EP2654946A1

EP2654946A1 - Spherical material based on heteropolyanions trapped in a mesostructured oxide matrix and use thereof as catalyst in hydrocarbon refining processes

Info

Publication number: EP2654946A1
Application number: EP11808894.7A
Authority: EP
Inventors: Alexandra Chaumonnot; Clément Sanchez; Cédric BOISSIERE; Frédéric COLBEAU-JUSTIN; Karine MARCHAND; Elodie Devers; Audrey Bonduelle; Denis Uzio; Antoine Daudin; Bertrand Guichard
Original assignee: Centre National de la Recherche Scientifique CNRS; Universite Pierre et Marie Curie Paris 6; IFP Energies Nouvelles IFPEN
Current assignee: Centre National de la Recherche Scientifique CNRS; Universite Pierre et Marie Curie Paris 6; IFP Energies Nouvelles IFPEN
Priority date: 2010-12-22
Filing date: 2011-12-15
Publication date: 2013-10-30
Also published as: JP5860900B2; US20140005031A1; FR2969509B1; CN103501894B; FR2969509A1; ZA201304071B; WO2012085355A1; CN103501894A; JP2014510615A

Abstract

An inorganic material is described consisting of at least two elementary spherical particles, each of said spherical particles comprising metallic particles in the form of polyoxometalate of formula (X_xM_mO_yH_h)^q- where H is hydrogen, O is oxygen, X is an element chosen from phosphorus, silicon, boron, nickel and cobalt and M is one or more elements chosen 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, 11, 12 and 18, y being between 17 and 72, h being between 0 and 12 and q being between 1 and 20 (y and q being integers). Said metallic particles are present within a mesostructured matrix based on an oxide of an element Y chosen from the group consisting of silicon, aluminium, titanium, tungsten, zirconium, gallium, germanium, tin, antimony, lead, vanadium, iron, manganese, hafnium, niobium, tantalum, yttrium, cerium, gadolinium, europium and neodymium and the mixture of at least two of these elements. Said matrix has pores with a diameter between 1.5 and 50 nm and amorphous walls with a thickness between 1 and 30 nm, said elementary spherical particles having a maximum diameter of 200 microns.

Description

SPHERICAL MATERIAL BASED ON HETEROPOLYANIONS TRAPS IN A

MATRIX

The present invention relates to the field of inorganic oxide materials, in particular those containing transition metals, having an organized and uniform porosity in the field of mesoporosity. It also relates to the preparation of these materials which are obtained by the use of the so-called "aerosol" synthesis technique. It also relates to the use of these materials after sulfurization as catalysts in various processes relating to the fields of hydrotreating, hydroconversion and the production of hydrocarbon feeds.

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 Topsee, 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 following the calcination step (sintering phenomenon) occur (BS Clausen, HT Topsee, 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 support of an aluminic nature, these are 1) crystallites of MoO ₃ , NiO, CoO, COOMO 4 or CO ₃ O ₄ , of sufficient size to be detected in XRD, and / or 2) type Al ₂ (MoO ₄ ) 3, CoAl ₂ 0 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. of Anderson of formula [Al (OH) ₆ Mo ₆ O 1 ₈ ] ^{3 "} , themselves precursors of the phases refractory to sulfurization The presence of all these species leads to a non-negligible indirect loss of the activity catalytic converter since 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 these is immobilized in little or non-active species, the catalytic performances of the conventional catalysts described above could therefore be improved, especially in new methods of preparing these catalysts which would allow:

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. Over the past ten years, other catalysts whose supports have a hierarchical and controlled porosity have been developed. In the context of applications related to hydrotreating, hydroconversion and hydrocarbon feedstock production, beyond the compromise of accessibility (related to pore size) / developed surface area (related to specific surface area) It is important to control parameters such as the length of the pores, the tortuosity or the connectivity between the pores (defined by the number of accesses of each cavity). The structural properties related to a periodic arrangement and to a particular morphology of the pores are essential parameters to be controlled. For example, US Patent 2007/152181 teaches that it is advantageous to use, for the transformation of various petroleum fractions, mesotructured alumina catalyst supports having a large specific surface area and a homogeneous pore size distribution.

Summary of the invention

The present invention relates to an inorganic material consisting of at least two elementary spherical particles, each of said spherical particles comprising metal particles in the form of polyoxometalate of the formula (X _x M _m O _y H _h) ^{q ~} where H is the hydrogen atom, 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, where x is 0, 1, 2 or 4, m being 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), said metal particles being present at within a mesostructured matrix based on an oxide of at least one element Y selected from the group consisting of silicon, aluminum, titanium, tungsten, zirconium, gallium, germanium, tin, antimony, lead, vanadium, iron, manganese, hafnium, niobium, tantalum, yttrium , cerium, gadolinium, europium and neodymium and the mixture of at least two of these elements, said matrix having pores with a diameter of between 1.5 and 50 nm and having amorphous walls of thickness between 1 and 30 nm, said elementary spherical particles having a maximum diameter of 200 microns. The general formula (H _h X _x M _m O _y ) ^{q '} is noted formula (I) in the following description.

The material according to the invention is prepared according to the particular synthetic technique known as "aerosol".

The mesostructured inorganic material according to the invention is used, after sulfurization, as a catalyst in various processes for the conversion of hydrocarbon feedstocks, in particular in the hydrodesulfurization processes of gasoline and diesel fractions, the hydrocracking and hydroconversion processes. heavy hydrocarbon feedstocks, processes for hydrotreatment of heavy hydrocarbon feedstocks and hydrocarbon feeds containing triglycerides. Interest of the invention

The material according to the invention comprising metal particles in the form of polyoxometallates, preferably in the form of heteropolyanions, trapped in the mesostructured matrix of each of the elementary spherical particles constituting said material, is an advantageous catalytic precursor. It simultaneously presents the properties specific to the presence of polyoxometalates, preferably heteropolyanions, in particular a better dispersion of the active phase, a better synergy between the metallic species, a decrease in the phases that are refractory to sulphidation, and the structural, textural and optionally acid-baseicity and oxidation-reduction specific to the oxide-based mesostructured materials of at least one Y-element, including non-limiting material transfer of reagents and reaction products and the high value of the surface active. The polyoxometalates, preferentially the heteropolyanions, are the precursor species of the active sulphide phase present in the catalyst derived from the material according to the invention after sulfurization.

The diffusion properties of the reagents and of the reaction products, associated with the inorganic material according to the invention consisting of spherical elementary particles having a maximum diameter equal to 200 μηι, are increased compared with those of other mesostructured materials known to the state. of the technique, obtained off-air and in the form of elementary particles of non-homogeneous shape, that is to say, irregular, and of size much greater than 500 nm. In addition to the specific properties on the one hand to the polyoxometallates, preferably to the heteropolyanions (HP A), and on the other hand to the mesostructured oxide matrix present in each of the spherical particles of the material according to the invention, the trapping of the polyoxometallates, preferably heteropolyanions, within the mesostructured oxide matrix generates favorable additional technical effects such as controlling the size of said metal particles in the form of polyoxometalates, increasing the thermal stability of the polyoxometallates, preferably heteropolyanions, the development of HPA interactions / original support.

On the other hand, the method of aerosol preparation of the material according to the invention makes it possible to easily develop in a single step (one pot) various precursors, based on polyoxometalates (in particular HPA), catalysts sulfur.

In addition, compared with known syntheses of mesostructured materials outside the aerosol route, the preparation of the material according to the invention is carried out continuously, the preparation time is reduced (a few hours compared with 12 to 24 hours using autoclaving) and the stoichiometry of the non-volatile species present in the initial solution of the reagents is maintained in the material of the invention.

Presentation of the invention

The present invention relates to an inorganic material consisting of at least two elementary spherical particles, each of said spherical particles comprising metal particles in the form of polyoxometalate of the formula (X _x M _m O _y H _h) ^{q ~} where H is the hydrogen atom, 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, where x is 0, 1, 2, or 4, where m is 5, 6, 7, 8, 9 , 10, 11, 12 and 18, ranging from 17 to 72, h being between 0 and 12 and q being between 1 and 20 (y, h and q being integers), said metal particles being present within an oxide-based mesostructured matrix of at least a Y element selected from the group consisting of silicon, aluminum, titanium, tungsten, zirconium, gallium, germanium, tin, antimony, lead, vanadium, iron, manganese , hamium, niobium, tantalum, yttrium, cerium, gadolinium, europium and neodymium and the mixture of at least two of these elements, said matrix having pores of diameter between 1, 5 and 50 nm and having amorphous walls with a thickness of between 1 and 30 nm, said elementary spherical particles having a maximum diameter of 200 microns. The general formula (X _x M _m Y _y H _h ) ^{q "} is denoted formula (I) in the remainder of the description: By 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.

According to the invention, the element Y present in oxide form in the mesostructured matrix included in each of said spherical particles of the material according to the invention is chosen from the group consisting of silicon, aluminum, titanium, tungsten, zirconium, gallium, germanium, tin, antimony, lead, vanadium, iron, manganese, hamium, niobium, tantalum, yttrium, cerium, gadolinium , europium and neodymium and the mixture of at least two of these elements and preferably said element Y present in oxide form is chosen from the group consisting of silicon, aluminum, titanium, zirconium, gallium, germanium and cerium and the mixture of at least two of these elements. Even more preferably, said element Y present in oxide form is selected from the group consisting of silicon, aluminum, titanium, zirconium and the mixture of at least two of these elements. According to the invention, said mesostructured matrix is preferably composed of aluminum oxide, silicon oxide or a mixture of silicon oxide and aluminum oxide. In the preferred case where said mesostructured matrix is a mixture of silicon oxide and aluminum oxide (aluminosilicate), said matrix has an Si / Al molar ratio of at least 0.02, preferably between 0, 1 and 1000 and very preferably between 1 and 100.

Said matrix based on at least one oxide of said element Y is mesostructured: it has an organized porosity at the mesopore scale of each of the elementary particles of the material according to the invention, ie an organized porosity at the pore scale having a uniform diameter of between 1.5 and 50 nm, preferably between 1.5 and 30 nm and even more preferably between 4 and 20 nm and homogeneously and uniformly distributed in each of said particles (mesostructuration of the matrix). The material located between the mesopores of the mesostructured matrix is amorphous and forms walls, or walls, whose thickness is between 1 and 30 nm and preferably between 1 and 10 nm. The thickness of the walls corresponds to the distance separating a first mesopore from a second mesopore, the second mesopore being the pore closest to the first mesopore. The organization of the mesoporosity described above leads to a structuring of said matrix, which may be hexagonal, vermicular or cubic and preferably vermicular. The mesostructured matrix advantageously has no porosity in the field of microporosity. The material according to the invention also has an interparticle textural macroporosity. The mesostructured matrix included in each of said spherical particles of the material according to the invention contains metal particles in the form of polyoxometalate of the formula (X _x M _m O _y H _h) ^{q "wherein} X is an element selected from phosphorus, silicon , boron, nickel and cobalt and M is one or more elements selected from vanadium, niobium, tantalum, molybdenum, tungsten, cobalt and nickel, where x is 0, 1, 2, or 4, preferably x is 0, 1 or 2, m being 5, 6, 7, 8, 9, 10, 11, 12 and 18, y being between 17 and 72, preferably between 23 and 42, h being between 0 and 12 and q being between 1 and 20, preferably between 3 and 12 (y, h and q are integers), more precisely said metal particles are trapped in the mesostructured matrix. have an average size of between 0.6 and 3 nm, preferably between 0.6 and 2 nm, and in this way e still more preferably it is greater than or equal to 0.6 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 trapped in the mesostructured oxide matrix included in each of said spherical particles of the material according to the invention advantageously have M atoms whose oxidation state is equal to + IV, + V and / or + VI. The metal particles are homogeneously and uniformly trapped in the matrix. Said metal particles are characterized by the presence of at least one wave number band between 750 and 1050 cm ^-1 in Raman spectroscopy Raman spectroscopy is a technique well known to those skilled in the art. In the invention, said metal particles in the form of polyoxometalate are chosen from isopolyanions and heteropolyanions (HPA) .The isopolyanions and heteropolyanions trapped in the mesostructured matrix included in each of said spherical particles of the material according to the invention are fully described in FIG. Heteropoly and Isopoly Oxometallates, Pope, Ed Springer-Verlag, 1983. Preferably, said metal particles are heteropolyanions, said metal particles, preferably in the form of heteroplyanions, are salts carrying a negative charge q compensated by positively charged counterions of the same or different nature. The counter ions are advantageously provided by metal cations, in particular Group VIII metal cations such as Co ²⁺ , Ni ²⁺ , H ⁺ protons and / or NH ₄ ⁺ ammonium cations. When all the counter-ions are H ⁺ protons, the term heteropoly acid is commonly used to designate the form in which the said metal particles are. Such a heteropoly acid is, for example, phosphomolybdic acid (3H ⁺ , PMo ₁₂ O ₄₀ ^{3 "} ) or also phosphotungstite acid (3H ⁺ , PWi ₂ O ₄₀ ^3" ).

According to the first embodiment of trapping metal particles in the form of isopolyanions in each of said mesostructured matrices, the element X in the general formula (I) above is absent and x = 0. The element M is one or more elements selected 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, a mixture of Mo and W atoms, a mixture of W and Nb atoms, a mixture of Mo and V atoms, or a mixture of W atoms and of V, 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 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 Wi ₂ 0 ₄ o ^{6 ~} (h = 2, m = 12, y = 40, q = 6) or the formula Mo ₇ 0 ₂₄ ^{6 '} (h = 0, m = 7, y = 24, q = 6).

According to the second embodiment of trapping metal particles in the form of heteropolyanions (denoted HPA) in each of said mesostructured 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 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 atoms or W atoms, or a mixture of Mo and W atoms, or a mixture of atoms of W and Nb, either a mixture of Mo and V atoms, or a mixture of W and V atoms, or a mixture of Mo and Co atoms, or a mixture of Mo atoms and of Ni, 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) advantageously trapped in the mesostructured matrix included in each of said spherical particles of the material according to the invention is such that said heteropolyanions have 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 ₁₀ O 3 ₈ H _h ^{q "} (where 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 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 ₂₄ H ₆ ^4" are good examples of Anderson heteropolyanions entrapped in each of said mesostructured matrices, wherein Co and Ni are the X-heteroelements of the HPA structure. Such Anderson heteropolyanions of formula CoMo ₆ 0 ₂ 4H ₆ ^{3 '} and NiMo ₆ 0 ₂₄ H ₆ ^{4 "} have the advantage when in the form of cobalt or nickel salts (i.e. where cobalt or nickel are present as cations to compensate for the negative charge of ΓΗΡΑ), 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 optimal 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 into account for the calculation of this atomic ratio being Co and or the Ni present as counterions and heteroelements X of the HPA structure, for example the cobalt or nickel salts of the monomenium 6-molybdocobaltate ion (of formula CoMo ₆ 0 ₂₄ H _e ^{3 "} , 3 / 2CO ^{2 +,} or CoMo _fi 4H ₂ 0 ₆ ^{3 ",} 3/2 Ni ²⁺⁾ or cobalt salts or nickel ion dimeric decamolybdocobaltate (formula 3Co ²⁺ or Co ₂ Mo ₁₀ O38H 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 cobalt salts or nickel ion dimeric decamolybdonickellate (formula N12 010O38H4 ^"4co and Ni ₂ Moio0 ₃₈ ^H4" 4Ni) 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 Ni present as counterions and heteroelements X of the HPA structure In the case where ΗΡΑ 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 In the case where ΗΡΑ contains within its structure nickel (X = Ni) and molybdenum (M = Mo), it is preferably monomeric. Monomeric and dimeric forms of said HPA can also be used. Very preferably, Anderson used to obtain the material according to the invention is a dimeric HPA containing cobalt and molybdenum within its structure and the counterion of the HPA salt may be cobalt Co ^{1 I} 3 [Co ^III ₂ Mo, o0 ₃₈ H ₄ ] or nickel A second preferred category of heteropolyanions (second embodiment) advantageously trapped in the mesostructured matrix included in each of said spherical particles of the material according to the invention is such that said heteropolyanions have the formula XMi ₂ O ₀ H _h ^{q "} (x = 1, m = 12, y = 40, h = 0 to 12, q = 3 to 12) and / or the formula XM _n 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 given in the general formula (I) above. Heteropolyanions of formula XM ₁₂ O ₄₀ H _h ^{q "are} heteropolyanion having a Keggin structure and the heteropoly anions of the formula XM _n 0 ₃ 9HH ^q" are heteropolyanion having a lacunary Keggin structure. The heteropolyanions of Keggin structure are obtained, for variable pH ranges, according to the pathways described in the publication by A. Griboval, P. Blanchard, E. Payen, M. Fournier, JL Dubois, Chem. Lett., 1997, 12, 1259. Keggin structure heteropolyanions are also known in substituted forms in which a group VIII metal element, preferably cobalt or nickel, is substituted for the metal M present in the formula XM | 0 ₄ oH _h ^{q ':} such species substituted Keggin are eg heteropolyanion PNiMouO ₄₀ H ^{6 "or} PCoMo _n O ₄₀ H ^6" (one Mo atom substituted respectively by one atom of Ni or a Co atom) . The species PCoMonO ₄₀ H ^{6 "} is for example prepared according to the protocol described in the publication by LGA van de Water et al J. Phys Chem B 2005, 109, 14513. Other substituted Keggin species, advantageously trapped in the mesostructured matrix included in each of said spherical particles of the material according to the invention are the species PVMo _n o 0 ₄ ^{4 ",} ⁵ PV2M010O _^40", ₄₀ PV3M09O ^{6 'or} PV ₄ Mo ₈ O ₀ ^{7 (1} or more carbon V substitution of 1 or more Mo atoms as element M): 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 the species PM03W9O40 ^{3 '} , PMo ₆ W ₆ O ₄₀ ^3' , PMo ₉ W ₃ O ₄ o ^{3 "} . Substituted species of Keggin heteropolyanions and their method of preparation are described in the patent application FR 2.764.21 1: said species have the formula Z _w XMnO ₄ oZ'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 counter ion as Z, w is 0 to 4.5, z is a value between 7 and 9. heteropoly compounds (heteropolyanions against + ions) particularly suitable for the implementation of the material according to the invention and corresponding to this formula are, for example PCoMo species, 0 ₄ oH (NH ₄₎ _6, PNiMo _n O ₄₀ H (NH ₄₎ ₆ Sicomo _n O ₄₀ H ₂ (NH ₄₎ ₆ CO ₃ PCoMonO ₄₀ H, Co ₃ PNiMo O ₄₀ H whose preparation is specifically described in application FR 2 764 1. The heteropolyanions described in patent application FR 2.764.21 1 are advantageous because they have an atomic ratio between the group VIII and group VI element of up to 0.5.

