin, substituted Keggin The following heteropolyanions may be mentioned in particular: boromolybdic acid and its salts, borotungstic acid and its salts, the source of boron in the form of heteropolyanions is then introduced at the same time. step b) of the preparation process according to the invention In the case where the source of boron is introduced by impregnation, said impregnation step with the boron source is carried out using, for example, a boric acid solution in a water / alcohol mixture or in a water / ethanolamine mixture. The source of boron may also be impregnated using a mixture of boric acid, hydrogen peroxide and a basic organic compound containing nitrogen such as ammonia, primary amines and cyclic amines, compounds of the pyridine family and quinolines and compounds of the pyrrole family.

The phosphorus source used as a precursor of said phosphorus-based dopant species is preferably chosen from orthophosphoric acid H ₃ PO ₄ , its salts and esters, such as ammonium phosphates. When the metal particles are in the form of heteropolyanions as described above in the present description, the phosphorus may also be introduced at the same time as one or more of the elements M chosen in the list given above (M = vanadium). , niobium, tantalum, molybdenum, tungsten, iron, copper, zinc, cobalt and / or nickel) in the form of heteropolyanions (X = P in the formula X _x M _m O _y H _h ^{q "} ), in particular heteropolyanions of Keggin, lacunary eggin, substituted Keggin or Strandberg type, which may be mentioned in particular the following heteropolyanions: phosphomolybdic acid and its salts, phosphotungstic acid and its salts, the source of phosphorus in the form of heteropolyanions is then introduced in step b) of the preparation process according to the invention In the case where the phosphorus source is introduced by impregnation, said impregnation step with the phosphorus source is carried out using for example a mixture of phosphoric acid and a basic organic compound containing nitrogen such as ammonia, primary and secondary amines, cyclic amines, compounds of the pyridine family and quinolines and the compounds of the pyrrole family.

Many sources of silicon may be employed as precursors of said silicon-based dopant species. Thus, it is possible to use ethyl orthosilicate Si (OEt) ₄ , siloxanes, polysiloxanes, silicones, silicone emulsions, halide silicates, such as ammonium fluorosilicate (NH ₄ ) ₂ SiF ₆ or sodium fluorosilicate Na ₂ SiF ₆ . When the metal particles are in the form of heteropolyanions as described above in the present description, the silicon can also be introduced at the same time as one or more of the elements M chosen from the list given above (M = vanadium). , niobium, tantalum, molybdenum, tungsten, iron, copper, zinc, cobalt and / or nickel) in the form of heteropolyanions (X = Si in the formula X _x M _m O _y H _h ^{q '} ), in particular heteropolyanions of Keggin, Keggin lacunary, substituted Keggin. Mention may in particular be made of the following heteropolyanions: silicomolybdic acid and its salts, silicotungstic acid and its salts. The silicon source in the form of heteropolyanions is then introduced during step b) of the preparation process according to the invention. In the case where the silicon source is introduced by impregnation, said impregnation step with the silicon source is carried out using, for example, a solution of ethyl silicate in a water / alcohol mixture. The silicon source may be further impregnated using a silicone silicon compound or silicic acid suspended in water.

The fluorine sources used as precursors of said fluorine-based dopant species are well known to those skilled in the art. For example, the fluoride anions can be introduced in the form of hydrofluoric acid or its salts. These salts are formed with alkali metals, ammonium or an organic compound. They are for example introduced during step b) of the preparation process according to the invention. In the case where the fluorine source is introduced by impregnation, said impregnation step with the fluorine source is carried out using for example an aqueous solution of hydrofluoric acid or ammonium fluoride or ammonium bifluoride. The distribution and location of said dopant species chosen from boron, fluorine, silicon and phosphorus are advantageously determined by techniques such as the Castaing microprobe (distribution profile of the various elements), transmission electron microscopy coupled with X analysis (that is to say an EDX analysis which makes it possible to know the qualitative and / or quantitative elemental composition of a sample from the measurement by a diode Si (Li) of the energies of the photons X emitted by the region of the sample bombarded by the electron beam) elements present in the inorganic material prepared according to the method according to the invention, or else by establishing a distribution map of the elements present in said material by electron microprobe . These techniques make it possible to highlight the presence of these doping species. The analysis of the Group VIII metals and that of the organic species as an additional element are generally carried out by elemental X-ray fluorescence analysis.

Said doping species belonging to the list of doping elements constituted by phosphorus, fluorine, silicon, boron and the mixture of these elements is introduced in a quantity such that the total content of doping species is between 0.1 and 10 % by weight, preferably between 0.5 and 8% by weight, and even more preferably between 0.5 and 6% by weight, expressed in% by weight oxide, relative to the weight of the inorganic material prepared according to the process according to the invention . This content is total, that is to say that it takes into account the presence of the element constituting the doping species both as element X in the polyoxometallate particles, in particular in the form of heteropolyanions. , and as a doping species. This is the case in particular for the elements P, Si and B. The atomic ratio between the doping species and the element (s) chosen from V, Nb, Ta, Mo and W is preferably between 0.05 and 0.9, more preferably between 0.08 and 0.8, the doping species and the element (s) chosen from V, Nb, Ta, Mo and W taken into account for the calculation of this ratio corresponding to the total content, in the material prepared according to the method according to the invention, phosphorus and element (s) chosen (s) among V, Nb, Ta, Mo and W regardless of the mode of introduction.

