FR2931834A1 - PROCESS FOR THE PRODUCTION OF MEDIUM DISTILLATES BY HYDROCRACKING FISCHER-TROPSCH-LIKE CHARGES WITH A CATALYST BASED ON CRYSTALLIZED MATERIAL - Google Patents

Abstract

The invention relates to a method for producing middle distillates from a paraffinic feedstock produced by Fischer-Tropsch synthesis, using a hydrocracking / hydroisomerization catalyst comprising: at least one support formed from at least one crystallized material comprising structured hierarchical porosity silicon composed of at least two elementary spherical particles, each of said spherical particles comprising a mesotransitrated silicon oxide matrix having a mesopore diameter of between 1.5 and 30 nm and having microporous and crystallized walls with a thickness of between 1.5 and 60 nm, said elementary spherical particles having a maximum diameter of 200 μm, - at least one active phase containing at least one group VIB hydro-dehydrogenating element and / or Group VIII of the Periodic Table.

Description

The present invention relates to a method for producing middle distillates from a paraffinic feedstock produced by Fischer-Tropsch synthesis, using a hydrocracking / hydroisomerisation catalyst comprising: at least one support formed of at least one crystallized material comprising structured hierarchical porosity silicon composed of at least two elementary spherical particles, each of said spherical particles comprising a mesotransitrated silicon oxide matrix having a mesopore diameter of between 1.5 and 30 nm and having microporous and crystallized walls of thickness between 1.5 and 60 nm, said elementary spherical particles having a maximum diameter of 200 m, - at least one active phase containing at least one group VIB hydro-dehydrogenating element and / or Group VIII of the Periodic Table.

STATE OF THE PRIOR ART In the Fischer-Tropsch process, the synthesis gas (CO + H2) is catalytically converted into oxygenates and essentially linear hydrocarbons in gaseous, liquid or solid form. These products are generally free of heteroatomic impurities such as, for example, sulfur, nitrogen or metals. They also contain practically little or no aromatics, naphthenes and more generally cycles especially in the case of the use of cobalt catalysts. On the other hand, they may have a significant content of oxygenated products which, expressed by weight of oxygen, is generally less than about 5% by weight and also an unsaturated content (olefinic products in general) generally less than 10% by weight. . However, these products, mainly made of normal paraffins, can not be used as such, in particular because of their cold-holding properties that are not very compatible with the usual uses of petroleum fractions. For example, the pour point of a linear hydrocarbon containing 20 carbon atoms per molecule (boiling point equal to about 340 ° C., that is often included in the middle distillates cut) is + 37 ° C. about which makes its use impossible, the specification being -15 ° C for diesel. Starting charges intended to be treated in a gasification unit producing a gas consisting essentially of carbon monoxide and hydrogen, known to those skilled in the art as synthesis gas, said synthesis gas then making it possible to recompose a set of hydrocarbon cuts using the Fischer Tropsch process can be derived from renewable sources such as, for example, lignocellulosic type feedstocks, such as waste wood or straw. Lignocellulosic products are mainly lignins and cellulose. The impurities contained in this type of lignocellulosic biomass feedstock are essentially solid impurities, metals in particular alkaline (Na, K), and sulfur compounds, as well as chlorinated and nitrogenous compounds. The feedstocks may also be derived from renewable sources, such as oils and fats of plant or animal origin, or mixtures of such fillers, containing triglycerides and / or fatty acids and / or esters. Among the possible vegetable oils, they can be raw or refined, wholly or in part, and derived from the following plants: rapeseed, sunflower, soybean, palm, palm kernel, olive, coconut, jatropha this list is not limiting. Algae or fish oils are also relevant. Among the possible fats, there may be mentioned all animal fats such as bacon or fats consisting of residues from the food industry or from the food service industries. The charges thus defined contain triglyceride and / or fatty acid structures, whose fatty chains contain a number of carbon atoms of between 8 and 25.

Starting charges intended to be treated in a gasification unit producing a gas consisting essentially of carbon monoxide and hydrogen, known to those skilled in the art as synthesis gas, said synthesis gas then making it possible to recompose a set of hydrocarbon cuts using the Fischer Tropsch process may also be derived from the finely ground coal and purified so as to contain a reduced ash concentration.

The hydrocarbons resulting from the Fischer-Tropsch process comprising mainly n-paraffins must be converted into more valuable products such as, for example, diesel fuel or kerosene, which are obtained, for example, after catalytic hydroisomerisation reactions.

All the catalysts currently used in hydroconversion and / or hydroisomerization are of the bifunctional type associating an acid function with a hydrogenating function. The acid function is provided by supports with large surface areas (typically 150 to 800 m2) with surface acidity, such as halogenated alumina (chlorinated or fluorinated, in particular), phosphorus aluminas, and combinations of boron oxides. and aluminum, silica-aluminas and silica aluminas. The hydrogenating function is provided either by one or more metals of group VIII of the periodic table of the elements, such as the elements iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium and platinum, or by an association of at least one Group VI metal such as chromium, molybdenum and tungsten and at least one Group VIII metal.

The balance between the two functions, acid and hydrogen, is the fundamental parameter that governs the activity and the selectivity of the catalyst. A weak acidic function and a strong hydrogenating function give catalysts which are not very active and selective towards isomerization whereas a strong acid function and a low hydrogenating function give very active and cracking-selective catalysts. A third possibility is to use a strong acid function and a strong hydrogenating function to obtain a very active catalyst but also very selective towards isomerization. It is therefore possible, by judiciously choosing each of the functions to adjust the activity / selectivity couple of the catalyst. Conventional catalysts for catalytic hydrocracking are for the most part constituted by weakly acidic supports, such as silica-aluminas, for example. These systems are more particularly used to produce middle distillates of very good quality. Many of the hydrocracking market catalysts are based on Group VIII metal silica-alumina. These systems have a very good selectivity in middle distillates, and the products formed are of good quality (US 6,733,657). The disadvantage of all these silica-alumina catalyst systems is, as mentioned, their low activity. On the other hand, catalyst systems based on zeolite (in particular zeolite USY or beta) are very active for the hydrocracking reaction but are not very selective. In the quest for new aluminosilicate materials, so-called "mesostructured" materials, discovered in the early 1990s, represent an attractive alternative (G. J. de A. A.

Soler-Illia, C. Sanchez, B. Lebeau, J. Patarin, Chem. Rev., 2002, 102, 4093). Indeed, thanks to so-called "soft chemistry" synthesis methods, amorphous mesoporous materials whose size and pore morphology are controlled have been obtained. These mesostructured materials are thus generated at low temperature by the coexistence in aqueous solution or in polar solvents of inorganic precursors with structuring agents, generally molecular or supramolecular, ionic or neutral surfactants. The control of electrostatic or hydrogen bonding interactions between the inorganic precursors and the structuring agent together with hydrolysis / condensation reactions of the inorganic precursor leads to a cooperative assembly of the organic and inorganic phases generating micellar aggregates of uniformly sized surfactants. and controlled within an inorganic matrix. This phenomenon of cooperative self-assembly, governed inter alia by the concentration of structuring agent, can be induced by progressive evaporation of a solution of reagents whose concentration of structuring agent is lower than the critical micelle concentration, which can lead by example to the formation of a mesostructured powder after atomization of the solution (aerosol technique). The release of the porosity is then obtained by removing the surfactant, which is conventionally carried out by chemical extraction processes or by heat treatment. Depending on the nature of the inorganic precursors and the structuring agent used as well as the operating conditions imposed, several families of mesostructured materials have been developed. For example, the M41S family originally developed by Mobil (JS Beck, JC Vartuli, WJ Roth, ME Leonowicz, CT Kresge, KD Schmitt, CT-W Chu, DH Oison, EW Sheppard, SB McCullen, JB Higgins, JL Schlenker, J. Am Chem Soc., 1992, 114, 27, 10834), consisting of mesoporous materials obtained via the use of ionic surfactants such as quaternary ammonium salts, having a generally hexagonal, cubic or lamellar structure, pores of uniform size in a range of 1.5 to 10 nm and amorphous walls of the order of 1 to 2 nm thick has been extensively studied. Similarly, the use of amphiphilic macromolecular structuring agents of the block copolymer type has led to the development of the family of materials called SBA, these solids being characterized by a generally hexagonal, cubic or lamellar structure, large pores uniform in a range of 4 to 50 nm and amorphous walls of thickness in a range of 3 to 7 nm. However, it has been shown that, although having particularly interesting textural and structural properties (in particular for the treatment of heavy loads), the mesostructured aluminosilicate materials thus obtained developed a catalytic activity which was in all respects similar to that of their porous counterparts. unorganized (D. Zaho, J. Feng, Q. Huo, N. Melosh, GH Fredrickson, BF Chmelke, GD Stucky, Science, 1998, 279, 548, Y.-H. Yue, A. Gideon, J.- L. Bonardet, JB d'Espinose, Melosh N., J. Fraissard, Surf Stud Sci.Cat., 2000, 129, 209). Numerous studies have therefore been undertaken with the aim of developing materials having a microporosity of zeolite nature and a mesostructured porosity so as to simultaneously benefit from the zeolite-specific catalytic properties and from the catalytic and especially textural properties of the organized mesoporous phase. A large number of synthetic techniques making it possible to generate materials exhibiting this bi-porosity have thus been listed in the literature (US 6,669,924;

Zhang, Y. Han, Xiao F., Qiu S., Zhu L, Wang R, Y. Yu, Zhang Z., Zou Y, Wang Y., Sun H, Zhao D, Wei Y., J. Am. Chem. Soc., 2001, 123, 5014; A. Karisson, M. Stecker, R. Schmidt, Micropor. Mesopor. Mater., 1999, 27, 181; P. Prokesova, S. Mintova, J. Cejka, T. Bein, Micropor. Mesopor. Mater., 2003, 64, 165; D. T. On, S. Kaliaguine, Angew. Chem. Int. Ed., 2002, 41, 1036). From an experimental point of view, contrary to the "aerosol" technique mentioned above, the aluminosilicate materials with hierarchical porosity thus defined are not obtained by a progressive concentration of inorganic precursors and (s) the agent (s). ) structuring (s) within the solution where they are present but are conventionally obtained by direct precipitation in an aqueous solution or in polar solvents by varying the value of the critical micelle concentration of the structuring agent.

In addition, the synthesis of these materials obtained by precipitation requires a curing step in an autoclave and a filtration step of the generated suspension. The elementary particles usually obtained do not have a regular shape and are generally characterized by a size generally ranging between 200 and 500 nm and sometimes more.

By attempting to develop hydrocracking and paraffinic charge hydroisomerization catalysts such as Fischer-Tropsch synthesis feeds, the Applicant has discovered a process for producing middle distillates from a paraffinic feedstock produced by synthesis. Fischer-Tropsch, using a hydrocracking / hydroisomerization catalyst comprising: - at least one support formed of at least one crystallized material comprising silicon with hierarchical and organized porosity and consisting of at least two elementary spherical particles, each said spherical particles comprising a mesostructured silicon oxide matrix having a mesopore diameter in the range of 1.5 to 30 nm and having microporous and crystallized walls having a thickness of 1.5 to 60 nm, said particles elemental spheres with a maximum diameter of 200 μm, - at least one active phase containing at least one hydro-dehydrogenating element of group VIB and / or group VIII of the periodic table.

OBJECT OF THE INVENTION The present invention thus relates to a process for the production of middle distillates. This process makes it possible to increase the amount of average distillates available by hydrocracking the heavier paraffinic compounds, present in the outlet effluent of the Fischer-Tropsch unit, and which have boiling points higher than those of the kerosene cuts. and diesel, for example the 370 ° C` fraction.

More specifically, the invention relates to a process for producing middle distillates from a paraffinic feedstock produced by Fischer-Tropsch synthesis employing a particular catalyst as defined in the description which follows. The present invention relates to a method for producing middle distillates from a paraffinic feedstock produced by Fischer-Tropsch synthesis, using a hydrocracking / hydroisomerization catalyst comprising at least one hydro-dehydrogenating metal chosen from the group formed by the Group VIB metals and Group VIII of the Periodic Table and a support comprising at least one crystallized material comprising structured and hierarchical porosity silicon, said process preferably operating at a temperature between 270 and 400 ° C, a pressure of between 1 and 9 MPa, a space velocity of between 0.5 and 5 h -1 and a hydrogen flow rate adjusted to give a ratio of 400 to 1500 normal liters of hydrogen per liter of feed. According to the invention, said crystallized material comprising structured hierarchical porosity silicon consists of at least two elementary spherical particles, each of said particles comprising a mesostructured silicon oxide-based matrix having a mesopore diameter included between 1.5 and 30 nm and having microporous and crystallized walls with a thickness of between 1.5 and 60 nm, said elementary spherical particles having a maximum diameter of 200 microns. The microporous and crystallized walls are advantageously constituted by zeolite entities at the origin of the microporosity of the material. Said zeolite entities are prepared from reagents used for the synthesis of zeolites or related solids developing acidity properties. Thus, formulations resulting in any zeolite or related solid developing acidity properties can be used. As a result, said matrix based on silicon oxide comprises, in addition, at least one element X, the chemical nature of X being a function of the composition of said formulations used and which can be non-exhaustively one of the following elements : aluminum, iron, germanium, boron and titanium. Advantageously, X is the aluminum element. The present invention also relates to the preparation of the catalyst according to the invention.

Advantage of the invention The crystallized material comprising silicon having hierarchical and organized porosity constituting the catalyst according to the invention consisting of a mesostructured inorganic matrix, based on silicon oxide, with microporous and crystallized walls, simultaneously exhibits the structural properties and textural properties of silicon oxide-based materials and, more specifically, mesostructured aluminosilicate materials and acid-base properties superior to the acid-base properties of prior amorphous aluminosilicate materials, lacking zeolite entities, and prepared according to synthetic protocols well known to those skilled in the art using inorganic precursors of silica and alumina. Moreover, the presence within the same spherical particle of micrometric or even nanometric size of organized mesopores in a microporous and crystallized inorganic matrix leads to a privileged access of the reagents and products of the reaction to the microporous sites during the use of material as constituent element of the catalyst according to the invention in processes for the conversion of charges containing hydrocarbons, in particular accompanied by hydroisomerization of the long n-paraffins contained in said charges. In addition, the material according to the invention consists of spherical elementary particles, the diameter of these particles being at most equal to 200 m, preferably less than 100 m, advantageously varying from 50 nm to 20 m, very advantageously to 50 nm. at 10 m and even more advantageously from 50 nm to 3 μm. The limited size of these particles as well as their homogeneous spherical shape makes it possible to have a better diffusion of the reagents and the products of the reaction when the material is used as constitutive element of the catalyst according to the invention in processes for the conversion of Hydrocarbon-containing feeds The set of properties specific to the crystallized material comprising structured hierarchical porosity silicon thus induces specific catalytic properties of the catalyst according to the invention comprising said material when it is used in a process for producing middle distillates from of a paraffinic filler produced by Fischer-Tropsch synthesis. Indeed, while attempting to develop hydrocracking catalysts and hydroisomerization of paraffinic feedstocks resulting from the Fischer-Tropsch synthesis, the applicant has discovered a process for producing middle distillates from a paraffinic feedstock produced by Fischer synthesis. Tropsch, using a novel hydrocracking / hydroisomerization catalyst comprising at least one hydrodehydrogenating metal selected from the group consisting of Group VIB metals and Group VIII of the Periodic Table and a support comprising at least one of said crystallized material comprising silicon with hierarchical and organized porosity.

Characterization techniques The crystallized material comprising silicon having a hierarchical and organized porosity constituting the catalyst according to the invention is characterized by several analysis techniques and in particular by X-ray diffraction at low angles (low-angle XRD), by diffraction of the rays. X at large angles (XRD), nitrogen volumetry (BET), Transmission Electron Microscopy (TEM) and X Fluorescence (FX). The technique of low-angle X-ray diffraction (values of the angle between 0.5 and 3 °) makes it possible to characterize the periodicity at the nanoscale generated by the organized mesoporosity of the crystallized material present in the catalyst according to the invention. 'invention. In the following discussion, the X-ray analysis is performed on powder with a diffractometer operating in reflection and equipped with a rear monochromator using copper radiation (wavelength 1.5406 A). The peaks usually observed on the diffractograms corresponding to a given value of the angle 20 are associated with the inter-reticular distances d (hkl) characteristic of the structural symmetry of the material, ((hkl) being the Miller indices of the reciprocal lattice) by the Bragg relation: 2 d (hkl) * sin (0) = n * X. This indexation 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 structure , or vermicular obtained and characteristic of the periodic organization of the mesopores of the crystallized material present in the catalyst according to the invention. The X-ray diffraction technique at large angles (values of the angle between 5 and 70 °) makes it possible to characterize a crystalline solid defined by the repetition of a unitary unit or unit cell at the molecular scale. As for X-ray diffraction at low angles, the peaks observed on the diffractograms corresponding to a given value of the angle 20 are associated with the inter-reticular distances d (hkl) characteristic of the structural symmetry (s) ( s) of the material, ((hkl) being the Miller indices of the reciprocal lattice) by the Bragg relation: 2 d (hkl) * sin (0) = n * X. This indexation then allows the determination of the mesh parameters ( abc) from the direct network. The wide-angle XRD analysis is therefore adapted to the structural characterization of the zeolite entities constituting the crystallized wall of the matrix of each of the elementary spherical particles constituting the material present in the catalyst according to the invention. In particular, it provides access to the micropore diameter of the zeolite entities. Nitrogen volumetry, which corresponds to the physical adsorption of nitrogen molecules in the porosity of the material via a progressive increase in pressure at constant temperature, provides information on the textural characteristics (pore diameter, porosity type, specific surface area) particular of the material present in the catalyst according to the invention. In particular, it provides access to the total value of the microporous and mesoporous volume of the material present in the catalyst according to the invention. The shape of the nitrogen adsorption isotherm and the hysteresis loop can provide information on the presence of the microporosity linked to the zeolite entities constituting the crystallized walls of the matrix of each of the spherical particles of the material present in the catalyst. according to the invention and the nature of the mesoporosity. The quantitative analysis of the microporosity of the material according to the invention is carried out using methods "t" (method Lippens-De Boer, 1965) or "as" (method proposed by Sing) that correspond to transformations of the starting adsorption isotherm as described in the book "Adsorption by powders and porous solids, Principles, methodology and applications" written by F. Rouquerol, Rouquerol J. and K. Sing, Academic Press, 1999. These methods allow to access in particular to the value of the microporous volume characteristic of the microporosity of the material present in the catalyst according to the invention as well as to the specific surface of the sample. The reference solid used is silica SiChrospher Si-1000 (M. Jaroniec, M. Kruck, J. P. Olivier, Langmuir, 1999, 15, 5410). Concerning the mesostructured matrix, the difference between the value of the mesopore diameter d) and the correlation distance between mesopores d defined by DRX at the low angles as described above allows access to the magnitude e where e = d - d and is characteristic of the thickness of the crystallized walls of the mesostructured matrix of the material present in the catalyst according to the invention. Similarly, the curve Vads (ml / g) = f (as) obtained via the method as mentioned above is characteristic of the presence of microporosity within the material present in the catalyst according to the invention and leads to a value of microporous volume in a range of 0.01 to 0.4 ml / g. Determination of the total microporous and mesoporous volume and the microporous volume as described above results in a mesoporous volume of the material present in the catalyst according to the invention in a range of 0.01 to 1 ml / g. Transmission electron microscopy (TEM) analysis is a technique also widely used to characterize the organized mesoporosity of the crystallized material present in the catalyst according to the invention, which allows the formation of an image of the solid studied, the contrasts observed being characteristics of the structural organization, texture, morphology or chemical composition of the particles observed, the resolution of the technique reaching a maximum of 0.2 nm. from microtome sections of the sample to visualize a section of an elemental spherical particle of the material present in the catalyst. According to the invention, the analysis of the image also makes it possible to access the parameters d, c and e characteristic of the mesostructured matrix and defined previously. The analysis of the image also makes it possible to visualize the presence of the zeolite entities constituting the walls of the material present in the catalyst according to the invention.