Keggin heteropolyanions of the formula XM ₁₂ O ₀ ^{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 a counterstain Ions have been described in US Pat. No. 2,547,380 and FR 2,749,778. In particular, US Pat. No. 2,547,380 teaches the beneficial use in hydrotreating processes of heteropoly acid salts of group metals. VIII such as the cobalt or nickel salts of phosphomolybdic, silicomolybdic, phosphotungstic or silicotungstic acids for hydrotreating applications By way of example, it is possible to use nickel phosphotungstate of formula 3 / 2Ni ² * PWi ₂ O ₀ ^{3 "} Ni / W ratio of 0.125 and cobalt phosphomolybdate of formula 3 / 2Co ²⁺ _ ΡΜθι ₂ Ο ₄₀ ^3" A method of preparation is particularly described in patent application FR 2,749,778 for the specific preparation of heteropoly compounds Co _7/2 PMo ₂ O ₄ o, Co ₄ SiMo ₂ O ₄₀ , Co _7/2 SiMo ₂ O ₄₀ and Co ₆ PMO ₂ O ₄₀ , which are particularly suitable as metal particles trapped in the mesostructured matrix included in each of the particles spherical material according to 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 lacunar Keggin structure and particularly adapted for the implementation of the material according to the invention are described in the patent application FR 2,935,139. They have the formula _{Ni + 2} Xwi i- _y 0 ₃ 9. ₅ / _2y, bH ₂ 0 wherein Ni is nickel, X is selected from phosphorus, silicon and boron, W is tungsten, O is 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 a counterposition 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 implementation of the material according to the invention have the formula Ni ₄ SiW _n 0 ₃₉ and

A third preferred category of heteropolyanions (second embodiment) advantageously trapped in the mesostructured matrix included in each of said spherical particles of the material according to the invention is such that said heteropolyanions have the formula H _h P ₂ Mo ₅ 0 ₂₃ ^{(6 ' h)} , with h = 0, 1 or 2. Such heteropolyanions are called Strandberg heteropolyanions The preparation of Strandberg HPA is described in 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 H2P2M05O ₂₃ ^{4 '} was particularly advantageous for hydrotreatment applications.

Advantageously, the elementary spherical particles constituting said inorganic material according to 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 as a mixture the HPA PW ₁₂ O ₄₀ ^{3 "} type HPA Keggin PMo, ₂ 0 ₄ o ^3" , PCoMo _n 0 ₄ oH ^{6 "} and H ₂ P ₂ Mo ₅ 0 ₂₃ ^{4 '} goods known to those skilled in the art.

The inorganic material according to the invention comprises a mass content of element (s) vanadium, niobium, tantalum, molybdenum and tungsten of between 1 and 40%, expressed as% by weight of oxide relative to the mass of final material in oxide form preferably between 4 and 35% by weight, preferably between 4 and 30% and even more preferably between 4 and 20%. The inorganic material according to the invention comprises an overall mass content of metal (ux) of group VIII, in particular nickel and / or cobalt, of between 0 and 15%, expressed in% by weight of oxide relative to the mass of the final material in oxide form, preferably between 0.5 and 10% by weight and even more preferably between 1 and 8% by weight.

The quantity of metal particles in the form of polyoxometalates, preferably in the form of heteropolyanions, is such that said particles advantageously represent from 2 to 50% by weight, preferably from 4 to 40% by weight and very preferably from 6 to 30% by weight. % weight of the material of the invention.

According to a first particular embodiment of the material according to the invention, each of the spherical particles constituting said material further comprises zeolitic nanocrystals. Said zeolite nanocrystals are trapped with the metal particles in the polyoxometallate form in the mesostructured matrix contained in each of the elementary spherical particles. According to this embodiment of the invention consisting in trapping zeolite nanocrystals in the mesostructured matrix, the material according to the invention has both, in each of the elementary spherical particles, a mesoporosity within the matrix itself (mesopores with a uniform diameter of between 1.5 and 50 nm, preferably between 1.5 and 30 nm and even more preferably between 4 and 20 nm) and a zeolite-type microporosity generated by the zeolitic nanocrystals trapped in the mesostructured matrix. Said zeolitic nanocrystals have a pore size of between 0.2 and 2 nm, preferably between 0.2 and 1 nm and very preferably between 0.2 and 0.8 nm. Said zeolite nanocrystals advantageously represent from 0.1 to 30% by weight, preferably from 0.1 to 20% by weight and very preferably from 0.1 to 10% by weight of the material of the invention. The zeolitic nanocrystals have a maximum size, generally a maximum diameter, of 300 nm and preferably have a size, generally a diameter, of between 10 and 100 nm. Any zeolite and particularly but not limited to those listed in "Atlas of zeolite framework types", 6 ^th revised Edition, 2007, Ch. Baerlocher, LBLMcCusker, DH Oison can be used in the zeolite nanocrystals present in each of the elementary spherical particles constituting the material according to the invention. The zeolitic nanocrystals preferably comprise at least one zeolite chosen from zeolites IZM-2, ZSM-5, ZSM-12, ZSM-48, ZSM-22, ZSM-23, ZBM-30, EU-2 and 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, the zeolitic nanocrystals comprise at least one zeolite chosen from zeolites of structural type MFI, BEA, FAU and LTA. Nanocrystals of different zeolites and in particular zeolites of different structural type may be present in each of the spherical particles constituting the material according to the invention. In particular, each of the spherical particles constituting the material according to the invention may advantageously comprise at least first zeolitic nanocrystals whose zeolite is chosen 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, 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, preferably among the structural type zeolites MFI, BEA, FAU and LTA and at least second zeolitic nanocrystals of which the zeolite is different from that of the first zeolitic nanocrystals and is chosen from 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, preferably from the structural type zeolites MFI, BEA, FAU, and LTA. The zeolitic nanocrystals advantageously comprise at least one zeolite either entirely silicic or containing, in addition to silicon, at least one element T chosen from among aluminum, iron, boron, indium, gallium and germanium, preferably aluminum.

According to a second particular embodiment of the material according to the invention, independent or not of said first mode described above, each of the spherical particles constituting said material further comprises one or more additional element (s) chosen (s) among organic agents, the metals of group VIII of the periodic table of elements and doping species belonging to the list of doping elements constituted by phosphorus, fluorine, silicon and boron and their mixtures. 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 as% by weight of oxide, by relative to the weight of the mesostructured inorganic material according to the invention. According to the invention, said elementary spherical particles constituting the material according to 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 even more advantageously from 50 nm to 10 μπι. More specifically, they are present in the material according to the invention in the form of powder, beads, pellets, granules, extrudates (hollow or non-hollow cylinders, multilobed cylinders with 2, 3, 4 or 5 lobes, for example twisted cylinders) or rings. The material according to the invention advantageously has a specific surface area of between 50 and 1100 m ² / g and very advantageously between 50 and 600 m ² / g and even more preferably between 50 and 400 m ² / g.

The present invention also relates to a process for preparing the material according to the invention.

Said preparation process according to the invention comprises at least the following successive stages:

a) the mixture in solution

at least one surfactant,

at least one precursor of at least one Y element selected from the group consisting of silicon, aluminum, titanium, tungsten, zirconium, gallium, germanium, tin, antimony, lead, vanadium, iron, manganese, hafhium, niobium, tantalum, yttrium, cerium, gadolinium, europium and neodymium and the mixture of two or more of these elements,

- metal particles in the form of polyoxometalate of the formula (X _x M _m O _y H _h) ^{q "where} H is hydrogen, O is an oxygen atom, X is an element 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 wherein x is 0, 1, 2 or 4, where m is 5, 6, 7, 8, 9, 10, 11, 12 and 18, y is 17 to 72, h is 0 to 12; , and q being between 1 and 20, or at least one metal precursor of said metal particles

optionally at least one colloidal solution in which are dispersed crystals of zeolites of maximum nanometric size equal to 300 nm;

b) the aerosol atomization of said solution obtained in step a) to lead to the formation of spherical liquid droplets; c) drying said droplets; d) removing at least said surfactant to obtain said mesostructured inorganic material in which the metal particles are trapped in the form of polyoxometalate.

Said preparation process according to the invention advantageously comprises, subsequent to said step d), at least one step e) of regeneration of the polyoxometallate species and then at least one step f) of drying the solid resulting from said step e). The implementation of said steps e) and f) is carried out when the polyoxometalate species are partially or completely decomposed during step d) of the preparation process according to the invention. At the end of the implementation of said steps e) and f), the inorganic material according to the invention is obtained in which metal particles, preferentially HPA, are trapped within each of the mesostructured matrices present in each of the elementary spherical particles constituting the material of the invention. According to step a) of the method for preparing the material according to the invention, said metal particles are either isopolyanions or heteropolyanions, preferably they are heteropolyanions. They are prepared according to synthetic methods known to those skilled in the art or commercially available.

In a general manner and in a manner known to those skilled in the art, the isopolyanions are formed by reaction of oxoanions of M0 ₄ '^{' type} (the value of n depending on the nature 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. the molybdic compounds are well known for this type of reaction, since depending on the pH, the molybdic compound in solution can be in the MoO ^{2 'form} or in the form of an isopolyanion Mo ₇ 0 ₂ 4 ^{6 "} obtained according to the reaction : 7 Mo0 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 generating Γα-metatungstate, 12 times condensed : 12 W0 ₄ ^{2 "} + 18 H ⁺ → H ₂ W ₁₂ O ₄₀ ^{6 '} + 8 H ₂ 0. These isopo species Lyanions, in particular the species Mo ₇ 0 ₂₄ ^{6 "} and H ₂ W ₁₂ O ₄₀ ^6" are advantageously employed as metal particles for the preparation of the material 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 M: n being preferably equal to 2 when M = Mo or W and preferably 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 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 member selected from P, Si, B, Ni and Co. There is then elimination 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 species in solution, the nature of the solvent, and the ratio of the number of M / X atoms. 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 a) of the preparation process according to the invention are described in the patent applications FR 2 935.139 and FR 2.764.21. 1, FR 2,749,778 and FR 2,843,050. Other particular methods of preparation of heteropolyanions as metal particles for the preparation of the material according to the invention are described in the various publications indicated above for the description of the various categories of HPA.

For example, for the implementation of said step a) of the process according to the invention, the metal particles in the polyoxometallate form of formula (I), preferentially the heteropolyanions, are easily prepared from the multimetal precursors necessary to obtain them. which are either dissolved before the implementation of said step a), in a solvent before being introduced into said mixture according to step a) are introduced directly into said mixture according to step a). In the case where the said multimetal precursors are placed in solution, before the said step a), the solvent used for the dissolution of the precursor (s) is aqueous and the solution obtained after the dissolution in solution the precursor (s) metal (s), prior to step a), containing said precursors, is clear and neutral pH or acid, preferably acidic. Said metal particles, preferably heteroplyanions, may also be used in solid and isolated form, and may be introduced directly into the mixture according to said step a) of the preparation process according to the invention or may be introduced in solution in an aqueous solvent prior to to be introduced into the mixture according to step a). According to step a) of the process for preparing the mesostructured inorganic material according to the invention, the precursor (s) of at least one Y element chosen from the group consisting of silicon, aluminum and titanium. , tungsten, zirconium, gallium, germanium, tin, antimony, lead, vanadium, iron, manganese, hafnium, niobium, tantalum, yttrium, cerium, gadolinium, europium and neodymium, and the mixture of at least two of these elements, preferably selected from the group consisting of silicon, aluminum, titanium, zirconium, gallium, germanium and cerium and the mixture of at least two of these elements is (are) an inorganic oxide precursor (s) well known to those skilled in the art. The precursor (s) of at least said element Y may be any compound comprising the element Y and capable of releasing this element in solution, for example in aqueous-organic solution, preferably in aqueous-organic solution. acid, in reactive form. In the preferred case where Y is selected from the group consisting of silicon, aluminum, titanium, zirconium, gallium, germanium and cerium and the mixture of at least two of these elements, the precursor (s) of at least said element Y is (are) advantageously an inorganic salt of said element Y of formula YZ, "(n = 3 or 4), Z being a halogen, the group N0 ₃ or a perchlorate, preferably Z is chlorine. The precursor (s) of at least one of said Y element (s) may also be an alkoxide precursor (s) of the formula Y (OR) "where R = ethyl, isopropyl, n butyl, s-butyl, t-butyl, etc. or a chelated precursor such as Y (C ₅ H ₈ O ₂ ) ", with n = 3 or 4. The precursor (s) of at least said Y element considered may still be oxide (s) or hydroxide (s) of said element Y. Depending on the nature of the element Y, the precursor of the element Y considered employed can also be of the form YOZ ₂ , Z being a monovalent anion such as a halogen or the N0 ₃ group. Preferably, said element (s) Y is (are) chosen from the group consisting of silicon, aluminum, titanium, zirconium, gallium, germanium and cerium and the mixture of at least two of these elements. In a very preferred manner, the mesostructured oxide matrix preferably comprises aluminum oxide, silicon oxide (Y = Si or Al) or comprises, preferably, an oxide mixture of silicon and aluminum oxide (Y = Si + Al). In the particular case where Y is silicon or aluminum or a mixture of silicon and aluminum, the silicic and / or aluminic precursors used in step a) of the process for preparing the material according to the invention are precursors of inorganic oxides well known to those skilled in the art. The silicic precursor is obtained from any source of silica and advantageously from a sodium silicate precursor of formula Na ₂ SiO ₃ , a chlorinated precursor of formula SiCl ₄ , an alkoxide precursor of formula Si (OR) where R = H, methyl, ethyl or a chloroalkoxide precursor of formula Si (OR) ₄ . _a _Cl where R = H, methyl, ethyl, a is between 0 and 4. The silicic precursor can also advantageously be an alkoxide precursor having the formula Si (OR) _4. _is R _'where R = H, methyl, ethyl and R' is an alkyl chain or a chain functionalized alkyl, for example with a thiol, amino, β-diketone or sulfonic acid group, a being between 0 and 4. The aluminum precursor is advantageously an inorganic aluminum salt of formula A1Z ₃ , Z being a halogen or the N0 group ₃ . Preferably, Z is chlorine. The aluminum precursor can also be an alkoxide precursor of formula Al (OR ") ₃ or R" = ethyl, isopropyl, n-butyl, s-butyl or t-butyl or a chelated precursor such as aluminum acetylacetonate (Al (CH) ₇ 0 ₂ ) 3). The aluminum precursor may also be an aluminum oxide or hydroxide.

The surfactant used for the preparation of the mixture according to step a) of the process for preparing the material according to the invention is an ionic or nonionic surfactant or a mixture of both. Preferably, the ionic surfactant is chosen from phosphonium and ammonium ions and very preferably from quaternary ammonium salts such as cetyltrimethylammonium bromide (CTAB). Preferably, the nonionic surfactant may be any copolymer having at least two parts of different polarities conferring properties of amphiphilic macromolecules. These copolymers may comprise at least one block that is part of the non-exhaustive list of the following families of polymers: fluorinated polymers (- [CH ₂ -CH ₂ -CH ₂ -CH ₂ -O-CO-RI- with R 1 = C ₄ F ₉ , C ₈ F ₁₇ , etc.), biological polymers such as polyamino acids (poly-lysine, alginates, etc.), dendrimers, polymers consisting of poly (alkylene oxide) chains. In general, any copolymer of an amphiphilic nature known to those skilled in the art may be used (S. Forster, M. Antionnetti, Adv.Mater, 1998, 10, 195-217, S. Forster, T.Plantenberg, Angew. Chem Int.Ed., 2002, 41, 688-714, H. Colfen, Macromol Rapid Rapid, 2001, 22, 219-252). Preferably, in the context of the present invention, a block copolymer consisting of poly (alkylene oxide) chains is 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 by (PEO) _w 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 of formula (PEO) _w - (PPO) _y - (PEO) _z where w is between 5 and 300 and y is between 33 and 300 and z is from 5 to 300. Preferably, the values of w and z are the same. A compound is advantageously used in which w = 20, y = 70 and z = 20 (PI 23) and a compound in which w = 106, y = 70 and z = 106 (F 127). Commercial nonionic surfactants known as Pluronic (BASF), Tetronic (BASF), Triton (Sigma), Tergitol (Union Carbide), Brij (Aldrich) are useful as nonionic surfactants. For a four-block copolymer, two of the blocks consist of a chain of poly (alkylene oxide) hydrophilic nature and the other two blocks consist of a chain of poly (oxides) of alkylene hydrophobic nature. In a preferred manner, the mixture of an ionic surfactant such as CTAB and a nonionic surfactant such as PI 23 or F127. According to step a) of the preparation process according to the invention, the colloidal solution in which are dispersed crystals of zeolites of maximum nanometer size equal to 300 nm, optionally added to the mixture referred to in said step a), is obtained either by prior synthesis, in the presence of a structuring agent, of zeolite nanocrystals of maximum nanometric size equal to 300 nm or by the use of zeolitic crystals, which have the characteristic of dispersing in the form of nanocrystals of maximum nanometric size equal to 300 nm in solution for example in aquo-organic acid solution. As regards the first variant consisting of a prior synthesis of the zeolitic nanocrystals, these are synthesized according to operating protocols known to those skilled in the art. In particular, the synthesis of zeolite Beta nanocrystals has been described by T. Bein et al., Micropor. Mesopor. Mater., 2003, 64, 165. The synthesis of zeolite Y nanocrystals has been described by TJ Pinnavaia et al., J. Am. Chem. Soc., 2000, 122, 8791. The synthesis of faujasite zeolite nanocrystals has been described in Kloetstra et al., Microporous Mater., 1996, 6, 287. The synthesis of ZSM-5 zeolite nanocrystals has been described by R. Mokaya et al., J. Mater. Chem., 2004, 14, 863. The synthesis of Silicalite nanocrystals (or MFI structural type) has been described in several publications: R. de Ruiter et al., Synthesis of Microporous Materials, Vol. I; ML Occelli, HE Robson (eds.), Van Nostrand Reinhold, New York, 1992, 167; AE Persson, BJ Schoeman, J. Sterte, J.-E. Otterstedt, Zeolites, 1995, 15, 61 1-619. Zeolitic nanocrystals are generally synthesized by preparing a reaction mixture containing at least one silicic source, optionally at least one source of at least one element T chosen from aluminum, iron, boron, indium, gallium and germanium, preferably at least one aluminum source, and at least one structuring agent. The reaction mixture for the synthesis of zeolitic nanocrystals is either aqueous or aquo-organic, for example a water-alcohol mixture. The reaction mixture is advantageously placed under hydrothermal conditions under autogenous pressure, optionally by adding gas, for example nitrogen, at a temperature of between 50 and 200 ° C., preferably between 60 and 170 ° C. and even more preferential at a temperature not exceeding 120 ° C until the formation of zeolitic nanocrystals. At the end of said hydrothermal treatment, a colloidal solution is obtained in which the nanocrystals are in the dispersed state. The structuring agent may be ionic or neutral depending on the zeolite to be synthesized. It is common to use the structuring agents of the following non-exhaustive list: nitrogenous organic cations, elements of the family of alkalis (Cs, K, Na, etc.), ethercouronnes, diamines and any other structuring agent well known to those skilled in the art. Regarding the second variant of directly using zeolite crystals, they are synthesized by methods known to those skilled in the art. Said zeolite crystals may already be in the form of nanocrystals. It is also advantageous to use zeolitic crystals larger than 300 nm, for example between 300 nm and 200 μιη, which are dispersed in solution, for example in aqueous-organic solution, preferably in aqueous-organic acid solution, in the form of nanocrystals. of maximum nanometric size equal to 300 nm. Obtaining zeolite crystals that disperse in the form of nanocrystals with a maximum nanometer size equal to 300 nm is also possible by performing functionalization of the surface of the nanocrystals. The zeolitic crystals used are either in their raw form of synthesis, that is to say still containing the structuring agent, or in their calcined form, that is to say freed of said structuring agent. When the zeolite crystals used are in their raw synthesis form, said structuring agent is removed during step d) of the preparation process according to the invention. The solution in which at least one surfactant, at least said metal particles in the form of polyoxometalate, at least one precursor of at least one Y element and optionally at least one stable colloidal solution in which large size zeolite crystals are dispersed are mixed. maximum nanometer equal to 300 nm according to step a) of the process for preparing the material according to the invention may be acidic or neutral. Preferably, said solution is acidic and has a maximum pH equal to 5, preferably between 0 and 4. The acids optionally used to obtain an acid solution are, in a non-exhaustive manner, hydrochloric acid, sulfuric acid and nitric acid. Said solution according to said step a) may be aqueous or may be a water-organic solvent mixture, the organic solvent preferably being a polar solvent miscible with water, especially an alcohol, preferably ethanol. Said solution according to said step a) of the preparation process according to the invention can also be substantially organic, preferably substantially alcoholic, the quantity of water being such that the hydrolysis of the inorganic precursors is ensured (stoichiometric amount). Very preferably, said solution according to said step a) of the preparation process according to the invention in which at least one surfactant, at least said metal particles in the form of polyoxometalate, are mixed with at least one precursor of at least said element Y and optionally at least one stable colloidal solution in which are dispersed crystals of zeolites of maximum nanometer size equal to 300 nm is an acidic aqueous-organic mixture, very preferably an acid-alcohol water mixture. The quantity of zeolitic nanocrystals dispersed in the colloidal solution, obtained according to the variant by prior synthesis, in the presence of a structuring agent, of zeolite nanocrystals of maximum nanometric size equal to 300 nm or according to the variant by the use of zeolite crystals, which have the characteristic of being dispersed in the form of nanocrystals of maximum nanometer size equal to 300 nm in solution, for example in aqueous-organic acid solution, optionally introduced during step a) of the preparation process according to the invention, is such that the zeolitic nanocrystals advantageously represent from 0.1 to 30% by weight, preferably from 0.1 to 20% by weight and very preferably from 0.1 to 10% by weight of the material of the invention.

