MXPA97001647A - Catalyst that comprises a philosilicato 2: 1trioctaedrico prepared in a fluorated medium and hydroconversion proposal of cargaspetrole - Google Patents

Abstract

The present invention relates to a catalyst comprising at least one catalytic element, and a support containing 20-99% by weight of at least one matrix, 1-80% by weight of at least a trioctahedral 2: 1 phyllosilicate containing fluorine and 0.30% by weight of at least one Y zeolite. The catalytic element belongs to groups VI and / or VIII. Phosphorus may be present. The invention also relates to a hydroconversion process using said catalyst.

Description

CATALYST THAT COMPRISES A PHILOSILICATE 2: 1 TRIOCTAEDRICO PREPARED IN A FLUORATED MEDIUM AND PROCEDURE OF HYDROCONVERSION OF OIL LOADS FIELD OF THE INVENTION The present invention relates to a catalyst comprising at least one catalytic element and a support containing at least one trioctahedral 2: 1 phyllosilicate containing fluorine, optionally and preferably with bridges, at least one matrix and optionally at least one Y zeolite of the structure of the faujasite. The invention also relates to a hydroconversion process of heavy oil charges using this catalyst.

BACKGROUND OF THE INVENTION The hydrocracking or hydrodisintegration of heavy oil cuts is a very important refining process that allows to produce, from surplus heavy loads and low value, the lighter fractions such as gasolines, fuel for reactors and gasoles or light gas oils, which you want the refiner to adapt its production to the structure of demand. With respect to catalytic cracking, the interest of catalytic hydrocracking is Ref. 24216 that of providing intermediate distillates, fuels It will give reactors v aasols or gasoils, of very good quality. In contrast, the gasoline produced has an octane number much lower than that output from catalytic cracking. The catalysts used in hydrocracking are all of the bifunctional type that aiate an acid function with a hydrogenating function. The acid function is provided by supports of large surfaces (150 to 800 m 2.g-1 generally) that have a surface acidity, such as halogenated aluminas (especially chlorinated or fluorinated), combinations of boron and aluminum oxides, amorphous silica-aluminas and zeolites. The hydrogenating function is provided either by one or several metals of group VIII of the periodic classification of the elements, such as iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium and platinum, or by an aiation of at least one metal of group VI of the periodic classification such as chromium, molybdenum and tungsten and at least one metal of group VIII. The balance between the two acid and hydrogenating functions is the fundamental parameter that governs the activity and selectivity of the catalyst. A weak acid function and a strong hydrogenating function give little active catalysts, which work at a generally high temperature (greater than or equal to 390 ° C), and at a reduced feed space velocity (VVH expressed in volume of charge to treat per unit volume of the catalyst and per hour, in general it is less than or equal to 2) but endowed with a very good selectivity in the intermediate distillates. Conversely, a strong acid function and a reduced hydrogenating function give very active catalysts but exhibit poor selectivity in the intermediate distillates. The judicious choice of each of the functions is a problem to be solved to adjust the activity / selectivity pair of the catalyst. Thus, it is of great interest in the operation of hydrocracking to present a great flexibility at various levels: flexibility at the level of the catalysts used, which brings or that causes a flexibility of the loads to be treated and the level of the products obtained . The catalytic catalytic hydrocracking catalysts are, for the most part, made up of weakly acidic supports, such as amorphous silica-aluminas, for example. These systems are used to produce intermediate distillates of very good quality, and still, when acidity is very low, oil bases. In the low acid supports, there is the silica family - amorphous aluminas. Many of the catalysts for the operation of the hydrocracking are constituted by the aiated silica-alumina, or a metal of group VIII or, preferably when the contents in heteroatomic toxins of the load to be treated exceed 0.5% by weight, from an association of sulphides of the metals of groups VIB and VIII. These systems have a very good selectivity in the intermediate distillates, and the products formed are of very good quality. These catalysts, for the less acidic among them, can also produce lubricating bases. The disadvantage of all these catalytic systems based on the amorphous support is, as already mentioned, its reduced activity. The research carried out by the applicant on numerous zeolites and crystallized microporous solids has led to the discovery that, surprisingly, a catalyst containing at least a trioctahedral 2: 1 phyllosilicate containing fluorine and preferably synthesized in a fluorinated medium and Bridged preference, possibly and advantageously associated with a zeolite Y of the structure of faujasite, allows to obtain a selectivity in the intermediate distillates clearly improved with respect to the catalysts known in the prior art. The trioctahedral 2: 1 phyllosilicates are minerals that result from the stacking of the elemental leaves. Each sheet comprises two tetrahedral layers located on one side and on the other an octahedral layer. The tetrahedral layer is based on tetrahedra? OA »3 vertices on 4 are common to two tetrahedra and one vertex is free, which gives the formula? O,", "..,. ,? represents a tetrahedral cavity and 0 an oxygen atom. The octahedral layer is based on D? Fi octahedra, the 6 vertices are common to 3 tetrahedra, which gives the formula J ?, "J represents an octahedral cavity. Limiting the content of the sheet to a half-mesh, 4 tetrahedra ^ 0 (6 + 41 are located two to two on the one hand and the other of 3 octahedrons LJ., 0, have in common 4 vertices? 4a3 ° (( 1122)) Two atoms 0 of the octahedral layer do not participate in this pooling and are saturated by the H atoms:? Q "0. (0H)".