The composition of the crystallized material present in the catalyst according to the invention can be determined by Fluorescence X (FX). The overall composition of the catalyst comprising at least one hydro-dehydrogenating metal selected from the group consisting of Group VIB metals and Group VIII of the Periodic Table and a support comprising at least one crystallized material comprising hierarchized and organized porosity silicon may be determined by X-ray Fluorescence or Atomic Absorption depending on the nature of the constituent elements of the catalyst. In the case of a catalyst shaped in the form of beads, extruded, for example, the distribution of the constitutive elements of the catalysts within the balls, extruded, for example, can be evaluated by means of elemental microanalysis by electronic probe (microprobe de Castaing), or even for example the book "Physico-chemical analysis of industrial catalysts", Technip, 2001. Measurement of the dispersion of metals of group VIB and group VIII can also be carried out by any method known to man of career. By way of example, the measurement of the dispersion of the noble metals of group VIII such as platinum can be carried out by the H2 / 02 titration method. Finally, the analytical techniques mentioned for characterizing the crystallized material comprising hierarchized and organized porosity silicon can also be used to characterize the catalyst, in particular X-ray diffraction at low angles (X-ray at low angles), the volumetry at low angles. Nitrogen (BET) and Transmission Electron Microscopy (TEM).

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing middle distillates from a paraffinic feedstock produced by Fischer-Tropsch synthesis, using a hydrocracking / hydroisomerization catalyst comprising: at least one support formed from at least one crystallized material comprising silicon having a hierarchical and organized porosity and comprising at least two elementary spherical particles, each of said spherical particles comprising a mesotransmitted silicon oxide matrix having a mesopore diameter included between 1.5 and 30 nm and having microporous and crystallized walls with a thickness of between 1.5 and 60 nm, said elementary spherical particles having a maximum diameter of 200 μm, - at least one active phase containing at least one hydro element -dehydrogenating group VIB and / or group VIII of the Periodic Table. Said method advantageously operates at a temperature of between 270 and 400 ° C. and preferably between 300 and 390 ° C., at a pressure of between 1 and 9 MPa and preferably between 2 and 8 MPa, at a space velocity of between 0.degree. , 5 and 5 h-1 and preferably between 0.8 and 3 h-1 and at a rate of hydrogen adjusted to obtain a ratio of 400 to 1500 normal liters of hydrogen per liter of filler and preferably a ratio 600 and 1300 normal liters of hydrogen per liter of charge.

The hydrocracking and hydroisomerization catalyst Preferably, said hydrocracking / hydroisomerization catalyst comprises: 0.1 to 60%, preferably 0.1 to 50% and even more preferably 0.1 to 40% % of at least one hydro-dehydrogenating metal selected from the group consisting of Group VIB and Group VIII metals, and from 40 to 99.9% of a support comprising: 0 to 99% and preferably 2 to at 98%, preferably from 5% to 95%, of at least one amorphous or poorly crystalline porous inorganic binder of the oxide type, 0.01% to 60%, preferably 0.05% to 40%, more preferably 0.05% to 40%; 0.05 to 35% and very preferably 0.05 to 20% of a crystallized material comprising silica with hierarchical and organized porosity, the percentages being expressed as a percentage by weight relative to the total mass of the catalyst.

a) The hydro-dehydrogenating function. According to the invention, the catalyst comprises at least one hydro-dehydrogenating metal selected from the group consisting of Group VIII metals and Group VIB metals, taken alone or in admixture. Preferably, the group VIII elements are chosen from iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium or platinum, taken alone or as a mixture.

In a preferred embodiment, the group VIII elements are the noble metals selected from platinum and palladium. In another preferred embodiment, the group VIII elements are non-noble metals selected from iron, cobalt and nickel. Preferably, the group VIB elements of the catalyst according to the present invention are selected from tungsten and molybdenum.

In the case where the hydrogenating function comprises a group VIII element and a group VIB element, the following metal combinations are preferred: nickel-molybdenum, cobalt-molybdenum, iron-molybdenum, iron-tungsten, nickel-tungsten, cobalt- tungsten, and very preferably: nickel-molybdenum, cobalt-molybdenum, nickel-tungsten. It is also possible to use combinations of three metals such as for example nickel-cobalt-molybdenum. When a combination of Group VI and Group VIII metals is used, the catalyst is then preferably used in a sulfurized form. The content of the hydro-dehydrogenating element cludit catalyst according to the present invention selected from the group formed by the metals of group VIB and group VIII is advantageously between 0.1 and 60% by weight relative to the total mass of said catalyst preferably between 0.1 and 50% by weight and very preferably between 0.1 and 40% by weight. When the hydro-dehydrogenating element is a noble metal of group VIII, the catalyst preferably contains a noble metal content of between 0.05 and 10% by weight, even more preferably from 0.1 to 5% by weight relative to to the total mass of said catalyst.

b) The crystallized material comprising silicon with hierarchical and organized porosity. According to the invention, said crystallized material comprising structured hierarchical porosity silicon consists of at least two elementary spherical particles, each of said particles comprising a mesostructured silicon oxide-based matrix having a mesopore diameter included between 1.5 and 30 nm and having microporous and crystallized walls with a thickness of between 1.5 and 60 nm, said elementary spherical particles having a maximum diameter of 200 microns.

For the purposes of the present invention, a material having a hierarchized and organized porosity means a material having a double porosity on the scale of each of said spherical particles: a mesoporosity, that is to say the presence of pores organized on the mesoporous scale having a uniform diameter of between 1.5 and 30 nm and preferably between 2 and 20 nm, distributed homogeneously and uniformly in each of said particles (mesostructuration) and a zeolite-type microporosity whose characteristics (structural type of the zeolite, chemical composition of the zeolite framework) are a function of the zeolite entities constituting the crystallized walls of the matrix of each of the spherical particles of the material present in the catalyst according to the invention. The material present in the catalyst according to the invention also has intra or (/ and) interparticle textural macroporosity (s). It should be noted that a porosity of microporous nature may also result from the imbrication of the surfactant, used during the preparation of the material present in the catalyst according to the invention, with the inorganic wall at the level of the organic-inorganic interface. developed during the mesostructuration of the inorganic component of said material present in the catalyst according to the invention. Advantageously, none of the spherical particles constituting the material present in the catalyst according to the invention has macropores. Preferably, the matrix based on silicon oxide each forming spherical particles of the material present in the catalyst according to the invention has crystallized walls consisting exclusively of zeolitic entities, which are at the origin of the microporosity present within of each of the spherical particles of the material present in the catalyst according to the invention. Any zeolite or related solid developing acidity properties and in particular, but not exhaustively, those listed in the Atlas of zeolite framework types ", 5th revised edition, 2001, C. Baerlocher, WM Meier, DH Oison may be used for the formation of zeolite entities constituting exclusively the crystallized walls of the matrix of each of the particles of the material present in the catalyst according to the invention as soon as the dissolution of the precursor elements of these entities, namely at least one structuring agent at least one silicic precursor and at least one precursor of at least one element X, X being advantageously aluminum, according to step a) of the first process for preparing the crystalline material with hierarchical and organized porosity described hereinafter , that obtaining zeolite nanocrystals of maximum nanometric size equal to 60 nm from at least one agent st ructurant, at least one silicic precursor and at least one precursor of at least one element X, X being advantageously aluminum, according to step a ') of the second process for preparing the crystalline material with hierarchical and organized porosity described herein after and the solution redispersion of zeolitic crystals according to step a ") of the third process for preparing the crystalline material with hierarchical and organized porosity as described below, leads to obtaining a stable solution, that is to say, limpid or colloidal, and atomizable. The zeolite entities constituting exclusively the crystallized walls of the matrix of each of the particles of the material present in the catalyst according to the invention and at the origin of the microporosity thereof preferably comprise at least one zeolite chosen from aluminosilicates ZSM- 5, ZSM-48, ZSM-22, ZSM-23, ZBM-30, EU-1, EU-2, EU-11, Beta, zeolite A, Y, USY, VUSY, SDUSY, mordenite, NU-87, NU -88, NU-86, NU-85, IM-5, IM-12, IZM-2 and Ferrierite and / or at least one related solid selected from SAPO-11 and SAPO-34 silicoaluminophosphates. Very preferably, the zeolite entities constituting integrally the crystallized and microporous walls of the matrix of each of the particles of the material present in the catalyst according to the invention are species for the primer of at least one zeolite chosen from the aluminosilicates of structural type MFI, BEA, FAU, LTA and / or at least one related solid selected from silicoaluminophosphates of structural type AEL, CHA. As a result, said matrix based on silicon oxide comprises, in addition, at least one element X, the chemical nature of X being a function of the chemical nature of said zeolitic entities used and which can be non-exhaustively one of the aluminum, iron, germanium, boron and titanium. Advantageously, X is the aluminum element. In this case, the matrix of the material is a crystallized aluminosilicate. The term zeolite or related solid well known to those skilled in the art all crystalline microporous oxide solids whose atomic elements constituting the inorganic framework have a coordination IV. By definition, the name "zeolite" is attributed to said microporous silicic or aluminosilicic oxide solids.

Similarly, the term "related solid" refers to all crystallized microporous oxide solids whose atomic elements constituting the inorganic framework have an IV coordination, said microporous silicic or aluminosilicic oxide solids being excluded. Any zeolite or related solid having at least one trivalent atomic element at the origin of the presence of a negative charge of said framework and which can be compensated by a positive charge of protonic nature can develop acidity properties. In particular, aluminosilicate zeolites and related solids of silicoaluminophosphate type develop such properties. The mesostructuration of the crystalline material with hierarchical and organized porosity present in the catalyst according to the invention may be of the vermicular, cubic or hexagonal type depending on the nature of the surfactant used for the implementation of the material present in the catalyst according to the invention. . According to the invention, said elementary spherical particles constituting the hierarchical and organized porosity material present in the catalyst according to the invention have a maximum diameter equal to 200 microns, preferably less than 100 microns, advantageously between 50 nm and 20 pm , very advantageously between 50 nm and 10 m, and even more advantageously between 50 nm and 3 pm. More specifically, they are present in the material present in the catalyst according to the invention in the form of aggregates.

The crystalline material with hierarchical and organized porosity present in the catalyst according to the invention advantageously has a specific surface area of between 100 and 1100 m 2 / g and very advantageously between 250 and 1000 m 2 / g. The crystalline material with hierarchical and organized porosity present in the catalyst according to the invention advantageously has a mesoporous volume measured by nitrogen volumetry of between 0.01 and 1 ml / g and a microporous volume measured by nitrogen volumetry included. between 0.01 and 0.4 ml / g. The crystalline material with hierarchical and organized porosity comprising constituent silicon of the catalyst according to the invention is obtained according to three possible methods of preparation. A first embodiment of the process for preparing said crystalline material with hierarchical and organized porosity, hereinafter referred to as "the first process for preparing said material present in the catalyst according to the invention", comprises: a) the preparation of a clear solution containing the precursor elements of zeolitic entities, namely at least one structuring agent, at least one silicic precursor and at least one precursor of at least one element X, X being advantageously aluminum; b) the solution mixture of at least one surfactant and at least said clear solution obtained according to a) such that the ratio of the inorganic and organic organic matter volumes is between 0.26 and 4; c) aerosol atomizing said solution obtained in step b) to lead to the formation of spherical droplets; d) drying said droplets; e) autoclaving the particles obtained according to d); f) drying said particles obtained according to e) and g) the removal of said structuring agent and said surfactant to obtain a crystallized material with hierarchical and organized porosity in the fields of microporosity and mesoporosity. A second embodiment of the process for preparing said crystalline material with hierarchical and organized porosity, hereinafter referred to as "second process for preparing said material present in the catalyst according to the invention", comprises the steps of: a) the preparation, from at least one structuring agent, at least one silicic precursor and at least one precursor of at least one element X, X being advantageously aluminum, of a solution containing zeolite nanocrystals of maximum nanometric size equal to 60 nm in order to obtain a colloidal solution in which said nanocrystals are dispersed; b ') the solution mixture of at least one surfactant and at least said solution obtained according to a') such that the ratio of inorganic and inorganic organic matter volumes is between 0.26 and 4; c ') aerosol atomizing said solution obtained in step b') to lead to the formation of spherical droplets; d ') drying said droplets; and g ') removing said structuring agent and said surfactant to obtain a crystallized material with hierarchical and organized porosity in the fields of microporosity and mesoporosity. According to a first variant of said second process for preparing the material present in the catalyst according to the invention, said step d ') is advantageously followed by a step e') consisting in autoclaving the particles obtained according to d ') and then d a step f ') of drying said particles obtained according to e'), said step f ') being followed by said step g'). According to a second variant of said second process for preparing the material present in the catalyst according to the invention, step b ') is carried out by mixing in solution at least one surfactant, at least said colloidal solution obtained according to step a and at least one clear solution containing the precursor elements of zeolitic entities, namely at least one structuring agent, at least one silicic precursor and at least one precursor of at least one element X, X being advantageously aluminum. Said mixture is produced under conditions such that the ratio of inorganicorganicorganic inorganic and organic material contents engaged in this step b ') is between 0.26 and 4. According to this variant, step d') of said second preparation method of the material present in the catalyst according to the invention is followed by a step e ') consisting of autoclaving the particles obtained according to d') and then a step f ') of practicing the drying of said particles obtained according to e before the implementation of said step g ') described above for carrying out said second process for preparing the material present in the catalyst according to the invention. A third method for preparing the crystalline material with hierarchical and organized porosity, hereinafter referred to as the "third process for preparing said material present in the catalyst according to the invention", comprises the steps of: a ") the solution redispersion of zeolitic crystals in a to obtain a colloidal solution of zeolite nanocrystals of maximum nanometric size equal to 60 nm, b ") the solution mixture of at least one surfactant, at least said colloidal solution obtained according to a) and at least one solution limpid containing the precursor elements of zeolitic entities, namely at least one structuring agent, at least one silicic precursor and at least one precursor of at least one element X, X being advantageously aluminum, said mixture being such that the ratio volumes of inorganic and organic inorganic organic matter are between 0.26 and 4; c ") the aerosol atomization of said solution obtained in step b ") to lead to the formation of spherical droplets; d ") drying said droplets; e") autoclaving the particles obtained according to d "); f") drying said particles obtained according to e ") and g") removing said structuring agent and said surfactant for the obtaining a crystallized material with hierarchical and organized porosity in the fields of microporosity and mesoporosity. The clear solution containing the precursor elements of zeolitic entities prepared during step a) of the first process for preparing the material present in the catalyst according to the invention, of step b ') of the second variant of the second process for preparing the material present in the catalyst according to the invention and step b ") of the third process for preparing the material present in the catalyst according to the invention, and the colloidal solution containing zeolite nanocrystals of maximum nanometric size equal to 60 nm prepared in steps a ') and a ") respectively of the second and third processes for preparing the material present in the catalyst according to the invention are prepared from operating protocols known to those skilled in the art. The silicic precursor used for the implementation of steps a), a ') and b ") respectively of the first, second and third processes for preparing the material present in the catalyst according to the invention as well as for the implementation of the step b ') of the second variant of the second process for preparing the material present in the catalyst according to the invention is advantageously chosen from the precursors of silicon oxide well known to those skilled in the art. advantageously a silicic precursor chosen from the silica precursors usually used in the synthesis of zeolites or related solids, for example using powdered solid silica, silicic acid, colloidal silica, dissolved silica or silica. tetraethoxysilane, also called tetraethylorthosilicate (TEOS), the silicic precursor is preferably the TEOS, the precursor of the element X, used for r carrying out steps a), a ') and b ") respectively of the first, second and third processes for preparing the material present in the catalyst according to the invention as well as for the implementation of step b' ) of the second variant of the second process for preparing the material present in the catalyst according to the invention may advantageously be any compound comprising the element X and capable of releasing this element in solution, in particular in aqueous or aqueous-organic solution, in the form of reactive. In the advantageous case where X is aluminum, the aluminum precursor is an inorganic aluminum salt of formula AIZ3, Z being a halogen, a nitrate or a hydroxide. Preferably, Z is chlorine. The aluminum precursor may also be an aluminum sulfate of formula AI 2 (SO 4) 3. The aluminum precursor can also be an organometallic precursor of formula AI (OR) 3 or R = ethyl, isopropyl, n-butyl, s-butyl (Al (OsC 4 H 9) 3) or t-butyl or a chelated precursor such as aluminum acetylacetonate (AI (C5H8O2) 3). Preferably, R is s-butyl. The aluminum precursor may also be sodium or ammonium aluminate or alumina proper in one of its crystalline phases known to those skilled in the art (alpha, delta, theta, gamma), preferably in hydrated form or which can be hydrated.