The amount of metal particles in the form of polyoxometalates is such that said particles advantageously represent from 4 to 50% by weight, preferably from 5 to 40% by weight and very preferably from 6 to 30% by weight of the material of the invention.

The initial concentration of surfactant introduced into the mixture according to said step a) of the preparation process according to the invention is defined by c ₀ and c ₀ is defined relative to the critical micelle concentration (c _mc ) well known to humans. of career. The c _mc is the limit concentration beyond which occurs the phenomenon of self-assembly of the molecules of the surfactant in the solution. The concentration c ₀ may be less than, equal to or greater than the c _mc , preferably it is less than c _mc . In a preferred implementation of the method of preparation of the material according to the invention, the concentration c ₀ is lower than the c _mc and said solution referred to in step a) of said preparation process according to the invention is an acidic water mixture -alcohol. In the case where the solution referred to in step a) of the preparation process according to the invention is a water-based mixture. organic solvent, preferably acid, it is preferred during said step a) of the preparation process according to the invention that the surfactant concentration at the origin of the mesostructuration of the matrix is below the critical micelle concentration so that the evaporation of said aqueous-organic solution, preferably acidic, during step b) of the preparation process according to the invention by the aerosol technique induces a phenomenon of micellization or self-assembly leading to mesostructuring the matrix of the material according to the invention around said metal particles in the form of polyoxometalates and optionally zeolitic nanocrystals which remain unchanged in their shape and size during steps b) and c) of the preparation process of the invention. When c ₀ <c _rac , the mesostructuration of the matrix of the material according to the invention and prepared according to the method described above is consecutive to a progressive concentration, within each droplet, of at least the precursor of said element Y and surfactant, up to a concentration of surfactant c> c _mc resulting from evaporation of the aqueous-organic solution, preferably acid.

In general, the increase in the combined concentration of at least one precursor of said hydrolysed Y element and the surfactant causes the precipitation of at least said hydrolyzed precursor of said element Y around the self-organized surfactant and consequently the structuring of the matrix of the material according to the invention. Inorganic / inorganic phase interactions, organic / organic phases and organic / inorganic phases lead by a cooperative self-assembly mechanism to the condensation of at least said precursor of said hydrolysed Y element around the self-organized surfactant. During this self-assembly phenomenon, said metal particles in the form of polyoxometalate and optionally the zeolitic nanocrystals are trapped in said mesostructured matrix based on at least one of said element Y contained in each of the elementary spherical particles constituting the material of the invention.

The aerosol technique is particularly advantageous for the implementation of said step b) of the preparation process of the invention so as to constrain the reagents present in the initial solution to interact with each other, no loss of material except for the solvents, that is to say the solution, preferably the aqueous solution, preferably acidic, and optionally added with a polar solvent, not being possible, all of said (s) element (s) Y, said metal particles under polyoxometallate form and optionally zeolitic nanocrystals, initially present being thus perfectly preserved throughout the process of preparation of the invention instead of being potentially eliminated during filtration and washing steps encountered in conventional synthesis processes known to the skilled person.

The step of atomizing the solution according to said step b) of the preparation process according to the invention produces spherical droplets. The size distribution of these droplets is lognormal. The aerosol generator used in the context of the present invention is a commercial apparatus of model 9306 A provided by TSI having a 6-jet atomizer. The atomization of the solution is carried out in a chamber in which a carrier gas is sent, preferably a 0 ₂ / N ₂ mixture (dry air), at a pressure P equal to 1.5 bars. The diameter of the droplets varies depending on the aerosol apparatus employed. In general, the droplet diameter is between 150 nm and 600 μηι.

According to step c) of the preparation process according to the invention, said droplets are dried. This drying is carried out by transporting said droplets by the carrier gas, preferentially the mixing 0 ₂ / Ν ₂ , in PVC tubes, which leads to the gradual evaporation of the solution, for example the aquo-organic acid solution obtained during said step a) and thus to obtaining particles spherical elementals. 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 c) of the preparation process according to the invention is advantageously followed by a passage in an oven at a temperature of between 50 and 150 ° C. The removal of the surfactant introduced into said step a) of the preparation process according to the invention and optionally of the structuring agent used for synthesizing said zeolitic nanocrystals, according to step d) of the preparation process according to the invention in order to obtaining the mesostructured material according to the invention is advantageously carried out by heat treatment and preferably by calcination in air (optionally enriched in O ₂ ) in a temperature range of 300 to 1000 ° C and more precisely in a range of 500 to 600 ° C for a period of 1 to 24 hours and preferably for a period of 3 to 15 hours.

The preparation process according to the invention advantageously comprises, following the implementation of said step d), a step e) of regenerating said metal particles in the form of polyoxometallate optionally decomposed during step d). Said regeneration step e) is preferably carried out by washing the solid resulting from said step d) 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 e) is carried out for a period of 1 to 24 hours, preferably 1 to 8 hours. Said regeneration step e) is carried out when said metal particles in the form of polyoxometalate are decomposed during said step d). 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 d), can be partial or total. Said step e) is a step of partial or total regeneration of said metal particles.

Said step e) is followed by a drying step f) which is advantageously carried out at a temperature between 40 and 100 ° C and very advantageously between 40 and 85 ° C. Said step f) is carried out for a period of between 12 and 48 hours. Said step f) is preferably implemented only when the preparation method according to the invention comprises the implementation of said step e).

According to a first particular embodiment of the process for preparing the material according to the invention, at least one sulfur compound is introduced into the mixture according to said step a), or during the implementation of said step d) or still during the implementation of said step e) so as to obtain the mesostructured inorganic material according to the invention, at least partly but not totally, in sulphide form. Said sulfur compound is chosen from compounds containing at least one sulfur atom and whose decomposition with low temperature (80-90 ° C) causes the formation of H ₂ S. For example, said sulfur compound is thiourea or thioacetamide. According to said first particular embodiment, the sulfurization of said material according to the invention is partial so that the presence of sulfur in said mesostructured inorganic material does not completely affect the presence of said metal particles in the form of polyoxometalate. After sulphurisation, the particles in the form of polyoxometalates, preferably in the form of heteropolyanions, represent from 2 to 50% by weight, preferably from 4 to 40% by weight and very preferably from 6 to 30% by weight of the material of the invention. 'invention.

The mesostructured inorganic material according to the invention consisting of elementary spherical particles comprising metal particles in the form of polyoxometalate, trapped in a mesostructured matrix based on the oxide of at least one element Y, can be shaped into a powder form, balls, pellets, granules, extrudates (hollow cylinders or not, multilobed cylinders with 2, 3, 4 or 5 lobes for example, twisted rolls), or rings, etc., these formatting operations being carried out by conventional techniques known to those skilled in the art. Preferably, the material according to the invention is obtained in powder form, which consists of elementary spherical particles having a maximum diameter of 200 μηι.

The shaping operation of the mesostructured inorganic material according to the invention consists in mixing said mesostructured 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, montmorillonnite, 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 with a faujasite structure and in particular stabilized and ultrastabilized Y zeolites (USY) are advantageously employed in at least one form. partially exchanged with metal cations, for example alkaline earth metal cations and / or rare earth metal cations of atomic number 57 to 71 inclusive, or in the 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.

According to a second particular embodiment of the process for preparing the material according to the invention, independent or not of said first embodiment, one or more additional element (s) is introduced into the mixture according to said step a) of the preparation method according to the invention, and / or by impregnation of the material resulting from said d) with a solution containing at least said additional element and / or by impregnation of the material resulting from said f) with a solution containing at least said additional element and / or by impregnation of the mesostructured material according to the invention, previously shaped, 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. According to said second particular embodiment, one or more additional element (s) as defined above is (are) introduced during the implementation of the process for the preparation of the material according to the invention into a or several 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 an air calcination step, 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). 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. 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) . as heteropolyanion (X = boron in formula X _x m _m O _y h ^q _h ^"), in particular heteropoly Keggin, lacunary Keggin, substituted Keggin particularly may be mentioned the following heteropolyanion: acid The source of boron in the form of heteropolyanions is then introduced during step a) of the preparation process according to the invention. introduced by impregnation, said impregnation step with the boron source is carried out using, for example, a solution of boric acid in a water / alcohol mixture or in a water / ethanolamine mixture, the source of boron may also be impregnated with using a m a mixture of boric acid, hydrogen peroxide 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.

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. Phosphorus can 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 in the form of heteropolyanions, especially Keggin heteropolyanions, Keggin lacunary, Keggin substituted or Strandberg type. Mention may in particular be made of 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 during step a) 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, pyridine and quinoline family compounds, and pyrrole family compounds. 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 . Silicon may also be introduced together with one or more of the elements M selected from the list given above (M = vanadium, niobium, tantalum, molybdenum, tungsten, iron, copper, zinc, cobalt and / or nickel) as heteropolyanion (X = Si in the formula X _x m _m O _y h ^q _h ^") in the form heteropolyanion including heteropolyanion Keggin, lacunary Keggin, substituted Keggin. there may be mentioned in particular the following heteropolyanions: silicomolybdic acid and its salts, silicotungstic acid and its salts The source of silicon in the form of heteropolyanions is then introduced during step a) of the preparation process according to the invention. 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 a) of the process for preparing the material 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 mesostructured inorganic material according to the invention, or else by the establishment of 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 mesostructured inorganic material 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 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 metal (s) (ux) M preferably chosen from V, Nb, Ta, Mo and W is preferably between 0.05 and 0.9, even more preferably between 0.08 and 0.8, the dopant species and the metal (s) (ux) M preferably 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 according to the invention, of doping species and metal (ux) M preferably chosen from 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.

The mesostructured inorganic material according to the invention consisting of elementary spherical particles comprising metal particles in the form of polyoxometalates, trapped in a mesostructured oxide matrix, having an organized and uniform porosity in the field of mesoporosity, is characterized by several analysis techniques. and in particular by X-ray diffraction at low angles (XRD at low angles), X-ray diffraction at high angles (XRD), nitrogen volumetry (BET), transmission electron microscopy (TEM), microscopy scanning electron (SEM), by X-ray fluorescence (FX). The presence of polyoxometalates, especially heteropolyanions, is demonstrated by various techniques, in particular by Raman, UV-visible or infrared spectroscopies as well as by microanalysis. Techniques such as nuclear magnetic resonance (NMR) or electron paramagnetic resonance (EPR) (especially for reduced HPA, some of whose atoms have a reduced degree of oxidation compared to the initial degree of oxidation), may also be used. to be used according to the HPA employed.

The X-ray diffraction technique at low angles (values of the angle 2Θ between 0.5 and 5 °) makes it possible to characterize the periodicity at the nanoscale generated by the organized mesoporosity of the mesostructured matrix of the material of the invention. In the following description, the X-ray analysis is carried out on powder with a diffractometer operating in reflection and equipped with a rear monochromator using copper radiation (wavelength of 1.5406 Å). 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 of the material ((hkl) being the Miller indices of the reciprocal lattice) by the Bragg relation: 2 d _(h ki) * sin (θ) = n * λ. This indexing then allows the determination of the mesh parameters (abc) of the direct network, the value of these parameters being a function of the hexagonal, cubic or vermicular structure obtained. By way of example, the low angle X-ray diffractogram of a mesostructured material according to the invention consisting of elementary spherical particles comprising a mesostructured matrix based on silicon and aluminum obtained according to the preparation method according to the invention. invention via the use of the quaternary ammonium salt CH ₃ (CH ₂ ) 15 N (CH 3) 3 Br (CTAB), methyltrimethylammonium bromide has a perfectly resolved correlation peak corresponding to the characteristic p a vermicular-type structure defined by the Bragg relation 2

The X-ray diffraction technique at large angles (values of the angle 2Θ between 6 and 100 °) makes it possible to characterize a crystalline solid defined by the repetition of a unitary unit or unit cell at the molecular scale. It follows the same physical principle as that governing the low-angle X-ray diffraction technique. The DRX technique at large angles is therefore used to analyze the materials of the invention because it is particularly suitable for the structural characterization of zeolitic nanocrystals possibly present in each of the elementary spherical particles constituting the material defined according to the invention. In particular, it provides access to the pore size of these zeolitic nanocrystals. For example, during the eventual occlusion of zeolite nanocrystals of the ZSM-5 (MFI) type, the diffractogram at large angles associated with the peaks attributed to the group of symmetry Pnma (No. 62) zeolite ZSM-5. The value of the angle obtained on the diffractogram RX makes it possible to go back to the correlation distance d according to the Bragg law: 2 d _(hk | ₎ * sin (θ) = n * λ. The nitrogen volumetry corresponding to the physical adsorption of nitrogen molecules in the porosity of the material via a progressive increase in the pressure at constant temperature gives information on the particular textural characteristics (pore diameter, pore volume, specific surface area) of the material. material according to the invention. In particular, it 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", 19 1, 73, 373, written by EP Barrett, LG Joyner and PP Halenda. In the following description, the diameter of the mesospores φ of the mesostructured matrix corresponds to the average diameter at the adsorption of nitrogen defined as being a diameter such that all the pores smaller than this diameter constitute 50% of the pore volume (Vp) measured on the adsorption branch of the nitrogen isotherm. In addition, the shape of the nitrogen adsorption isotherm and the hysteresis loop can provide information on the nature of the mesoporosity and on the possible presence of microporosity essentially related to zeolitic nanocrystals when present in the mesostructured oxide matrix. By way of example, the nitrogen adsorption isotherm relative to a mesostructured material according to the invention, obtained according to the preparation process according to the invention and consisting of elementary spherical particles comprising a mesostructured matrix based on aluminum and silicon prepared via the use of the quaternary ammonium salt CH ₃ (CH ₂ ) i ₅ N (CH ₃ ) ₃ Br bromide (CTAB) is characterized by a Class IVc adsorption isotherm (IUPAC classification) with presence an adsorption step for values of Ρ / Ρ0 (where P0 is the saturating vapor pressure at the temperature T) of between 0.2 and 0.3 associated with the presence of pores of the order of 2 to 3 nm as confirmed by the associated porous distribution curve.

Concerning the mesostructured matrix, the difference between the value of the pore diameter φ and the mesh parameter defined by XRD at low angles as described above gives access to the magnitude e where e = a - φ and is characteristic of the thickness of the amorphous walls of the mesostructured matrix included in each of the spherical particles of the material according to the invention. Said mesh parameter a is connected to the distance d of correlation between pores by a geometric factor characteristic of the geometry of the phase. For example, in the case of a vermicular structure e = d - φ.

Transmission electron microscopy (TEM) is also widely used to characterize the structure of these materials. This allows the formation of an image of the studied solid, the contrasts observed being characteristic of the structural organization, the texture or the morphology of the particles observed, the resolution of the technique reaching a maximum of 1 nm. In the following description, the MET photos will be made from microtome sections of the sample in order to visualize a section of an elementary spherical particle of the material according to the invention. For example, the MET images obtained for a material according to the invention consisting of elementary spherical particles comprising metal particles trapped in a mesostructured matrix based on silicon oxide and aluminum which has been prepared via the use of the quaternary ammonium salt bromide of cetyltrimethylammonium CH ₃ (CH ₂ ) 15N (CH ₃ ) 3Br (CTAB) have within a same spherical particle a vermicular mesostructure (the material being defined by dark areas) within which opaque objects representing the zeolitic nanocrystals trapped in the mesostructured matrix. The analysis of the image also makes it possible to access the parameters d, φ and e, characteristics of the mesostructured matrix defined above. The morphology and size distribution of the elementary particles were established by scanning electron microscopy (SEM) photo analysis.

The mesostructuration of the material according to the invention can be vermicular, cubic or hexagonal depending on the nature of the surfactant chosen as a structuring agent.