Very often the tetrahedral cavities are occupied by silicon atoms and the 3 octahedral cavities CJ by the magnesium atoms: Si, Mg-0- "(0H) 2. This construction is electrically neutral. In addition, the element of tetrahedral silicon can be replaced in whole or in part by trivalent elements such as for example aluminum or gallium. In the same way, the element of octahedral magnesium can be replaced by trivalent elements (Al or Fe for example) and / or divalent (Co for example) and / or monovalent (Li for example). These substitutions entail negative charges to the construction. The same causes the existence of interchangeable compensation cations located in the interfoliar space (the space between each elementary sheet). The thickness of the interfoliar space depends on the nature of the compensation cations and their hydration status. This space on the other hand is capable of receiving other chemical species such as water, amines, salts, alcohols, bases, etc ... The existence of -OH groups cause a thermal instability due to the reaction of dehydroxylation of the equation: 2 -OH > -0- + H20. In this respect, the introduction, at the time of synthesis, of the fluorine element in the structure instead of the 0-H groups leads to the thermally improved stability of the phyllosilicates. The general chemical formula (for a semi-mesh) of the 2: 1 trioctahedral phyllosilicates synthesized in a fluorinated medium before the provision of bridges, is as follows: ^ x + ey) / mt (Si (4-x) T?) ^ 3-y 0100H (2-z) Fz ^ (X + ey) "'nH20 wherein S is at least one element selected from the group consisting of the monovalent element Li, the divalent elements Zn, Ni, Co, Mn, Fe and Cu, and the tivalent elements Al and Ga, where T represents an element chosen from group IIIA and iron, where M is at least one compensation cation provided by the reaction medium or is introduced by at least one ion exchange process, chosen from the group consisting of the elements of groups IA, IIA, and VIII of the periodic classification of the elements, the cations of the rare earths (cations of the atomic number elements from 57 to 71 inclusive), the organic cations containing nitrogen (among which are preferred the alkylammoniums and the aryammoniums, the ammonium cation, the proton), where m is the valence of the cation M, where x is a number between 0 and 2, and is a number between 0 and 1, z is a number greater than 0 and less than or equal to 2, n is a positive or negative number, 20 and where £ is equal to 1 when S is a monovalent element equals 0 when S is a divalent element is equal to -1 when S is a trivalent element.

The diffraction diagram of the X-rays is characterized by the presence of the following rays: a corresponding line a value of hkl equal to 1.52 + 0.01 10 • 10m; two other stripes at the values of d,, - equal to 4.53 + 0.02 10 ~ 10 m and 2.56 + 0.045 10 ~ 10m; at least one reflection 001 in such a way that n n-i is equal to 10.5 and 19.5 10 m according to the chemical formula of said phyllosilicate.

Preferably, the fluorine content is such that the F / Si molar ratio is between 0.1 and 4. Said phyllosilicates are synthesized in a fluorinated medium in the presence of the HF acid and at a pH below 7. The preparation of this type of solids in a fluorinated medium and their characterization, are described in patent FR-A-2, 682, 371 whose teaching is included in the present description. The invention also encompasses any type of trioctahedral 2: 1 phyllosilicate containing fluorine.