The organic agents used as precursors of said additional element based on at least one organic agent are chosen from organic agents having chelating or non-reducing or non-reducing properties. Said organic agents are, for example, optionally etherified mono-, di- or polyalcohols, carboxylic acids, sugars, non-cyclic mono-, di- or polysaccharides, such as glucose, fructose, maltose, lactose or sucrose, esters. ethers, crown ethers, compounds containing sulfur or nitrogen such as nitriloacetic acid, ethylenediaminetetraacetic acid, or diethylenetriamine.

According to a third preferred embodiment of the preparation method according to the invention, independent or not of said first mode or of said second embodiment and of the different variants described above, at least one sulfur compound is introduced into the mixture according to said step b), or during the implementation of said step g) or during the implementation of said step h) so as to obtain the inorganic material, at least partly but not completely, in sulphide form. Said sulfur compound is chosen from compounds containing at least one sulfur atom and whose decomposition at low temperature (80-90 ° C) causes the formation of H ₂ S. For example, said sulfur compound is thiourea or thioacetamide. According to said third embodiment, the sulphidation of said material is partial so that the presence of sulfur in said inorganic material does not completely affect the presence of said metal particles.

According to the invention, the material obtained according to the process of the invention advantageously has a specific surface area of between 50 and 1100 m ² / g and advantageously between 50 and 600 m ² / g and very preferably between 50 and 400 m ² / g. Said spherical elementary particles constituting the material obtained according to the process of the invention have a maximum diameter equal to 200 μπι, preferably less than 100 μπι, advantageously varying from 50 nm to 50 μηι, very advantageously from 50 nm to 30 μπι and from even more advantageously from 50 nm to 10 μπι. More specifically, they are present in the material obtained according to the process of the invention in the form of aggregates.

The subject of the present invention is also a process for the conversion of a hydrocarbon feedstock comprising 1) bringing the inorganic material obtained in accordance with the preparation method according to the invention into contact with a feedstock comprising at least one sulfur compound and then 2) placing in contact with said material from said step 1) with said hydrocarbon feedstock.

The inorganic material used for the implementation of said step 1) is an amorphous inorganic material if it is obtained according to said main process according to the invention or a crystallized inorganic material if it is obtained according to said secondary process according to the invention .

According to said step 1) of the transformation process according to the invention, the metal particles are sulphurized, in the form of oxide nanoparticles or in polyoxometallate form, preferably in the form of heteropolyanions, trapped within the matrix of each of the particles. spherical constituting the inorganic material prepared according to the process according to the invention. The transformation of said metal particles into their associated sulfide-active phase is carried out after treatment in temperature of said inorganic material obtained according to the process according to the invention in contact with hydrogen sulphide at a temperature of between 200 and 600 ° C. and more preferably between 300 and 600 ° C. and 500 ° C according to methods well known to those skilled in the art. More specifically, said sulfurization step 1) according to the conversion process according to the invention is carried out either directly in the reaction unit of said conversion process using a sulfur-containing filler in the presence of hydrogen and hydrogen sulphide. (H ₂ S) introduced as such or from the decomposition of an organic sulfur compound (in situ sulphurization) or prior to the loading of said material prepared according to the process according to the invention into the reaction unit of said transformation process (ex sulphidation). if you). In the case of ex situ sulfurization, gaseous mixtures such as H ₂ / H ₂ S or N ₂ / H ₂ S are advantageously used for the implementation of said step 1). Said material prepared according to the process according to the invention may also be ex situ sulphurized in accordance with said step 1) from molecules in the liquid phase, the sulphurizing agent then being chosen from the following compounds: dimethyl disulphide (DMDS), dimethyl sulphide , n-butyl mercaptan, polysulfide compounds tertiononylpolysulfide type (for example TPS-37 or TPS-54 marketed by the company ATOFI A), these being diluted in an organic matrix composed of aromatic or alkyl molecules. Said sulfurization step 1) is preferably preceded by a heat treatment step of said inorganic material prepared according to the process of the invention according to methods well known to those skilled in the art, preferably by calcination under air in a range of temperature between 300 and 1000 ° C and more precisely in a range between 500 and 600 ° C for a period of 1 to 24 hours and preferably for a period of 6 to 15 hours.

According to the invention, said hydrocarbon feedstock subjected to the conversion process according to the invention comprises molecules containing at least hydrogen and carbon atoms in a content such that said atoms represent at least 80% by weight, preferably at least 85% weight, of said load. Said molecules advantageously comprise, in addition to hydrogen atoms and carbon atoms, heteroelements, in particular nitrogen, oxygen and / or sulfur. The various processes for converting hydrocarbon feeds in which the inorganic material in sulphurized form, resulting from said step 1), is advantageously used are in particular the hydrotreatment processes, more particularly the hydrodesulphurization and hydrodenitrogenation processes, and hydroconversion processes, more particularly hydrocracking processes, of hydrocarbon feeds comprising saturated and unsaturated aliphatic hydrocarbons, aromatic hydrocarbons, oxygenated organic compounds and organic compounds containing nitrogen and / or sulfur as well as compounds organic compounds containing other functional groups. More particularly, said inorganic material in sulphurized form, resulting from said step 1), is advantageously used in processes for the hydrotreatment of hydrocarbon feeds of gasoline type and middle distillates (gas oil and kerosene) and hydroconversion processes and / or hydrotreating heavy hydrocarbon cuts such as vacuum distillates, desalphated oils, atmospheric residues or vacuum residues. Said inorganic material in sulphurized form, resulting from said step 1), is still advantageously used in a process for hydrotreating a hydrocarbon feedstock comprising triglycerides.