The metal particles in the form of polyoxometalates, more preferably in the form of heteropolyanions (HP A), 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 is obtained of the order of 2 cm ^" '. The recorded spectral region 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 polyoxometalates, in particular HPAs. These include ³¹ P and ²⁹ Si NMR analyzes recorded on 300 or 400 MHz spectrometers. The subject of the present invention is also a process for converting a hydrocarbon feedstock comprising 1) bringing the mesostructured inorganic material into contact with a feedstock comprising at least one sulfur-containing compound, and then 2) bringing said material into contact with the feedstock. of said step 1) with said hydrocarbon feedstock. At the end of the implementation of said step 1) of the transformation process according to the invention, said inorganic mesostructured material is bifunctional, that is to say that it has both a hydro-dehydrogenating function, provided by the presence of a metal sulphide phase derived from polyoxometalates, preferentially heteropolyanions, and an acid function. The acid function is ensured by acidity properties intrinsic to said mesostructured matrix based on at least one oxide of said element Y and in which nanocrystals of zeolites are advantageously trapped. The acidity of the mesostructured matrix is generated when the material according to the invention comprises, for example, an acidic mesostructured oxide matrix possibly with trapping of nanocrystals of zeolites, themselves acidic or otherwise, or an oxide matrix. non-acidic mesostructured with trapping nanocrystals of zeolites themselves acidic. An acidic mesostructured oxide matrix advantageously comprises aluminum, titanium, germanium and / or tin as element Y.

According to said step 1) of the conversion process according to the invention, the metal particles in polyoxometallate form are sulphurized, preferably in the form of heteropolyanions, trapped within the mesostructured matrix of each of the spherical particles constituting the inorganic material according to the invention. The transformation of the metal particles in polyoxometallate form, preferably in the form of HPA, into their associated sulfide-active phase is carried out after temperature treatment of said inorganic material according to the invention in contact with hydrogen sulphide at a temperature of between 200 and 600 ° C. and more preferably between 300 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 according to the invention in the reaction unit of said transformation process (ex situ sulphurization). 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 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 sold by the company ATOFINA), 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 according to the invention according to methods that are well known to those skilled in the art, preferably by calcination under air in a temperature range of 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.

According to a first particular embodiment of the conversion process according to the invention, the hydrocarbon feedstock conversion process according to the invention is a hydrodesulfurization process of a gasoline cut made in the presence of a catalyst whose mesostructured material according to the invention. the invention is a precursor, said material being subjected to said sulfurization step i) to fulfill its role of catalyst.

Said hydrodesulfurization process, object of said first particular embodiment of the conversion process according to the invention, consists essentially in eliminating the sulfur compounds present in said gasoline cut in order to reach the environmental standards in force (sulfur content allowed up to at 10 ppm since 2009). Said gasoline cut contains a weight content of sulfur of between 200 and 5000 ppm, preferably between 500 and 2000 ppm. Said gasoline cuts, particularly the gasoline produced by catalytic cracking, contain a significant portion of branched olefins, thus constituting a good basis for high quality gasolines (high RON search octane number). However, they also contain diolefinic compounds, which cause the deactivation of the catalysts used in the processes of hydrodesulfurization by gum formation. One of the challenges associated with this hydrodesulfurization process therefore consists in a first step of selectively hydrogenating the diolefins and in a second step in hydrodesulfurizing the gasoline cut while maintaining a high proportion of olefins. Optimal reaction selectivity is sought, selectivity being defined as the ratio of catalytic activity in hydrodesulfurization to catalytic activity in hydrogenation.

Said mesostructured material according to the invention used, after sulfurization, as a catalyst in the hydrodesulfurization process according to the invention leads to very satisfactory catalytic performances, especially in terms of selectivity. It allows a thorough hydrodesulphurization of a gasoline cut, in particular a gasoline cut from a catalytic cracking unit, with high selectivity and reduced hydrogen consumption.

Preferably, the material according to the invention used, after sulphurization, as a catalyst for the implementation of said hydrodesulphurization process has a composition such that said metal particles trapped in each of said mesostructured matrices are in the form of heteropolyanions, in particular Anderson heteropolyanions, Keggin heteropolyanions and Strandberg heteropolyanions. Said heteropolyanions preferably have a formula such that the element X is preferably phosphorus and the element M is preferably one or more elements selected from molybdenum, tungsten, cobalt, nickel. The mesostructured matrix in which said heteropolyanions are trapped is preferably based on aluminum oxide, silicon oxide, a mixture of aluminum oxide and silicon, titanium oxide and aluminum oxide. zirconium. Preferred heteropolyanions are Anderson heteropolyanions of formula H ₆ CoMo ₆ 0 ₂₄ ^{3 "} and H ⁴ CO ² M0 ₁₀ O ³ S ^{6 '} , Keggin heteropolyanions of formula PMo ₁₂ O ₄₀ ^{3 ~} and substituted Keggin of formula PCoMonO ₄₀ ^7" or heteroplyanions Strandberg of formula H _h P ₂ Mo ₅ C> ₂ 3 ^{(6 "h) '} with h = 0, 1 or 2. Anderson heteropolyanions of formula H ₆ CoMo ₆ 0 ₂₄ ^3" and H ₄ Co ₂ Moio0 ₃ 8 ^{6 "} may be present singly or in combination Charges (first particular embodiment of the transformation process)

Said gasoline cut, treated according to said hydrodesulfurization process according to the invention, is a gasoline cut containing sulfur and olefinic hydrocarbons. It contains hydrocarbons having at least 2 carbon atoms per molecule, preferably at least 5 carbon atoms per molecule and has a final boiling point of less than or equal to 250 ° C. Said essence cut is preferably derived from a coking unit (coking according to the English terminology), a visbreaking unit (visbreaking according to the English terminology), a steam cracking unit (according to the terminology). Anglo-Saxon) or a fluid catalytic cracking unit (Fluid Catalytic Cracking, FCC according to the English terminology). Advantageously, said cut may optionally be composed of a significant fraction of gasoline from other production processes such as atmospheric distillation (gasoline from a direct distillation (or straight run gasoline according to the English terminology) or conversion processes (coking or steam-cracking gasoline), said gasoline cut is very preferably a cut gasoline from a catalytic cracking unit whose boiling point range extends from the boiling points of the 5-carbon hydrocarbons up to 250 ° C.

Operating conditions (first particular embodiment of the transformation process)

The hydrodesulphurization process of a gasoline cut, particularly a gasoline catalytic cracking cut, according to the invention is carried out under the following operating conditions: a temperature of between about 200 and 400 ° C., preferably between 250 and 350 ° C, a total pressure of between 1 MPa and 3 MPa and more preferably between 1 MPa and 2.5 MPa with a volume ratio of hydrogen gasoline volume volume of between 100 and 600 liters per liter and more preferably between 200 and and 400 liters per liter. Finally, the Hourly Volumetric Velocity (VVH) is the inverse of the contact time expressed in hours. It is defined by the ratio of the volume flow rate of the liquid gasoline fraction to the volume of catalyst charged to the reactor. It is generally between 1 and 10 h ^"1, preferably between 2 and 8 ^h".

Embodiments (first particular embodiment of the transformation method)

The technological implementation of the hydrodesulfurization process according to the invention is carried out, for example, by injecting the gasoline cutter and hydrogen into at least one fixed-bed, moving-bed or bubbling bed reactor, preferably in a reactor. fixed bed.

According to a second particular embodiment of the conversion process according to the invention, the hydrocarbon feedstock conversion process according to the invention is a process for the hydrodesulfurization of a gas oil fraction carried out in the presence of a catalyst whose mesostructured material according to the invention is a precursor, said material being subjected to said sulfurization step i) to fulfill its role of catalyst.

Said hydrodesulfurization process (HDS) according to the invention aims to eliminate the sulfur compounds present in said diesel fuel cup so as to reach the environmental standards in force, namely a sulfur content allowed up to 10 ppm since 2009.

The catalyst obtained after sulphurisation of the material according to the invention is a more active catalyst than the catalysts conventionally employed in the processes of hydrodesulphurization of the gas oil cuts, the improvement of the activity being related to a better dispersion of the active metallic sulphide phase. resulting from polyoxometalates, preferably HPA.

Preferably, the material according to the invention used, after sulfurization, as a catalyst for carrying out said method of hydrodesulfurization of a gas oil cut has a composition such that said metal particles trapped in each of said mesostructured matrices are presented in the form of heteropolyanions in which the element X is preferentially chosen from phosphorus and silicon, the element M is preferably chosen from molybdenum, tungsten and the mixture of these two elements, or the element M is preferentially selected from a mixture of molybdenum and a Group VIII metal selected from cobalt and nickel, a mixture of tungsten and a Group VIII metal selected from cobalt and nickel. The mesostructured matrix in which said heteropolyanions are trapped is preferably based on aluminum oxide, silicon oxide or a mixture of aluminum oxide and silicon (Y = Si, Al and their mixture). Preferred heteropolyanions are the heteropolyanions HPCoMol iO ₄₀ ^{6 '} , PMo ₁₂ O ₄₀ ^{3 "} and PW ₁₂ 0 ₄ o ^3" or else Strandberg heteroplyanions of formula H _h P ₂ Mo 50 23 ^{(6 "h)"} with h = 0, 1 or 2. Charges (second particular embodiment of the transformation process)

The diesel to hydrodesulfurized cut according to the process of the invention contains from 0.04 to 5% by weight of sulfur. It is advantageously derived from the straight distillation (or straight run diesel according to English terminology), a coking unit (coking according to the English terminology), a visbreaking unit (visbreaking according to the English terminology). Saxon), a steam cracking unit (steam cracking in the English terminology) and / or a fluid catalytic cracking unit (Fluid Catalytic Cracking, FCC according to the English terminology). Said gasoil fraction has a boiling point preferably between 250 and 400 ° C.

Operating conditions (second particular embodiment of the transformation process)

The hydrodesulfurization process according to the invention is carried out under the following operating conditions: a temperature of between approximately 200 and 400 ° C., preferably between 330 and 380 ° C., a total pressure of between 2 MPa and 10 MPa and more preferably between 3 MPa and 7 MPa with a volume ratio of hydrogen per volume of hydrocarbon feedstock of between 100 and 600 liters per liter and more preferably between 200 and 400 liters per liter and an hourly space velocity (VVH) of between 1 and 10 h ^" ', preferably between 2 and 8 h ^{" 1} . The VVH is the inverse of the contact time expressed in hours and is defined by the ratio of the volume flow rate of the liquid hydrocarbon feedstock by the volume of catalyst charged to the reaction unit implementing the hydrotreatment process of the gas oils according to the invention. invention.

Embodiments (second particular embodiment of the transformation method)

The reaction unit implementing the hydrodesulfurization process for gas oils according to the invention is preferably carried out in a fixed bed, in a moving bed or in a bubbling bed, preferably in a fixed bed. According to a third particular embodiment of the conversion process according to the invention, the hydrocarbon feedstock conversion process according to the invention is a hydrocracking process of a hydrocarbon feedstock of which at least 50% by weight of the compounds have a point d initial boiling greater than 340 ° C. and a final boiling point of less than 540 ° C., said process being carried out in the presence of a catalyst whose mesostructured material according to the invention is a precursor, said material being subjected to said step sulfurization i) to fulfill its role of catalyst.

Said hydrocracking process essentially consists in producing lighter fractions such as medium-grade essences or distillates of very good quality, in particular light jet fuels and gas oils, from heavy loads that can not be upgraded. It also provides a highly purified residue that can provide excellent bases for oils. In general, the hydrocracking catalysts used in the hydrocracking processes are all of the bifunctional type associating an acid function with a hydro-dehydrogenating function. According to the hydrocracking process of the invention, the acid function is provided either by using, as a mesostructured matrix in the material of the invention, an aluminosilicate acid matrix or by introducing / trapping zeolite nanocrystals in the mesostructured oxide matrix. , preferably based on an aluminum oxide or a silicon oxide, or again using as mesostructured matrix in the material of the invention an acidic matrix of aluminosilicate type in which are trapped zeolite nanocrystals. The balance between the two acid and hydro-dehydrogenating functions is one of the key parameters that govern the activity and selectivity of the catalyst. According to said hydrocracking process according to the invention, the hydro-dehydrogenating function is provided by the element or elements M present in the metal particles in the form of polyoxometalates, preferably in the form of heteropolyanions, the said (s) ) element (s) M being defined as above.

The catalyst obtained after sulfurization of the material according to the invention leads to optimum catalytic performance when used in a hydrocracking process in comparison with the catalysts conventionally used in such a process. In particular, it makes it possible to obtain catalytic performances at least equivalent to those obtained with the existing catalysts while requiring a substantially reduced content in the active phase, in particular in the metal (ux) providing the hydro-dehydrogenating function such as molybdenum and / or tungsten.

The catalyst obtained after sulfurization of the material according to the invention is advantageous for improving the dispersion of the hydro-hydrogenating phase and controlling the size of the sulphide particles. Preferably, the material according to the invention used, after sulfurization, as a catalyst for carrying out said process for hydrocracking a hydrocarbon feedstock, has a composition such that said metal particles trapped in each of said mesostructured matrixes are present in the form of heteropolyanions in which the element X is preferentially chosen from phosphorus and silicon, the element M is preferably chosen from molybdenum, tungsten and the mixture of these two elements, or the element M is preferentially chosen from a mixture of molybdenum and a Group VIII metal selected from cobalt and nickel, a mixture of tungsten and a Group VIII metal selected from cobalt and nickel. The mesostructured matrix in which said heteropolyanions are trapped is preferably based on aluminum oxide, silicon oxide or a mixture of aluminum oxide and silicon oxide (Y = Si, Al and their mixed). Preferred heteropolyanions are the heteropolyanions of eggin, especially the heteropolyanion of formula PWi ₂ O ₀ ^{3 "} .

Charges (third particular embodiment of the transformation process)

Said hydrocarbon feedstock used in the hydrocracking process according to the invention is a hydrocarbon feedstock of which at least 50% by weight of the compounds have an initial boiling point of greater than 340 ° C. and a final boiling point of less than 540 ° C. C., preferably at least 60% by weight, preferably at least 75% by weight and more preferably at least 80% by weight of the compounds have an initial boiling point greater than 340 ° C. and a d final boiling below 540 ° C.

Said hydrocarbon feedstock is advantageously chosen from vacuum distillates (DSV), effluents from a catalytic cracking unit FCC (Fluid Catalytic Cracking), light gas oils from a catalytic cracking unit ( or LCO for Light Cycle Oil according to the English terminology), the heavy cutting oils (HCO for Heavy Cycle Oil according to the English terminology), the paraffinic effluents resulting from the Fischer Tropsch synthesis, the effluents resulting from the distillation under such as, for example, gas oil fractions of the VGO (Vacuum Gas Oil) type, the effluents resulting from the process of liquefying coal, the feedstocks resulting from the biomass or the effluents resulting from the conversion of feedstock from the biomass, and the aromatic extracts and fillers derived from aromatics extraction units, taken alone or as a mixture. Preferably, said hydrocarbon feed is a vacuum distillate cut. The vacuum distillate cut is generally derived from the vacuum distillation of crude oil. Said vacuum distillate slice comprises aromatic compounds, olefinic compounds, naphthenic compounds and / or paraffinic compounds. Said vacuum distillate cutoff advantageously comprises heteroatoms chosen from nitrogen, sulfur and the mixture of these two elements. When the nitrogen is present in said feedstock to be treated, the nitrogen content is greater than or equal to 500 ppm, preferably said content is between 500 and 10000 ppm by weight, more preferably between 700 and 4000 ppm by weight and so even more preferred between 1000 and 4000 ppm. When the sulfur is present in said feedstock to be treated, the sulfur content is between 0.01 and 5% by weight, preferably between 0.2 and 4% by weight and even more preferably between 0.5 and 3%. % weight Said vacuum distillate cut may advantageously contain metals, in particular nickel and vanadium. The cumulative nickel and vanadium content of said vacuum distillate fraction is preferably less than 1 ppm by weight. The asphaltene content of said hydrocarbon feedstock is generally less than 3000 ppm, preferably less than 1000 ppm, even more preferably less than 200 ppm.

In a preferred embodiment, said vacuum distillate type hydrocarbon feedstock (DSV) may be used such that it, that is to say alone or in mixture with other hydrocarbon cuts, preferably chosen from the effluents from a FCC (Fluid Catalytic Cracking) catalytic cracking unit, light gas oils from a catalytic cracking unit (or LCO for Light Cycle Oil according to the English terminology), heavy cutting oils (HCO for Heavy Cycle Oil according to the English terminology), atmospheric residues and vacuum residues resulting from the atmospheric and vacuum distillation of crude oil, paraffinic effluents resulting from Fischer Tropsch synthesis, effluents resulting from vacuum distillation, such as that, for example, gas oil fractions of the VGO type (Vacuum Gas Oil according to the English terminology), the dehalphalated oils or DAO (Deasphalted Oil according to the English terminology), the s effluents from the coal liquefaction process, biomass feedstocks or effluents from the conversion of feedstock from biomass, and aromatic extracts and feedstocks from aromatics extraction units, taken alone or in mixture. In the preferred case where said vacuum distillate type hydrocarbon feedstock (DSV) is used in admixture with other hydrocarbon cuts, said hydrocarbon fractions added alone or as a mixture, are present at at most 50% by weight of said mixture, preferably at at most 40% by weight, preferably at most 30% by weight and more preferably at most 20% by weight of said mixture.

Operating conditions (third particular embodiment of the transformation process)

The hydrocracking process according to the invention is carried out under operating conditions (temperature, pressure, hydrogen recycling rate, hourly space velocity) which can be very variable depending on the nature of the feedstock, the quality of the feedstock and the feedstock. desired products and facilities available to the refiner. According to the hydrocracking process according to the invention, said hydrocracking catalyst is advantageously brought into contact, in the presence of hydrogen, with said hydrocarbon feedstock at a temperature above 200 ° C., often between 250 and 480 ° C. advantageously between 320 and 450 ° C, preferably between 330 and 435 ° C, under a total pressure greater than 1 MPa, often between 2 and 25 MPa, preferably between 3 and 20 MPa, the space velocity (volume flow rate) load divided by the volume of the catalyst) being between 0, 1 and 20h ^'! and preferably between 0, 1 and 6h ^" , preferably between 0.2 and 3h ^" , and the amount of hydrogen introduced is such that the volume ratio by liter of hydrogen / liter of hydrocarbon is between 80 and 50001/1 and most often between 100 and 2000 1/1 These operating conditions used in the hydrocracking process according to the invention generally make it possible to achieve pass conversions, products having boiling points from plus 370 ° C and advantageously of at most 340 ° C, greater than 15% and even more preferably between 20 and 95% Embodiments (third particular embodiment of the conversion process)

The hydrocracking process covers the pressure and conversion ranges from mild hydrocracking to high pressure hydrocracking. Mild hydrocracking means hydrocracking leading to moderate conversions, generally less than 40%, and operating at low pressure, generally between 2 MPa and 10 MPa. The catalyst used in said hydrocracking process according to the invention can be used alone, in one or more fixed bed or bubbling bed catalytic beds, in one or more reactors, in a one-step hydrocracking scheme or in two steps well known to those skilled in the art, with or without liquid recycling of the unconverted fraction, optionally in combination with a hydrorefining catalyst located upstream of the catalyst used in the hydrocracking process according to the invention. According to a fourth particular embodiment of the conversion process according to the invention, the hydrocarbon feedstock conversion process according to the invention is a hydroconversion process of a heavy hydrocarbon feedstock of which at least 55% by weight of the compounds have a point. boiling point greater than or equal to 540 ° C., said process being carried out in the presence of a catalyst whose mesostructured material according to the invention is a precursor, said material being subjected to said sulphurization step i) to fulfill its role of catalyst .