This fluoride can be introduced in the synthesis or after the synthesis. Any method of preparation is convenient and the one described above will be used very advantageously. These 2: 1 trioctahedral phyllosilicates can be bridged by any of the techniques known to the person skilled in the art., but more particularly by the bridge provisioning procedure developed by the applicant and described in patents FR-A-2,720,386 and FR-A-2, 720, 387 whose teaching is included in the present description. This process comprises at least one treatment comprising a first step of contacting a solution of the polycations and the phyllosilicate to be provided with bridges comprising the interchangeable cations, thus forming the reaction mixture; then a second stage where the exchange between the polycations and the interchangeable cations of the filosilicato is allowed to develop; and finally a third stage where the product obtained is separated by filtration and washed; said treatment is characterized in that: the clay mass to be bridged by total volume of the solution is between 1 and 200 g / 1. the second stage of exchange is made at a temperature between 15 and 100 ° C; said second stage has a duration comprised between 1 minute and 3 hours. the separation time of the third stage is between 20 seconds and 60 minutes per liter of the solution containing in suspension the product to be separated.

This method of providing bridges allows simple and rapid introduction, for example, of the polycations [Al. «0, (0H) 2, (H20), 21 still called Keggin ions, or polycations containing at least one element selected from the group consisting of zirconium, titanium, molybdenum and vanadium, such as and title 8+ of non-limiting examples: [Zr, (0H) "(H20).], or even [ZrOCl2Al8 (OH) 20] 4+. The catalyst of the present invention can thus contain a Y zeolite of the faujasite structure (Sieves Structure Molecular Zolite, chemistry and uses, D. W. BRECK, J. WILLEY and Sons 1973). Among the Y zeolites that can be used, a stabilized Y-zeolite, commonly called "ultra-stable" or "USY", will be preferably used either in the form at least partially exchanged with the metal cations, for example the cations of the alkaline earth metals and / or the cations of rare earth metals of atomic number 57 to 71 inclusive, or in the form of hydrogen.

An acid zeolite HY is particularly advantageous and is characterized by different specifications: a molar ratio Si02 / Al20"comprised between approximately 8 and 70 and preferably between approximately 12 and 40: a sodium content lower than 0.15% by weight determined on the zeolite calcined at 1100 ° C; a crystalline parameter a of the elemental mesh comprised between 24.55 x 10 m and 24.24 x 10 m and preferably between 24.38 x 10 m and 24.26 x 10 m; a CNa capacity for recovery of sodium ions, expressed in grams of Na per 100 grams of modified zeolite, neutralized, then calcined, greater than approximately 0.85; a specific surface determined by the method B.E.T. greater than about 400 m2 / g and preferably greater than 550 ma / g, a water vapor adsorption capacity at 25 ° C for a partial pressure of 2.6 torr (ie 34.6 MPa), greater than about 6%, a porous partition comprising between 1 and 20% and preferably between 3 and 15% of the porous volume contained in the pores of diameter located between 20 x 10 m and 80 x 10 m, the rest of the porous volume is contained in the pores diameter less than 20.10 m. The catalyst of the present invention also contains at least one usually amorphous or poorly crystallized matrix chosen, for example, from the group consisting of alumina, silica, magnesia, titanium oxide, zirconium, aluminum, titanium or phosphate phosphates. zirconium, the combinations of at least two of these compounds and the combinations of alumina-boron oxide. The matrix is preferably chosen from the group consisting of silica, alumina, magnesia, silica-alumina combinations, silica-magnesia combinations. The catalyst support of the present invention contains the following: a) from 20 to 99%, or even from 30 to 96%, preferably from 40 to 90% and still more preferably from 50 to 85% by weight of the matrix (s). b) from 1 to 80%, or even from 4 to 70%, preferably from 10 to 60% and still more preferably from 15 to 50% by weight of the trioctahedral 2: 1 phyllosilicate (s) ( s) synthesized in a fluorinated medium, optionally bridged, c) from 0 to at most 30%, or even from 0.1 to 30%, preferably from 0 to 30% or even from 0.1 to 20% and still more preferred from 0 to at most 30% or even from 0.1 to 10% of zeolite (s) Y of the faujasite structure, which preferably has the characteristics given hereinbefore.