It is also possible to use mixtures of the precursors mentioned above. Some or all of the aluminic and silicic precursors may optionally be added in the form of a single compound comprising both aluminum atoms and silicon atoms, for example an amorphous silica-alumina. The structuring agent used for the implementation of steps a), a ') and b ") respectively of the first, second and third processes for preparing the material present in the catalyst according to the invention as well as for the implementation of step b ') of the second variant of the second process for preparing the material present in the catalyst according to the invention may be ionic or neutral depending on the zeolite or the related solid to be synthesized. the following non-exhaustive list: nitrogenous organic cations such as tetrapropylammonium (TPA), elements of the family of alkalis (Cs, K, Na, etc.), ethercurons, diamines and any other well-known structuring agent of Those skilled in the art for zeolite synthesis The clear solution containing precursor elements of zeolite entities (step a) of the first process for preparing the material present in the zeolite an analyzer according to the invention, step b ') of the second variant of the second process for preparing the material present in the catalyst according to the invention and step b ") of the third process for preparing the material present in the catalyst according to the invention) as well as the colloidal solution (step a ') of the second process for preparing the material present in the catalyst according to the invention, step a ") of the third process for preparing the material present in the catalyst according to the invention) containing zeolitic nanocrystals , used for the implementation of the various steps of the different processes for preparing the material present in the catalyst according to the invention, are synthesized according to operating protocols known to those skilled in the art. In particular, clear solutions containing precursor elements of beta-type zeolitic entities or colloidal solutions containing beta-type zeolitic nanocrystals are produced from the operating protocol described by P. Prokesova, S. Mintova, J. Cejka, T. Bein et al., Micropor. Mesopor. Mater., 2003, 64, 165. Clear solutions containing precursor elements of zeolitic entities of the FAU type or colloidal solutions containing zeolitic nanocrystals of the FAU type are produced from the operating protocols described by Y. Liu, WZ Zhang, TJ Pinnavaia et al., J. Am. Chem.

Soc., 2000, 122, 8791 and KR Kloetstra, HW Zandbergen, JC Jansen, H. van Bekkum, Microporous Mater., 1996, 6, 287. Clear solutions containing precursor elements of zeolitic entities of ZSM-5 type or Colloidal solutions containing zeolitic nanocrystals of the ZSM-5 type are produced from the operating protocol described by AE Persson, BJ Schoeman, J. Sterte, J.-E. Otterstedt, Zeolites, 1995, 15, 611. limpid containing the precursor elements of zeolitic entities according to steps a), b ') and b ") respectively of the first, second variant of the second and third processes for preparing the material present in the catalyst according to the invention or the colloidal solution containing zeolitic nanocrystals of maximum nanometric size equal to 60 nm according to step a ') of the second process for preparing the material present in the catalyst according to the invention by preparing a reaction mixture containing at least one silicic precursor, at least one precursor of at least one element X, X being advantageously aluminum and at least one structuring agent. The reaction mixture is either aqueous or aquo-organic, for example a water-alcohol mixture. According to step a) of the first process for preparing the material present in the catalyst according to the invention, the reaction mixture may be placed under hydrothermal conditions under autogenous pressure, optionally by adding a gas, for example nitrogen, at a temperature between room temperature and 200 ° C, preferably between room temperature and 170 ° C and still more preferably at a temperature not exceeding 120 ° C until a clear solution containing the precursor elements of the zeolite entities, which exclusively constitute the crystallized walls of the matrix of each of the spherical particles of the material present in the catalyst according to the invention. According to a preferred procedure, the reaction mixture containing at least one structuring agent, at least one silicic precursor and at least one precursor of at least one element X, X being advantageously the aluminum is matured at room temperature for a period advantageously between 15 and 20 hours, so as to obtain a clear solution containing the precursor elements of zeolitic entities capable of generating the formation of crystallized zeolite entities during step e) of autoclaving said first process for preparing the material present in the catalyst according to the invention. The clear solution containing zeolitic entity precursors according to step b ') of the second variant of said second process for preparing the material present in the catalyst according to the invention and that according to step b ") of said third preparation process of the material present in the catalyst according to the invention are advantageously prepared in the same manner as said clear solution containing zeolitic entity precursors according to step a) of said first process for preparing the material present in the catalyst according to the invention. According to step a ') of the second process of the material present in the catalyst according to the invention, the reaction mixture is advantageously placed under hydrothermal conditions under autogenous pressure, optionally by adding gas, for example nitrogen, to a temperature between 50 and 200 ° C, preferably between 60 and 170 ° C and still more preferably lle at a temperature between 60 and 120 ° C until the formation of zeolite nanocrystals of maximum nanometric size equal to 60 nm. Preferably, the reaction mixture is cured at a temperature between 70 ° C and 100 ° C for a period of between 3 and 6 days. At the end of said hydrothermal treatment, a colloidal solution is obtained in which said nanocrystals are in the dispersed state. The synthesis of said zeolite nanocrystals is followed by X-ray diffraction at large angles and the size of said nanocrystals is controlled by light scattering and Transmission Electron Microscopy. Those skilled in the art will be able to adjust the operating conditions so as to obtain said colloidal solution in which said nanocrystals, of maximum nanometric size equal to 60 nm, are in the dispersed state. It is preferred to work in a basic reaction medium during the various stages of the first and second processes for preparing the material present in the catalyst according to the invention in order to promote the development of the zeolite entities constituting the crystallized walls of the matrix of each of the particles of the material present in the catalyst according to the invention. The basicity of the clear solution according to step a) of said first preparation method or of the colloidal solution according to step a ') of said second preparation method or of the clear solution according to step b') of the second variant said second process for preparing the material present in the catalyst according to the invention is advantageously ensured by the basicity of the structuring agent used or by basification of the reaction mixture by the addition of a basic compound, for example a metal hydroxide alkali, preferably sodium hydroxide, in step a), a ') or b'). According to step a ") of the third process for preparing the material present in the catalyst according to the invention, zeolite crystals are advantageously used, said zeolitic crystals may have a size of greater than 60 nm. related compound developing acidity properties known in the state of the art which has the property of dispersing in solution, for example in aqueous-organic solution, in the form of nanocrystals of maximum nanometric size equal to 60 nm is suitable for of step a "). The dispersion of said zeolite crystals is advantageously carried out by any method known to those skilled in the art, for example by sonication. Said zeolite crystals are advantageously synthesized by methods known to those skilled in the art. The zeolitic crystals used in step a ") may already be in the form of nanocrystals.The obtaining of zeolitic crystals dispersing in the form of nanocrystals of maximum nanometric size equal to 60 nm is also possible by performing functionalization of the The zeolitic crystals used are advantageously found 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 zeolitic crystals used are in their raw synthesis form, said structuring agent is advantageously removed during step g ") of the third process for preparing the material present in the catalyst according to the invention.

According to step b), step b ') and step b ") respectively of the first, second and third process for preparing the material present in the catalyst according to the invention, the surfactant used is advantageously an ionic surfactant or a nonionic surfactant or a mixture of both, the ionic surfactant is preferably chosen from anionic surfactants such as sulphates, for example sodium dodecyl sulphate (SDS), and preferably the nonionic surfactant may be any copolymer having at least two parts of different polarities giving them properties of amphiphilic macromolecules.These copolymers may comprise at least one block forming part of the non-exhaustive list of the following families of polymers: fluorinated polymers (- [CH2-CH2-CH2-CH2-O- CO-R1-with R1 = C4F9, C8F, etc.), biological polymers such as polyamino acids (polylysine, alginates, etc.), dendrimers, polymers, etc. stained with poly (alkylene oxide) chains. Any other amphiphilic copolymer known to those skilled in the art can be used if it makes it possible to obtain a stable solution, that is to say clear or colloidal, in steps b), b ') and b " ) respectively first, second and third processes for preparing the material present in the catalyst according to the invention, such as poly (styrene-b-acrylamide) for example (S. Forster, M. Antionnetti, Adv Mater., 1998, 10, 195, S. Fdrster, T. Plantenberg, Angew Chem Int.Ed., 2002, 41, 688, H. Colfen, Macromol, Rapid Commun., 2001, 22, 219). In the context of the present invention, a block copolymer consisting of poly (alkylene oxide) chains, said block copolymer is preferably a block copolymer having two, three or four blocks, each block consisting of a poly (oxide) chain. For a two-block copolymer, one of the blocks consists of a poly (alkylene oxide) chain of the other block consists of a chain of poly (alkylene oxide) hydrophobic nature. For a copolymer with three blocks, at least one of the blocks consists of a chain of poly (alkylene oxide) hydrophilic nature while at least one of the other blocks consists of a poly ( alkylene oxide) of hydrophobic nature. Preferably, in the case of a three-block copolymer, the hydrophilic poly (alkylene oxide) chains are poly (ethylene oxide) chains denoted (PEO) X and (PEO) Z and the Poly (alkylene oxide) chains of hydrophobic nature are poly (propylene oxide) chains denoted (PPO), 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, it consists of two poly (ethylene oxide) chains and a poly (propylene oxide) chain. More specifically: a compound of formula (PEO) X (PPO) y- (PEO) Z is advantageously used, where x is between 5 and 300 and y is between 33 and 300 and z is between 5 and 300. Preferably , the values of x and z are identical. A compound in which x = 20, y = 70 and z = 20 (P123) and a compound in which x = 106, y = 70 and z == 106 (F127) is most advantageously used. Commercial nonionic surfactants known as Pluronic (BASF), Tetronic (BASF), Triton (Sigma), Tergitol (Union Carbide), Brij (Aldrich) can be used as nonionic surfactants in steps b) b ') and b ") respectively of the first, second and third processes for preparing the material present in the catalyst according to the invention For a four-block copolymer, two of the blocks consist of a poly (oxide) chain. alkylene) of hydrophilic nature and the other two blocks consist of a chain of poly (alkylene oxide) of hydrophobic nature.

The solution obtained at the end of steps b), b ') and b ") respectively of the first, second and third processes for preparing the material present in the catalyst according to the invention may be acidic, neutral or basic. said solution is basic and preferably has a pH greater than 9, this pH value being generally imposed by the pH of the clear solution containing the precursor elements of zeolitic entities according to step a) of the first process for preparing the material present in the catalyst according to the invention or else the colloidal solution containing zeolitic nanocrystals of maximum nanometric size equal to 60 nm according to step a ') and a ") respectively of said second and third processes for preparing the material present in the catalyst according to the invention. The solution obtained at the end of steps b), b ') and b ") may be aqueous or may be a water-organic solvent mixture, the organic solvent preferably being a polar solvent, in particular an alcohol, preferably ethanol The amount of organic compounds, that is to say in surfactant and structuring agent, present in the mixture according to steps b), b ') and b ") respectively of the first, second and third processes for the preparation of the material present in the catalyst according to the invention is defined with respect to the amount of inorganic material present in said mixture following the addition of the clear solution containing the zeolite entity precursor elements according to step a) of the first process for preparing the material present in the catalyst according to the invention or following the addition of the colloidal solution containing zeolite nanocrystals of nanometric size ue maximum equal to 60 nm according to step a ') of the second process for preparing the material present in the catalyst according to the invention and optionally the addition of the clear solution according to step b') if the material present in the catalyst according to the invention is prepared according to the second variant of said second preparation process or else following the addition of the colloidal solution containing zeolite nanocrystals of maximum nanometric size equal to 60 nm according to step a ") and the clear solution introduced in step b ") of the third process for preparing the material present in the catalyst according to the invention. The amount of inorganic material corresponds to the amount of silicic precursor material and that of the element X precursor when present. The volume ratio OrganicorganicOrganic is such that the organic-inorganic binary system formed during atomization steps c), c ') and c ") respectively of the first, second and third processes for preparing the material present in the catalyst according to the invention undergoes a process of mesostructuration by self-assembly of the surfactant together with the hydrolysis / condensation reactions of the various inorganic precursors.This volume ratio OrganicorganicWild is defined as follows: Organic / organic wine = (minorg * Porg) / (morg * pinorg) where minorg is the final mass of the inorganic fraction in the form of oxide (s) condensed in the solid elemental particle obtained by atomization, morg is the total mass of the nonvolatile organic fraction found in the solid elemental particle obtained by atomization Porg and pinorg are the densities respectively associated with the nonvolatile and inorganic organic fractions. In the context of the invention, when the element X is aluminum and for a simplification of the calculations (approximations valid for a large majority of nonvolatile organic fraction and for an inorganic fraction of the "aluminosilicate network" type), it is considered that that porg = 1 and pinorg = 2. In the context of the invention, minorg generally corresponds to the mass of SiO2 added to that of the mass of AIO2, when X is aluminum, and morg corresponds to the mass of the structuring agent, for example TPAOH, added with the mass of the surfactant, for example the surfactant F127. The polar solvent preferentially ethanol, as well as water and sodium hydroxide, do not enter into account in the calculation of said ratio Organicorganic wine • The species comprising an element X, advantageously the aluminic species, introduced after the implementation of said step b), b ') or b ") respectively of the first, second or third process for preparing the material present in the catalyst are not taken into account for the calculation of the organic-inorganic organic matter ratio defined above. the amount of organic material and the amount of inorganic material in the mixture obtained after the implementation of step b), b ') and b ") respectively of the first, second and third processes for preparing the material present in the The catalyst according to the invention is such that the ratio of inorganic organicorganic is in a range from 0.26 to 4, preferably in a range from 0.3 to 2. In steps b), b ') and b ") respectively of the first, second and third processes for preparing the material present in the catalyst according to the invention, the initial concentration of surfactant introduced into the mixture, defined by co is such that that co is less than or equal to cmc, the cmc parameter representing the critical micellar concentration well known to those skilled in the art, that is to say the limit concentration beyond which the phenomenon of self-arrangement occurs molecules of the surfactant in the solution obtained at the end of steps b), b ') and b ") respectively of the first, second and third processes for preparing the material present in the catalyst according to the invention. Before atomization, the concentration of surfactant molecules of the solution obtained at the end of steps b), b ') and b ") respectively of the first, second and third processes for preparing the material present in the catalyst according to the invention Therefore, in a preferred implementation of the different preparation methods according to the invention, the concentration estc is less than the cmc, the ratio of organic to organic is such that the composition of the binary system satisfies the requirements of the invention. the composition conditions for which a mesostructuring mechanism occurs by cooperative self-assembly of the reagents (OrganicorganicOrganic between 0.26 and 4, preferably between 0.3 and 2) and said solution referred to in steps b), b ') and b ") respectively of the first, second and third processes for preparing the material present in the catalyst according to the invention is a mixture basic water-alcohol. The step of atomizing the mixture according to steps c), c ') and c ") respectively of the first, second and third processes for preparing the material present in the catalyst according to the invention produces spherical droplets. of these droplets is of the lognormal type The aerosol generator used here is a commercial apparatus of model 9306A supplied by TSI having a 6-jet atomizer The atomization of the solution is done in a chamber in which a carrier gas is sent , a mixture O 2 / N 2 (dry air), at a pressure P equal to 1.5 bar, according to steps d), d ') and d ") respectively of the first, second and third processes for preparing the material present in the catalyst according to the invention, said droplets are dried. This drying is carried out by transporting said droplets via the carrier gas, the O2 / N2i mixture in PVC tubes, which leads to the gradual evaporation of the solution, for example from the aqueous-organic solution, preferentially from the solution. basic aquo-organic, obtained during steps b), b ') and b ") respectively of the first, second and third processes for preparing the material present in the catalyst according to the invention, and thus to obtain elementary particles This drying is perfect by a passage of said particles in a furnace 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 one second, the particles are then collected on a filter, and a pump placed at the end of the circuit facilitates the transport of the species in the experimental device. The drying of the droplets according to steps d), d) and d ") respectively of the first, second and third processes for preparing the material present in the catalyst according to the invention is advantageously followed by a passage in the oven. at a temperature between 50 and 150 ° C. According to steps e), e ') and e ") of the first variant (s) of the second and third processes for preparing the material present in the catalyst according to the invention, it is possible to carry out an autoclaving of the dried particles obtained in the the result of steps d), d) and d ") of the three different processes for preparing the material present in the catalyst according to the invention in the presence of a solvent. This step advantageously consists in placing said particles in a closed chamber in the presence of a solvent at a given temperature so as to work with autogenous pressure inherent to the operating conditions chosen. The solvent used is advantageously a protic polar solvent. Preferably the solvent used is water. The volume of solvent introduced is advantageously defined with respect to the volume of the autoclave chosen, the mass of dry powder introduced and the treatment temperature. Thus the volume of solvent introduced is advantageously in a range of 0.01 to 20% relative to the volume of the autoclave chosen, preferably in a range of 0.05 to 5% and more preferably in a range of 0.05 to 1%. The autoclaving temperature is advantageously between 50 and 200 ° C., preferably between 60 and 170 ° C. and still more preferably between 60 and 120 ° C. so as to allow the growth of zeolite entities in the walls of the matrix of each of the particles of the material present in the catalyst according to the invention without generating large zeolite crystals which would disorganize the mesostructuration of each particle of the material present in the catalyst according to the invention. The autoclaving is advantageously maintained over a period of 1 to 196 hours and preferably over a period of 10 to 72 hours. According to steps f), f ') and f ") respectively of the first variant (s) of the second and third processes for preparing the material present in the catalyst according to the invention, the drying of the particles after autoclaving is advantageously carried out by means of incubation at a temperature between 50 and 150 ° C. In the case where the element X is advantageously aluminum and where the sodium element is present in the solution obtained according to the steps a), a ') , b ') and b ") respectively of the first, second, second variant of the second and third processes for preparing the material present in the catalyst according to the invention via the use of sodium hydroxide and / or an agent soda structuring ensuring the basicity of said solution or present in the precursor zeolite crystals of step a ") of the third process for preparing the material present in the catalyst according to the invention, it is preferred to performing an additional ion exchange step for exchanging the Na + cation by the NH 4 + cation between steps f) and g) if the material present in the catalyst according to the invention is prepared according to said first preparation process, between the steps f ') and g') if the material present in the catalyst according to the invention is prepared according to the second preparation process, between steps f ') and g') if the material present in the catalyst according to the invention is prepared according to one of the variant (s) of said second preparation process, between steps f ') and g ") if the material present in the catalyst according to the invention is prepared according to said third preparation process. This exchange, which leads to the formation of H + protons after steps g), g ') and g ") respectively of the first, second and third processes for preparing the material present in the catalyst according to the invention in the preferred case where the The removal of the structuring agent and the surfactant is carried out by calcination under air, and is advantageously carried out according to operating protocols that are well known to those skilled in the art.One of the usual methods consists in suspending the dried solid particles resulting from the steps f ), d) and f ') respectively of the first, second and third processes for preparing the material present in the catalyst according to the invention and of step f') of one of the variants of the second process for preparing the material present in the catalyst according to the invention if it is practiced, in an aqueous solution of ammonium nitrate, the whole is then advantageously brought to reflux during a hard period of time. The particles are then advantageously recovered by filtration (centrifugation at 9000 rpm), washed and then dried by passing in an oven at a temperature of between 50 and 150 ° C. This ion exchange / washing / drying cycle can be advantageously repeated several times and preferably two more times. This exchange cycle may advantageously also be carried out after steps f) and g) of said first preparation process, after steps d ') and g') of said second preparation process, after steps f ') and g') of one of the variants of said second preparation process and after the steps ') and g ") of said third preparation process, in which case the steps g), g') and g") respectively of the first, second and third processes for preparing the material present in the catalyst according to the invention is then reproduced after the last exchange cycle so as to generate the protons H + as explained above. According to steps g), g ') and g ") respectively of the first, second and third processes for preparing the material present in the catalyst according to the invention, the elimination of the structuring agent and the surfactant, in order to obtain the crystallized material according to the invention having hierarchical and organized porosity in the fields of microporosity and mesoporosity, is advantageously carried out by chemical extraction processes or by heat treatment and preferably by calcination under air in a temperature range of 300 to 1000 ° C and more precisely in a range of 400 to 600 ° C for a period of 1 to 24 hours and preferably for a period of 2 to 12 hours, in the case where the solution referred to in steps b), b ') and b ") respectively of the first, second and third processes for preparing the material present in the catalyst according to the invention, is a water-organic solvent mixture, preferably However, it is essential during said steps b), b ') and b ") that the surfactant concentration at the origin of the mesostructuration of the matrix is lower than the critical micellar concentration and that the ratio of organicorganic wine is between 0.26 and 4, preferably between 0.3 and 2 so that the evaporation of said aqueous-organic solution, preferably basic, during steps c), c ') and c ") respectively of the first, second and third process for preparing the material present in the catalyst according to the invention by the aerosol technique induces a phenomenon of micellization or self-assembly leading to the mesostructuration of the matrix of the material present in the catalyst according to the invention. When co <cmo, the mesostructuration of the matrix of the material present in the catalyst according to the invention is consecutive to a progressive concentration, within each droplet, of the precursor elements of zeolitic entities of the clear solution obtained at the stage a) the first process for preparing the material present in the catalyst according to the invention or zeolitic nanocrystals of the colloidal solution obtained in step a ') of said second preparation process, or zeolitic nanocrystals of the colloidal solution obtained in step a ') and zeolitic entity precursor elements of the clear solution obtained in step b') of the second variant of said second preparation process or else zeolitic nanocrystals of the colloidal solution obtained at step a ") and precursor elements of zeolitic entities of the clear solution obtained in step b") of said third process of preparation and at least one surfactant introduced in steps b), b ') and b ") of the three processes for preparing the material present in the catalyst according to the invention, up to a concentration of surfactant c> cmc resulting from evaporation of the aquo-organic solution. According to a first preferred embodiment of each of the three processes for preparing the material present in the catalyst according to the invention, at least one precursor of at least one element X, X being advantageously aluminum, is introduced for the implementation of process of step b) of the first process for preparing the material present in the catalyst according to the invention, step b ') of the second process for preparing the material present in the catalyst according to the invention, step b ') of one of the variants of said second process for preparing the material present in the catalyst according to the invention or of step b ") of said third process for preparing the material present in the catalyst according to the invention.