The material obtained according to the preparation method of the invention is characterized by several analysis techniques and in particular by large angle X-ray diffraction (XRD), by nitrogen volumetry (BET), by mercury porosimetry, by Transmission electron microscopy (TEM) with possible coupling to X analysis, scanning electron microscopy (SEM), X-ray fluorescence (FX). The presence of the metal particles as described above in the present description is demonstrated by various techniques, in particular by Raman, UV-visible or infrared spectroscopies as well as by microanalyses. Techniques such as nuclear magnetic resonance (NMR) or electronic paramagnetic resonance (EPR) can also be used according to the metal precursors used. When at least one dopant species chosen from boron, fluorine, phosphorus and silicon is introduced, the assaying analysis techniques of these species are described above in the present description.

The X-ray diffraction technique at large angles (values of the angle 2Θ between 5 and 70 °) makes it possible to characterize a crystalline solid defined by the repetition of a unitary unit or unit cell at the molecular scale. In the following discussion, the X-ray analysis is performed on powder with a diffractometer operating in reflection and equipped with a rear monochromator using copper radiation (wavelength 1.5406 A). The peaks usually observed on the diffractograms corresponding to a given value of the angle 2Θ are associated with the inter-reticular distances d _(hk i ₎ characteristic of the structural symmetry (s) of the material, ((hkl) being the Miller indices of the reciprocal lattice) by the Bragg relation: 2 d ^ _hk i ₎ * sin (θ) = n * λ. This indexing then allows the determination of the mesh parameters (abc) of the direct network. The wide-angle XRD analysis is therefore adapted to the structural characterization of the crystallized zeolite entities when they are constitutive of the matrix wall of each of the elementary spherical particles constituting the material prepared according to the secondary method according to the invention.

Nitrogen volumetry, which corresponds to the physical adsorption of nitrogen molecules in the porosity of the material via a progressive increase in pressure at constant temperature, provides information on textural characteristics (pore diameter, porosity type, specific surface area). of the material obtained according to the process of the invention. In particular, it provides access to the total value of the microporous and mesoporous volume of the material. The appearance of the nitrogen adsorption isotherm and of the hysteresis loop can provide information on the presence of the microporosity related to the proto-zeolitic entities or to the zeolitic entities constituting the respectively amorphous or crystallized walls of the matrix of each spherical particles of the material obtained respectively according to the main process according to the invention or the secondary process according to the invention and on the nature of the mesoporosity. The quantitative analysis of the microporosity of the material obtained according to the process of the invention is carried out using methods "t" (method Lippens-De Boer, 1965) or "a _s " (method proposed by Sing) that correspond to transformants of the starting adsorption isotherm as described in the book "Adsorption by powders and porous solids, Principles, methodology and applications" written by F. Rouquerol, J. Rouquerol and K. Sing, Academy Press, 1999. These methods make it possible to access in particular the value of the microporous volume characteristic of the microporosity of the material obtained according to the method of the invention. The reference solid used is LiChrospher Si-1000 silica (M. Jaroniec, M. Kruck, JP Olivier, Langmuir, 1999, 15, 5410). In addition, this technique provides access to the specific surface and the mesoporous distribution of the material. Specific surface area is understood to mean the BET specific surface area (S _B AND in m ² / g) determined by nitrogen adsorption in accordance with the ASTM D 3663-78 standard established from the BRUNAUER-EMMETT-TELLER method described in the periodical. "The Journal of the American Society", 1938, 60, 309. The representative porous distribution of a mesopore population centered in a range of 2 to 50 nm (IUPAC classification) is determined by the Barrett-Joyner-Halenda (BJH) model. . The nitrogen adsorption-desorption isotherm according to the BJH model thus obtained is described in the periodical "The Journal of the American Society", 1951, 73, 373, written by EP Barrett, LG Joyner and PP Halenda. In the following description, the diameter of the mesospores φ of the matrix based on silicon oxide corresponds to the value of the maximum diameter read on the pore size distribution curve obtained from the adsorption branch of the isothermal nitrogen. The mercury porosimetry analysis corresponds to the intrusion of a volume of mercury characteristic of the existence of mesopores and macropores in the material obtained according to the process of the invention according to the ASTM D4284-83 standard at a maximum pressure of 4000 bars, using a surface tension of 484 dyne / cm, and a contact angle of 140 ° (value chosen according to the recommendations of the book "Technique of the engineer, treated analysis and characterization ", page 1050, written by J. Charpin and B. Rasneur) and the pores are assumed to be cylindrical in shape.This technique is perfectly suited to the analysis of mesoporous and macroporous samples in addition to the analysis technique In particular, this technique makes it possible to access the value of the mesoporous mercury volume (V _Hgn uiso in ml / g) defined as the mercury volume adsorbed by all the pores having a diameter in the range of mesopores namely between 3.6 nm and 50 nm (value of the upper limit as defined by the IUPAC standard) .Also, the macroporous mercury volume (V _Hg m_cro in ml / g) is defined as the mercury volume adsorbed by all pores with a diameter greater than 50 nm Transmission electron microscopy (TEM) is also a technique used to characterize mesoporosity and macropor osité material obtained according to the method of the invention. This allows the formation of an image of the studied solid, the observed contrasts being characteristic of the structural organization, the texture, the morphology or the chemical composition of the particles observed, the resolution of the technique reaching the maximum lnm. In the following description, the TEM photos will be made from microtome sections of the sample in order to visualize a section of an elementary spherical particle of the material obtained according to the method of the invention.