The catalyst of the present invention can be prepared by any of the methods well known to the person skilled in the art. One of the preferred methods in the present invention is to knead a trioctahedral 2: 1 phyllosilicate synthesized in a fluorinated medium and optionally bridged, and optionally a Y zeolite in a wet gel of suspended alumina a few tenths of minutes, then pass the paste thus obtained through a row to form extruded materials with a diameter comprised between 0.4 and 4 mm. The catalyst also contains at least one catalytic element, for example a metal having a hydro-dehydrogenating function. The hydro-dehydrogenating function is ensured by at least one metal or metal compound of group VIII such as nickel and cobalt especially. A combination of at least one metal or metal compound of group VI (especially molybdenum or tungsten and at least one metal or metal compound of group VIII (especially cobalt or nickel) of the periodic classification of the groups may be used. The total concentration of metal oxides of groups VI and / or VIII is between 1 and 40% by weight of the catalyst and preferably between 3 and 30%, advantageously between 8 and 40%, even 10 to 40% and better 10-30%, and the weight ratio expressed in metal oxide of the metal (or metals) of group III on the metal (or metals) of group VIII is between 1.25 and 20 and preferably between 2 and 10. In addition, this catalyst may contain phosphorus The phosphorus content, expressed as a phosphorus oxide concentration, will advantageously be less than 15% by weight and preferably less than 10% by weight The hydrogenating function such as that defined above ( elements of group VIII or an association of elements of groups VI and VIII) can be introduced into the catalyst at various levels of the preparation and in various ways. It can be introduced (in the case, for example, of associations of groups VI and VIII) or in its entirety at the time of the kneading of the trioctahedral 2: 1 phyllosilicate synthesized in a fluorinated medium and optionally provided by means of bridges with the gel of oxide chosen as the matrix. It can be introduced by one or several ion exchange operations on the calcined support based on the trioctahedral 2: 1 phyllosilicate synthesized in a fluorinated medium and optionally bridged, dispersed in the chosen matrix, with the help of solutions containing the precursor salts of the metals chosen and especially for the salts of the elements of group VIII. It can be introduced by one or several operations of impregnation of the support put in shape and calcined, by a solution of the precursors of the oxides of the metals of group VIII (especially cobalt and nickel) when the precursors of the oxides of group VI metals (especially molybdenum or tungsten) have been previously introduced at the time of the kneading of the support. Finally, it can be introduced by one or several impregnation operations of the support, advantageously pre-calcined, based on a trioctahedral 2: 1 phyllosilicate synthesized in a fluorinated medium and optionally provided with bridges and matrix, by one of the solutions containing the precursors of the oxides of the metals of groups VI and / or VIII, the precursors of the oxides of the metals of group VIII are preferably introduced after those of group VI or possibly at the same time as these last. In the case where the oxides of the metals are introduced into various impregnations of the corresponding precursor salts, preferably, an intermediate calcining step of the catalyst should be carried out at a temperature comprised between 250 and 600 ° C. The impregnation of molybdenum can be facilitated by the addition of phosphoric acid in the solutions of ammonium paramolybdate. The catalysts thus obtained are used for the hydrocracking of the heavy cuts, and have an improved activity with respect to the prior art, and also have an improved selectivity for the production of intermediate distillates of very good quality. The fillers used in the process are, for example, gasoles, vacuum distillates, gasoles under vacuum, deasphalted or hydrotreated waste or equivalents. The charges strongly charged with N and S have preferably been previously hydrotreated. They preferably consist of at least 80% by volume of the compounds whose boiling points are at least 350 ° C., preferably between 350 and 580 ° C (ie corresponding to the compounds containing at least 15 to 20 carbon atoms). They generally contain heteroatoms such as sulfur or nitrogen. The nitrogen content is usually between 1 and 5 000 ppm by weight and the sulfur content between 0.01 and 5% by weight. Hydrocracking conditions, such as temperature, pressure, hydrogen recirculation rate, volumetric velocity per hour, could be very variable depending on the nature of the load, the quality of the desired products, the facilities for storing the refiner. The temperatures are generally higher than 230 ° C and often comprise between 300 ° C and 480 ° C and preferably lower than 450 ° C. The pressure is greater than or equal to 2 MPa and in general greater than 3 MPa inclusive of 10 MPa, and less than 30 MPa. The amount of hydrogen is generally at least 100 1/1 of the charge and frequently included between 260 and 3,000 liters of hydrogen per liter of the charge. The volumetric velocity per hour is generally comprised between 0.2 and 10 h. The results that matter to the refiner are the activity and the selectivity of the intermediate distillates. The objectives set must be carried out in conditions compatible with economic reality. Thus, the refiner will seek to lower the temperature, the pressure, the amount of hydrogen and maximize the volumetric speed per hour. It is already known that the conversion can be increased by a rise in temperature, but this is often to the detriment of selectivity. The selectivity in the intermediate distillates is improved with an increase in the pressure or amount of hydrogen, but this is to the detriment of the economics of the process. This type of catalyst makes it possible to achieve the classical operating conditions of the selectivities in the intermediate distillates with a boiling point between 150 ° C and 380 ° C higher than 65%, and this for conversion levels, of knitted products. of boiling below 380 ° C, greater than 55% by volume. In the less severe conditions of mild hydrocracking, the selectivities in the intermediate distillates are greater than 65% (and generally greater than 75%) for the conversion levels above 30%, generally set at around 40-50%, and more frequently less than 55%. This catalyst also has remarkable stability under these conditions. Finally, due to the composition of the catalyst, it is easily regenerable. The following examples illustrate the present invention without however limiting the scope.