Thus, the mixture in solution of at least one surfactant and at least said clear solution obtained according to step a) of the first process for preparing the material present in the catalyst according to the invention, or at least one surfactant and at least said colloidal solution obtained according to step a ') of the second process for preparing the material present in the catalyst according to the invention, or at least one surfactant, of at least said colloidal solution obtained according to step a ') and at least said clear solution obtained according to step b') of the second variant of said second preparation method, or at least one surfactant, of at least said colloidal solution obtained according to step a ") and at least said clear solution obtained according to step b") of said third preparation process is carried out in the presence of molin a precursor of said element X, X being preferably aluminum, preferably among the precur aluminums, described above in the present description, for example for the implementation of said step a) of said first process for preparing the material present in the catalyst according to the invention. According to said first preferred embodiment of each of the three processes for preparing the material present in the catalyst according to the invention, the preparation of the clear solution according to step a), step b ') or step b " ) respectively of the first, second variant of the second or third process for preparing the material present in the catalyst according to the invention and that of the colloidal solution according to step a ') of said second preparation process is carried out either in the presence or in the absence of at least one precursor of at least one element X.

According to a second preferred embodiment of each of the three processes for preparing the material present in the catalyst according to the invention, at least one precursor of at least one element X, X being advantageously aluminum, is introduced either during the implementation of said step d) and / or of said step f) and / or of said g) of said first process for preparing the material present in the catalyst according to the invention, either during the implementation of said step d) and / or said step g ') of said second process for preparing the material present in the catalyst according to the invention, either during the implementation of said step d') and / or said step f) ') and / or of said step g') of one of the variants of said second preparation method is still during the implementation of said step d ") and / or said step f ') and / or said step g ") of said third preparation process, with a view to producing a surface modification of the material present in the catalyst according to the invention. According to said second preferred embodiment of each of the three processes for preparing the material present in the catalyst according to the invention, said precursor of at least one element X, X being advantageously aluminum, is introduced during the implementation of at least one of the steps mentioned above (d, d ', d ", f, f, f", g, g' and g ") by any well-known surface modification technique of Those skilled in the art such as the grafting of at least one precursor of at least one element X, the dry impregnation of at least one precursor of at least one element X and the impregnation in excess of at least one precursor of at least one element X. Said precursor of at least one element X, advantageously an aluminum precursor, introduced during the implementation of at least one of the steps mentioned above (d, d). , d ", f, f, f", g, g 'and g ") by a surface modification technique, is selected from the precursors of said element X, advantageously among the aluminum precursors, described above in the present description, for example those used for the implementation of said step a) of said first process for preparing the material present in the catalyst according to the invention. According to said second preferred embodiment of each of the three processes for preparing the material present in the catalyst according to the invention, step a) and step a ') of the first and second preparation processes of the invention are carried out in the presence or in the absence of at least one precursor of at least one element X, advantageously an aluminum precursor, and step b), step b ') or step b ") respectively of the first second or third process for preparing the material present in the catalyst according to the invention is carried out in the presence or in the absence of at least one precursor of at least one element X, advantageously an aluminum precursor. preparation of the material present in the catalyst according to the invention, said first preferred embodiment of each of the three processes for preparing the material present in the catalyst according to the invention and said second preferred embodiment of each of the three processes for preparing the material present in the catalyst according to the invention are only optional variants of each of the three processes for preparing the material present in the catalyst according to the invention.

Also, the element X, advantageously aluminum, is introduced, when the material is prepared according to the first process for preparing the material present in the catalyst according to the invention, or during said step a) of the first method of preparation of the material present in the catalyst according to the invention for the preparation of said clear solution, either during said step b) in accordance with said first preferred embodiment of the first process for preparing the material present in the catalyst according to the invention, or again during said step d) and / or said step f) and / or said step g) according to said second preferred embodiment of the first process for preparing the material present in the catalyst according to the invention. When the material is prepared according to said second process for preparing the material present in the catalyst according to the invention, said element X, advantageously aluminum, is introduced either during said step a '), or during said step b ') according to said first preferred embodiment of the second process for preparing the material present in the catalyst according to the invention is still during said step d') and / or said step f ') and / or step g ') according to said second preferred embodiment. When the material is prepared according to said second variant of said second process for preparing the material present in the catalyst according to the invention, said element X, advantageously aluminum, is introduced either during said step a '), or during step b ') for preparing said clear solution, either during said step b') according to said first preferred embodiment or during said step d ') and / or step f') and / or step g ') according to said second preferred embodiment. When the material is prepared according to said third process for preparing the material present in the catalyst according to the invention, the element X, advantageously aluminum, is introduced either during said step b ") for the preparation of said clear solution either during said step b ") according to said first preferred embodiment or again during said d") and / or step f ') and / or step g ") according to said second embodiment of preferred embodiment. The element X, advantageously aluminum, can also be introduced, several times, during the implementation of several steps in all possible combinations of the embodiments described above. In particular, it is advantageous to introduce the aluminum during said step a) and said step b) or during said step a) and said step d) and / or said step e) when the material present in the catalyst according to the invention is prepared according to said first process for preparing the material present in the catalyst according to the invention. In the case where the element X is advantageously aluminum, the crystallized aluminosilicate, obtained according to one of the three processes for preparing the material present in the catalyst according to the invention, then has a molar ratio Si / Al defined at from the amount of silicon element introduced during steps a), a '), a "), b') and b") respectively of the first, second, third, second variant of the second and third processes for preparing the material present in the catalyst according to the invention and the total amount of aluminum element introduced into the step (s) of one of the three preparation methods according to the different preferred embodiments described above. Under these conditions and preferably, the range of the molar ratio Si / Al of the crystallized material according to the invention is between 1 and 1000. When said first preferred embodiment of each of the three processes for preparing the material present in the catalyst according to the invention is applied, the amounts of organic and inorganic material to be introduced for the implementation of step b), step b ') or step b ") are to be adjusted according to the amount of additional material X element, advantageously aluminum, introduced in said step b), b ') or b ") according to said first mode so that the total amount of organic and inorganic material introduced for the preparation of the material according to the invention allows a phenomenon of micellization leading to the mesostructuration of the matrix of each particle of said material. Element X, advantageously aluminum, introduced for the implementation of said second preferred embodiment of each of the three processes for the preparation of the material present in the catalyst according to the invention does not intervene in the calculation of the ratio of organicorganic organ such as defined above in the present description since it is introduced after the step allowing a micellization phenomenon leading to the mesostructuration of the matrix of each particle of said material present in the catalyst according to the invention. It is specified that throughout the text of the description of the present invention, the expression "second process for preparing the material present in the catalyst according to the invention" applies equally well to the case where the material present in the catalyst according to the invention is prepared according to the second process for preparing the material present in the catalyst according to the invention (without application of either of the two variants), in the case where the material according to the invention is prepared according to the first variant of said second process for preparing the material present in the catalyst according to the invention and also in the case where the material present in the catalyst according to the invention is prepared according to the second variant of said second process for preparing the material present in the catalyst according to the invention. The crystallized material with hierarchical and organized porosity in the fields of the microporosity and the constituent mesoporosity of the catalyst of the present invention can advantageously be obtained in the form of powder, beads, pellets, granules, or extrudates, the operations shaping being performed by conventional techniques known to those skilled in the art. Preferably, the crystalline material with a hierarchical and organized porosity in the fields of the microporosity and the mesoporosity present in the catalyst according to the invention is obtained under the firm of powder, which consists of elementary spherical particles having a maximum diameter of 200 m , which facilitates the diffusion of the reagents during the use of the material as a constituent element of the catalyst according to the invention in a hydroisamerization process and hydrocracking of feeds from the Fischer-Tropsch process.

c) The mineral binder.

The catalyst according to the invention may advantageously contain an amorphous or poorly crystalline porous inorganic binder of the oxide type, the preferred binder being of the alumina type. The alumina compounds advantageously used according to the invention are partially soluble in acid medium. They are advantageously chosen wholly or partly from the group of alumina compounds of general formula AI203, nH2O. In particular, it is possible to use hydrated alumina compounds such as: hydrargillite, gibbsite, bayerite, boehmite, pseudo-boehmite and amorphous or essentially amorphous alumina gels. It is also advantageous to use the dehydrated forms of these compounds which consist of transition aluminas and which comprise at least one of the phases taken from the group: rho, khi, eta, gamma, kappa, theta, and delta, which differ essentially in the organization of their crystalline structure. The alpha alumina commonly called corundum can advantageously be incorporated in a small proportion in the support according to the invention. The aluminum hydrate Al 2 O 3, nH 2 O used more preferably is advantageously boehmite, pseudo-boehmite and amorphous alumina gels.

essentially amorphous. A mixture of these products under any combination may be used as well. Boehmite is generally described as an aluminum monohydrate of formula AI2O3, nH2O which in fact encompasses a wide continuum of materials of variable degrees of hydration and organization with more or less well-defined boundaries: the most hydrated gelatinous boehmite , with n being greater than 2, pseudo-boehmite or microcrystalline boehmite with n between 1 and 2, then crystalline boehmite and finally well crystallized boehmite in large crystals with n close to 1. The morphology of the monohydrate of aluminum can advantageously vary within wide limits between these two acicular and prismatic extreme forms. A whole set of variable shapes can be used between these two forms: chain, boats, interwoven plates. Relatively pure aluminum hydrates can advantageously be used in powder form, amorphous or crystallized or crystallized containing an amorphous part. The aluminum hydrate can also advantageously be introduced in the form of aqueous suspensions or dispersions. The aqueous suspensions or dispersions of aluminum hydrate used according to the invention may advantageously be gelable or coagulable. The aqueous dispersions or suspensions may also advantageously be obtained as is well known to those skilled in the art by peptization in water or acidulated water of aluminum hydrates.

The aluminum hydrate dispersion may advantageously be produced by any method known to those skilled in the art: in a "batch" reactor, a continuous mixer, a kneader, a colloid mill. Such a mixture may advantageously also be carried out in a piston-flow reactor and in particular in a static mixer. Lightnin reactors can be mentioned.

In addition, it is also advantageous to use as a source of alumina an alumina having been previously subjected to a treatment that may improve its degree of dispersion. By way of example, it will be possible to improve the dispersion of the alumina source by a preliminary homogenization treatment. For homogenization, it is advantageous to use at least one of the homogenization treatments described in the text that follows. The aqueous dispersions or suspensions of alumina which may be used include aqueous suspensions or dispersions of fine or ultra-fine boehmites which are composed of particles advantageously having dimensions in the colloidal field.

The fine or ultra-fine boehmites advantageously used according to the present invention may in particular have been obtained according to the French patent FR-B-1 261 182 and FR-B-1 381 282 or in the European patent application EP-A- 196. It is also advantageous to use the aqueous suspensions or dispersions obtained from pseudo-boehrnite, amorphous alumina gels, aluminum hydroxide gels or ultra-fine hydrargillite gels. Aluminum monohydrate may advantageously be purchased from a variety of commercial sources of alumina, such as, in particular, PURAL, CATAPAL, DISPERAL, DISPAL sold by SASOL or HIQ marketed by ALCOA, or according to the methods known to man. It can advantageously be prepared by partial dehydration of aluminum trihydrate by conventional methods or it can advantageously be prepared by precipitation. When these aluminas are in the form of a gel, they are advantageously peptized with water or an acidulated solution. In precipitation, the acid source may advantageously be for example chosen from at least one of the following compounds: aluminum chloride, aluminum sulphate, aluminum nitrate. The basic aluminum source may be selected from basic aluminum salts such as sodium aluminate and potassium aluminate. d) Preparation of a support constituted by the crystallized material comprising structured hierarchical porosity silicon and the binder.