The morphology and size distribution of the elementary particles were established by scanning electron microscopy (SEM) photo analysis.

The metal particles, either in the form of oxide nanoparticles or in the form of polyoxometalates, more preferably in the form of heteropolyanions (HPA), as described above in the present description are in particular characterized by Raman spectroscopy. Raman spectra were obtained with a dispersive Raman spectrometer equipped with a 532 nm exciter wavelength laser. The laser beam is focused on the sample using a microscope equipped with a χ 50 long working distance lens. The laser power at the sample level is of the order of 1 mW. The Raman signal emitted by the sample is collected by the same objective and is dispersed using a 1800 rpm network and then collected by a CCD (Charge Coupled Device). The spectral resolution obtained is of the order of 2 cm ^-1 .The recorded spectral zone is between 300 and 1500 cm ^-1 . The acquisition duration was set at 120 s for each registered Raman spectrum.

Nuclear magnetic resonance spectroscopy (NMR) is also advantageously used to characterize metal particles in the form of polyoxometalates, in particular in the form of HPA. These include ³ 'P and ² Si NMRs recorded on 300 or 400 MHz spectrometers. Nuclear magnetic resonance spectroscopy (NMR), in particular NMR of ^9S Mo and of ¹⁸³ W, is also advantageously used to characterize the metal oxide nanoparticles described above in the present description.

The invention is illustrated by means of the following examples. Examples

In the examples which follow, the aerosol technique used is that described above in the description of the invention. The dispersive Raman spectrometer used is a LabRAM Aramis commercial apparatus supplied by Horiba Jobin-Yvon. The laser used has an excitation wavelength of 532 nm. The operation of this spectrograph, for carrying out the following Examples 1 to 5, has been described above.

For each of Examples 1 to 5 below, one calculates the ratio V i _inorganiqu JV _organ _that the mixture from step b) and containing the metal particles or their precursors, the precursors entities (proto) -zéolithiques and surfactant (P 123 or F127). This report is defined as follows: Vj _norgan i _that / V _organ i _q ue

i / Pinorg i) / Σj (mor _g / p _{org j} ) with i ranging from 1 to the total number of inorganic precursors and ranging from 1 to the total number of surfactants and structuring agents and where m _inorg j is the mass of the oxide associated with the inorganic precursor i condensed in the solid elementary particle obtained by atomization, m _{org j} is the mass of the surfactant or nonvolatile structuring agent found in the solid elementary particle obtained by atomization and p _org and p _inorg j are the densities respectively associated with each of the nonvolatile and inorganic organic compounds i. The density of the oxide associated with the inorganic precursor i is equal to the density of the corresponding crystalline oxide decreased by 15%. for the following examples, Σi (m _{inorg f} / p _itlorg j) generally corresponds to the sum of the mass ratios of oxides Mo0 ₃ , NiO, CoO and / or P ₂ 0 ₅ plus the masses of Si0 ₂ and A1 ₂ 0 ₃ on their respective density. Similarly, Σ _j (m _orgj / p _orgj ) generally corresponds to the sum of the ratios of the mass of the structuring agent, for example TPAOH, added with the mass of the surfactant, that is to say the surfactant P123 or F127, on their respective density. The polar solvent, ie ethanol in Examples 1 to 5, as well as water are not taken into account in the calculation of said ratio inorganiqu </ _organ V j _which; . If inorganic precursors other than those mentioned above are present in the mixture resulting from step b) of the preparation process, the mass of the associated oxides is to be taken into account in the calculation of V _inorg . The complexing agent P2000 used in several of the examples below is taken into account in the calculation _j (m _orgj / p _orgj ).

Example 1 (Invention): Preparation of a Material Having Strandberg HPA H ₂ P ₂ Mo ₅ 0 ₂₃ ^{4 ~} , 2Co ²⁺ , 10 wt% MoO 3, 2.08 wt% CoO and 1 97% by weight of P ₂ 0 ₅ relative to the final material. The matrix is of mesoporous and macroporous porosity whose microporous amorphous walls consist of proto-zeolitic entities based on ZSM-5 (MFI) such that the molar ratio Si / Al = 12.