Example 1: Preparation of the trioctahedral 2: 1 phyllosilicate provided with PP1 bridges which enters the composition of the catalyst Cl according to the invention.

For this preparation, 36 ml of distilled water are added successively and according to the indications provided: 0. 94 g of 40% HF acid (Fluka), 7.20 g of salt (CH3C02) 2Mg, 4H20 (Prolabo) under vigorous stirring, and 0.093 g of NaF salt (Prolabo), 0.16 g of oxide A100H (Catapal B Vista), 2.50 g of pulverized Si02 oxide (Aerosil 130 of Degussa) under moderate agitation.

The composition of the hydrogel thus prepared, reported for one mole of Si02 oxide is: 1. 0 Si02; 0.026 Al203; 0.053 NaF; 0.79 Mg0; 0.45 HF; 48 H20 or in terms of the molar ratio; Mg / Si = 0.79 Al / Si - 0.052 Na / Si = 0.053 F ~ / Si - 0.503 acid / Si = 0.45 H20 / Si = 48 This composition does not take into account the water provided by the magnesium source, aluminum and HF acid. The hydrogel thus obtained is matured 4 hours at room temperature (20 ° C) under moderate agitation. The pH is then close to 4.5.

The crystallization is carried out immediately in a steel autoclave, jacketed by a Teflon coating, of a content of 120 ml, at 220 ° C, under autogenous pressure for 260 hours without agitation. The autoclave is cooled immediately exposed to the ambient air. The product is recovered immediately, filtered and washed abundantly with distilled water. It is then dried at 40-50 ° C for 24 hours. After 24 hours, the product obtained is characterized by its X-ray diffraction diagram indicated hereinafter, the recording is carried out at room temperature and humidity. hkl (A) I / I 14. 1 100 b 4.53 31 b 2.579 15 b 2.275 1 1.710 5 1.518 12 broadband (the dhkl value of the maximum intensity of the band is indicated) This diffractogram is characteristic of that of the trioctahedral 2: 1 phyllosilicates according to the invention.

The fluorine content of the phyllosilicate obtained is 5%. The trioctahedral 2: 1 phyllosilicate thus prepared is called Pl. The latter will immediately undergo a bridge provision stage according to the operating mode described hereinafter. 8 g of the trioctahedral phyllosilicate 2: 1 thus prepared and named Pl are placed in solution directly in 160 ml of a solution of Keggin ions [Al. ~ 0, (OH) ", (H20), 2] whose concentration is of the order of 9.10 mol / 1 and the pH equal to 4. By way of example this solution is prepared following the operating mode published by Urabe K. et al, Advanced Materials 3 No. 11, (1991). The mass of clay to be bridged by total volume of the solution is thus 50 g / 1. After an exchange period of 10 minutes under stirring at room temperature and a filtration step of 2 minutes, the product is washed with distilled water, for 2 minutes, then dried at 90 ° C overnight (about 15 hours) . The mass of the phyllosilicate that is to be bridged, after ion exchange and drying at 60 ° C, is 8.5 g. The grid distance d001 is of the order of 1.79 nm and the specific surface area measured by the BET method is of the order of 194 m2 / g. After 5 hours of calcination at 550 ° C under air, the bridged clay thus prepared has a net distance d001 of the order of 1.83 nm and a specific surface BET of the order of 182 m2 / g. The trioctahedral 2: 1 phyllosilicate thus prepared is called PP1.