Said hydroconversion process according to the invention consists in hydrotreating and converting "heavy" petroleum fractions containing metallic impurities into lighter fractions in order to produce fillers that can be used in conversion processes such as catalytic cracking in a fluidized bed ( FCC) or hydrocracking or to produce fuels, including fuels, respecting the specifications in force. Thus, said hydroconversion process allows a reduction in the sulfur content: present in a content of between 3 and 6% by weight in the feeds to be treated, the sulfur content is generally less than 1% by weight in the effluent from hydroconversion process according to the invention. Similarly, the nitrogen content is advantageously reduced by at least 70% by weight and the elimination of the metals, in particular nickel and vanadium, initially present in the feedstocks to be treated at a level of a few tens to a few hundred ppm is advantageously pushed to reach conversions of the order of 80 to 90%, (that is to say that most often the content of metals, in particular nickel and vanadium, is less than 100 ppm by weight, preferably less than at 50 ppm weight in the effiuent).

The catalyst obtained after sulfurization of the material according to the invention makes it possible to limit the sintering phenomenon of the active phase while ensuring good accessibility of the reagents and reaction products to the active surface of the catalyst. In particular, it allows a better stability vis-à-vis the sintering during the implementation at high temperature or during regeneration treatments that the known catalysts whose active phase is not derived from polyoxometallate species, in particular heteropolyanions.

Preferably, the material according to the invention used, after sulfurization, as a catalyst for carrying out said hydroconversion process of a heavy hydrocarbon feedstock, has a composition such that said metal particles trapped in each of said mesostructured matrices are in the form of heteropolyanions in which the element X is preferentially chosen from phosphorus, silicon and boron, the element M is preferably chosen from molybdenum, tungsten and the mixture of these two elements; M element is preferably selected from a mixture of molybdenum and a Group VIII metal selected from cobalt and nickel, a mixture of tungsten and a Group VIII metal selected from cobalt and nickel. The mesostructured matrix in which said heteropolyanions are trapped is preferably based on aluminum oxide, silicon oxide or a mixture of aluminum oxide and silicon oxide (Y = Si, Al and their mixed). Preferred heteropolyanions are Strandberg heteropolyanions, for example the heteropolyanion of the formula H ₂ P ₂ O ₅ O ₂ 3 ^- .

These steps are generally carried out under high hydrogen pressure and at high temperature in fixed bed or bubbling type reactors depending on the level of metal contaminants contained in the charges.

Charges (fourth particular embodiment of the transformation process)

The hydrocarbon feedstock used in the hydroconversion process according to the invention is a hydrocarbon feedstock of which at least 55% by weight of the compounds have an initial boiling point of greater than 540 ° C., preferably at least 65% by weight, preferably at least 75% by weight and more preferably at least 85% by weight of the compounds have an initial boiling point greater than 540 ° C. Said hydrocarbon feedstock of which at least 55% by weight of the compounds have an initial boiling point of greater than 540 ° C. is advantageously chosen from deasphalted oils, atmospheric residues and vacuum residues, taken alone or as a mixture, and preferably charge is a deasphalted oil or DAO also called Deasphalted Oil according to the English terminology. Said dehalphalated oil is also called dehalphalted residue in the rest of the text.

Said deasphalted residue feed or DAO has the advantage of not containing an asphaltenic fraction containing a large amount of coke precursors and metals. Said deasphalted residue feedstock or DAO is obtained from vacuum distillation residue (RSV) cuts resulting from the vacuum distillation of crude oil, or from conversion process residues such as coking, after a desalphating treatment allowing to eliminate asphaltenes by a paraffinic solvent extraction operation preferably chosen from propane, pentane and heptane. The residual asphaltene content in said deasphalted residue feedstock at the end of this desalting step is preferably less than 1% by weight and makes it possible to obtain significantly longer cycle times for the consecutive conversion processes of said feedstock. deasphalted residue type.

In a preferred embodiment, said deasphalted residue feedstock or DAO may be used such that it, that is to say alone or in mixture with other hydrocarbon cuts, preferably chosen from vacuum distillate slices whose boiling point varies between 340 ° C and 540 ° C, effluents from an FCC catalytic cracking unit, light gas oils from a catalytic cracking unit (or LCO), heavy cut (HCO), distillates from processes for the desulphurisation or hydroconversion of atmospheric residues and / or residues under vacuum in a fixed bed or in a bubbling bed, paraffinic effluents resulting from Fischer Tropsch synthesis, effluents resulting from vacuum distillation, such as, for example, gasoil fractions of the VGO (Vacuum Gas Oil) type, the effluents resulting from the process of liquefying coal, the feedstocks resulting from the biomass or the effluents resulting from the conversion of feedstock from the biomass, and aromatic extracts and fillers from aromatics extraction units, alone or in admixture. In the preferred case where said deasphalted residue feed or DAO is used in admixture with other hydrocarbon cuts, said hydrocarbon cuts added alone or in admixture, are present at most at 45% by weight of said mixture, preferably at most % by weight, preferably at most 25% by weight and more preferably at most 15% by weight of said mixture.

Operating conditions and embodiment (fourth particular embodiment of the transformation process)

The hydroconversion catalyst, the mesostructured material according to the invention is a precursor, can be used in a fixed bed reactor at a temperature generally between 320 and 450 ° C, preferably between 350 and 410 ° C under a hydrogen partial pressure of between approximately 3 and 30 MPa, preferably between 10 and 20 MPa, and at a volume hourly velocity of between 0.05 and 5 volumes of filler per volume of catalyst and per hour, preferably between 0 and , 2 and 0.5. The ratio of hydrogen gas to liquid feedstock, expressed in normal cubic meters, is between 200 and 5000 Nm ³ , preferably between 500 and 1500 Nm ³ .

The hydroconversion catalyst, whose mesostructured material according to the invention is a precursor, can also be used in a bubbling bed reactor at a temperature of between 320 and 470.degree. C., preferably between 400 and 450.degree. at a hydrogen partial pressure of between 3 and 30 MPa, preferably between 10 and 20 MPa, at a volume hourly velocity of between 0.1 and 10 volumes of filler per volume of catalyst and per hour, preferably between 0, 2 and 2 and with an input hydrogen gas ratio on liquid charge volume of between 100 and 3000 Nm ³ , preferably between 200 and 1200 Nm ³ .

Preferably, said hydroconversion catalyst is implemented in a bubbling bed reactor.

According to a fifth particular embodiment of the conversion process according to the invention, the hydrocarbon feedstock conversion process according to the invention is a process for the hydrotreatment of a heavy hydrocarbon feedstock of which at least 50% by weight, preferably at least 70% by weight, hydrocarbon compounds present in said feed have a boiling point greater than or equal to 370 ° C, said process comprising at least a first step of hydrodemetallation of said feedstock followed by a second hydrotreating step carried out in presence of a catalyst whose mesostructured material according to the invention is a precursor, said material being subjected to said sulphurization step i) to fulfill its role of catalyst.

Said two-stage hydrotreating process according to said fifth particular embodiment makes it possible, for example, to produce a heavy fuel oil of improved purity meeting the specifications in force or else a charge which can be valorized in conversion processes such as catalytic cracking or hydrocracking. which can then serve as a basis for producing fuels. The said two-stage hydrotreatment process is intended to treat a heavy hydrocarbon feed, of which at least 50% by weight, preferably at least 70% by weight, of the hydrocarbon compounds present in the said feedstock have a boiling point greater than or equal to 370 ° C. C, so as to obtain a hydrocarbon fraction having an improved hydrogen to carbon ratio (H / C), that is to say higher, and whose impurity content is substantially reduced. The impurities present in said feed are in particular sulfur, nitrogen, conradson carbon, asphaltenes, metals, especially vanadium and nickel. The hydrotreatment process comprises a first step of pretreating said hydrocarbon feedstock to reduce the content of metals (hydrodemetallation), asphaltenes, nitrogen and carbon conradson. The second step, following the first step, consists of reducing the sulfur content (hydrodesulfurization), nitrogen (hydrodenitrogenation) and aromatic compounds. More particularly, said second step essentially aims at reducing the sulfur content of the feedstock pretreated in said first step and is advantageously assimilated to a hydrodesulfuratton step. The feedstock treated by the catalyst carrying out the implementation of said second step, said catalyst being obtained after sulphurisation of the material according to the invention, is substantially depleted of metals and asphaltenes. The material according to the invention used, after sulfurization, as a catalyst for the implementation of said second step makes it possible to optimize the transfer of material inside said catalyst and to develop within said catalyst a better active phase. dispersed and therefore more active than the active phases conventionally used in hydrotreatment heavy load. The material according to the invention used, after sulfurization, as a catalyst also makes it possible to limit the risks of sintering of the active phase which are well known to those skilled in the art.

Charges (fifth particular embodiment of said transformation process)

The heavy hydrocarbon feedstocks, of which at least 50% by weight, preferably at least 70% by weight, of the hydrocarbon compounds have a boiling point greater than or equal to 370 ° C., to be hydrotreated according to the method, object of said fifth embodiment, Examples are vacuum distillates, atmospheric residues, vacuum residues from direct distillation, deasphalted oils, residues from conversion processes such as those from a coker unit or a hydroconversion unit. in a fixed bed, in a bubbling bed, or in a moving bed and mixtures of each of these sections. Said hydrocarbon feeds to be hydrotreated are advantageously constituted by either one or more cuts or one or more of said fraction (s) diluted with a hydrocarbon fraction or a mixture of hydrocarbon fractions which may be chosen from a light cutting oil ( LCO according to the initials of the Anglo-Saxon name of Light Cycle Oil), a heavy cutting oil (HCO according to the initials of the English name of Heavy Cycle Oil), a decanted oil (OD according to the initials of the Anglo-Saxon name). Decanted Oil), a slurry (pre-sludge), the products resulting from the FCC process or that can come directly from the distillation, the gas oil fractions especially those obtained by vacuum distillation called according to the English terminology VGO (Vaccuum Gas Oil). Said heavy hydrocarbon feeds to be hydrotreated may advantageously comprise, in certain cases, one or more cuts from the liquefaction process of the coal as well as aromatic extracts.

Said heavy charges to be hydrotreated according to the process, object of said fifth embodiment, may advantageously be mixed with coal in powder form, this mixture is generally called slurry (petroleum sludge). Said charges then advantageously comprise by-products derived from the conversion of the coal and re-mixed with fresh coal. The coal content in said heavy loads at hydrotreating is such that the volume ratio filler / coal is between 0.1 and 1, preferably between 0.15 and 0.3. The coal may contain lignite, be a sub-bituminous coal (according to Anglo-Saxon terminology), or bituminous. Any other type of coal is suitable for carrying out said hydrotreatment process.

Said heavy hydrocarbon feedstocks to be hydrotreated according to said two-stage hydrotreatment process advantageously contain from 0.5 to 6% by weight of sulfur. They generally have more than 1% by weight of molecules having a boiling point greater than 500 ° C. They have a metal content, especially nickel and vanadium, greater than 1 ppm by weight, preferably greater than 20 ppm by weight, an asphaltenes content, defined as the fraction of the charge precipitating in heptane, greater than 0.05. % by weight, preferably greater than 1% by weight.

Operating conditions (fifth particular embodiment of said transformation process)

Said hydrodemetallization step (first step) and said hydrotreating step, more preferably said hydrodesulfurization step (second step), implemented in the hydrotreatment process according to the invention can be carried out in fixed bed reactors. or in bubbling bed. Advantageously, said hydrodemetallization step is carried out in a reactor operating in a bubbling bed and said hydrotreating step, more preferably said hydrodesulfurization step, is carried out in a reactor operating in a fixed bed.

When one and / or the other of said first and second stages is (are) implemented in a reactor operating in a fixed bed, the operating conditions are as follows: a temperature of between 320 and 450 ° C., preferably between 350 and 410 ° C under a hydrogen partial pressure of between about 3 and 30 MPa, preferably between 10 and 20 MPa, and at an hourly space velocity of between 0.05 and 5 volumes of filler by volume of catalyst and per hour, preferably between 0.2 and 0.5. The gaseous hydrogen input to liquid charge ratio, expressed in normal cubic meters, is between 200 and 5000 Nm ³ , preferably between 500 and 1500 Nm ³ .

When one and / or the other of said first and second stages is (are) implemented in a reactor operating as a bubbling bed, the operating conditions are as follows: a temperature of between 320 and 470.degree. preferably between 400 and 450 ° C, under a hydrogen partial pressure of between 3 and 30 MPa, preferably between 10 and 20 MPa, at an hourly space velocity of about 0.1 to 10 volumes of filler per volume of catalyst and per hour, preferably between 0.2 and 2, and with an input hydrogen gas ratio on liquid charge volume of between 100 and 3000 Nm ³ , preferably between 200 and 1200 Nm ³ .

Embodiment (fifth particular embodiment of said transformation method)

The hydrotreatment catalyst, whose mesostructured material according to the invention is a precursor, can be used in any process known to those skilled in the art, allowing the hydrotreatment of heavy hydrocarbon feeds, for example atmospheric or vacuum residues. It can be implemented in any type of reactor operated in fixed bed or moving bed or bubbling bed. The catalyst used for the implementation of said first step, said step of hydrodemetallization or pretreatment, of said two-stage hydrotreating process advantageously has a bimodal porosity (US 7.1 19.045) or multimodal porosity (EP 0.098.764 and EP 1.579 .909) on which metals of the group are deposited VIB (molybdenum or tungsten) and group VIII (nickel, cobalt or iron) or the group VB (vanadium). The hydrodemetallation catalyst comprises from 1 to 30% by weight relative to the total mass of the trioxide of at least one group VIB element, preferably from 2 to 20% by weight and even more preferably from 2 to 10% by weight. . The hydrodemetallization catalyst also comprises from 0 ^"to 2.2% by weight relative to the total mass of the oxide of at least one element from group VIII, preferably from 0.5 to 2% by weight, and most still more preferably from 0.5 to 1.5% by weight In addition, the hydrodemetallization catalyst contains between 0 and 15% by weight, based on the total weight of at least one element of group VB, preferably between 0 and 10% by weight and even more preferably between 0.2 and 5% by weight It may contain doping elements chosen from phosphorus, boron, titanium, silicon or fluorine The content of boron or phosphorus pentoxide is advantageously between 0 and 10% by weight, preferably between 0.2% and 7%, and even more preferably between 0.5% and 5%, The catalyst used in the first stage of the hydrotreatment process has BET surface greater than 50 m ² / g, preferably greater than 80 m ² / g.The pore volume occupied p the pores with a diameter greater than 50 nm are greater than or equal to 0.1 ml / g, preferably greater than or equal to 0.15 ml / g. The total pore volume, measured by mercury porosimetry, is advantageously between 0.5 and 1.5 ml / g, preferably between 0.7 and 1.2 ml / g and even more preferably between 0.8 ml. and 1.2 ml / g, with a mesopore porous distribution (diameter less than 50 nm) centered on a mean diameter of between 4 and 17 nm, preferably between 7 and 16 nm and even more preferably between 10 and 16 nm. and 15 nm.

The material according to the invention used, after sulfurization, as a catalyst for the implementation of said second step of the hydrotreatment process has a composition and structure that is advantageous for reducing the content of sulfur (hydrodesulfurization), nitrogen (hydrodenitrogenation ) and aromatic compounds and further reducing the metal content, engaged in said first step. Preferably, the material according to the invention used, after sulfurization, as a catalyst for the implementation of said second step has a composition such that said metal particles trapped in each of said mesostructured matrices are in the form of heteropolyanions in which the element X is preferably chosen from phosphorus and silicon, the element M is preferably chosen from molybdenum, tungsten and the mixture of these two elements, or the element M is preferably chosen from a mixture of molybdenum and a Group VIII metal selected from cobalt and nickel, a mixture of molybdenum and a Group VB metal selected from vanadium, niobium and tantalum. The mesostructured matrix in which said heteropolyanions are trapped is preferably based on aluminum oxide, silicon oxide or a mixture of aluminum oxide and silicon (Y = Si, Al and their mixture). Preferred heteropolyanions are the heteropolyanions PMoi ₂ 0 ₄ o ^{3 "} , HPNiMo _n 0 ₄ o ^{6 '} , and ΡνΜθπΟ ₄₀ ^"

The total mass content of molybdenum and / or tungsten is advantageously between 1 and 30% expressed in% by weight of oxide relative to the mass of the final material, preferably between 2 and 20% and even more preferably between 4 and 15%. The total mass content of metal of group VIII chosen from cobalt and nickel and the group VB metal chosen from vanadium, niobium and tantalum is advantageously between 0 and 15% expressed in% by weight of oxide relative to the mass of the final material, preferably between 0.5 and 10% and even more preferably between 1 and 8%. A doping element chosen from phosphorus, silicon, boron and fluorine is advantageously added. The preferred doping element is phosphorus. The contents of doping elements are between 0.5 and 10% by weight, preferably between 1 and 8% by weight, and even more preferred between 2 and 6% weight. The atomic ratio between the doping element and the group VIII element chosen from cobalt and nickel is preferably chosen between 0 and 0.9, even more preferably between 0.2 and 0.8. According to a sixth particular embodiment of the conversion process according to the invention, the hydrocarbon feedstock conversion process according to the invention is a process for hydrotreating a hydrocarbon feedstock comprising triglycerides, said process being carried out in the presence of a catalyst whose mesostructured material according to the invention is a precursor, said material being subjected to said sulfurization step 1) to fulfill its role of catalyst.

More particularly, said hydrotreatment process consists in producing hydrocarbon bases of the middle distillate type (gas oil, kerosene) from hydrocarbon feedstocks derived from renewable sources.