An aqueous solution containing 3.61 mol / l of M0O3, 1.44 mol / l of H ₃ PO ₄ , 1.44 mol / l of Co (OH) ₂ is prepared with stirring at room temperature. Raman analysis, performed on the final material, reveals the presence of ΗΡΑ Strandberg H ₂ P ₂ Mo ₅ 0 ₂₃ ^{4 "} , 2Co ²⁺ as the majority species.

0.44 g of tri-sec-butoxide of aluminum are mixed with 3.20 g of aqueous TPAOH solution (40% by weight). After stirring for 10 minutes at room temperature, 22.4 g of deionized water are added. After homogenization, 4.43 g of TEOS are added and then allowed to hydrolyze for 16 hours with stirring at room temperature. After the hydrolysis, the solution is diluted with a solution containing 1.46 g of P123 (Sigma-Aldrich), 45.5 g of deionized water and 5.79 g of ethanol. A solution composed of 10 g of permutated water, 0.33 ml of the aqueous solution of Strandberg H2P2M05O23 ^{4 '} , 2Co ²⁺ to 0.72 mol / l in HPA and 0.22 g of thiourea is prepared. After 5 min of stirring, this solution was added to the above solution containing PI 23. The report _inorganic V / V j _organ _that of the mixture is equal to 0.27 and is calculated as described above. The mixture is left stirring for 30 min then is sent into the atomization chamber of the aerosol generator and the solution is sprayed in the form of fine droplets under the action of the carrier gas (dry air) introduced under pressure (P = 1.5 bar). The droplets are dried according to the protocol described in the disclosure of the invention above: they are conveyed via an O2 N2 mixture in PVC tubes. The temperature of the drying oven is set at 350 ° C. The harvested powder is then calcined under air for 5 hours at T = 550 ° C. The HPA is then regenerated by washing with Soxhlet of the solid with methanol for 4 hours. The solid is finally dried at 80 ° C for 24 hours. The solid is characterized by nitrogen volumetry, by mercury porosimetry, by TEM, by SEM, by FX, by Raman spectroscopy. The TEM analysis shows that the final material has a hierarchized porosity in the field of mesoporosity and macroporosity, and not organized in the field of mesoporosity. The analysis by nitrogen volumetric combined with the analysis by the method _s leads to a value of the micropore volume V _micr0 (N ₂₎ of 0.06 ml / g, a value of the mesopore volume V _meso (N ₂ ) of 0.37 ml / g and a specific surface area of the final material of S = 259 m ² / g. The mesoporous diameter φ characteristic of the unorganized matrix is characterized by a broad adsorption porous distribution greater than 7.0 nm. The macroporous mercury volume defined by mercury porosimetry is 0.20 ml / g (the value of the mercury mercury volume also obtained by mercury porosimetry is in perfect agreement with the value obtained by nitrogen volumetry). The Si / Al molar ratio obtained by FX is 12. An SEM image of the spherical elementary particles thus obtained indicates that these particles have a size characterized by a diameter ranging from 50 nm to 30 μm, the size distribution of these particles being centered. around 15 μηι. The Raman spectrum of the final material reveals the presence of the HPA Strandberg H2P2M05O23 ^{4 "with} a band characteristic of the heteropolyanion to 942 ^{cm" 1} and side strips 893, 395 and 370 cm ^"1. Example 2 ^(invention") : preparation of a material having Strandberg HPA H2P2M05O23 ^{4 "} , 2Ni ²⁺ , 5 wt.% MoO3, 1.04 wt.% NiO and 0.99 wt.% P ₂ 0 ₅ with respect to final material The matrix is of mesoporous and macroporous porosity whose microporous amorphous walls consist of proto-zeolitic entities based on ZSM-5 (MFI) such that the Si / Al molar ratio = 25. An aqueous solution containing 3, 61 mol / 1 Mo03, 1, 44 mol / 1 of H ₃ P0 _4, 1, 44 mol / 1 Ni (OH) ₂ was prepared with stirring at room temperature. the Raman analysis, performed on the final material, reveals the presence of Strandberg HPA H2P2M05O23 ^{4 "} , 2Ni ²⁺ as the majority species.