Shaping The shaping of the support according to the invention can advantageously be carried out according to all the methods well known to those skilled in the art. The crystallized material may advantageously be introduced according to any method known to those skilled in the art and at any stage of the preparation of the support or catalyst. According to a preferred method of preparation, the crystallized material may advantageously be introduced during the dissolution or suspension of the alumina compounds advantageously used according to the invention. The crystallized material may be, without limitation, for example in the form of powder, ground powder, suspension, suspension having undergone deagglomeration treatment. Thus, for example, the crystallized material may advantageously be slurried acidulated or not at a concentration adjusted to the final content of crystallized material referred to the support. This suspension 35

commonly called a slip is then advantageously mixed with the alumina compounds. The support can advantageously be shaped by any technique known to those skilled in the art. The shaping can advantageously be carried out for example by extrusion, by pelletization, by the method of drop coagulation ("oil-drop"), by rotating plate granulation or by any other method well known to those skilled in the art. . The shaping can advantageously also be carried out in the presence of the various constituents of the catalyst and extrusion of the obtained mineral paste, by pelletizing, shaped into beads at the rotating bezel or drum, drop coagulation, "oil-drop" , "oil-up", or any other known method of agglomeration of a powder containing alumina and optionally other ingredients selected from those mentioned above. The catalysts used in the process according to the invention are in the form of spheres or extrudates. It is however advantageous that the catalyst is in the form of extrudates with a diameter of between 0.5 and 5 mm and more particularly between 0.7 and 2.5 mm. The shapes are cylindrical (which can be hollow or not), cylindrical twisted, multilobed (2, 3, 4 or 5 lobes for example), rings. The cylindrical shape is preferably used in a preferred manner, but any other form may advantageously be used. Furthermore, these supports used according to the present invention may advantageously have been treated as is well known to those skilled in the art by additives to facilitate the shaping and / or improve the final mechanical properties of the supports. By way of example of additives, mention may be made in particular of cellulose, carboxymethylcellulose, carboxyethylcellulose, tall oil, xanthan gums, surfactants, flocculating agents such as polyacrylamides, carbon black, starches, stearic acid, polyacrylic alcohol, polyvinyl alcohol, biopolymers, glucose, polyethylene glycols, etc. Water may be advantageously added or removed to adjust the viscosity of the paste to be extruded. This step can advantageously be carried out at any stage of the kneading step. In order to adjust the solid content of the paste to be extruded to make it extrudable, it is also advantageous to add a predominantly solid compound and preferably an oxide or a hydrate. A hydrate is preferably used and even more preferably an aluminum hydrate. The loss on ignition of this hydrate is advantageously greater than 15%. Extrusion can advantageously be performed by any conventional tool, commercially available. The paste resulting from the mixing is advantageously extruded through a die, for example by means of a piston or a single screw or twin extrusion screw. This extrusion step can advantageously be performed by any method known to those skilled in the art. The support extrusions according to the invention advantageously have generally a crush strength of at least 70 N / cm and preferably greater than or equal to 100 N / cm.

Heat treatment Drying is advantageously carried out by any technique known to those skilled in the art.

To obtain the support of the present invention, it is preferable to calcine preferably in the presence of molecular oxygen, for example by conducting an air sweep, at a temperature of less than or equal to 1100 ° C. At least one calcination may advantageously be carried out after any one of the steps of the preparation. This treatment, for example, can be carried out in crossed bed, in a licked bed or in a static atmosphere. For example, the furnace used may advantageously be a rotating rotary kiln or be a vertical kiln with radial traversed layers. The calcination conditions (temperature and time) depend mainly on the maximum temperature of use of the catalyst. The preferred calcination conditions are advantageously between more than one hour at 200 ° C and less than one hour at 1100 ° C. The calcination can advantageously be carried out in the presence of water vapor. The final calcination may optionally be carried out in the presence of an acidic or basic vapor. For example, the calcination can advantageously be carried out under partial pressure of ammonia.

e) Deposit of the hydro-dehydrogenating function.

The hydro-dehydrogenating function may advantageously be introduced at any stage of the preparation, very preferably after forming the support. The shaping is advantageously followed by calcination. Under these conditions, the hydrodehydrogenating function can also advantageously be introduced before or after this calcination. The preparation generally ends with calcination at a temperature of 250 to 600 ° C. Another preferred method according to the present invention advantageously consists in shaping the support after kneading thereof, then passing the dough thus obtained through a die to form extrudates with a diameter of between 0.4 and 4. mm. The hydro-dehydrogenating function may advantageously then be introduced in part only or in full, at the time of mixing. It can also advantageously be introduced by one or more ion exchange operations on the calcined support. In a preferred manner, the support is impregnated with an aqueous solution. The impregnation of the support is preferably carried out by the "dry" impregnation method well known to those skilled in the art. The impregnation may advantageously be carried out in a single step by a solution containing all of the hydro-dehydrogenating elements constituting the final catalyst. The hydro-dehydrogenating function may advantageously be introduced by one or more impregnation operations of the shaped and calcined support, with a solution containing at least one precursor of at least one oxide of at least one metal chosen from the group formed. by the metals of group VIII and the metals of group VIB, the precursor (s) of at least one oxide of at least one metal of group VIII being preferably introduced after that (those) of the group VIB or at the same time as the latter (s), if the catalyst contains at least one Group VIB metal and at least one Group VIII metal. In the case where the catalyst advantageously contains at least one element of group VIB, for example molybdenum, it is for example possible to impregnate the catalyst with a solution containing at least one element of group VIB, to dry, to calcine. The impregnation of molybdenum may advantageously be facilitated by the addition of phosphoric acid in the ammonium paramolybdate solutions, which also makes it possible to introduce the phosphorus so as to promote the catalytic activity.

The following elements: boron and / or silicon and / or phosphorus can be introduced into the catalyst at any level of the preparation and according to any technique known to those skilled in the art. A preferred method according to the invention consists in depositing the selected promoter element or elements, for example the boron-silicon pair, on the calcined or non-calcined support, preferably calcined. For this purpose, an aqueous solution of at least one boron salt, such as ammonium biborate or ammonium pentaborate, is prepared in an alkaline medium and in the presence of hydrogen peroxide, and a so-called dry impregnation is carried out in which the pore volume of the support is filled with the solution containing, for example, boron. In the case where, for example, silicon is also deposited, for example a solution of a silicon-type silicon compound or a silicone oil emulsion is used.

The element (s) promoter (s) chosen (s) in the group formed by silicon, boron and phosphorus can (may) advantageously be introduced (s) by one or more impregnation operations with excess solution on the calcined support. The boron source may advantageously be boric acid, preferably orthoboric acid H3BO3, ammonium biborate or pentaborate, boron oxide, boric esters. The boron may for example be introduced in the form of 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 family of pyridine and quinolines and compounds of the pyrrole family. Boron may be introduced for example by a boric acid solution in a water / alcohol mixture. The preferred phosphorus source is orthophosphoric acid H 3 PO 4, but its salts and esters such as ammonium phosphates are also suitable. The phosphorus may for example be introduced in the form of a mixture of phosphoric acid and a basic organic compound containing nitrogen such as ammonia, primary and secondary amines, cyclic amines, compounds of the family of pyridine and quinolines and compounds of the pyrrole family. Many sources of silicon can advantageously be employed. Thus, it is possible to use tetraethylorthosilicate Si (OEt) 4, siloxanes, polysiloxanes, silicones, silicone emulsions, halide silicates such as ammonium fluorosilicate (NH4) 2SiF6 or sodium fluorosilicate Na SiF6. Silicomolybdic acid and its salts, silicotungstic acid and its salts can also be advantageously employed. Silicon may advantageously be added for example by impregnation of ethyl silicate in solution in a water / alcohol mixture. The silicon may be added, for example, by impregnating a silicone or silicic acid silicon compound suspended in water. The noble metals of group VIII of the catalyst of the present invention may advantageously be present in whole or in part in metal (s) or (/ and) oxide form.

The sources of noble elements of group VIII which can advantageously be used are well known to those skilled in the art. For the noble metals halides are used, for example chlorides, nitrates, acids such as chloroplatinic acid, hydroxides, oxychlorides such as ruthenium ammoniacal oxychloride. It is also advantageous to use cationic complexes such as ammonium salts when it is desired to deposit the platinum on the crystallized material comprising silicon with a hierarchical porosity organized by cation exchange.

Embodiments of the invention a) First embodiment. According to a preferred embodiment of the invention, the process comprises the following stages starting from a feed resulting from the Fischer-Tropsch synthesis: a) separation of a single so-called heavy fraction with an initial boiling point of between 120 200 ° C., b) hydrotreatment of at least a portion of said heavy fraction, c) fractionation into at least 3 fractions: at least one intermediate fraction having an initial boiling point TI of between 120 and 200 ° C. and a final boiling point T 2 greater than 300 ° C and lower than 410 ° C, at least one light fraction boiling below the intermediate fraction, at least one heavy fraction boiling above the fraction intermediate, d) passing at least part of said intermediate fraction over a hydroisomerizing catalyst, e) passing at least a portion of said heavy fraction over the hydrocracking / hydroisomerization catalyst according to the invention, f) distillation of hydrocracked / hydroisomerized fractions to obtain middle distillates, and recycling of the residual fraction boiling above said middle distillates in step (e). The description of this embodiment will be made with reference to Fig. 1 without Fig. 1 limiting the interpretation.

Step (a) The effluent from the Fischer-Tropsch synthesis unit arriving via line 1 is fractionated in a separating means (2) (for example by distillation) in at least two fractions: at least one light fraction and a heavy fraction with an initial boiling point of between 120 and 200 ° C and preferably between 130 and 180 ° C and even more preferably at a temperature of about 150 ° C, in others In other words, the cutting point is between 120 and 200 ° C. The light fraction of Figure 1 leaves the pipe (3) and the heavy fraction through the pipe (4).

This fractionation can be achieved by methods well known to those skilled in the art such as flash, distillation, etc. By way of non-limiting example, the effluent from the Fischer-Tropsch synthesis unit will be flashed, decanted to remove water and distilled to obtain at least the two fractions described above. .

The light fraction is not treated according to the process of the invention but may for example constitute a good load for petrochemicals and more particularly for a steam cracking unit (5). The heavy fraction previously described is treated according to the process of the invention.

Step (b) At least a portion of said heavy fraction (step a) is allowed in the presence of hydrogen (line 6) in a zone (7) containing a hydrotreatment catalyst which aims to reduce the content of compounds olefinic and unsaturated as well as possibly decompose the oxygenates present in the fraction, as well as possibly break down any traces of sulfur and nitrogen compounds present in the heavy fraction. This hydrotreating step is non-converting, that is to say that the conversion of the 370 ° C + fraction to 370 ° C fraction is preferably less than 20% by weight, preferably less than 10% by weight and very preferably less than 5% by weight.

The catalysts used in this step (b) are non-crunchy or slightly cracking hydrotreatment catalysts comprising at least one Group VIII metal and / or a Group VI metal of the periodic table. The catalyst preferably comprises at least one metal of the metal group formed by nickel, molybdenum, tungsten, cobalt, ruthenium, indium, palladium and platinum and comprises at least one support. A combination of at least one Group VI metal (especially molybdenum or tungsten) and at least one Group VIII metal (especially cobalt and nickel) of the Periodic Table of Elements may be used. The non-noble group VIII metal concentration, when used, is from 0.01 to 15% by weight of equivalent relative to the finished catalyst and that of the Group VI metal (in particular molybdenum or tungsten). is from 5% to 30% by weight of oxide equivalent relative to the finished catalyst. When a combination of Group I / Group VIII metals is used, the catalyst is then preferably used in a sulfide form. Advantageously, at least one element selected from P, B, Si is deposited on the support.

This catalyst may advantageously contain phosphorus; indeed, this compound provides two advantages to hydrotreatment catalysts: an ease of preparation, particularly in the impregnation of nickel and molybdenum solutions, and a better hydrogenation activity.

In a preferred catalyst, the total concentration of metals of groups VI and VIII, expressed as metal oxides, is between 5 and 40% by weight and preferably between 7 and 30% by weight and the weight ratio expressed as metal oxide. (or metals) of group VI on metal (or metals) of group VIII is between 1.25 and 20 and preferably between 2 and 10. Advantageously, if there is phosphorus, the concentration of phosphorus oxide P2O5 will be less than 15% by weight and preferably less than 10% by weight. It is also possible to use a catalyst containing boron and phosphorus; advantageously boron and phosphorus are promoter elements deposited on the support, as is for example taught according to patent EP 297 949. The sum of the amounts of boron and phosphorus, respectively expressed by weight of boron trioxide and phosphorus pentoxide , relative to the carrier weight, is about 5 to 15% and the boron phosphorus atomic ratio is about 1: 1 to 2: 1 and at least 40% of the total pore volume of the finished catalyst is contained in pore diameter of greater than 13 nanometers. Preferably, the amount of Group VI metal such as molybdenum or tungsten is such that the atomic phosphorus to Group VIB metal atomic ratio is from about 0.5: 1 to 1.5: 1; the amounts of Group VIB metal and Group VIII metal, such as nickel or cobalt, are such that the atomic ratio of Group VIII metal to Group VIB metal is about 0.3: 1 to 0.7 1. The amounts of Group VIB metal expressed in weight of metal relative to the weight of finished catalyst is about 2 to 30% and the amount of Group VIII metal expressed as weight of metal based on the weight of finished catalyst is about 0.01 to 15%. Another particularly advantageous catalyst contains promoter silicon deposited on the support. An interesting catalyst contains BSi or PSi. Ni-sulfide catalysts on alumina, NiMo on alumina, NiMo on alumina doped with boron and phosphorus and NiMo on silica-alumina are also preferred. Advantageously, eta or gamma alumina will be chosen as support. In the case of the use of noble metals (platinum and / or palladium), the metal content is preferably between 0.05 and 3% by weight relative to the finished catalyst and preferably between 0.1 and 2% by weight. weight of the finished catalyst. The noble metal is preferably used in its reduced and non-sulphurized form. It is also possible to use a catalyst to

reduced nickel base and not sulphured. In this case the metal content in its oxide form is between 0.5 and 25% by weight relative to the finished catalyst. Preferably, the catalyst also contains a group IB metal such as copper, in proportions such that the mass ratio of the group IB metal and nickel on the catalyst is between 1 and 1:30. These metals are deposited on a support which is preferably an alumina, but which may also be boron oxide, magnesia, zirconia, titanium oxide, a clay or a combination of these oxides. These catalysts can be prepared by any method known to those skilled in the art or can be acquired from companies specializing in the manufacture and sale of catalysts. In the hydrotreating reactor (7), the feedstock is brought into contact with the catalyst in the presence of hydrogen at operating temperatures and pressures which make it possible to hydrogenate the olefins present in the feedstock. Preferably, the catalyst and the operating conditions chosen will also make it possible to carry out the hydrodeoxygenation, that is to say the decomposition of the oxygenated compounds (mainly alcohols) and / or the hydrodesulfurization and / or the hydrodenitrogenation of the possible traces of sulfur compounds and / or nitrogen compounds present in the load. The reaction temperatures used in the hydrotreatment reactor are between 100 and 400 ° C, preferably between 150 and 350 ° C, even more preferably between 150 and 300 ° C. The total pressure range used varies from 5 to 150 bar, preferably from 10 to 100 bar and even more preferably from 10 to 90 bar. The hydrogen which feeds the hydrotreatment reactor is introduced at a rate such that the volume ratio hydrogen / hydrocarbons is between 50 to 3000 normal liters per liter, preferably between 100 and 2000 normal liters per liter and even more preferably between 150 and 1500 normal liters per liter. The charge rate is such that the hourly volume velocity is between 0.1 and 10 h -1, preferably between 0.2 and 5 h -1, and even more preferably between 0.2 and 3 h -1. Under these conditions, the content of unsaturated and oxygenated molecules is reduced to less than 0.5% by weight and to less than 0.1% by weight in general. The hydrotreatment step is conducted under conditions such that conversion to products having boiling points greater than or equal to 370 ° C to products having boiling points below 370 ° C is limited to 20% by weight. weight, preferably less than 10% by weight and even more preferably less than 5% by weight. Step (c) The effluent from the hydrotreatment reactor is fed through a line (8) to a fractionation zone (9) where it is fractionated into at least three fractions: at least one light fraction (exiting via line 10) ) whose constituent compounds have boiling points below a temperature Ti of between 120 and 200 ° C, and preferably between 130 and 180 ° C and even more preferably at a temperature of about 150 ° C. In other words the cutting point is between 120 and 200 ° C, at least one intermediate fraction (line 11) comprising the compounds whose boiling points are between the cut point Ti, previously defined, and a T2 temperature greater than 300 ° C, even more preferably greater than 350 ° C and less than 410 ° C or more preferably 370 ° C, at least one so-called heavy fraction (line 12) comprising the compounds having boiling points greater than the previously defined cutting point T2. Step (d) At least a portion of said intermediate fraction is then introduced (line 11), as well as possibly a stream of hydrogen (line 13) into the zone (14) containing a hydroisomerization catalyst. The operating conditions under which this step (d) is carried out are as follows.

The pressure is maintained between 2 and 150 bar and preferably between 5 and 100 bar and advantageously between 10 and 90 bar, the space velocity is between 0.1 h-1 and 10 h-1 and preferably between 0, 2 and 7 h -1 and preferably between 0.5 and 5.0 h -1. The hydrogen flow rate is adjusted to obtain a ratio of 100 to 2000 normal liters of hydrogen per liter of filler and preferably between 150 and 1500 normal liters of hydrogen per liter of filler. The temperature used in this step is between 200 and 450 ° C. and preferably between 250 ° C. and 450 ° C., advantageously between 300 and 450 ° C., and even more advantageously above 320 ° C. or for example between 320 and 420 ° C. vs. The hydroisomerization step (d) is advantageously carried out under conditions such that the pass conversion to products with boiling points greater than or equal to 150 ° C. to products having boiling points below 150 ° C. is the lowest possible, preferably less than 50%, even more preferably less than 30%, and very preferably less than 15% by weight, and allows to obtain middle distillates (gas oil and kerosene) having properties cold (pour point and freezing) sufficiently good to meet the specifications in force for this type of fuel.

Thus, in this step (d), it is sought to promote hydroisomerization rather than hydrocracking. The catalysts used are of the bifunctional type, that is to say that they have a hydro / dehydrogenating function and a hydroisomerizing function. The hydro / dehydrogenating function is generally provided either by noble metals (Pt and / or Pd) active in their reduced form or by non-noble metals of group VI (particularly molybdenum and tungsten) in combination with non-noble metals of Group VIII (particularly nickel and cobalt), preferably used in their sulfurized form. The hydroisomerizing function is provided by acidic solids, such as zeolites, halogenated alumina, pillar clays, heteropolyacids or sulphated zirconia.