Purpose of the process

The international context of the years 2005-2010 is marked first and foremost by the rapid growth in need of fuels, in particular diesel fuel bases, in the European community and then by the importance of the problems related to global warming and the emission of greenhouse gas. The result is a desire to reduce energy dependence on fossil-based raw materials and to reduce C0 ₂ emissions. In this context, the search for new hydrocarbon feedstocks from renewable sources that can be easily integrated into the traditional pattern of refining and fuel production is an issue of growing importance. As such, the integration into the refining process of new products of plant origin, resulting from the conversion of lignocellulosic biomass or from the production of vegetable oils or animal fats, has in recent years experienced a very lively renewed interest due to the rising cost of fossil fuels. Similarly, traditional biofuels (mainly ethanol or methyl esters of vegetable oils) have acquired a real status of complement to petroleum bases in fuel pools.

The very high molecular weight (greater than 600 g / mol) of triglycerides, essential components of renewable sources, and the high viscosity of the feedstocks considered make their direct or mixed use in diesel fuel a problem for modern HDI engines. which are diesel engines with direct injection and turbocharger (incompatibility with very high pressure injection pumps, problem of fouling of the injectors, uncontrolled combustion, low yields, emissions of unburnt toxic). However, the hydrocarbon chains that are present in the triglycerides are essentially linear and their length (number of carbon atoms) is compatible with the hydrocarbons present in the gas oils. It is therefore necessary to transform these charges to obtain a good quality diesel base and / or a kerosene cut meeting the specifications in force, after mixing or adding additive known to those skilled in the art. For diesel, the final fuel must meet the EN590 standard and for kerosene it must meet the specifications outlined in IATA (International Air Transport Association) Guidance Material for Aviation Turbine Fuel Specifications, 6th Edition, May 2008 such as ASTM Elm D1655. The hydrotreatment of hydrocarbon feeds comprising triglycerides, especially vegetable oils, implements complex reactions which are favored by a hydrogenating catalytic system. These reactions include:

the hydrogenation of the unsaturations, that is to say the carbon-carbon double bonds present on the hydrocarbon chains of the triglycerides and of all the fatty substances present in the feed to be hydrotreated,

deoxygenation according to two reaction routes:

- the hydrodeoxygenation: elimination of oxygen by consumption of hydrogen and leading to the formation of water,

decarboxylation / decarbonylation: removal of oxygen by formation of carbon monoxide and carbon dioxide: CO and CO ₂ ,

hydrodenitrogenation: elimination of nitrogen by formation of NH ₃ .

The presence of unsaturations makes said charge unstable thermally. Moreover, the hydrogenation of these unsaturations is strongly exothermic. The process for hydrotreatment of hydrocarbon feedstocks comprising triglycerides is particularly flexible in order to be able to treat very different feeds in terms of unsaturations, such as, for example, soybean and palm oils, or oils of animal origin or derived from algae. and enables the hydrogenation reaction of the unsaturations to be initiated at the lowest possible temperature by avoiding heating in contact with a wall which would cause hot spots of said charge, inducing the formation of gums and causing fouling and increasing the pressure drop of the catalyst bed (s).

The catalyst obtained after sulfurization of the material according to the invention leads to optimal catalytic performances when it is used in a hydrotreatment process of a hydrocarbon feed comprising triglycerides. In particular, it allows the production of paraffins, from loads derived from renewable hydrocarbon sources, meeting the fuel specifications and in particular the standards in force for diesel fuel and kerosene. It makes it possible to limit the formation of phase refractory to sulphurization and to implement the hydrotreatment process at a more moderate temperature.

Preferably, the material according to the invention used, after sulphurization, as a catalyst for carrying out said hydrotreatment process for a hydrocarbon feedstock, has a composition such that said metal particles trapped in each of said mesostructured matrixes are present in the form of heteropolyanions in which the element X is preferably selected from phosphorus, boron and silicon, the element M is preferably selected from molybdenum, tungsten and the mixture of these two elements or the M element is preferably selected from a mixture of molybdenum and a Group VIII metal selected from cobalt and nickel, a mixture of tungsten and a Group VIII metal selected from cobalt and nickel. The mesostructured matrix in which said heteropolyanions are trapped is preferably based on aluminum oxide, silicon oxide or a mixture of aluminum oxide and silicon oxide (Y = Si, Al and their mixed). Preferred heteropolyanions are Strandberg heteropolyanions, in particular the heteropolyanion of the formula H2P2M05O ₂ 3 ^{4 -} . Charges (sixth particular embodiment of the transformation process)

Among the feedstock from renewable sources that can be used in the hydrotreatment process according to the invention, mention may be made, for example, of vegetable oils (whether or not they are food) or derived from algae, animal fats or used frying oils, crude or pre-treated, as well as mixtures of such fillers. These fillers essentially contain triglyceride-type chemical structures which the person skilled in the art also knows under the name tri-ester of fatty acids. A triester of fatty acid or triglyceride is composed of three hydrocarbon chains of fatty acids. The hydrocarbon chains which constitute these triglyceride-type molecules are essentially linear and have a number of unsaturations per chain generally between 0 and 3, but which may be higher, especially for oils derived from algae. Vegetable oils and other fillers of renewable origin also have different impurities, in particular compounds containing heteroatoms such as nitrogen, and elements such as Na, Ca, P, Mg. The feedstocks from renewable sources used in the hydrotreatment process according to the present invention are advantageously chosen from oils and fats of vegetable or animal origin, and mixtures of such fillers, containing triglycerides. They also advantageously contain free fatty acids and / or esters of free fatty acids. Vegetable oils can advantageously be crude or refined, wholly or in part, and derived from the following plants: rapeseed, sunflower, soybean, palm, palm kernel, olive, coconut, jatropha, this list not being limiting. Algae or fish oils are also relevant. Animal fats are advantageously chosen from lard or fats composed of residues from the food industry or from the catering industries. These fillers essentially contain triglyceride-type chemical structures composed of three fatty acid chains. They can also contain. fatty acid chains in the form of free fatty acids. All of the fatty acid chains present in the feed each have a number of unsaturations per chain, also called the number of carbon-carbon double bonds per chain, generally between 0 and 3, but which may be higher, in particular for oils derived from algae which may have a number of unsaturations per chain of 5 to 6. The molecules present in the feeds from renewable sources used in the present invention therefore have a number of unsaturations, expressed per molecule of triglyceride, advantageously between 0 and 18. In these fillers, the unsaturation level, expressed as the number of unsaturations per hydrocarbonaceous fatty chain, is advantageously between 0 and 6. Charges from renewable sources generally also comprise different impurities, and especially heteroatoms. such as nitrogen. Nitrogen levels in vegetable oils are generally between about 1 ppm and about 100 ppm by weight, depending on their nature. They can reach up to 1% weight on particular loads. These fillers can be used pure or in admixture with petroleum effluents such as direct distillation gas oils, distillates under vacuum. Operating conditions (sixth particular embodiment of the transformation process)

The hydrotreatment process according to the invention is carried out under the following operating conditions: a temperature of between 250 ° C. and 400 ° C., a pressure of between 1 MPa and 10 MPa, preferably between 3 MPa and 10 MPa. and even more preferably between 3 MPa and 6 MPa, an hourly volume velocity of between 0.1 hr ^-1 and 10 hr ^-1 and preferably between 0.2 and 5 hr ^-1 . The total amount of hydrogen mixed with the liquid feed to be hydrotreated is such that the hydrogen / hydrocarbons entering the catalytic zone or zones is between 200 and 2000 Nm ³ hydrogen / m ³ of feedstock, preferably between 200 and 1800 and very preferably between 500 and 1600 Nm ³ of hydrogen / m ³ of filler. The hydrogen-rich gas stream may advantageously come from a hydrogen booster and / or the recycling of the gaseous effluent resulting from the separation step described below, the gaseous effluent containing a hydrogen-rich gas having previously undergone one or more intermediate purification treatments before being recycled and mixed.

Embodiments (sixth particular embodiment of the transformation method)

The hydrotreatment catalyst, the mesostructured material according to the invention is a precursor, can be used in any process known to those skilled in the art, allowing the production of gas oils and / or kerosene. It can be implemented in any type of reactor operated in fixed bed, alone or in combination with another catalyst. Following the hydrotreatment step, the effluent produced is subjected to a separation step to obtain a gaseous effluent and a hydrotreated liquid effluent, at least a portion of which is recycled upstream of the hydrotreatment reaction zone. The gaseous effluent contains mainly hydrogen, carbon monoxide and carbon dioxide, light hydrocarbons of 1 to 5 carbon atoms and water vapor. The purpose of this separation step is therefore to separate the gases from the liquid, and in particular to recover the hydrogen-rich gases and at least one hydrotreated liquid effluent preferably having a nitrogen content of less than 1 ppm by weight.

The hydrotreated liquid effluent consists essentially of n-paraffins which are advantageously incorporated into the diesel pool and / or the kerosene pool. In order to improve the cold properties of this hydrotreated liquid effluent, an optional hydroisomerization step is preferably carried out to transform n-paraffins into branched paraffins having better properties when cold. The hydroisomerization step is advantageously carried out in a separate reactor, nevertheless, in the case where the hydroisomerization catalyst is identical to that of the hydrotreatment step and therefore to the catalyst of the invention, the whole The process can be conducted in a single step in the same reactor containing one or more catalytic zones. The optional hydroisomerization step operates at a temperature between 150 and 500 ° C, preferably between 150 ° C and 450 ° C, and very preferably between 200 and 450 ° C, at a pressure of between 1 MPa and 10 MPa, preferably between 2 MPa and 10 MPa and very preferably between 1 MPa and 9 MPa, at an hourly space velocity advantageously between 0.1 h ^-1 and 10 h ^-1 , preferably between 0, 2 and 7 h ^-1 and very preferably between 0.5 and 5 h ^-1 , at a hydrogen flow rate such that the volume ratio hydrogen / hydrocarbons is advantageously between 70 and 1000 Nm ³ / m ³ of load between 100 and 1000 normal m ³ of hydrogen per m ³ of filler and preferably between 150 and 1000 normal m ³ of hydrogen per m ³ of filler. Preferably, the optional hydroisomerization step operates cocurrently.

The hydrotreated effluent or the hydrotreated and hydroisomerized effluent is then advantageously subjected at least in part, and preferably in all, to one or more separations. The purpose of this step is to separate the gases from the liquid, and in particular to recover the hydrogen-rich gases that may also contain light such as the Ci-C ₄ cut and various liquid effluents, in particular at least one gas oil cut (cut 250 ° C +), at least one kerosene cut (cut 150-250 ° C) of good quality and at least one naphtha cut which may advantageously be sent-in-a steam cracking or catalytic reforming unit.

The products, diesel base and kerosene, obtained according to the hydrotreatment process according to the invention and in particular after hydroisomerization are endowed with excellent characteristics. The diesel base obtained, after mixing with a petroleum diesel fuel derived from renewable fuels such as coal or lignocellulosic biomass, and / or with an additive, is of excellent quality: its sulfur content is less than 10 ppm by weight, its content in total aromatics is less than 5% by weight, and the content of polyaromatic less than 2% by weight, its cetane number is excellent, namely greater than 55, its density is less than 840 kg / m ³ , and most often higher at 820 kg / m ³ , its kinematic viscosity at 40 ° C is 2 to 8 mm ² / s, its cold-holding properties are compatible with the standards in force, with a filterability limit of less than -15 ° C and a cloud point below -5 ° C.

The kerosene cut obtained after mixing with a petroleum kerosene derived from a renewable filler such as lignocellulosic coal or biomass and / or with an additive has the following characteristics: a density of between 775 and 840 kg / m ³ , a viscosity at 20 ° C less than 8 mm ² / s, a point of disappearance of crystals less than -47 ° C, a flash point higher than 38 ° C, a smoke point greater than 25 mm.

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. On the basis of the synthesis protocols described, the amounts of catalyst material are adapted according to the intended applications. 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 examples which follow, has been described above.

Example 1 Preparation of a Material A According to the Invention Having Anderson Type HPA of Formula

total equal to 21.3% weight MoO? and 5.5% weight CoQ relative to the final material in a mesostructured oxide-based silicon matrix.

An aqueous solution containing 2.10 mol / l of M0O3 (Axens) and 12.6 mol / l of H ₂ 0 ₂ is prepared with stirring at room temperature. A solution of Co (CO ₃ ) ₂ (Alfa Aesar) is then carefully introduced to avoid any exotherm, so as to obtain a final concentration of 1.05 mol / l of Co (CO ₃ ) ₂ . Raman analysis, performed on the final material, reveals the presence of HPA Anderson H ₆ CoMo ₆ 0 ₂₄ ^{3 '} , 3 / 2Co ²⁺ and H ₄ Co ₂ Mo ₁₀ O38 ^6' , ₃ Co ²⁺ as majority species . 2.94 ml of this 0.21 mol / l solution in HPA are removed and added to a solution containing 10.6 g of TEOS previously hydrolysed for 16 hours in 18.9 g of water and 6.90 mg of HCl. A solution containing 3.79 g of F127 (BASF Corporation) and 12.8 mg of HCl in 18.7 g of water and 8.31 g of ethanol is prepared and stirred at room temperature for 16 hours. The solution containing the HPA salts and the hydrolysed TEOS is homogenized for 10 minutes and is then mixed dropwise with the F127-containing solution. The whole is stirred 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. 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 salts are then regenerated by washing with Soxhlet of the solid with methanol for 2 hours. The solid is finally dried at 80 ° C for 24 hours. The solid is characterized by low angle XRD, nitrogen volumetric, TEM, SEM, FX, and Raman spectroscopy. The TEM analysis shows that the final material has an organized mesoporosity characterized by a vermicular structure. The nitrogen volumetric analysis leads to a specific surface area of the final material of S _B ET ⁼ 328 m ² / g and to a mesoporous diameter of 7.4 nm. The small-angle XRD analysis leads to the visualization of a correlation peak at the angle 2Θ = 0.78. The Bragg 2 ratio d * sin (0.39) = 1.5406 makes it possible to calculate the correlation distance d between the pores of the mesostructured matrix, ie d = 14.6 nm. The thickness of the walls of the matrix of the mesostructured material defined by e = d - φ is therefore e = 7.2 nm. An SEM image of the spherical elementary particles thus obtained indicates that these particles have a size characterized by a diameter ranging from 50 to 700 nm, the size distribution of these particles being centered around 300 nm. The Raman spectrum of the final material shows the characteristic bands of the two Anderson HPA salts: Co ₂ Mo ₁₀ (Co) at 957, 917, 602, 565, 355, 222 cm ^-1 and CoMo ₆ (Co) at 952. , 903, 575, 355, 222 cm ^-1 .

Example 2 Preparation of a Material B According to the Invention Having HPA Keggin Type HPCoMonC ^{6 '} . 3Co ²⁺ and PMonO ^' . 3 / 2Co ²⁺ with a total content of 20% by weight of MoO ₂ and 3.8% by weight of CoO and 0.8% by weight of P ₂ Qs relative to the final material in a mesostructured matrix based on silicon.

A solution containing 0.30 mol / 1 of H3PM012O40, 13H ₂ 0 is prepared at room temperature. To this solution are added 0.97 mol / l, relative to the final solution, of Ba (OH) ₂ , 8H ₂ O and 1, 31 mol / l, relative to the final solution, of COSO 4, 7H ₂ O After stirring for two hours, a precipitate of BaSO ₄ is formed. This is separated from the solution by two successive filtrations. The HPA salts are obtained by dry evaporation of the filtrate. Raman analysis, performed on the final material, reveals the presence of Keggin HPCoMo _n O4 ₀ ^{6 '} and PMoi ₂ O ₄₀ ^{3 "} HPA, a solution containing 10.8 g of TEOS and 18.9 g of water and 6.90 mg of HCl is hydrolysed for 16 h Another solution is prepared by dissolving 3.78 g of F127 in 8.30 g of EtOH and 35.1 g of water for 12 hours. After the hydrolysis, 1.03 g of the salts of HPA are added to the solution containing TEOS After 10 minutes of stirring, this solution is added dropwise. to the aquoethanol solution of F127, the whole is stirred 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 The temperature of the drying oven is fixed at 350 ° C. The harvested powder is then calcined in air for 5 hours at T = 550 ° C. The HPA is then regenerated by Soxhlet washing of the solid with methanol for 2 hours. The solid is finally dried at 80 ° C for 24 hours. The solid is characterized by low angle XRD, nitrogen volumetric, TEM, SEM, FX, and Raman spectroscopy. The TEM analysis shows that the final material has an organized mesoporosity characterized by a vermicular structure. The nitrogen volumetric analysis gives a specific surface area of the final material of S _B ET = 335 m ² / g and a mesoporous diameter of 7.4 nm. The small-angle XRD analysis leads to the visualization of a correlation peak at the angle 2Θ = 0.78. The Bragg 2 ratio d * sin (0.39) = 1.5406 makes it possible to calculate the correlation distance d between the pores of the mesostructured matrix, ie d = 14.6 nm. The thickness of the walls of the matrix of the mesostructured material defined by e = d - φ is therefore e = 7.2 nm. An SEM image of the spherical elementary particles thus obtained indicates that these particles have a size characterized by a diameter ranging from 50 to 700 nm, the size distribution of these particles being centered around 300 nm. The material obtained has a Raman spectrum comprising bands characteristic of the heteropolyanion salts of the HPCoMo O ₄₀ ^{6 '} and the PMoi ₂ O ₄₀ ^{3 "} eg HPCoMonO ₄₀ ^6' main bands are at 232, 366, 943 and 974. cm ^"1 . The most intense band characteristic of this type of Keggin lacunar HPA is 974 cm- ^{1, the} main bands of PMo ₁₂ 0 ₄ o ^{3 '} being 251, 603, 902, 970, 990 cm- ¹ . The most intense band characteristic of this Keggin HPA is 990 cm ^-1 .

Example 3 Preparation of a Material C According to the Invention Having Keggin Type HPA of Formula

relative to the final material. The mesostructured oxide matrix is based on aluminum and silicon, the molar ratio Si / Al being equal to 0.37. Impregnation of Ni with a total content equal to 2.6% by weight of NiO with respect to the final material.