0.23 g of tri-sec-butoxide of aluminum are mixed with 3, 19 g of aqueous TPAOH solution (40% by weight). After stirring for 10 minutes at room temperature, 22.3 g of deionized water are added. After homogenization, 4.82 g of TEOS are added and then allowed to hydrolyze for 16 hours with stirring at room temperature. At the end of the hydrolysis, the solution is diluted with a solution containing 1.45 g of P123 (Sigma-Aldrich), 0.29 g of polypropylene glycol P 2000 (Sigma Aldrich), 45.4 g of permutated water and 5.78 g of ethanol. A solution composed of 10 g of deionized water and 0.15 ml of the aqueous solution of Strandberg H ₂ 2 O ₅ O ₂ 3 ^" , 2Ni ²⁺ to 0.72 mol / l of HPA is prepared. agitation, this solution was added to the above solution containing PI 23. the report _norganique Vj / V i _that _organ of the mixture is equal to 0.27 and is calculated as described above. The mixture is left stirring for 30 min then is sent into the atomization chamber of the aerosol generator and the solution is sprayed in the form of fine droplets under the action of the carrier gas (dry air) introduced under pressure (P = 1.5 bar). The droplets are dried according to the protocol described in the disclosure of the invention above: they are conveyed via an O2 / N2 mixture in PVC tubes. The temperature of the drying oven is set at 350 ° C. The harvested powder is then calcined under air for 5 hours at T = 550 ° C. The HPA is then regenerated by washing with Soxhlet of the solid with methanol for 4 hours. The solid is finally dried at 80 ° C for 24 hours. The solid is characterized by nitrogen volumetry, by mercury porosimetry, by TEM, by SEM, by FX, by Raman spectroscopy. The TEM analysis shows that the final material has a hierarchized porosity in the field of mesoporosity and macroporosity, and not organized in the field of mesoporosity. Nitrogen volumetric analysis combined with analysis by the oc _s method leads to a microporous V _micro (N ₂ ) volume value of 0.07 ml / g, a mesoporous V _meso (N ₂₎ volume value. ) of 0.43 ml / g and a specific surface area of the final material of S = 263 m ² / g. The mesoporous diameter characteristic of the unorganized matrix is characterized by a wide adsorption porous distribution greater than 9.0 nm. The macroporous mercury volume defined by mercury porosimetry is 0.22 ml / g (the value of the mercury mercury volume also obtained by mercury porosimetry is in perfect agreement with the value obtained by nitrogen volumetry). The Si / Al molar ratio obtained by FX is 25. An SEM image of the spherical elementary particles thus obtained indicates that these particles have a size characterized by a diameter ranging from 50 nm to 30 μm, the size distribution of these particles being centered. around 15 μπι. The Raman spectrum of the final material reveals the presence of ⁴ Strandberg HPA H2P2M05O23 with a characteristic band of this heteropolyanion at 940 cm- ¹ and secondary bands at 891, 393 and 368 cm- ¹ .

Example 3 (Invention): Preparation of a material comprising oxide nanoparticles based on molybdenum and cobalt at 10% by weight of MoO ₃ and 2.08% by weight of CoO relative to the final material. The matrix is of mesoporous and macroporous porosity whose microporous amorphous walls consist of ZSM-5-based protozeic entities (MFI) such that the molar ratio Si / Al = 12.

An aqueous solution containing 0.1 mol / l of MoCl 5 and 0.08 mol / l of Co (OH) ₂ is prepared with stirring at room temperature.

0.45 g of tri-sec-butoxide of aluminum are mixed with 3, 18 g of aqueous TPAOH solution (40% by weight). After stirring for 10 minutes at room temperature, 22.3 g of deionized water are added. After homogenization, 4.59 g of TEOS are added and then allowed to hydrolyze for 16 hours with stirring at room temperature. At the end of the hydrolysis, a solution composed of 1. 58 g of F127 (Sigma-Aldrich), 45.3 g of deionized water and 5.77 g of ethanol is added to the solution containing the precursors of the protozeolithic entities. After 5 minutes of homogenization, the solution containing MoCI5 and Co (OH) ₂ is added dropwise.

The ratio V i _that _inorgan / V _organiquc of the mixture is equal to 0.26 and is calculated as described above. The mixture is left stirring for 30 min then is sent into the atomization chamber of the aerosol generator and the solution is sprayed in the form of fine droplets under the action of the carrier gas (dry air) introduced under pressure (P = 1.5 bar). The droplets are dried according to the protocol described in the disclosure of the invention. above: they are conveyed via a 0 ₂ / N ₂ mixture in PVC tubes. The temperature of the drying oven is set at 350 ° C. The harvested powder is then calcined under air for 5 hours at T = 550 ° C. The solid is characterized by nitrogen volumetry, by mercury porosimetry, by TEM, by SEM, by FX, by aman spectroscopy. The TEM analysis shows that the final material has a hierarchized porosity in the field of mesoporosity and macroporosity, and not organized in the field of mesoporosity. Nitrogen volumetric analysis combined with analysis by the cc _s method leads to a microporous volume value V _micr0 (N ₂ ) of 0.02 ml / g, a mesoporous volume value V _raeso (N ₂ ) of 0.25 ml / g and a specific surface of the final material of S = 152 m ² / g. The mesoporous diameter φ characteristic of the unorganized matrix is characterized by a broad adsorption porous distribution greater than 4.7 nm. The macroporous mercury volume defined by mercury porosimetry is 0.19 ml / g (the value of the mesoporous mercury volume also obtained by mercury porosimetry is in perfect agreement with the value obtained by nitrogen volumetry). The Si / Al molar ratio obtained by FX is 12. An SEM image of the spherical elementary particles thus obtained indicates that these particles have a size characterized by a diameter ranging from 50 nm to 30 μm, the particle size distribution being centered. around 15 μηι. The Raman spectrum of the final material reveals the presence of polymolybdate species, interacting with the matrix, with characteristic bands of these species at 952 and 889 cm ^-1 .