An alumina binder may also be used during the catalyst shaping step. The metal function can be introduced on the catalyst by any method known to those skilled in the art, such as for example comalaxing, dry impregnation, exchange impregnation. In the case where the hydroisomerization catalyst comprises at least one noble metal of group VIII, the noble metal content is advantageously between 0.01 and 5% by weight relative to the finished catalyst, preferably between 0.1 and 4% by weight and very preferably between 0.2 and 2% by weight. Before use in the reaction, the noble metal contained in the catalyst must be reduced. One of the preferred methods for conducting the reduction of the metal is hydrogen treatment at a temperature of from 150 ° C to 650 ° C and a total pressure of from 1 to 250 bar. For example, a reduction consists of a plateau at 150 ° C. for two hours and then a rise in temperature up to 450 ° C. at a rate of 1 ° C./min and then a two-hour stage at 450 ° C. throughout this reduction step, the hydrogen flow rate is 1000 normal liters of hydrogen / liter catalyst and the total pressure kept constant at 1 bar. Note also that any ex-situ reduction method is suitable. In the case where the hydroisomerization catalyst comprises at least one group VI metal in combination with at least one group VIII non-noble metal, the group VI metal content of the hydroisomerization catalyst is advantageously comprised, in oxide equivalent. between 5 and 40% by weight relative to the finished catalyst, preferably between 10 and 35% by weight and very preferably between 15 and 30% by weight and the group VIII metal content of said catalyst is advantageously included, in oxide equivalent, between 0.5 and 10% by weight relative to the finished catalyst, preferably between 1 and 8% by weight and very preferably between 1.5 and 6% by weight. Prior to use in the reaction, group VI and non-noble Group VIII metals must be sulfided. Any in-situ or ex-situ sulphurization method known to those skilled in the art is suitable.

The hydro / dehydrogenating metal function can advantageously be introduced on said catalyst by any method known to those skilled in the art, such as, for example, comalaxing, dry impregnation, exchange impregnation. According to step (d) of hydroisomerization of the process according to the invention, the hydroisomerisation catalyst comprises at least one molecular sieve, preferably at least one zeolite molecular sieve and more preferably at least one zeolite molecular sieve. 10 MR one-dimensional as a hydroisomerizing function. Zeolite molecular sieves are defined in the "Atlas of Zeolite Structure Types" classification, W. M. Meier, D. H. Oison and Ch. Baerlocher, 5th revised edition, 2001, Elsevier to which the present application also refers. Zeolites are classified according to the size of their pore openings or channels. One-dimensional 10 MR zeolite molecular sieves have pores or channels whose opening is defined by a ring of 10 oxygen atoms (10 MR aperture). The zeolite molecular sieve channels having a 10 MR aperture are advantageously unidirectional one-dimensional channels that open directly to the outside of said zeolite. The one-dimensional 10 MR zeolite molecular sieves present in said hydroisomerization catalyst advantageously comprise silicon and at least one element T selected from the group formed by aluminum, iron, gallium, phosphorus and boron, preferably aluminum. The Si / Al ratios of the zeolites described above are advantageously those obtained in the synthesis or obtained after post-synthesis dealumination treatments well known to those skilled in the art, such as and not limited to the hydrothermal treatments followed. or not acid attacks or even direct acid attacks by solutions of mineral or organic acids. They are preferably almost completely in acid form, that is to say that the atomic ratio between the monovalent compensation cation (for example sodium) and the element T inserted in the crystalline lattice of the solid is advantageously less than 0.1, preferably less than 0.05 and most preferably less than 0.01. Thus, the zeolites used in the composition of said selective hydroisomerization catalyst are advantageously calcined and exchanged by at least one treatment with a solution of at least one ammonium salt so as to obtain the ammonium form of the zeolites which, once calcined, leads to to the acid form of said zeolites. The said monodimensional 10 MR zeolite molecular sieve of said hydroisomerization catalyst is advantageously chosen from zeolite molecular sieves of structure type TON (chosen from ZSM-22 and NU-10, taken alone or as a mixture), FER (chosen from ZSM). -35 and ferrierite, taken alone or as a mixture), EUO (selected from EU-1 and ZSM-50, taken alone or as a mixture), SAPO-11 or zeolitic molecular sieves ZBM-30 or ZSM 48, taken alone or mixed. Preferably, said one-dimensional 10 MR zeolite molecular sieve is chosen from zeolitic molecular sieves ZBM-30, NU-10 and ZSM-22, taken alone or as a mixture. Very preferably, said one-dimensional 10 MR zeolite molecular sieve is ZBM-30 synthesized with the organic structuring agent triethylenetetramine. Indeed, the use of said ZBM-30 produces much better results in terms of yield and activity than other zeolites and in particular that the ZSM 48.

The one-dimensional 10 MR zeolite molecular sieve content is advantageously between 5 and 95% by weight, preferably between 10 and 90% by weight, more preferably between 15 and 85% by weight and very preferably between 20 and 80% by weight. % by weight relative to the finished catalyst. The catalysts obtained are shaped in the form of grains of different shapes and sizes. They are generally used in the form of cylindrical or multi-lobed extrusions such as bilobed, trilobed, straight-lobed or twisted, but may optionally be manufactured and used in the form of crushed powders, tablets, rings, beads. , wheels. The shaping can be carried out with other matrices than alumina, such as, for example, magnesia, amorphous silica-aluminas, natural clays (kaolin, bentonite, sepiolite, attapulgite), silica, titanium, boron oxide, zirconia, aluminum phosphates, titanium phosphates, zirconium phosphates, coal and mixtures thereof. It is preferred to use matrices containing alumina, in all its forms known to those skilled in the art, and even more preferably aluminas, for example gamma-alumina. Other techniques than extrusion, such as pelletizing or coating, can be used.

Step (e) At least part of said heavy fraction is introduced via line (12) into a zone (15) where it is placed, in the presence of hydrogen (25), in contact with a catalyst used in the method according to the present invention and under the operating conditions of the process of the present invention to produce a cut middle distillates (kerosene and diesel) having good cold properties. The catalyst used in the zone (15) of step (e) to carry out the hydrocracking and hydroisomerization reactions of the heavy fraction is the catalyst defined in the first part of the patent application. It should be noted that the catalysts used in the reactors (14) and (15) may be strictly identical or different (for example, by varying the proportion and the nature of the acid solid in the catalyst, the nature of the binder or the quantity and nature of the hydrogenating phase). During this step (e) the fraction entering the reactor undergoes in contact with the catalyst and in the presence of hydrogen essentially hydrocracking reactions which, accompanied by hydroisomerization reactions of n-paraffins, will allow to improve the quality of the formed products and more particularly the cold properties of kerosene and diesel, and also to obtain very good yields of middle distillates. The conversion to products having boiling points greater than or equal to 370 ° C in products with boiling points below 370 ° C is greater than 50% by weight, often at least 60% and preferably greater than or equal to; at 70%.

Stage (f) The effluents leaving the reactors (14) and (15) are sent via lines (16) and (17) to a distillation train, which incorporates an atmospheric distillation and optionally a vacuum distillation, and which has for the purpose of separating on the one hand the light products inevitably formed during steps (d) and (e) for example the gases (C1-C4) (line 18) and a gasoline section (line 19), and distilling at least a diesel cut (line 21) and a kerosene cut (line 20). The gas oil and kerosene fractions can be recycled (line 23) partly, jointly or separately, at the top of the hydroisomerization reactor (14) of step (d). It is also distilled a fraction (line 22) boiling over diesel fuel, that is to say whose compounds which constitute it have boiling points higher than those of middle distillates (kerosene + diesel). This fraction, called the residual fraction, generally has an initial boiling point of at least 350 ° C., preferably greater than 370 ° C. This fraction is advantageously recycled via line (22) at the top of the hydroisomerization and hydrocracking reactor (15) of the heavy fraction (step e). It may also be advantageous to recycle part of the kerosene and / or part of the gas oil in step (d), step (e) or both. Preferably, at least one of the kerosene and / or diesel fractions is partially recycled in step (d) (zone 14). It has been found that it is advantageous to recycle a portion of the kerosene to improve its cold properties. Advantageously and at the same time, the non-hydrocracked fraction is partially recycled in step (e) (zone 15).

It goes without saying that the diesel and kerosene cuts are preferably recovered separately, but the cutting points are adjusted by the operator according to his needs. In Figure 1, there is shown a distillation column (24), but two columns can be used to separately treat the sections from areas (14) and (15). In Figure 1, there is shown only the recycling of kerosene on the reactor catalyst (14). It goes without saying that one can also recycle a portion of the gas oil (separately or with kerosene) and preferably on the same catalyst as kerosene. b) Second embodiment. Another embodiment of the invention comprises the following steps: a) separation of at least a light fraction of the feedstock so as to obtain a single so-called heavy fraction with an initial boiling point of between 120-200.degree. b) optional hydrotreatment of said heavy fraction, optionally followed by a step c) removal of at least a portion of the water and optionally CO, CO2, NH3, H2S, d) passage over the hydrocracking catalyst / hydroisomerization according to the invention of at least part of said optionally hydrotreated fraction, conversion to the catalyst according to the invention described above, products with boiling points greater than or equal to 370 ° C. boiling below 370 ° C. is greater than 40% by weight, e) distillation of the hydrocracked / hydroisomerized fraction to obtain middle distillates, and recycling in step d) of the residual fraction boiling over said distillate s means.

The description of this embodiment will be made with reference to Figure 2 without Figure 2 limiting the interpretation.

Stage (a) The effluent from the Fischer-Tropsch synthesis unit arriving via line 1 is fractionated in a separation means (2) (for example by distillation) in at least two fractions: at least one light fraction and an initial boiling point heavy fraction at a temperature between 120 and 200 ° C and preferably between 130 and 180 ° C and even more preferably at a temperature of about 150 ° C, in other words the cutting point is between 120 and 200 ° C. The fractional fraction fractional fraction exits via line (3) and the heavy fraction through line (4).

This fractionation can be achieved by methods well known to those skilled in the art such as flash, distillation, etc. By way of non-limiting example, the effluent from the Fischer-Tropsch synthesis unit will be flashed, decanted to remove water and distilled to obtain at least the two fractions described above. .

The light fraction is not treated according to the process of the invention but may for example constitute a good load for petrochemicals and more particularly for a steam cracking unit (5). The heavy fraction previously described is treated according to the process of the invention. Step (b) Optionally, this fraction is allowed in the presence of hydrogen (line 6) in a zone (7) containing a hydrotreatment catalyst which aims to reduce the content of olefinic and unsaturated compounds as well as possibly to decompose oxygenates (mainly alcohols) present; in the heavy fraction described above, as well as possibly breaking down any traces of sulfur and nitrogen compounds present in the heavy fraction. This hydrotreatment step is non-converting, that is to say that the conversion of the 370 ° C + fraction to 370 ° C fraction is preferably less than 20% by weight, preferably less than 10% by weight, and very preferably less than 5% by weight.

The catalysts used in this step (b) are hydrotreatment catalysts described in step (b) of the first embodiment. In the hydrotreating reactor (7), the feedstock is brought into contact with the catalyst in the presence of hydrogen at operating temperatures and pressures which make it possible to hydrogenate the olefins present in the feedstock. Preferably, the catalyst and the operating conditions chosen will also make it possible to carry out the hydrodeoxygenation, ie the decomposition of the oxygenated compounds (mainly alcohols) and / or the hydrodesulfurization or hydrodenitrogenation of the possible traces of sulfur compounds. and / or nitrogen present in the charge. The reaction temperatures used in the hydrotreatment reactor are between 100 and 400 ° C, preferably between 150 and 350 ° C, even more preferably between 150 and 300 ° C. The total pressure range used varies from 5 to 150 bar, preferably from 10 to 100 bar and even more preferably from 10 to 90 bar. The hydrogen which feeds the hydrotreatment reactor is introduced at a rate such that the volume ratio hydrogen / hydrocarbons is between 50 to 3000 normal liters per liter, preferably between 100 and 2000 normal liters per liter and even more preferably between 150 and 1500 normal liters per liter. The charge rate is such that the hourly volume velocity is between 0.1 and 10 h -1, preferably between 0.2 and 5 h -1 and even more preferably between 0.2 and 3 h -1. Under these conditions, the content of unsaturated and oxygenated molecules is reduced to less than 0.5% by weight and to less than 0.1% by weight in general.The hydrotreating step is conducted under conditions such that the conversion to products having boiling points greater than or equal to 370 ° C in products having boiling points below 370 ° C is limited to 20% by weight, preferably less than 10% by weight and so Even more preferred is less than 5% by weight Step (c) The effluent (line 8) from the hydrotreatment reactor (7) is optionally introduced into a zone (9) of water removal which aims at least part of the water produced during the hydrotreating reactions is eliminated. with or without elimination of the gaseous fraction C4- which is generally produced during the hydrotreating step. The elimination of water is understood to mean the elimination of the water produced by the hydrodeoxygenation reactions of the oxygenated compounds, but it may also include the elimination at least partly of the saturation water of the hydrocarbons. The elimination of water can be carried out by any method and technique known to those skilled in the art, for example by drying, passing on a desiccant, flash, decantation.

Step (d) The heavy fraction (optionally hydrotreated) thus dried is then introduced (line 10) as well as optionally a stream of hydrogen (line 11) into the zone (12) containing the catalyst used in the process according to the invention and under the operating conditions of the process of the present invention. Another possibility of the process also according to the invention consists in sending all the effluent leaving the hydrotreating reactor (without drying) into the reactor containing the catalyst according to the invention and preferably at the same time as a stream of 'hydrogen. The catalyst used to carry out the hydrocracking and hydroisomerization reactions of the heavy fraction is the catalyst defined in the first part of the patent application. The operating conditions under which this step (d) is carried out are the operating conditions described according to the process according to the invention. The hydroisomerization and hydrocracking step is conducted under conditions such that the pass conversion to products having a boiling point greater than or equal to 370 ° C to products having boiling points below 370 ° C is greater than 40% by weight, and even more preferably at least 50%, preferably greater than 60%, so as to obtain middle distillates (gas oil and kerosene) having sufficiently good cold properties (pour point , freezing point) to meet the applicable specifications for this type of fuel.

Stage (e) The effluent (so-called hydrocracked and hydroisomerized fraction) leaving the reactor (12), stage (d), is sent to a distillation train (13), which incorporates an atmospheric distillation and optionally a vacuum distillation, which is intended to separate the conversion products having a boiling point of less than 340 ° C. and preferably less than 370 ° C., and especially including those formed during step (d) in the reactor (12), and of separating the residual fraction whose initial boiling point is generally greater than at least 340 ° C and preferably greater than or equal to at least 370 ° C. Among the conversion products, in addition to the light gases C1-C4 (line 14), at least one gasoline fraction (line 15) and at least one middle distillates fraction kerosene (line 16) and diesel (line 17) are separated. The residual fraction, whose initial boiling point is generally greater than at least 340 ° C. and preferably greater than or equal to at least 370 ° C., is recycled (line 18) at the top of the hydroisomerization reactor (12). hydrocracking.

It may also be advantageous to recycle (line 19) in step (d) (reactor 12) part of the kerosene and / or part of the gas oil thus obtained (s).

c) Third embodiment. Another embodiment of the invention comprises the following steps: a) fractionation of the feedstock in at least three fractions: at least one intermediate fraction having an initial boiling point T1 between 120 and 200 ° C., and final boiling point T 2 greater than 300 ° C and less than 410 ° C, - at least one light fraction boiling below the intermediate fraction, - at least one heavy fraction boiling above the intermediate fraction, b) hydrotreating at least a portion of the intermediate fraction, then passing through a process for treating at least a portion of the hydrotreated fraction on a hydroisomerizing catalyst, c) removing at least a portion of the water produced during hydrotreatment reactions and optionally CO, CO2, NH3, H2S,

d) passing over the hydrocracking / hydroisomerization catalyst according to the invention of at least a part of said heavy fraction with a product conversion of 370 ° C + to 370 ° C products greater than 40% by weight, e) and f) distilling at least a portion of the hydrocracked / hydroisomerized fractions to obtain middle distillates. The description of this embodiment will be made with reference to FIG. 3 without limiting the interpretation.

Step (a) The effluent from the Fischer-Tropsch synthesis unit comprises mainly paraffins, but also contains olefins and oxygenated compounds such as alcohols. It also contains water, CO 2, CO and unreacted hydrogen as well as light hydrocarbon compounds C 1 to C 4 in the form of gases, or even possibly sulfur or nitrogen impurities. The effluent from the Fischer-Tropsch synthesis unit arriving via line (1) is fractionated in a fractionation zone (2) in at least three fractions: at least one light fraction (leaving via line 3) whose Component compounds have boiling points below a T1 temperature of from 120 to 200 ° C, and preferably from 130 to 180 ° C and even more preferably at a temperature of about 150 ° C. In other words, the cutting point is situated between 120 and 200 ° C., at least one intermediate fraction (line 4) comprising the compounds whose boiling points are between the cut point T1, previously defined, and a T2 temperature greater than 300 ° C, even more preferably greater than 350 ° C and less than 410 ° C or more preferably 370 ° C, at least one so-called heavy fraction (line 5) comprising the compounds having boiling points greater than the previously defined cutting point T2. Cutting at 370 ° C makes it possible to separate at least 90% by weight of the oxygenates and olefins, and most often at least 95% by weight. The heavy cut to be treated is then purified and removal of the heteroatoms or unsaturated by hydrotreating is then not necessary. Fractionation is obtained here by distillation, but it can be carried out in one or more steps and by other means than distillation. This fractionation can be achieved by methods well known to those skilled in the art such as flash, distillation, etc. By way of non-limiting example, the effluent from the Fischer-Tropsch synthesis unit will be flashed, decanted to remove water and distilled to obtain at least the three fractions described above. . The light fraction is not treated according to the process of the invention but may for example constitute a good load for a petrochemical unit and more particularly for a steam cracker (steam cracking unit 6). The heavier fractions previously described are treated according to the process of the invention.