Example 2 Preparation of the catalyst Cl (according to the invention) The trioctahedral phyllosilicate 2: 1 PP1 as described in example 1 is kneaded with the alumina of type SB3 provided by the company Condéa. The kneaded dough is extruded immediately through a row with a diameter of 1.4 mm. The extruded materials are dry impregnated with a solution of a mixture of ammonium heptamolybdate, nickel nitrate and orthophosphoric acid, and finally calcined under air at 550 ° C in-situ in the reactor. The weight contents of active oxides are the following (with respect to the catalyst): 2. 5% by weight of phosphorus oxide 20-. 15% by weight molybdenum oxide MoO., 5% by weight NiO nickel oxide The clay content provided with bridges with respect to the total mass of the catalyst is 40% by weight.

Example 3 Preparation of catalyst C2 (according to the invention) The trioctahedral phyllosilicate 2: 1 PP1 as described in example 1 and a zeolite H-Y of mesh parameter 24.33x10 m are kneaded with an alumina of the type SB3 provided by the company Condéa. The kneaded dough is extruded immediately through a row with a diameter of 1.4 mm. The extruded materials are dry impregnated with a solution of a mixture of ammonium heptamolybdate, nickel nitrate and orthophosphoric acid, and finally calcined under air at 550 ° C in-situ in the reactor where they are low. the shape of a fixed bed. The weight contents of active oxides are the following (with respect to the catalyst): 2. 5% by weight of phosphorus oxide P? 0-. % by weight molybdenum oxide Mo0"5% by weight NiO nickel oxide The content of clay provided with bridges in the catalyst assembly is 35% by weight and the content of zeolite H-Y is 5% by weight.

Example 4 Preparation of catalyst C3 (not according to the invention) A silica-alumina prepared in the laboratory containing 25% by weight of S'i02 and 75% by weight of A120 ~ is used. 3% by weight of pure nitric acid at 67% is added with respect to the dry weight of the silica-alumina powder in order to obtain the peptization of the powder. After kneading, the paste obtained is extruded through a row with a diameter of 1.4 mm. The extruded materials are calcined then impregnated dry by a solution of a chloride salt of platinum tetramine Pt (NH ,,), Cl2 and finally calcined under air at 550 ° C. The platinum content of the final catalyst is 0.6% by weight.

Example 5 Evaluation of Cl, C2 and C3 catalysts in a hydrocracking test.

The catalysts Cl and C2, whose preparations are described in the preceding examples, are used under the conditions of hydrocracking on an oil charge whose main characteristics are the following: starting point 277 ° C point at 10% 381 ° C point at 50% 482 ° C point at 90% 531 ° C end point 545 ° C point of spill + 39 ° C density (20/4) 0.919 Sulfur (% by weight ) 2.46 Nitrogen (ppm by weight) 930 The catalytic test unit comprises a fixed bed reactor, an upward circulation of the load ("upward flow"), in which they are introduced 80 ml of catalyst. Each of the catalysts is sulfided by a mixture of n-hexane / DMDS + aniline just at 320 ° C. The total pressure is 9 MPa, the hydrogen cost is 1000 liters of gaseous hydrogen per liter of the injected load, the volumetric velocity per hour is l.Oh "1. The catalytic operations are expressed by the temperature that allows to achieve a gross conversion level of 70% and by gross selectivity These catalytic operations are measured on the catalyst after a stabilization period, generally of at least 48 hours, has been respected.The gross conversion CB is taken as equal to: CB = by weight 380- effluent 100 The gross selectivity SB is taken as equal to: CR = r Weight 150/380 effluents -. # 1f) f) weight 380 - effluents Example example T (° C) SB (70% CB) (70% CB) Catalyst Cl 415 72.9 in accordance with Catalyst C2 408 72.3 in accordance with Catalyst C3 438 73.8 non-compliant The use of a trioctahedral 2: 1 phyllosilicate provided with bridges by the polycations [Al1"0, (OH) 2, (H20), 2] allows the CB crude conversion temperature to be lowered in a substantial manner since a gain of approximately 23 ° C is observed between the catalyst with the trioctahedral 2: 1 phyllosilicate provided of bridges by the polycations [A1130, (0H) 2, (H20) 12] + (catalyst Cl) and the catalyst that does not contain it (catalyst C3). In a general way, the selectivity varies strongly with the conversion. The selectivity is therefore higher than the conversion is reduced. The use of such a trioctahedral 2: 1 phyllosilicate provided with bridges, thus allows a substantial gain of the iso-conversion temperature without this being to the detriment of the selectivity of the intermediate distillates. The use of a trioctahedral 2: 1 phyllosilicate provided with bridges together with a HY zeolite (catalyst C2) thus allows a reduction of the CB crude conversion temperature, gaining 30 ° C, with respect to the non-compliant C3 catalyst, without the same is to the detriment of the selectivity of intermediate distillates.