Example 4 (Invention): Preparation of a material comprising oxide nanoparticles based on molybdenum and nickel, 10% by weight of MoO ₃ and 2.08% by weight of NiO with respect to the final material. The matrix is of mesoporous and macroporous porosity whose microporous amorphous walls consist of ZSM-5-based protozeic entities (MFI) such that the molar ratio Si / Al = 12.

An aqueous solution containing 0.1 mol / l of MoCl ₅ and 0.08 mol / l of Ni (OH) ₂ is prepared with stirring at room temperature.

0.45 g of tri-sec-butoxide of aluminum are mixed with 3, 18 g of aqueous TPAOH solution (40% by weight). After stirring for 10 minutes at room temperature, 22.3 g of deionized water are added. After homogenization, 4.59 g of TEOS are added and then allowed to hydrolyze for 16 hours with stirring at room temperature. An aging step of the solution is carried out at 80 ° C for 24 hours. At the end of this step, a solution composed of 1. 58 g of F127 (Sigma-Aldrich), 0.32 g of polypropylene glycol P2000 (Sigma-Aldrich), 45.3 g of permutated water and 5.77 g of ethanol is added to the solution containing the precursors of the protozeolitic entities. After 5 minutes of homogenization, the solution containing MoCl ₅ and Ni (OH) ₂ is added dropwise.

The report V _inoi . _g / V of the mixture is 0.26 and calculated as described above. The mixture is left stirring for 30 min then is sent into the atomization chamber of the aerosol generator and the solution is sprayed in the form of fine droplets under the action of the carrier gas (dry air) introduced under pressure (P = 1.5 bar). The droplets are dried according to the protocol described in the disclosure of the invention above: they are conveyed via a 0 ₂ / N ₂ mixture in PVC tubes. The temperature of the drying oven is set at 350 ° C. The harvested powder is then calcined under air for 5 hours at T = 550 ° C. The solid is characterized by nitrogen volumetry, by mercury porosimetry, by TEM, by SEM, by FX, by Raman spectroscopy. The MET analysis shows that the final material has a hierarchical porosity in the fields of mesoporosity and macroporosity, and unorganized in the field of mesoporosity. Nitrogen volumetric analysis combined with analysis by the oc _s method leads to a microporous volume value V _micr0 (N ₂ ) of 0.04 ml / g, a mesoporous volume value V _meso (N ₂ ) of 0.32 ml / g and a specific surface of the final material of S = 154 m ² / g. The mesoporous diameter φ characteristic of the unorganized matrix is characterized by a wide absorption porous distribution greater than 6.0 nm. The macroporous mercury volume defined by mercury porosimetry is 0.20 ml / g (the value of the mercury mercury volume also obtained by mercury porosimetry is in perfect agreement with the value obtained by nitrogen volumetry). The Si / Al molar ratio obtained by FX is 12. An SEM image of the spherical elementary particles thus obtained indicates that these particles have a size characterized by a diameter ranging from 50 nm to 30 μm, the particle size distribution being centered. around 15 μπι. The Raman spectrum of the final material reveals the presence of polymolybdate species, interacting with the matrix, with characteristic bands of these species at 954 and 891 cm ^-1 .

Example 5 ( ^' Invention ^' ): Preparation of a material comprising oxide nanoparticles based on molybdenum and nickel, 10% by weight of MoO ₃ and 2.08% by weight of NiO with respect to the final material. The matrix is of mesoporous and macroporous porosity whose microporous walls consist of crystallized entities of zeolite ZSM-5 (MFI) such that the molar ratio Si / Al = 50.

0.12 g of tri-sec-butoxide of aluminum are mixed with 3.18 g of aqueous TPAOH solution (40% by weight). After stirring for 10 minutes at room temperature, 22.3 g of deionized water are added. After homogenization 4.89 g of TEOS are added and then allowed to hydrolyze for 16 hours with stirring at room temperature. An aging step of the solution is carried out at 80 ° C for 24 hours. At the end of this step, a solution composed of 1. 58 g of F127 (Sigma-Aldrich), 0.32 g of polypropylene glycol P2000 (Sigma-Aldrich), 45.3 g of permutated water and 5.77 g of ethanol is added to the solution containing the precursors of the zeolitic entities. After 5 minutes of homogenization, the solution containing MoCl ₅ and Ni (OH) ₂ is added dropwise. The ratio Vi _Norgan _QUC i / V i _that _organ of the mixture is equal to 0.27 and is calculated as described above. The mixture is left stirring for 30 min then is sent into the atomization chamber of the aerosol generator and the solution is sprayed in the form of fine droplets under the action of the carrier gas (dry air) introduced under pressure (P = 1.5 bar). The droplets are dried according to the protocol described in the disclosure of the invention above: they are conveyed via a 0 ₂ / N ₂ mixture in PVC tubes. The temperature of the drying oven is set at 350 ° C. The harvested powder is then dried for 12 hours in an oven at 95 ° C. 10 mg of powder are then placed in a 100 ml autoclave (closed chamber capable of withstanding temperatures of the order of 200 ° C. and pressures of the order of 5 bars) in the presence of 100 μl of demineralised water . The autoclave is provided with a system of "basket" or "cell" allowing the powder not to be in direct contact with the water introduced while bathing in the water vapor. The autoclave is then heated to a temperature of 95 ° C for 48 hours. The recovered powder is then dried in an oven at 95 ° C. for 12 hours. The powder is then calcined under air for 5 hours at T = 550 ° C. The solid is characterized by large-angle XRD, nitrogen volumetric, mercury porosimetry, TEM, SEM, FX, Raman spectroscopy. The TEM analysis shows that the final material has a hierarchical porosity in the areas of mesoporosity and macroporosity, and not organized in the field of mesoporosity. The presence of zeolite entities in the walls of the material is also clearly visible during the electron diffraction study of michronotropic sections with a thickness of the order of 50 nm. Nitrogen volumetric analysis combined with analysis by the cc _s method resulted in a microporous volume value V _{mi (0} of _0.14 ml / g (N ₂ ), a mesoporous volume value V _mes0 of 0.30 ml / g (N ₂ ) and a specific surface area of the final material of S = 1 10 m ² / g The mesoporous diameter φ characteristic of the unorganized matrix is characterized by a porous distribution at broad adsorption greater than 20.0 nm The macroporous mercury volume defined by mercury porosimetry is 0.25 ml / g (the value of the mercury mercury volume also obtained by mercury porosimetry is in perfect agreement with the value obtained by nitrogen volumetry) X-ray analysis at large angles leads to the characteristic diffractogram of zeolite ZSM-5. The Si / Ai molar ratio obtained by FX is 50. An SEM image of the spherical elementary particles thus obtained indicates that these particles have a size characterized by a diam ranging from 50 nm to 30 μπι, the size distribution of these particles being centered around 15 μηι. The Raman spectrum of the final material reveals the presence of polymolybdates species in interaction with the matrix, with characteristic bands of these species at 950 and 887 cm ^" '.