10.0 g of aluminum trichloride hexahydrate are dissolved in 21.1 g of water and 7.70 mg of HCl. After 10 min of dissolution 3.21 g of TEOS are added. Hydrolysis of this solution is carried out for 16 hours. A solution is prepared by dissolving 4.21 g of F127 in 36.9 g of water and 14.3 mg of HCl and 9.24 g of ethanol, the solution is stirred at room temperature for 16 h. 2.88 ml of an aqueous solution of H ₃ PW _{I 2} O ₄₀ at 0.37 mol / l of HPA are added to the solution containing TEOS and AICL, hydrolysed. After 10 minutes, this solution is added dropwise into the aquoethanol solution of the surfactant. The whole is stirred 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. 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 the solid with Soxhlet with methanol for 2 hours. The solid is finally dried at 80 ° C for 24 hours. The nickel promoter is deposited on the solid thus obtained by dry impregnation. The pore volume of the solid is filled with an aqueous solution of nickel nitrate at 1.02 mol / l. The solution is added dropwise to the solid in a dry impregnation mode. The solid is left to cure for 12 hours and is then dried in an oven at a temperature of 120 ° C for 12h. The solid is characterized by low angle PRX, nitrogen volumetric, TEM, SEM, FX, and Raman spectroscopy. The TEM analysis shows that the final material has an organized mesoporosity characterized by a vermicular structure. The nitrogen volumetric analysis leads to a specific surface area of the final S _{BET material} = 180 m ² / g and to a mesoporous diameter of 7.2 nm. The small angle XRD analysis leads to the visualization of a correlation peak at the angle 2Θ = 0.64. The Bragg 2 ratio d * sin (0.32) = 1.5406 makes it possible to calculate the correlation distance d between the pores of the mesostructured matrix, ie d = 14.2 nm. The thickness of the walls of the matrix of the mesostructured material defined by e = d - φ is therefore e = 7.0 nm. An SEM image of the spherical elementary particles thus obtained indicates that these particles have a size characterized by a diameter ranging from 50 to 700 nm, the size distribution of these particles being centered around 300 nm. The material obtained has a Raman spectrum comprising characteristic bands of the Keggin PWi ₂ O ₄₀ ^{3 "} type heteropolyanion, and the principal bands of PWi ₂ O ₄₀ ^3" are 216, 518, 990, 1004 cm ^-1 .

with a total content equal to 14% by weight of MoCK and 2.9% by weight of NiO and 2.8% by weight of P-> Q <relative to the final material in a mesostructured matrix based on aluminum and silicon with a Si / Si molar ratio Ai = 0.5.

An aqueous solution containing 3.61 mol / l MoO ₃ , 1.44 mol / l of H ₃ PO ₄ , 1.44 mol / l of Ni (OH) ₂ is prepared with stirring at room temperature. The Raman analysis, carried out on the final material, reveals the presence of 1ΉΡΑ Strandberg H2P ₂ M05O23 ^{4 "} as the majority species 8.60 g of aluminum trichloride hexahydrate are dissolved in 20.0 g of water and 7, After 10 min of dissolution, 3.71 g of TEOS are added, the hydrolysis of this solution is carried out for 16 h A solution is prepared by dissolving 4.01 g of F127 and 2.18 g of PPO (propylene oxide) in 35.7 g of water and 13.6 mg of HCl and 8.80 g of ethanol, the solution is stirred at room temperature for 16 hours. aqueous H2P2 05O23 ^{4 "to} 0.72 mol / 1 in HPA were added to the solution containing the TEOS and A1C1 ₃ hydrolyzed. After 10 minutes, this solution is added dropwise into the aquoethanol solution of the surfactant. The whole is stirred 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. 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 the solid with Soxhlet with methanol for 2 hours. The solid is finally dried at 80 ° C for 24 hours. The solid is characterized by low angle XRD, nitrogen volumetric, TEM, SEM, FX, and Raman spectroscopy. The TEM analysis shows that the final material has an organized mesoporosity characterized by a vermicular structure. Nitrogen volumetric analysis leads to a specific surface area of the final material of S _B ET ⁼ 180 m ² / g and a mesoporous diameter of 8.5 nm. The small-angle XRD analysis leads to the visualization of a correlation peak at the angle 2Θ = 0.63. The Bragg relation d * sin (0.31) = 1.5406 makes it possible to calculate the correlation distance d between the pores of the mesostructured matrix, ie d = 14 nm. The thickness of the walls of the matrix of the mesostructured material defined by e = d - φ is therefore e = 5.5 nm. An SEM image of the spherical elementary particles thus obtained indicates that these particles have a size characterized by a diameter ranging from 50 to 700 nm, the size distribution of these particles being centered around 300 nm. The material obtained has a Raman spectrum comprising characteristic bands of the Strandberg heteropolyanion H2P2M05O23 ^{4 "} .The principal bands of H2P2M05O23 ^4" are located at 370, 395, 893 and 942 cm ^"1 . such as HPA Strandberg is at 942 cm ^" '.

EXAMPLE 5 Preparation of a Material E According to the Invention with HPA Keggin PVMonOjn ^{4 "} Type.

NiO and 0.69% by weight of V ₂ Q <; relative to the final material in a mesostructured oxide matrix based on aluminum and silicon of molar ratio Si / Al = 0.1.

The HPA is obtained by dissolving in molybdenum water in M0O3 form and phosphorus in H3PO ₄ form in the concentrations of 1.88 mol / l and 0.17 mol / l respectively and after complete dissolution of vanadium V ₂ 0 ₅ in the concentration of 0.085 mol / 1. Raman and NMR phosphorus analysis, performed on the final material shows the presence of HPA substituted Keggin PVMOnO ^ ^", PV ₂ Mo ₁₀ 0 B ^{5 ',} ^{6 PV3M09O40"} and PV ₄ Mo ₈ OO ^{7 "} , as the majority species, 12.0 g of aluminum trichloride hexahydrate are dissolved in 19.7 g of water and 7.20 mg of HCl. 04 g of TEOS are added The hydrolysis of this solution is carried out for 16 hours A solution is prepared by dissolving 3.93 g of F127 and 2.19 g of PPO (propylene oxide) in 35.8 g of water and 13.3 mg of HCl and 8.63 g of ethanol, the solution was stirred at room temperature for 16 hours. 1.45 ml of an aqueous solution of ₄₀ PVMoiiO ^{4 ",} 4H ⁺ 0, 17 mol / l of HPA are added to the solution containing the hydrolysed TEOS and A1C1 ₃ . After 10 minutes, this solution is added dropwise into the aquoethanol solution of the surfactant. The whole is stirred 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. 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 the solid with Soxhlet with methanol for 2 hours. The solid is finally dried at 80 ° C for 24 hours. The solid is characterized by low angle XRD, nitrogen volumetric, TEM, SEM, FX, and Raman spectroscopy. The TEM analysis shows that the final material has an organized mesoporosity characterized by a vermicular structure. Nitrogen volumetric analysis leads to a specific surface area of the final material of S _B ET ⁼ 180 m ² / g and a mesoporous diameter of 8.5 nm. The small-angle XRD analysis leads to the visualization of a correlation peak at the angle 2Θ = 0.63. The Bragg relation d * sin (0.31) = 1.5406 makes it possible to calculate the correlation distance d between the pores of the mesostructured matrix, ie d = 14 nm. The thickness of the walls of the matrix of the mesostructured material defined by e = d - φ is therefore e = 5.5 nm. An SEM image of the spherical elementary particles thus obtained indicates that these particles have a size characterized by a diameter ranging from 50 to 700 nm, the size distribution of these particles being centered around 300 nm.

The particles thus obtained are then impregnated with a solution of nickel nitrate of a volume equal to the pore volume of the particles and such that the Ni / Mo ratio is equal to 0.35. The solid obtained is dried for 12 hours at 120 ° C. The Raman spectrum of the obtained material reveals the presence of a mixture of the 4 Keggin heteropolyanions of formula PVMo _u 0 ₄ o ^" , PV ₂ Moi ₀ 0 ₄ o ^5" , PV 3M0 ₉ O40 ^{6 '} and PV ₄ Mo ₈ 0 ₄ o ⁷ \ as evidenced by the presence of an intense band at 981 cm ^"1 accompanied by a shoulder at 967 ^cm" and subbands to 888 ^{cm -1,} 615 cm ^", 478 ^{cm" 1} and 256 cm ^{" 1} .

2Ni ²⁺ with a total content equal to 21% weight of MoQ ?. 4.3% weight of NiO and 4.1% by weight of P? Os relative to the final material in a mesostructured matrix based on aluminum and silicon with a Si / Al molar ratio = 0.1.

An aqueous solution containing 3.61 mol / l of M0O3, 1.44 mol / l of H ₃ PO ₄ , 1.44 mol / l of Ni (OH) ₂ is prepared with stirring at room temperature. The Raman analysis, performed on the final material, reveals the presence of ΓΗΡΑ Strandberg H2P2 05O23 ^{4 "} as the majority species, 10.3 g of aluminum trichloride hexahydrate are dissolved in 20.2 g of water and 7.40 After 10 min of dissolution, 0.89 g of TEOS are added, the hydrolysis of this solution is carried out for 16 hours and a solution is prepared by dissolving 4.04 g of F127 in 34.9 g of HCl. water and 13.7 mg of HCl and 8.86 g of ethanol, the solution was stirred at room temperature for 16 hours. 2.65 ml of an aqueous solution of H2P2M05O23 ^"to 0.72 mol / 1 HPA are added to the solution containing the hydrolysed TEOS and A1C1 ₃ . After 10 minutes, this solution is added dropwise into the aquoethanol solution of the surfactant. The whole is stirred 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. 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 the solid with Soxhlet with methanol for 2 hours. The solid is finally dried at 80 ° C for 24 hours. The solid is characterized by low angle XRD, nitrogen volumetry, TEM, FX, and Raman spectroscopy. The TEM analysis shows that the final material has an organized mesoporosity characterized by a vermicular structure. The nitrogen volumetric analysis gives a specific surface area of the final material of S _B ET ⁼ 180 m ² / g and a mesoporous diameter of 5.6 nm. The small angle XRD analysis leads to the visualization of a correlation peak at the angle 2Θ = 0.64. The Bragg 2 ratio d * sin (0.32) = 1.5406 makes it possible to calculate the correlation distance d between the pores of the mesostructured matrix, ie d = 13.1 nm. The thickness of the walls of the matrix of the mesostructured material defined by e = d - φ is therefore e = 7.5 nm. An SEM image of the spherical elementary particles thus obtained indicates that these particles have a size characterized by a diameter ranging from 50 to 700 nm, the size distribution of these particles being centered around 300 nm. The material obtained has a Raman spectrum comprising bands characteristic of Strandberg H ₂ P ₂ Mo ₅ 0 ₂ 3 ^{4 '} type heteropolyanion. The main bands of H2P2M05O23 ^{4 "} are 371, 394, 892 and 941 cm- ¹ . The most intense band characteristic of this type of Strandberg HPA is 941 cm ^"1 .

Example 7: Use of the material A as precursor of a catalyst A¾ for the hydrodesulphurization of a gasoline cut from model molecules representative of a catalytic cracking gasoline.

The catalyst obtained after sulphurization of material A is evaluated on a representative model charge of a catalytic cracking gasoline (FCC) containing 10% by weight of 2,3-dimethylbut-2-ene and 0.33% by weight of 3-methylthiophene ( 1000 ppm of sulfur with respect to the load). The solvent used is heptane. The catalyst obtained after sulphurization of the material A is noted A _s .

A conventional C0M0 catalyst denoted Al containing 2.9% by weight of CoO and 10.3% by weight of M0O ₃ supported on a transition alumina and having a specific surface area equal to 135 m ² / g and a pore volume equal to 1, 12 cnvVg is used as a reference. The cobalt and molybdenum present in this catalyst A1 are not in the form of HPA.

The material A and the catalyst Al are previously ex-situ sulphurized in the gas phase at 500 ° C. for 2 h under a stream of H ₂ S in H ₂ (15% by volume of H ₂ S in H ₂ ). The catalysts A _s (compliant) and Al _s (non-compliant) are thus obtained respectively. The material A is subjected to a shaping step prior to the sulphurization step, said shaping step consisting of pelletizing, crushing and sieving to recover only the samples having a particle size of between 1 and 2 mm . The catalyst Al is shaped in a manner analogous to the material A.

The hydrodesulfurization reaction is carried out in a closed Grignard reactor under a hydrogen pressure of 3.5 MPa at 250 ° C. Each of the catalysts A _s and A l _s are successively placed in said reactor. Samples are taken at different time intervals and are analyzed by gas chromatography to observe the disappearance of the reagents. The activity of the catalyst is expressed as the rate constant kHDS of the hydrodesulfurization reaction (HDS), normalized by volume of catalyst in sulphide form, assuming an order 1 with respect to the sulfur compounds. The selectivity of the catalyst is expressed in normalized ratio of the rate constants kHDS / kHDO, kHDO being the rate constant for the olefin hydrogenation reaction (HDO), namely in this case for the hydrogenation reaction of the 2, 3-dimethylbut-2-ene, normalized by volume of catalyst in sulphide form, assuming an order 1 with respect to olefins. The ratio kHDS / kHDO will be all the higher as the catalyst will be all the more selective. An increase in the ratio kHDS / kHDO is therefore favorable on the quality of the gasoline obtained after the hydrodesulfurization reaction, since the hydrogenation of the olefins has been limited, the loss of octane number of the resulting essence is greatly minimized.

The results of the catalytic performances are shown in Table 1. The values are normalized by taking the conventional CoMo / alumina catalyst as a reference and taking kHDS / kHDO = 100 and kHDS = 100.

Table 1: Catalytic performances of the catalyst A _s on a model load

The results in Table 1 demonstrate that a catalyst whose non-sulphured form (i.e. the oxide form) contains metal particles in the form of heteropolyanions trapped in a mesostructured matrix allows a significant gain in the selectivity without deterioration of the activity in HDS compared with the conventional catalyst Al _s . The catalyst A _s according to the invention is more selective than the conventional catalyst: it limits the hydrogenation of 2,3-dimethylbut-2-ene to 2,3-dimethylbut-2-ane making it possible to obtain a gasoline of better quality (better octane) than that obtained with the conventional catalyst A - It follows that for a low residual sulfur content in gasoline, the octane number will be much less reduced using the catalyst A _s according to the invention.

Example 8: Use of the material B as precursor of a catalyst for the hydrotreatment of a direct distillation gas oil feedstock.

In this example, a reference catalyst (denoted B 1) will be used: a CoMoP / alumina catalyst having the following composition: 21% by weight of MoO ₃ , 4.3% by weight of CoO and 4% by weight of P ₂ 0 ₅ with respect to solid final. It is marketed by the company Axens. Before in-situ sulphurization, the material B and the catalyst B 1 are subjected to a forming step consisting of pelletizing, crushing and sieving to recover only the samples having a particle size of between 1 and 2 mm.

The in situ sulphurisation of the material B and the catalyst B 1 (30 cm ³ of the material B respectively of the catalyst B 1 mixed with 10 cm ³ of SiC with a particle size of 0.8 mm) is carried out at 50 bar, at VVH = 2 hours ^{. 1} , with a ratio (of volume flow) H ₂ / HC (hydrocarbons) entry = 400 Std 1/1. The sulfurization charge (2% dimethyl disulphide additive gas oil, Evolution of Arkema) is introduced into the reactor under H ₂ when it reaches 150 ° C. After one hour at 150 ° C, the temperature is increased with a ramp of 25 ° C / hour up to 220 ° C, then with a ramp of 12 ° C / hour until reaching a plateau of 350 ° C, maintained 12 hours. The catalysts Bs (compliant) and B l _s (non-compliant) are thus obtained. After sulphurization, the temperature is lowered to 330 ° C and the test diesel fuel is injected. The catalytic test is carried out at a total pressure of 50 bar, with hydrogen lost (without recycling), at VVH = 2 h ^-1 , with an H ₂ / HC volume ratio at the inlet of 400 Std 1/1 (flow rate H ₂ = 24 Std lh ^"1 , flow rate = 60 cm ³ .h ^" ') and 340 ° C.

In order to be able to evaluate the performances of the B _s and B l _s catalysts in HDS, and to avoid the presence of H ₂ S in the effluents, the receptacle containing the effluents is stripped with nitrogen at a rate of 10 lh ^"1 .

The diesel fuel used here comes from a heavy Arab crude. It contains 0.89% by weight of sulfur, 100 ppm by weight of nitrogen, 23% by weight of aromatic compounds. Its weighted average temperature (TMP) is equal to 324 ° C and its density is equal to 0.848 g / cm ³ . TMP is defined as the ratio [(T ₅ + 2T ₅ o + 4T ₉₅ ) / 7] where T _x is the temperature at which "x"% weight is distilled. The TMP thus takes into account the temperature at which 5% by weight of the filler is vaporized, the temperature at which 50% by weight of the filler is vaporized and the temperature at which 95% by weight of the filler is vaporized.

Catalysts Performance B and B _s l _s are given in Table 2. They are expressed in relative activity, assuming that that of catalyst B l _s is equal to 100 and assuming they are of apparent order 1 5 with respect to sulfur. The relationship between activity and conversion to hydrodesulfurization (% HDS) is given by the formula

where% HDS is the conversion to HDS hydrodesulfurization and is defined by the following formula:

% HDS = ^S ^ ^{e ~ S} ^ "^> x 100

vs

charge

S representing sulfur.

The results obtained in hydrodesulfurization during this test were reported in Table 2 in which the catalyst B _s according to the invention was compared to the industrial catalyst B l _s .

Table 2: Relative activity (catalyst iso-volume) in HDS of straight run diesel

catalysts B _s and B l _s at T = 340 ° C

The results in Table 2 show the significant HDS gain in activity obtained with the catalyst B _s of the invention relative to the catalyst B l _s business. Example 9.1: Use of the material C as precursor of a C¾ catalyst for the hydrogenation of toluene in the presence of aniline.

Hydrogenation test of toluene in the presence of Aniline ("HTA" test) is intended to evaluate the HYDrogénante activity (HYD) of sulfide catalysts supported in the presence of H ₂ S and under hydrogen pressure. The isomerization and cracking that characterize the acid function of a hydrocracking catalyst are inhibited by the presence of NH ₃ (following the decomposition of the aniline) so that the HTA test allows to appreciate specifically the hydrogenating power of each of the catalysts tested. The aniline and / or NH ₃ will thus react via an acid-base reaction with the acid sites of the support. Each HTA test was performed on a unit with several microreactors in parallel. For each HTA test, the same charge is used for the sulphidation of the catalyst and for the actual catalytic test phase. 4 cm ³ of catalyst mixed with 4 cm ³ of carborundum (SiC, 60 μπι) are loaded into the reactors.

The load used for this test is as follows:

- Toluene 20% by weight,

Cyclohexane 73.62% by weight,

DMDS (DiMethylDiSulphide) 5.88% by weight (3.8% by weight in S),

Aniline 0.5% by weight (750 ppm N).

Material C is charged to the reactors in its oxide, non-active form. The activation (sulphurisation) is carried out in the unit with this same charge. It is the H ₂ S which, formed following the decomposition of the DMDS, sulphides the oxide phase. The amount of aniline present in the feed was chosen to obtain, after decomposition, about 750 ppm of NH ₃ . As a result of the sulphurization, the catalyst C is obtained. Prior to loading, the material C is subjected to a shaping step consisting of pelletizing, crushing and sieving to recover only the samples having a particle size of between 1. and 2 mm.

The operating conditions of the hydrogenation test of toluene are as follows:

- P = 6 MPa,

- VVH = 2 h ^-1 (charge flow = 8 cnvVh),

H ₂ / HC = 450 Nl / l, (H ₂ stream = 3.6 Nl / l),

- T = 350 ° C.