Example 6 Evaluation of Cl and C3 catalysts in a low pressure hydrocracking test The Cl and C3 catalysts have been compared in a low pressure hydrocracking test also called mild hydrocracking. The load used at the time of the catalytic test is the same as that used in example 5. The catalytic test unit comprises a fixed bed reactor, with upward circulation of the load ("upward flow"), in which 80 ml of the catalyst are introduced. Each of the catalysts is sulfided by a mixture of n-hexane / DMDS + analin just at 320 ° C. The total pressure is 5 MPa, the hydrogen expense is 500 liters of hydrogen gas per liter of the injected load, the volumetric velocity per hour is 0.5h. The catalytic operations are expressed by the crude conversion obtained at a given temperature ( here, 400 ° C) and by the gross selectivity for a gross conversion equal to 50%. These catalytic operations are measured on the catalyst after a period of stabilization, generally of at least 48 hours, has been respected. The gross conversion CB is taken as equal to; CB by weight 380- effluent 100 The gross selectivity SB is taken as equal to n StB, = r [_weight 150 / '380 ef cl, uentes?] * ", 10" 0_. weight 380 - effluents No. example CB SB at 400 ° C (50% CB) Catalyst Cl compliant 41.8 81.6 Catalyst C3 not compliant 38.3 81.0 The use of a trioctahedral 2: 1 phyllosilicate bridged by the polycations of [A11304 (0H) 24 (H20) 12] 7+ (catalyst Cl of example 2) allows a gain in conversion of about 3.5% at 400 ° C with respect to the catalyst that does not contain it (catalyst C3 of example 4). The selectivity obtained for 50% of the crude conversion is slightly higher in the case of the catalyst Cl of example 2, which carries a trioctahedral 2: 1 phyllosilicate bridged by the polycations [Al. «0, (0H) 2 (H20 ), 2] to the selectivity recorded in the case of the silica-alumina catalyst (catalyst C3 of Example 4). These results thus demonstrate that the catalyst contains the trioctahedral 2: 1 phyllosilicate bridged by the polycations [Al. «0, (OH) 2, (H20) .2] have a selectivity slightly higher than that of a silica- alumina and above all a stronger activity.

It is noted that in relation to this date the best method known by the applicant to carry out the aforemened inven, is that which is clear from the present description of the inven.

Having described the inven as above, the content of the following is claimed as property

Claims (17)

R E I V I N D I C A C I O N S

1. A catalyst, characterized in that it comprises a support containing 20-99% by weight of at least one matrix, 1-80% by weight of at least a trioctahedral 2: 1 phyllosilicate containing fluorine, and 0-30% by weight of at least one zeolite And, and at least one catalytic element.

2. The catalyst according to claim 1, characterized in that the catalytic element is chosen from among the elements of groups VI and / or VIII, and the catalyst contains 1-40% by weight of said element (s) .

3. The catalyst according to one of the preceding claims, characterized in that it also contains phosphorus.

4. The catalyst according to claim 3, characterized in that it contains less than 15% phosphorus.

5. The catalyst according to one of the preceding claims, characterized in that the trioctahedral 2: 1 phyllosilicate has been synthesized in a fluorinated medium.