Claims

A process for preparing a hierarchically porous inorganic material in the fields of microporosity, mesoporosity and macroporosity, said material consisting of at least two elementary spherical particles having a maximum diameter of 200 microns, each of said spherical particles comprising metal particles containing at least one or more metals selected from vanadium, niobium, tantalum, molybdenum, tungsten, iron, copper, zinc, cobalt and nickel, said metal particles being present in a matrix based on silicon oxide, said method comprising at least the following steps:

b) mixing in solution said metal particles or at least one metal precursor of said metal particles, at least one surfactant and at least said solution obtained according to a) such that the ratio νί _η0¾8ηΙς "/ is between 0 , 09 and 0.28,

d) drying said particles,

g) removing at least said structuring agent and at least said surfactant.

2. Preparation process according to claim 1, wherein, following said step d), a step e) of autoclaving the particles resulting from said step d) is carried out and then a step f) is carried out. drying said particles obtained after said e).

3. Preparation process according to claim 2 wherein the proto-zeolitic entities from said step a) are species for the primer of at least one zeolite selected from zeolites of structural type MFI, BEA, FAU and LTA.

4. Preparation process according to one of claims 1 to 3 wherein said metal particles have at least one wave number band between 750 and 1050 cm ^-1 in Raman spectroscopy.

5. Preparation process according to claim 4 wherein said metal particles are in the form of a polyoxometalate of the formula (X _x M _m O _y H _h) ^{q "(I)} where H is hydrogen, O is the oxygen atom, X is a member selected from phosphorus, silicon, boron, nickel and cobalt and M is one or more elements selected from vanadium, niobium, tantalum, molybdenum, tungsten , iron, copper, zinc, cobalt and nickel, x being equal to 0, 1, 2, or 4, m being equal to 5, 6, 7, 8, 9, 10, 1 1, 12 and 18, y being between 17 and 72, h being between 0 and 12 and q being between 1 and 20 (y, h and q being integers).

6. Preparation process according to claim 5 wherein said metal particles are heteropolyanions having the formula P ₂ Mo ₅ 023Hh ^{<6 "h)"} , with h = 0, 1 or 2.

7. Preparation process according to claim 4 wherein said metal particles are oxide nanoparticles comprising at least one metal selected from molybdenum and tungsten and the mixture of these two metals.

8. Preparation process according to one of claims 1 to 7 wherein said step a) is carried out in the presence of at least one precursor of at least one Y element selected from aluminum, iron, boron , indium and gallium.

9. Preparation process according to one of claims 1 to 8 wherein said metal particles are prepared by dissolving, prior to said step b), the (es) metal precursor (s) necessary (s) to obtain them, in a solvent, said solution then being introduced into the mixture according to said step b).

10. A method of preparation according to claim 5 or claim 6 as it comprises, following the implementation of said step g), a step h) of regenerating said metal particles in the form of polyoxometallate decomposed during of step g), said step h) being followed by a drying step i).

The process according to claim 7, wherein at least one monometallic precursor based on a metal selected from vanadium, niobium, tantalum, molybdenum and tungsten and at least one second monometallic precursor based on a group VIII metal are dissolved prior to the implementation of said step b), said solution then being introduced into the mixture according to said step b).

12. A process for converting a hydrocarbon feedstock comprising 1) contacting the inorganic material obtained according to the preparation method according to one of claims 1 to 1 1 with a feedstock comprising at least one sulfur compound and 2) the setting in contact with said material from said step 1) with said hydrocarbon feedstock.