Step (b) Said intermediate fraction is admitted via line (4), in the presence of hydrogen supplied by the pipe (7), in a hydrotreating zone (8) containing a hydrotreatment catalyst, which aims to reduce the content of olefinic and unsaturated compounds as well as possibly decompose the oxygenated compounds (mainly alcohols) present in the heavy fraction described above, as well as possibly break down any traces of sulfur and nitrogen compounds present in the heavy fraction. This hydrotreating step is non-converting, that is to say that the conversion of the 150 ° C + fraction to 150 ° C fraction is preferably less than 20% by weight, preferably less than 10% by weight, and very preferably less than 5% by weight.

The catalysts used in this step (b) are hydrotreatment catalysts described in step (b) of the first embodiment. In the hydrotreatment reactor (8), the feedstock is brought into contact with the catalyst in the presence of hydrogen and at operating temperatures and pressures which make it possible to hydrogenate the olefins present in the feedstock. Preferably, the catalyst and the operating conditions chosen will also make it possible to carry out the hydrodeoxygenation, ie the decomposition of the oxygenated compounds (mainly alcohols) and / or the hydrodesulfurization or hydrodenitrogenation of the possible traces of sulfur compounds. and / or nitrogen present in the charge. The reaction temperatures used in the hydrotreatment reactor are between 100 and 400 ° C, preferably between 150 and 350 ° C, even more preferably between 150 and 300 ° C. The total pressure range used varies from 5 to 150 bar, preferably from 10 to 100 bar and even more preferably from 10 to 90 bar. The hydrogen which feeds the hydrotreatment reactor is introduced at a rate such that the volume ratio hydrogen / hydrocarbons is between 50 to 3000 normal liters per liter, preferably between 100 and 2000 normal liters per liter and even more preferably between 150 and 1500 normal liters per liter. The charge rate is such that the hourly volume velocity is between 0.1 and 10 h -1, preferably between 0.2 and 5 h -1, and even more preferably between 0.2 and 3 h -1. Under these conditions, the content of unsaturated and oxygenated molecules is reduced to less than 0.5% by weight and to less than 0.1% by weight in general. The hydrotreating step is conducted under conditions such that the conversion to products having boiling points greater than or equal to 150 ° C to products having boiling points below 150 ° C is limited to 20% by weight. weight, preferably less than 10% by weight and even more preferably less than 5% by weight. Step (c) The effluent from the hydrotreatment reactor is optionally introduced into a water removal zone (9) which is intended to remove at least a portion of the water produced during the hydrotreatment reactions. . This removal of water can be carried out with or without elimination of the gaseous fraction C4- which is generally produced during the hydrotreating step. The elimination of water is understood to mean the elimination of the water produced by the hydrodeoxygenation reactions of the oxygenated compounds, but it may also include the elimination at least partly of the saturation water of the hydrocarbons. The elimination of water can be carried out by any method and technique known to those skilled in the art, for example by drying, passing on a desiccant, flash, decantation.

Step (d) The fraction thus possibly dried is then introduced (line 10), as well as possibly a stream of hydrogen (line 11) into the zone (12) containing a hydroisomerizing catalyst. Another possibility of the process also according to the invention consists in sending all of the effluent leaving the hydrotreating reactor (without drying) into the reactor containing the hydroisomerizing catalyst and preferably at the same time as a stream of hydrogen. The hydroisomerizing catalysts are as described in step (d) of the first embodiment. The operating conditions under which this step (d) is carried out are as follows. The pressure is maintained between 2 and 150 bar and preferably between 5 and 100 bar and advantageously between 10 and 90 bar, the space velocity is between 0.1 h-1 and 10 h-1 and preferably between 0.2 and 7 h -1 and advantageously between 0.5 and 5.0 h -1. The hydrogen flow rate is adjusted to obtain a ratio of 100 to 2000 normal liters of hydrogen per liter of filler and preferably between 150 and 1500 normal liters of hydrogen per liter of filler. The temperature used in this step is between 200 and 450 ° C. and preferably between 250 ° C. and 450 ° C., advantageously between 300 and 450 ° C., and even more advantageously above 320 ° C. or for example between 320 and 420 ° C. vs.

The hydroisomerization step (d) is advantageously carried out under conditions such that the pass conversion to products with boiling points greater than or equal to 150 ° C. to products having boiling points below 150 ° C. is the lowest possible, preferably less than 50%, even more preferably less than 30%, and makes it possible to obtain middle distillates (gas oil and kerosene) having cold properties (pour point and freezing point) sufficiently good to meet the specifications in force for this type of fuel. Thus, in this step (d), it is sought to promote hydroisomerization rather than hydrocracking. Step (e) Said heavy fraction whose boiling points are higher than the cut point T2, previously defined, is introduced via the line (5) into a zone (13) where it is placed, in the presence of hydrogen (26). ), in contact with a catalyst according to the invention and under the operating conditions of the process of the present invention in order to produce a cut middle distillates (kerosene + gas oil) having: good cold properties. The catalyst used in the zone (13) of step (e) to carry out the hydrocracking and hydroisomerization reactions of the heavy fraction is the catalyst defined in the first part of the patent application. It should be noted that the catalysts used in the reactors (12) and (13) may be strictly identical or different (for example, by varying the proportion and nature of the acidic solid in the catalyst, the nature of the binder or the quantity and nature of the hydrogenating phase). During this step (e) the fraction entering the reactor undergoes in contact with the catalyst and in the presence of hydrogen essentially hydrocracking reactions which, accompanied by hydroisomerization reactions of n-paraffins, will allow to improve the quality of the formed products and more particularly the cold properties of kerosene and diesel, and also to obtain very good yields of middle distillates. The conversion to products having boiling points greater than or equal to 370 ° C. in products with a boiling point of less than 370 ° C. is greater than 40% by weight, often at least 50% and preferably greater than or equal to 60%.

In this step (e), it will therefore seek to promote hydrocracking, but preferably by limiting the cracking of middle distillates. The choice of operating conditions makes it possible to finely adjust the quality of the products (gas oil, kerosene) and in particular the cold properties of kerosene, while maintaining a good yield of diesel and / or kerosene. The process according to the invention makes it quite interesting to produce both kerosene and diesel fuel which are of good quality while minimizing the production of lighter, unwanted cuts (naphtha, LPG).

Step (f) The effluent leaving the reactor (12), step (d) is sent to a distillation train, which incorporates an atmospheric distillation and optionally a vacuum distillation, and which is intended to separate on the one hand the light products inevitably formed during step (d), for example the gases (C1-C4) (line 14) and a petrol cut (line 15), and distilling at least one diesel cut (line 17) and a section kerosene (line 16). The gas oil and kerosene fractions can be recycled (line 25) partly, jointly or separately, at the top of the hydroisomerization reactor (12) of step (d). The effluent at the outlet of step (e) is subjected to a separation step in a distillation train so as to separate, on the one hand, the light products inevitably formed during step (e), for example the gases (C1-C4) (line 18) and a petrol cut (line 19), to distil a diesel cut (line 21) and a kerosene cut (line 20) and to distil the fraction (line 22) boiling over diesel fuel that is, the compounds which constitute it have boiling points higher than those of middle distillates (kerosene + gas oil). This fraction, called the residual fraction, generally has an initial boiling point of at least 350 ° C., preferably greater than 370 ° C. This non-hydrocracked fraction is advantageously recycled at the top of the hydroisomerization and hydrocracking reactor (13) of step (e). It may also be advantageous to recycle a portion of the kerosene and / or a part of the gas oil in step (d), step (f) or both. Preferably, at least one of the kerosene and / or diesel fractions is recycled in part (line 25) in step (d) (zone 12). It has been found that it is advantageous to recycle a portion of the kerosene to improve its cold properties. Advantageously and at the same time, the non-hydrocracked fraction is partially recycled in step (f) (zone 13).

It goes without saying that the diesel and kerosene cuts are preferably recovered separately, but the cutting points are adjusted by the operator according to his needs. In Figure 3, there is shown two columns (23) and (24) of distillation, but only one can be used to treat all cuts from areas (12) and (13). In Figure 3, there is shown only the recycling of kerosene on the reactor catalyst (12). It goes without saying that one can also recycle a portion of the gas oil (separately or with kerosene) and preferably on the same catalyst as kerosene. It is also possible to recycle part of the kerosene and / or a part of the gas oil produced in the lines (20) and (21).

d) Fourth embodiment. Another embodiment of the invention comprises the following steps: a) optionally fractionation of the feedstock into at least one heavy fraction with an initial boiling point of between 120 and 200 ° C., and at least one light fraction boiling between below said heavy fraction, b) optional hydrotreatment of at least part of the feedstock or heavy fraction, optionally followed by c) removal of at least part of the water, d) passage of a at least part of the effluent or the fraction possibly hydrotreated in the process according to the invention on a first hydrocracking / hydroisomerisation catalyst according to the invention e) distillation of the hydroisomerized and hydrocracked effluent to obtain middle distillates (kerosene , diesel) and a residual fraction boiling over the middle distillates, f) passing at least a portion of said residual heavy fraction and / or a part of said middle distillates in the process according to the invention on a second hydrocracking / hydroisomerization catalyst according to the invention, and distillation of the resulting effluent to obtain middle distillates. The description of this embodiment will be made with reference to FIGS. 4 and 5, without these figures limiting the interpretation.

Step (a) When this step is carried out, the effluent from the Fischer-Tropsch synthesis unit is fractionated (for example by distillation) into at least two fractions: at least one light fraction and at least one heavy fraction with initial boiling point equal to a temperature between 120 and 200 ° C e1: preferably between 130 and 180 ° C and even more preferably at a temperature of about 150 ° C, in other words the point cutting is located between 120 and 200 ° C. The heavy fraction generally has paraffin contents of at least 50% by weight. This fractionation can be achieved by methods well known to those skilled in the art such as flash, distillation, etc. By way of non-limiting example, the effluent from the Fischer-Tropsch synthesis unit will be flashed, decanted to remove water and distilled to obtain at least the two fractions described above. .

The light fraction is not treated according to the process of the invention but may for example constitute a good load for petrochemicals and more particularly for a steam cracking unit. At least one heavy fraction previously described is treated according to the method of the invention. Step (b) Optionally, this fraction, or at least part of the initial charge, is admitted via line (1) in the presence of hydrogen (supplied via line (2)) to a zone (3) containing a catalytic converter. hydrotreatment which aims to reduce the content of olefinic and unsaturated compounds as well as possibly to decompose the oxygenated compounds (mainly alcohols) present in the heavy fraction described above, as well as possibly to decompose possible traces of sulfur and nitrogen compounds present in the heavy fraction. This hydrotreating step is non-converting, that is to say that the conversion of the 370 ° C + fraction to 370 ° C fraction is preferably less than 20% by weight, preferably less than 10% by weight, and very preferably less than 5% by weight The catalysts used in this step (b) are described in step (b) of the first embodiment.In the hydrotreatment reactor (3), the charge is brought into contact in the presence of hydrogen and at operating temperatures and pressures which make it possible to carry out the hydrogenation of the olefins present in the feed, preferably, the catalyst and the operating conditions chosen will also make it possible to carry out the hydrodeoxygenation; the decomposition of oxygenated compounds (mainly alcohols) and / or the hydrodesulfurization or hydrodenitrogenation of possible traces of sulfur and / or nitrogen compounds present in The reaction temperatures used in the hydrotreating reactor are between 100 and 400.degree.

preferably between 150 and 350 ° C, even more preferably between 150 and 300 ° C. The total pressure range used varies from 5 to 150 bar, preferably from 10 to 100 bar and even more preferably from 10 to 90 bar. The hydrogen that feeds the hydrotreatment reactor is introduced at a rate such that the volume ratio hydrogen / hydrocarbons is between 50 and 3000 normal liters per liter, preferably between 100 and 2000 normal liters per liter and even more preferably between 150 and 1500 normal liters per liter. The charge rate is such that the hourly volume velocity is between 0.1 and 10 h -1, preferably between 0.2 and 5 h -1, and even more preferably between 0.2 and 3 h -1. Under these conditions, the content of unsaturated and oxygenated molecules is reduced to less than 0.5% by weight and to less than 0.1% by weight in general.The hydrotreating step is conducted under conditions such that the conversion to products having boiling points greater than or equal to 370 ° C in products having boiling points below 370 ° C is limited to 20% by weight, preferably less than 10% by weight and so even more preferred is less than 5% by weight.

Step (c) The effluent (line 4) from the hydrotreatment reactor (3) is optionally introduced into a zone (5) of water removal which is intended to eliminate at least partly the water produced during hydrotreatment reactions. This removal of water can be carried out with or without elimination of the gaseous fraction C4- which is generally produced during the hydrotreating step. The elimination of water is understood to mean the elimination of the water produced by the hydrodeoxygenation reactions of the oxygenated compounds, but it may also include the elimination at least partly of the saturation water of the hydrocarbons. The elimination of water can be carried out by any method and technique known to those skilled in the art, for example by drying, passing on a desiccant, flash, decantation.

Step (d) At least part and preferably all of the hydrocarbon fraction (at least part of the feed or at least part of the heavy fraction of step a) or at least part of the fraction or the hydrotreated and possibly dried feedstock) is then introduced (line 6) as well as possibly a stream of hydrogen (line 7) into the zone (8) containing the catalyst according to the invention. Another possibility of the process also according to the invention consists in sending part or all of the effluent leaving the hydrotreating reactor (without drying) into the reactor containing the catalyst according to the invention and preferably at the same time as a flow of hydrogen. Before use in the reaction, if the hydrogenating phase of the catalyst consists of at least one noble metal, the metal contained in the catalyst must be reduced. One of the preferred methods for conducting the reduction of the metal is hydrogen treatment at a temperature between 150 ° C and 650 ° C and a total pressure of between 1 and 250 bar. For example, a reduction consists of a stage at 150 ° C. for 2 hours then a rise in temperature up to 450 ° C. at the rate of 1 ° C./min and then a plateau of 2 hours at 450 ° C. throughout this reduction step, the hydrogen flow rate is 1000 normal liters of hydrogen per liter of catalyst. Note also that any ex-situ reduction method is suitable.

Step (e) The hydroisomerized and hydrocracked effluent leaving the reactor (8), step (d), is sent to a distillation train (9) which incorporates an atmospheric distillation and optionally a vacuum distillation which is intended to separate the boiling point conversion products of less than 340 ° C. and preferably less than 370 ° C. and including in particular those formed during step (d) in the reactor (8), and of separating the residual fraction of which the initial boiling point is generally greater than at least 340 ° C and preferably greater than or equal to at least 370 ° C. Among the conversion products and hydroisomerized it is separated, in addition to the light gases C1-C4 (line 10) at least one gasoline fraction (line 11), and at least one middle distillates fraction kerosene (line 12) and diesel (line 13) . Step (f) The process according to the invention uses a second zone (16) containing a hydrocracking and hydroisomerization catalyst described in the first part of the patent. It passes on this catalyst, in the presence of hydrogen (line 15) an effluent selected from a portion of the product kerosene (line 12), a portion of the gas oil (line 13) and the residual fraction and preferably the residual fraction of which the initial boiling point is generally greater than at least 370 ° C. During this step, the fraction entering the reactor (16) undergoes, in the presence of hydrogen, hydroisomerization and / or hydrocracking reactions in the reactor, which will make it possible to improve the quality of the products formed and more particularly the properties cold kerosene and diesel, and obtain improved middle distillate yields over the prior art. The choice of operating conditions makes it possible to finely adjust the quality of the products (middle distillates) and in particular the cold properties.

The operating conditions in which this step (f) is carried out are the operating conditions in accordance with the process according to the invention. The operator will adjust the operating conditions on the first and second hydrocracking and hydroisomerization catalyst so as to obtain the desired product qualities and yields.

Thus, generally speaking, on the first catalyst, the pass conversion to products with boiling points greater than or equal to 150 ° C. in products with boiling points below 150 ° C. is less than 50% by weight. preferably less than 30% by weight. These conditions allow the individual to adjust the ratio kerosene / diesel produced and the cold properties of middle distillates, and more particularly kerosene. Also generally, on the second catalyst, when the residual fraction is treated, the conversion by pass to products with boiling points greater than or equal to 370 ° C in products with boiling points lower than 370 ° C, is superior. 40% by weight, preferably greater than 50%, more preferably 60%. It can even be advantageous to have conversions of at least 80% weight.

When a part of the kerosene and / or a part of the gas oil is (are) treated on the second catalyst, the pass conversion into products with boiling points greater than or equal to 150 ° C into products with dots of boiling below 150 ° C is less than 50% by weight, preferably less than 30%. In general, the operating conditions applied in the reactors (8) and (16) may be different or identical. Preferably, the operating conditions used in the two hydroisomerization and hydrocracking reactors are chosen to be different in terms of operating pressure, temperature, hourly volume rate and H2 / filler ratio. This embodiment allows the operator to adjust the qualities and / or yields of kerosene and diesel.

The effluent from the reactor (16) is then sent via line (17) in the distillation train so as to separate the conversion products, gasoline, kerosene and diesel. FIG. 4 shows an embodiment with the residual fraction (line 14) passing through the hydroisomerization and hydrocracking zone (16) (step f), the effluent obtained being sent (line 17) in the zone (9) of separation.