6. The catalyst according to one of the preceding claims, characterized in that the trioctahedral 2: 1 phyllosilicate has: a) the approximate general chemical formula below (for a semi-mesh): wherein S is at least one element chosen from the group consisting of the monovalent element Li, the divalent elements Zn, Ni, Co, Mn, Fe and Cu, and the trivalent elements Al and Ga, where T represents an element chosen from the group formed by IIA of the periodic classification of the elements and the iron, wherein M is at least one compensation cation provided by the reaction medium, or is introduced by at least one ion exchange process, chosen from the group formed by the cations of the elements of groups IA, IIA and VIII of the classification periodic of the elements, the proton, the organic cations containing the nitrogen, the ammonium cation, the cations of the rare earths; where m is the valence of the cation M; where x is a number between 0 and 2; and is a number between 0 and 1 z is a number greater than 0 and less than or equal to 2, n is a positive or negative real number, where 8 is equal to 1 when S is a monovalent element, where £ is equal to 0 when S is a diva-lens element, where £ is equal to -1 when S is a trivalent element. an X-ray diffraction pattern characterized by the presence of the following rays: a line corresponding to a value of d hkl equal to: 1.52 + 0.01 10 ~ 10 m other two stripes to the values of dht1 equal to 4.53 + 0.02 10 ~ 10 m and 2.56 + 0.045 10 ~ 10 m at least one reflection 001 such that '001 is equal to: 10.5 and 19.5 10, -1 * 0v m according to the chemical formula of said phyllosilicate. c) a fluorine content such that the molar ratio F / Si is between 0.1 and 4.

7. The catalyst according to claim 6, characterized in that the phyllosilicate is synthesized in a medium of pH less than 7.

8. The catalyst according to the preceding claims, characterized in that the trioctahedral 2: 1 phyllosilicate is provided with bridges.

9. The catalyst according to claim 8, characterized in that the trioc-taredic 2: 1 phyllosilicate is provided with bridges by a process comprising at least one treatment comprising a first step of contacting a solution of polycations and the phyllosilicate which bridges will be provided, which comprises the interchangeable cations, thus forming the reaction mixture; then a second stage where the exchange between the polycations and the interchangeable cations of the filosilicato is allowed to develop; and finally a third stage where the product obtained by filtration is separated and where it is washed; said treatment is characterized because: the mass of the phyllosilicate to be bridged by total volume of the solution is between 1 and 200 g / 1, the second stage of exchange is made at a temperature between 15 and 100 ° C; said second stage has a duration comprised between 1 minute and 3 hours, the separation time of the third stage is comprised between 20 seconds and 60 minutes per liter of the solution containing in suspension the product to be separated.

10. The catalyst according to one of claims 8 or 9, characterized in that the polycations used are the polycations [Al. "0, (0H), (H20). and] or polycations containing at least one element selected from the group consisting of zirconium, titanium, molybdenum and vanadium, or 8+ polycations [Zr ^ (0H) Q (H20) 16] or polycations

11. The catalyst according to one of the preceding claims, characterized in that the catalyst support contains from 20 to 99% by weight of the matrix (matrices), from 1 to 80% by weight of the phyllosilicate (s). ) 2: 1 trioctahedral (s), and from 0 to 30% by weight of the zeolite (s) Y.

12. The catalyst according to one of the preceding claims, characterized in that the catalyst support contains from 30 to 96% by weight of the matrix (matrices), from 4 to 70% by weight of the phyllosilicate (s). ) 2: 1 trioctahedral (s) and from 0 to 20% of the zeolite (s) Y.

13. The catalyst according to one of the preceding claims, characterized in that the catalyst support contains from 50 to 85% of the matrix (matrices), from 15 to 50% of the phyllosilicate (s) 2: 1 trioctahedral (s) and 0 to 10% of the zeolite (s) Y.

14. The catalyst according to one of claims 1 to 11, characterized in that the support contains 0.1-30% of at least one Y zeolite.

15. The catalyst according to one of the preceding claims, characterized in that the matrix is chosen from the group consisting of alumina, silica, magnesia, titanium oxide, zirconia, aluminum phosphates, titanium phosphates, phosphates of zirconium, the combinations of alumina-boron oxide.

16. The catalyst according to one of the preceding claims, characterized in that it is prepared by impregnation of the shaped and calcined support, with at least one solution containing the element (s) of group VI, and, simultaneously or later , with at least one solution containing the element (s) of group VIII, then final calcination.

17. The hydrocracking method of heavy cuts, characterized in that it is carried out at a temperature higher than 230 ° C, a pressure higher than 2 MPa, an amount of hydrogen of at least 100 1/1 of the load, a volumetric velocity 0.2-10 h, and with a catalyst according to one of claims 1 to 15.