The percentage of converted toluene is evaluated and, assuming an order 1 of the reaction, the hydrogenating activity is deduced by the following relation:

, ioo

with% HYD, ₀ , _uene = percentage of converted toluene.

A commercial catalyst noted Cl of NiW formulation (27% by weight in WO ₃ ) prepared on a silica alumina type support and comprising 30% by weight of silica in the support is shaped and sulphurated according to the same protocol as those respectively carried out to obtain the catalyst C _$ . This gives the catalyst Cl _s which has an activity taken for reference equal to 100. The catalyst C _s (in accordance with the invention) has a relative activity equal to 105 relative to the commercial catalyst Cl _s , which demonstrates that the catalyst according to the invention has a hydrogenating activity per W atom much higher than the commercial catalyst which has 14% more W atoms than the catalyst of the invention. Catalyst C _s makes it possible to generate the same hydrogenating activity than a commercial catalyst which is loaded with 14% of atoms of additional W relative to catalyst C _s of the invention. EXAMPLE 9.2 Gentle Hydrocracking Evaluation of DSV Catalysts C (Invention) and Cl (Non-Conforming) The feed used is a vacuum distillate type feedstock (DSV), the main characteristics of which are given in the table below.

IT + 2T + 4T

*: Temperature Weighted Average = ^5% ^n% _w ith _x T o _{/ o} corresponding to the boiling temperature

7

x wt.% of hydrocarbon compounds present in the liquid cut.

This feed is additive of DMDS and aniline to present 2% by weight of sulfur and 900 ppmN.

4 cm ³ of material C in oxide form and then 4 cm ³ of catalyst Cl are charged into the reactors. Activation (sulfidation) is performed in the reaction unit before starting the test with the charge described above. It is the H ₂ S which, formed following the decomposition of the DMDS, sulphides the material C. The catalysts C ' _s and Cl' _{s are} respectively obtained.

The operating conditions applied during the test are as follows:

- P = 6 MPa,

- VVH = 0.6 h ^" ,

H ₂ / HC _output = 480 Nl / l,

- T = 380 ° C.

The catalytic results are summarized in Table 3. The crude conversion corresponds to the conversion of the hydrocarbon fraction having a boiling point greater than 370 ° C. present in the initial DSV feedstock to hydrocarbons having a boiling point below 370 ° C. ° C and present in the effluent. The gross conversion is determined to be equal to the weight fraction of hydrocarbons having a boiling point below 370 ° C and present in the effluent.

The catalytic results are summarized in Table 3 below. The catalyst C 'according to the invention makes it possible to maintain the crude conversion at a level as high as the commercial catalyst C1s while it contains 14% fewer tungsten atoms. The catalyst C 'is therefore as active as the commercial catalyst Cl' and has a hydrodesulphurizing activity as high as that of the commercial catalyst Cl ' _s . Table 3: Catalytic performances obtained for catalysts C ' _s and Cl' _s in mild hydrocracking.

Example 10: Use of the material D as precursor of a catalyst D. for the hydroconversion of heavy hydrocarbon cuts. Evaluation of the Bubble Bed Catalytic Performance on the C7 DAO Filler The hydrocarbon feedstock tested is a deasphalted oil (DAO), the characteristics of which are shown in Table 4.

Table 4: characteristics of the load CAD Cl.

The tests are carried out in a pilot unit equipped with a bubbling bed reactor. The catalyst is kept boiling permanently throughout the test. Before proceeding to the sulphurization step, the material D is subjected to a shaping step consisting of pelletizing, crushing and sieving to recover only the samples having a particle size of between 1 and 2 mm.

In a first step, the material D was sulphurized: 1 liter of material D was loaded into the reactor and then a distillation gas with added dimethyl disulphide was fed into the reactor while the temperature was gradually raised to 343 ° C. vs. The catalyst D _{s is} thus obtained. The charge (debloated oil) is then injected and the temperature adjusted to 430 ° C. to 1 10 bars of total pressure. The hourly volume velocity is set at 1.2 l / l / l / hour. The hydrogen flow corresponds to a ratio of 800 1/1 of charge. The operating conditions are of the isothermal type, which makes it possible to follow the deactivation of the catalyst D _s over time. The time is here expressed in barrels of filler / pound of catalyst (bbl / lb) which represents the amount of cumulative charge passed on the catalyst relative to the catalyst mass.

The catalytic performances are expressed by:

- Conversion rate of the residue (% wt) HD540 ^{o +} = 100 x [(wt% of 540 ^{o +} ) _load - (wt% of 540 ^{o +} ) _efflue " _t ] / (wt% of 540 ^{o +} ) _load

- carbon conversion rate Conradson HDCCR = 100 x (CCR _cha r _ge - CCR _effluent) / CCR _load

- Desulfurization rate HDS (% wt) = [(wt% S) _charse - (% wt S) _effluent J / [(% wt S) _load ] * 100

- Denitrogenation rate HDN (% wt) = [(wt% N) _load - (wt% N) _effluent ] / [(wt% wt) _load ] * 100.

The results in Table 5 are those obtained under steady state conditions.

Table 5: Stabilized catalytic results (4.1 bbl / lb).

It therefore appears that the hydroconversion process according to the invention carried out in the presence of the catalyst D _s , obtained after sulfurization of the material D according to the invention, leads to satisfactory catalytic performances.

Example 1 1: Use of the material E as precursor of a catalyst E. for the hydrotreatment in two stages of heavy hydrocarbon cuts. Evaluation of fixed bed catalvtic performance on an atmospheric residue charge.

The test implemented in this example illustrates a hydrotreatment process comprising a hydrodemetallation step (HDM) followed by a hydrodesulfurization step (HDS), each of said steps being carried out in a fixed bed tubular reactor, arranged in series with respect to one another. The catalytic evaluation of the catalyst E _s , obtained after sulfurization of the material E, was carried out in this configuration: it is placed downstream of a conventional HDM catalyst of NiMoP / alumina composition (9% by weight MoO ₃ , 1, 85% wt NiO, 1.78% wt P ₂ O ₅ , multimodal delta alumina).

The charge consists of an atmospheric residue (RA) of Middle East origin (Arabian Light). This residue is characterized by a high viscosity (45 mm ² / s), high conradson carbon content (10.2% by weight) and C7 asphaltenes (3.2% by weight) and a high amount of nickel (10, 6 ppm by weight), vanadium (41 ppm by weight) and sulfur (3.38% by weight). The full characteristics of the load are reported in Table 6.

Table 6: characteristics of the atmospheric residue to be hydrotreated.

Density 15/4 0.9712

Viscosity at 100 ° C 45 mm ^z / s

Sulfur 3.38% wt

Nitrogen 2257 ppm

Nickel 10.6 ppm

Vanadium 41.0 ppm

Aromatic carbon 24.8%

Carbon conradson (CCR) 10.2% wt

Asphaltenes C7 3.2% wt

Asphaltenes 3.5% wt

Simulated distillation PI (starting point 219 ° C)

distillation))

5% 299 ° C

10% 342 ° C

20% 409 ° C

30% 463 ° C

40% 520 ° C

50% 576 ° C

80% 614 ° C

The first reactor is charged with 3 ml of the conventional HDM catalyst and the second reactor is charged with 3 ml of the material E according to the invention (acting as HDS catalyst after sulfurization). In each reactor, the solid (i.e., the HDM catalyst in the first reactor and the material E in the second reactor) is diluted with 200 micron silicon carbide.

The material E having been prepared in the form of spherical elementary particles with a diameter ranging from 50 to 700 nm, centered around 300 nm, a preliminary shaping step was carried out before loading into the reactor. This shaping step consists of pelletizing, crushing and sieving to recover only the samples of particle size between 1 and 2 mm. A Packed Filling Density (DRT, catalyst mass for a given volume, after tamping) was then measured and the second reactor was loaded with 3 ml of material E thus shaped.

The flow of fluids (petroleum residues + hydrogen recycling) is downward in each of the reactors. This type of unit is representative of the operation of the reactors of the HYVAHL ^® unit for the hydrotreatment of fixed bed residues. The HDM catalyst makes it possible to significantly reduce the asphaltene content upstream of the catalyst E _s according to the invention.

After a step of sulfurization by circulation in each of the reactors of a gas oil fraction supplemented with DMDS at a final temperature of 350 ° C., the unit is operated with the atmospheric residue described above under the operating conditions of Table 7.

Table 7: Operating conditions implemented

The atmospheric residue is injected into the first reactor and then heated to the test temperature. After a stabilization period of 300 hours, the performances in hydrodesulfurization (HDS ratio), in hydrodemetallation (HDM rate), in the removal of conradson carbon (HDCCR rate), in the elimination of C7 asphalenes (rate of HDAsC7) and hydrodenitrogenation (HDN) are identified and presented in Table 8.

The HDS ratio is defined as follows:

HDS (% wt) = ((% wt S) _load - (wt% S) _emuent ) / (wt% S) _load x 100.

The HDM rate is defined as follows:

HDM (% wt) = ((ppm wt Ni + V) _feed - (ppm wt Ni + V) _effluent ) / (ppm wt Ni + V) _feed x ^' 100. On the same principle, we define a rate HDCCR (HDCCR (wt%) = ((wt% CCR) _load - (wt% CC) efiiuem) / (wt% CCR) rgc _cha * 100) for the removal of Conradson carbon, a rate HDAsC7 (HDAsC7 (wt%) = ((% w AsC7) arge- _ch ⁽⁰ / ^<1 wt HDAsC7) _effluent) / (wt% HDAsC7) _cha r _g ex 100) for removal asphaltenes C7 and finally a level of HDN (HDN (% wt) = ((wt% N) _load - (wt% N) _effluent ) / (wt% N) _load x 100) for the removal of nitrogen .

Table 8: HDS / HDM / HDN / HDCCR / HDAsC7 performance of catalyst E _s

It therefore appears that the hydrotreating process according to the invention combining a pretreatment step hydrodemetallization and hydrodesulfurization stage in the presence of catalyst E _s, E obtained after sulfurization of material according to the invention leads to both good HDS activity and good HDM activity. Catalyst E _s also possible to complete a level of removal of nitrogen, CCR and asphaltenes very satisfactory. These strong performances are attributable to an optimal transport of the reagents within the catalyst and to an optimized dispersion of metals, in particular vanadium and molybdenum.

Example 12: Use of the material F as precursor of a catalyst F _s for hydrotreating a feedstock from a renewable source. Evaluation of the catalytic performances on a rapeseed oil.

In a fixed-bed isothermal reactor charged with 100 ml of the material F, 50 ml / h of pre-refined rapeseed oil with a density of 920 kg / m ^{3 and} a sulfur content of less than 10 ppm by weight are introduced. cetane number equal to 35. 700 Nm ³ of hydrogen / m ³ of feed are introduced into the reactor maintained at a temperature of 300 ° C and a pressure of 5 MPa.

The main characteristics of the colza oil feed used in the hydrotreatment process illustrated here are shown in Table 9.

The rapeseed oil feed contains triglycerides whose hydrocarbon chains contain from 14 to 24 carbon atoms and have only an even number of carbon. The nomenclature of the triglycerides is in the form a: b, a corresponding to the number of carbon atoms of each of the hydrocarbon chains of triglycerides and b corresponding to the number of carbon-carbon double bonds present on each of said hydrocarbon chains.

Table 9: Characteristics of rapeseed oil feedstock.

Load Properties Values

Elemental analysis

S [ppm wt] 4

N [ppm wt] 23

P [ppm wt] 177

C [% wt] 77.2

H [% wt] 1 1, 6

O [% wt] 11, 2 Fatty acid composition (%)

14: 0 0, 1

16: 0 5.0

16: 1 0.3

18: 0 1.5

18: 1 trans <0.1

18: 1 cis 60,2

18: 2 trans <0.1

18: 2 cis 20.5

18: 3 trans <0, 1

18: 3 cis 9,6

20: 0 0.5

20: 1 1, 2

22: 0 0.3

22: 1 0.2

24: 0 0, 1

24: 1 0.2

The material F according to the invention is previously sulphurized in situ, at a temperature of 350 ° C. using a direct distillation diesel feed additive supplemented with 2% by weight of dimethyl disulphide (DMDS). After in situ sulphurisation in the pressure reaction unit which makes it possible to obtain the catalyst F _s , the rapeseed oil described in Table 9 is sent to the reaction unit.

In order to maintain the catalyst F _s in the sulfurized state, 50 ppm weight of sulfur in the form of DMDS is added to the rapeseed oil. Under the reaction conditions, the DMDS is completely decomposed to form methane and H ₂ S. The operating conditions of the hydrotreatment process and the catalytic results obtained are shown in Table 10.

Table 10: Operating conditions and catalytic performances in hydrotreatment of a rapeseed oil in the presence of the catalyst Fs.

Operating conditions

Temperature [° C] 300

Pressure [MPa] 5

H ₂ / load [m ³ / m ³ ] 700

Yields in formed products

C | -C ₇ cut [% weight] 5, 1

Cup 150 ° C + (kerosene (150-250 ° C and

85.4

diesel fuel (250 ° C +) [% weight] The 150 ° C + cut produced (that is to say having a boiling point greater than or equal to 150 ° C.) consists for the most part of linear paraffins (nCi ₄ to nC ₂ 4). These paraffins have an excellent cetane number (> 70) and are fully compatible with diesel fuel of fossil origin. Thus, the catalyst F _s according to the invention makes it possible to produce a diesel base (boiling point greater than 250 ° C.) of very high quality that can be incorporated as a mixture with petroleum diesel, as well as the production of a kerosene base ( boiling point of between 150 and 250 ° C) which can be incorporated as a mixture with petroleum kerosene. Hydrotreated products (kerosene and diesel) represent 85.4% by weight of the products formed. The yields of products formed were calculated from gas chromatographic analysis.

Claims

1. Inorganic material consisting of at least two elementary spherical particles, each of said spherical particles comprising metal particles in the form of polyoxometalate of the formula (X _x M _m O _y H _h) ^{q where} H is the hydrogen atom , 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, where x is 0, 1, 2, or 4, m being 5, 6, 7, 8, 9, 10, 1 1 , 12 and 18, being between 17 and 72, h being between 0 and 12 and q being between 1 and 20 (y, h and q being integers), said metal particles being present within a range of from 1 to 20; mesostructured matrix based on an oxide of at least one Y element selected from the group consisting of silicon, aluminum, titanium and tungsten , zirconium, gallium, germanium, tin, antimony, lead, vanadium, iron, manganese, hafhium, niobium, tantalum, yttrium, cerium, gadolinium, europium and neodymium and the mixture of at least two of these elements, said matrix having pores with a diameter of between 1.5 and 50 nm and having amorphous walls with a thickness of between 1 and 30 nm, said particles elementary spheres with a maximum diameter of 200 microns.

2. Material according to claim 1, wherein said mesostructured matrix consists of aluminum oxide, silicon oxide or a mixture of silicon oxide and aluminum oxide.

3. The material of claim 1 or claim 2 such that said matrix has pores with a diameter between 4 and 20 nm.

4. Material according to one of claims 1 to 3 such that said matrix has amorphous walls of thickness between 1 and 10 nm.

5. Material according to one of claims 1 to 4 such that the element M present in said metal particles of formula (X _x M _m O _Y H _h ) ^{q "} is one or more elements selected from vanadium, niobium, tantalum, molybdenum, tungsten, cobalt and nickel.

6. Material according to one of claims 1 to 5 such that said metal particles in the form of polyoxometalate are chosen from isopolyanions and heteropolyanions (HPA).

7. Material according to one of claims 1 to 6 such that said metal particles are heteropolyanions having the formula XM ₆ 0 ₂₄ H _h ^{q "} (with x = 1, m = 6, y = 24, q = 3 to 12 and h = 0 to 12) and / or formula X ₂ m, ₃₈ m o0 _h ^{q "(x} = 2, m = 10, y = 38, q = 3 to 12 and h = 0 to 12)

8. Material according to one of claims 1 to 6 such that said metal particles are heteropolyanions having the formula XM _l2 0 ₄ oH _h ^{q "} (x = 1, m = 12, y = 40, h = 0 to 12, q = 3-12) and / or formula XM _n 0 ₃ 9H _h ^{q "(x} = 1, m = 1 1, y = 39, h = 0 to 12, q = 3 to 12).

9. Material according to one of claims 1 to 6 such that said metal particles are heteropolyanions having the formula H _h P ₂ Mo ₅ 0 with h = 0, 1 or 2.

10. Material according to one of claims 1 to 9, wherein each of said spherical particles comprises zeolitic nanocrystals trapped with said metal particles in said mesostructured matrix.

1. Material according to one of claims 1 to 10 such that each of the spherical particles comprises one or more additional element (s) chosen from organic agents, the metals of group VIII of the periodic classification of doping elements and species belonging to the list of doping elements constituted by phosphorus, fluorine, silicon and boron and their mixtures.

12. Process for preparing a material according to one of claims 1 to 1 1 comprising at least the following successive steps:

a) the mixture in solution

at least one surfactant,

at least one precursor of at least one Y element selected from the group consisting of silicon, aluminum, titanium, tungsten, zirconium, gallium, germanium, tin, antimony, lead, vanadium, iron, manganese, hamium, niobium, tantalum, Tyrtrium, cerium, gadolinium, europium and neodymium and the mixture of two or more of these elements,

metal particles in the form of polyoxometalate of the formula (X _x M _m O _y H _h) ^{q "where} H is hydrogen, O is the oxygen atom, X is an element 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 from 1 to 20, or at least one metal precursor of said metal particles

b) the aerosol atomization of said solution obtained in step a) to lead to the formation of spherical liquid droplets; c) drying said droplets; d) removing at least one of said surfactant.

13. A process for converting a hydrocarbon feedstock comprising 1) contacting the mesostructured inorganic material according to one of claims 1 to 1 1 with a feedstock comprising at least one sulfur-containing compound and 2) contacting said material from of said step 1) with said hydrocarbon feedstock.

14. The method of transformation according to claim 13 such that said process is a hydrodesulfurization process of a gasoline cut.

15. The method of transformation according to claim 13 as said process is a hydrodesulfurization process of a gas oil cut.

16. The process according to claim 13, wherein said process is a process for hydrocracking a hydrocarbon feedstock of which at least 50% by weight of the compounds have an initial boiling point greater than 340 ° C. and a boiling point. final less than 540 ° C.

17. A process according to claim 13 wherein said process is a hydroconversion process of a heavy hydrocarbon feedstock of which at least 55% by weight of the compounds have a boiling point greater than or equal to 540 ° C.

18. The method of transformation according to claim 13, wherein said process is a process for the hydrotreatment of a heavy hydrocarbon feedstock of which at least 50% by weight of the hydrocarbon compounds present in said feed have a boiling point greater than or equal to 370 ° C. vs.

19. The process according to claim 13, wherein said process is a process for hydrotreating a hydrocarbon feed comprising triglycerides.