Advantageously, at the same time, the kerosene and / or the diesel fuel may be partially recycled (line 18) in the hydroisomerization and hydrocracking zone (step d) on the first catalyst. . In FIG. 5, a part of the kerosene and / or a part of the product gas oil passes into the hydroisomerization and hydrocracking zone (16) (step f), the effluent obtained being sent (conducting 17) in the separation zone (9). At the same time, the residual fraction (line 14) is recycled to the hydroisomerization and hydrocracking zone (8) (step d) on the first catalyst. It has been found that it is advantageous to recycle a portion of the kerosene on a hydrocracking and hydroisomerization catalyst to improve its cold properties. Figures 4 and 5 show only the recycling of kerosene. It goes without saying that one can also recycle a portion of the gas oil (separately or with kerosene) and preferably on the same catalyst as kerosene. The invention is not limited to these four embodiments.

The products obtained The obtained gas oil (s) has a pour point of at most 0 ° C, generally below -10 ° C and often below -15 ° C. The cetane number is greater than 60, generally greater than 65, often greater than 70.

The resulting kerosene (s) has a freezing point of not more than -35 ° C, generally less than -40 ° C. The smoke point is greater than 25 mm, usually greater than 30 mm. In this process, the production of gasoline (not sought) is as low as possible. The gasoline yield will always be less than 50% by weight, preferably less than 40% by weight, advantageously less than 30% by weight or even 20% by weight or even 15% by weight. The following examples illustrate the present invention without, however, limiting its scope. EXAMPLE 1 Preparation of the Hydrotreating Catalyst (Cl) The catalyst is an industrial catalyst based on a palladium on alumina noble metal with a palladium content of 0.3% by weight relative to the total weight of the finished catalyst, supplied by the company AXENS.

EXAMPLE 2 Preparation of a Hydroisomerization and Hydrocracking Catalyst According to the Invention (C4) a) Synthesis of a Crystallized Material Comprising Silo With Hierarchized and Organized Porosity In the Preparation Described Below, Calculates the ratio Organicorganic wine of the mixture resulting from step b). This ratio is defined as follows: inorganic inorganic V = (minorg * Porg) / (morg * Pinorg) where minorg is the final mass of the inorganic fraction in the form of condensed oxide (s), namely SiO 2 and AlO 2, in the solid elementary particle obtained by atomization, morg is the total mass of the non-volatile organic fraction found in the solid elementary particle obtained by atomization, namely the surfactant and the structuring agent, Porg and Pinorg are the densities respectively associated with the nonvolatile and inorganic organic fractions. In the following examples, it is considered that Porg = 1 and Pinorg = 2. Also the ratio OrganicorganicOrganic is calculated as being equal to OrganicOrganic = (msio2 + mAio2) / [2 * (structuring magent + mtensioactive)] Ethanol, the sodium, water does not enter into account in the calculation of said report Organicorganic wine • The preparation of the material C2 with hierarchical and organized porosity in the fields of microporosity and mesoporosity whose microporous and crystallized walls consist of zeolite entities aluminosilicates of ZSM-5 type such that the Si / Al molar ratio = 49 is carried out as follows. 6.86 g of a solution of tetrapropylammonium hydroxide (TPAOH 40% by weight in an aqueous solution) are added to 0.37 g of aluminum sec-butoxide (Al (OsC4Hg) 3).

After 30 min with vigorous stirring at room temperature, 27 g of demineralized water and 18.75 g of tetraethylorthosilicate (TEOS) are added. The whole is left stirring vigorously at room temperature for 18 hours so as to obtain a clear solution. To this solution is then added a solution containing 66.61 g of ethanol, 61.24 g of water and 5.73 g of surfactant F127 (pH of the mixture = 13.5). The inorganic inorganic V ratio of the mixture is equal to 0.32. The whole is left stirring for 10 minutes. The assembly is sent into the atomization chamber of the aerosol generator as described in the description above and the solution is sprayed in the form of fine droplets under the action of the carrier gas (dry air ) introduced under pressure (P = 1.5 bar). The droplets are dried according to the protocol described in the disclosure of the invention above: they are conveyed via an O2 / N2 mixture in PVC tubes. They are then introduced into an oven set at a drying temperature set at 350 ° C. The harvested powder is then dried for 18 hours in an oven at 95 ° C. 100 mg of this powder is placed in a 1 l autoclave in the presence of 0.6 ml of distilled water. The autoclave is heated at 95 ° C. for 48 hours. The powder is then dried at 100 ° C. in an oven and then calcined under air for 5 hours at 550 ° C. The solid is characterized by DR) (at low angles and at large angles, by 64 nitrogen volumetry, by TEM, by SEM, by FX.) The MET analysis shows that the final material has an organized mesoporosity characterized by a structure vermicular analysis by nitrogen volumetric analysis combined with analysis by the method a led to a value of the microporous volume Vmicro (N2) of 0.19 ml / g, a mesoporous volume value Vméso (N2) of 0 48 ml / g and a specific surface area of the final material of S = 760 m 2 / g The mesoporous diameter 4) characteristic of the mesostructured matrix is 6.5 nm. The small angle XRD analysis leads to the visualization of a correlation peak at the angle θ = 0.79 °. The Bragg relation d * sin (0) = 1.5406 makes it possible to calculate the correlation distance d between the organized mesopores of the material, ie d = 11 nm. The thickness of the walls of the mesostructured material defined by e = d - 4) is therefore e = 4.5 nm. The wide-angle XRD analysis leads to the visualization of diffraction peaks at angles 20 = 7.9 ° and 8.9 ° compatible with the crystal structure MFI of zeolite ZSM-5. The Si / Al molar ratio obtained by FX is 49. 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 3000 nm, the size distribution of these particles being centered around 300 nm.

b) Preparation of the "C2 / binder" support according to the invention (C3) A "C2 / binder" support according to the invention (called C3) is manufactured in the following manner: 5 grams of the C2 solid are mixed with 45 grams of a matrix composed of ultrafine tabular boehmite or alumina gel sold under the name SB3 by Condéa Chemie Gmbh. This powder mixture was then mixed with an aqueous solution containing 66% by weight nitric acid (7% by weight of acid per gram of dry gel) and then kneaded for 15 minutes. The kneaded paste is then extruded through a die having a diameter of 1.2 mm. The extrudates are then calcined at 500 ° C. (rise ramp of 5 ° C./min) for 2 hours in a bed traversed in dry air (1 l / h / gram of solid). This gives the solid C3.

c) Deposition of the hydro-dehydrogenating function (C4) The final catalyst (called C4) is obtained after deposition of the hydrogenating function on the support C3. The extrudates of the support C3 are subjected to a step of dry impregnation with an aqueous solution of hexachloroplatinic acid H 2 PtCl 6, allowed to mature in a water-based maturator for 24 hours at room temperature and then calcined at 500 ° C. (rising ramp of 5 ° C.). ° C / min) for two hours in bed traversed in dry air (2 I air / h / gram of solid). The platinum weight content of the finished catalyst after calcination is 1.01%. Its dispersion measured by H2 / 02 titration is 84% and the Platinum distribution coefficient measured by microprobe of Castaing is equal to 0.87.

Example 3 Treatment of a Fischer-Tropsch Filler According to the Process According to the Invention A Fischer-Tropsch synthesis feedstock on a cobalt catalyst is separated into two fractions, the heaviest fraction having the characteristics provided in Table 1. This heavy fraction is treated in a hydrogen traversed bed lost on the hydrotreating catalyst C1 under operating conditions that allow the elimination of olefinic and oxygen compounds and traces of nitrogen. The operating conditions selected are the following: - WH (charge volume / volume of catalyst / hour) = 2 h -1, total working pressure: 50 bar, - hydrogen / charge ratio: 200 normal liters / liter, temperature: 270 ° C.

Table 1: Characteristics of the heavy fraction. Simulated T distillation (5% weight): 175 ° C (25% weight): 246 ° C (50% weight): 346 ° C (75% weight): 444 ° C (95% weight): 570 ° C compounds 370 ° C + (by GC) 43% weight density at 15 ° C 0.797 nitrogen content 7 ppm sulfur content <limit detection detailed analysis of fraction C30 (GC) 82% weight n-paraffins 6% weight i-paraffins 11% weight Olefins 1% oxygenated weight After this hydrotreatment, the contents of olefins, oxygenates and nitrogenous compounds in the effluent fall below the detection thresholds, whereas the conversion of the 370 ° C + fraction to a 370 ° C fraction is negligible ( less than 5% by weight); see Table 2. Carbon monoxide and / or carbon dioxide and / or water and / or ammonia formed during hydrotreatment are removed by a flash and decant step. 2: characteristics of the heavy fraction after hydrotreatment. Simulated Distillation T (5% weight): 172 ° C (25% weight): 242 ° C (50% weight): 343 ° C (75% weight): 441 ° C (95% weight): 568 ° C compounds 370 ° C + (by GC) 41% weight density at 15 ° C 0.797 nitrogen content <limit detection sulfur content <limit detection detailed analysis of the fraction Cao (GC) 91% weight n-paraffins 9% weight i-paraffins < limit detection olefins <limit oxygen detection The hydrotreated effluent is the hydrocracking feedstock sent to the hydroisomerization and hydrocracking catalyst C4 according to the invention. Before testing, the catalyst C4 undergoes a reduction step under the following operating conditions: hydrogen flow rate: 1600 normal liters per hour and per liter of catalyst, rise in ambient temperature to 120 ° C.: 10 ° C. 1 hour at 120 ° C., rise from 120 ° C. to 450 ° C. at 5 ° C./min, two steps at 450 ° C., pressure: 1 bar. After reduction, the catalytic test is carried out under the following conditions: - total pressure of 80 bar, - H2 ratio on load of 950 normal liters, 20 - hourly volume velocity (WH) equal to 1.3 h -1. The conversion of the 370 ° C + fraction is taken as: C (370 ° C +) = [(% of 370 ° C-effluents) - (% of 370 ° C-load)] / [100 - (% of 370 °) C- load)] 5 with% 370 ° C-effluents = mass content of compounds with boiling points below 370 ° C in the effluents and% of 370 ° C-load = mass content of compounds with dots boiling below 370 ° C in the hydrocracking feed.

The reaction temperature is adjusted so as to obtain a conversion level of the 370 ° C + fraction equal to 65% by weight. The gas chromatographic analyzes make it possible to obtain the distribution of the various cuts in the hydrocracked effluent (Table 3): C1-C4 cut: hydrocarbons of 1 to 4 carbon atoms inclusive, C5-C9 cut: hydrocarbons of 5 to Including 9 carbon atoms (naphtha cut), C10-C14 cut: hydrocarbons with 10 to 14 carbon atoms inclusive (kerosene cut), C15-C22 cut: hydrocarbons with 15 to 22 carbon atoms inclusive (gas oil cut), C22 + cuts : hydrocarbons with more than 22 carbon atoms included (370 ° C + cut).

Table 3: Cross-sectional distribution of the hydrocracked effluent (GC analysis 0/0 cut weight C1-C4 6.5 cut C5-C9 17.7 cut C10-C14 36.8 cut C15-C22 20.6 cut C22 + 18, These results show (Table 3) that the use of a hydroisomerization and hydrocracking catalyst according to the invention and in a process according to the invention makes it possible by hydrocracking and hydroisomerization of a paraffinic filler resulting from the synthesis process. Fischer-Tropsch to produce middle distillates (kerosene and diesel).

Claims (16)

Revendications1. Process for producing middle distillates from a paraffinic feedstock produced by Fischer-Tropsch synthesis, using a hydrocracking / hydroisomerization catalyst comprising: at least one support formed of at least one crystallized material comprising porous silicon hierarchical and organized and consisting of at least two elementary spherical particles, each of said spherical particles comprising a mesotructured silicon oxide-based matrix having a mesopore diameter of between 1.5 and 30 nm and having microporous walls and crystallites having a thickness of between 1.5 and 60 nm, said elementary spherical particles having a maximum diameter of 200 m; at least one active phase containing at least one group VIB and / or group VIII hydro-dehydrogenating element; periodic classification. 2. The method of claim 1 wherein said method operates at a temperature between 270 and 400 ° C, at a pressure between 1 and 9 MPa, at a space velocity between 0.5 and 5 h-1 and at a Hydrogen flow rate adjusted to obtain a ratio of 400 to 1500 normal liters of hydrogen per liter of charge. 3. Method according to one of claims 1 or 2 wherein said hydrocracking / hydroisomerization catalyst comprises: - 0.1 to 60% of at least one hydro-dehydrogenating metal selected from the group consisting of Group VIB metals and of group VIII, from 40 to 99.9% of a support comprising: 0 to 99% of at least one amorphous or poorly crystallized porous inorganic binder of oxide type, 0.01 to 60% of a crystallized material comprising silicon with a hierarchical and organized porosity, the percentages being expressed as a percentage by weight relative to the total mass of the catalyst. 4. Method according to one of claims 1 to 3 wherein the elements of group VIII are selected from iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium or platinum , taken alone or in combination.35 5. The method of claim 4 wherein the group VIII elements are the noble metals selected from platinum and palladium. 6. The method of claim 4 wherein the group VIII elements are non-noble metals selected from iron, cobalt and nickel. 7. The method of claim 4 wherein the group VIB elements are selected from tungsten and molybdenum. 8. Method according to one of claims 3 to 7 wherein the content of hydrodehydrogenating element selected from the group consisting of metals of group VIB and non-noble group VIII is between 0.1 and 60% by weight relative to the total mass of said catalyst. 9. Method according to one of claims 3 to 7 wherein the content of hydrodehydrogenating element selected from the group formed by the noble metals of group VIII is between 0.05 and 10% by weight relative to the total weight of said catalyst. 10. Method according to one of claims 1 to 9 wherein said crystallized walls consist exclusively of zeolite entities. 11. The method of claim 10 wherein the zeolite entities preferably comprise at least one zeolite selected from aluminosilicates ZSM-5, ZSM-48, ZSM-22, ZSM-23, ZBM-30, EU-1, EU-2. , EU-11, I3eta, zeolite A, Y, USY, VUSY, SDUSY, mordenite, NU-87, NU-88, NU-86, NU-85, IM-5, IM-12, IZM-2 and Ferrierite and / or at least one related solid selected from SAPO-11 and SAPO-34 silicoaluminophosphates. 12. The method of claim 11 wherein the zeolite entities are species for the primer of at least one zeolite selected from aluminosilicates of structural type MFI, BEA, FAU, LTA and / or at least one related solid selected from silicoaluminophosphates of structural type AEL, CHA. 13. Method according to one of claims 1 to 12 wherein said process comprises the following steps: a) separation of a single so-called heavy fraction initial boiling point between 120-200 ° C, b) hydrotreating d at least part of said heavy fraction, c) fractionation into at least 3 fractions: - at least one intermediate fraction having an initial boiling point Ti of between 120 and 200 ° C, and a final boiling point T 2 greater than 300 ° C and below 410 ° C, - at least one light fraction boiling below the intermediate fraction, - at least one heavy fraction boiling above the intermediate fraction, d) passage of at least a portion of said intermediate fraction on a hydroisomerizing catalyst, e) passing at least a portion of said heavy fraction over the hydrocracking / hydroisomerization catalyst according to the invention, f) distillation of the hydrocracked / hydroisomerized fractions to obtain middle distillates, and recycling of the residual fraction boiling over said middle distillates in step (e). 14. Process according to one of claims 1 to 12, in which said process comprises the following steps: a) separation of at least a light fraction of the feedstock so as to obtain a single so-called heavy fraction with initial boiling point between 120-200 ° C, b) optional hydrotreatment of said heavy fraction, optionally followed by a step c) removal of at least a portion of the water and optionally CO, CO2, NH3, H2S, d) passing over the hydrocracking / hydroisomerization catalyst according to the invention of at least a portion of said optionally hydrotreated fraction, conversion to the catalyst according to the invention described above products with boiling points greater than or equal to 370 ° C in products with boiling points below 370 ° C is greater than 40% by weight, e) distillation of the hydrocracked / hydroisomerized fraction to obtain middle distillates, and recycling in step d) of the residual fraction boiling above said middle distillates. 15. Method according to one of claims 1 to 12 wherein said method comprises the following steps: a) fractionation of the feedstock in at least three fractions: at least one intermediate fraction having an initial boiling point T1 between 120 and 200 ° C, and a final boiling point T 2 greater than 300 ° C and lower than 410 ° C, - at least one light fraction boiling below the intermediate fraction, - at least one heavy fraction boiling above of the intermediate fraction, b) hydrotreatment of at least a portion of said intermediate fraction, then passage into a process for treating at least a portion of the hydrotreated fraction on a hydroisomerizing catalyst, c) removal of at least a portion water produced during the hydrotreatment reactions and optionally CO, CO2, NH3, H2S, d) passing on the hydrocracking / hydroisomerization catalyst according to the invention of at least a part of said heavy fraction with a product conversion of 370 ° C + to 370 ° C products greater than 40% by weight, e) and f) distillation of at least a portion of the hydrocracked / hydroisomerized fractions to obtain middle distillates. 16. Method according to one of claims 1 to 12 wherein said process comprises the following steps: a) possible fractionation of the feedstock in at least one heavy fraction with initial boiling point between 120 and 200 ° C, and at minus a light fraction boiling below said heavy fraction, b) optional hydrotreatment of at least part of the feedstock or heavy fraction, optionally followed by c) removal of at least part of the water (d) passing at least a portion of the effluent or the optionally hydrotreated fraction over a first hydrocracking / hydroisomerization catalyst according to the invention, e) distillation of the hydroisomerized and hydrocracked effluent to obtain middle distillates and a residual fraction boiling over the middle distillates, f) passing at least a portion of said residual heavy fraction and / or a portion of said middle distillates over a second hydrocracking catalyst / h The isomerization according to the invention, and distillation of the resulting effluent to obtain middle distillates.