MXPA97001427A - Catalyst that comprises a philosilicate 2: 1dioctaedrico prepared in a fluorated medium and proof of hydroconversion of the 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 dioctahedral 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

CATALYZER QÜE COMPRISES A PHILOSILICATE 2; 1 DIOCTAEDRICO PREPARED IN A FLUORATED MEDIUM AND PROCEDURE OF HYDROCONVERSION OF THE 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 2: 1 dioctahedral 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.

DESCRIPTION OF THE INVENTION Hydrogenating or hydrocracking cracking of heavy oil cuts is a very important refining process that allows to produce, from surplus heavy loads and low value, very light fractions such as gasoline, motor fuels and light gasols that are desired by the refiner for adapt its production to the structure of the demand. With respect to catalytic cracking, the interest of catalytic hydrocracking Ref. 24188 co is to provide intermediate distillates, fuel for reactors and gasoles, 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 associate an acidic function with a hydrogenating function. The acid function is provided by supports of large surfaces (150 to 800 m.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 the association 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 an elevated temperature in general (higher or equal to 390 ° C), and at a reduced spatial feed rate (the VVH expressed in volume of load at treat per unit volume of the catalyst and per hour is generally less than or equal to 2) but provided with a very good selectivity in the middle distillates. Conversely, a strong acid function and a weak hydrogenating function give very active catalysts but have a 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 hydrocracking, to present a great flexibility at various levels: flexibility at the level of the catalysts used, which 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, or even, when their acidity is very low, oil bases. In the low-acid supports, there is the family of amorphous silica-aluminas. Many of the catalysts of the hydrocracking operation are composed of silica-alumina associated, either of a metal of group VIII or, preferably when the contents in poisons or 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 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 discover that, surprisingly, a catalyst containing at least a dioctahedral phyllosilicate containing fluorine 2: 1, and preferably sintered in a fluoride medium and preferably with bridges, optionally and advantageously associated with a zeolite Y of the faujasite structure, makes it possible to obtain a selectivity in the intermediate distillates clearly improved with respect to the catalysts known in the prior art. The 2: 1 dioctahedral phyllosilicates are minerals that result from the stacking of elementary leaves. Each sheet comprises two tetrahedral layers located apart and others with an octahedral layer. The tetrahedral layer is based on tetrahedra ??,, 3 vertices on 4 are common for two tetrahedra and one vertex is free, which gives the formula (3/2 + 1) 'represents a tetrahedral cavity and 0 an oxygen atom. The octahedral layer is based on octahedra LÜO ,, the 6 vertices are common to 3 tetrahedra, which gives the formula L_J0,, ", Q represents an octahedral cavity.

Limiting the content of the sheet to a semimalla, 4 tetrahedra '"A ® (f, +? ^ Are located two by two on the one hand and the other with 3 octahedrons t__ 0, and have in common 4 vertices: __A Two atoms of 0 of the octahedral layer do not participate in this sharing and are saturated by H atoms:? Q 0-o (0H) «. Most of the time the < tetrahedral cavities? they are occupied by silicon atoms and two octahedral cavities Q on 3 by aluminum atoms: Si, Al "Q 0. ^ (OH)". 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 octahedral aluminum element can be replaced by divalent elements (Mg or Fe for example) and / or monovalent (Li for example). These substitutions confer negative charges to the construction. They cause the existence of exchangeable compensation cations located in the interfoliar space (the space between each elemental sheet). The thickness of the interfoliar space depends on the nature of the compensation cations and their state of dehydration. This space on the other hand is capable of receiving other chemical species such as water, amines, salts, alcohols, bases, etc. The existence of the -OH groups causes a thermal instability due to the dehydroxylation reaction of the equation: 2 -OH -0- + H20. In this regard, the introduction, at the time of synthesis, of the fluorine element in the structure instead of the H-0 groups, leads to the finely-enhanced thermal stability of the silicosilicates. The general chemical formula (for a half-grain) of the 2: 1 dioctahedral phyllosilicates synthesized in a fluoride medium having a bridge is as follows; ) x- - where T represents a chosen element of the group IIIA and the iron, - where M is at least one compensation cation left from the reaction medium or 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 periodic classification of the elements, the cations of the rare earths (cations of the elements of atomic number from 57 to 71 inclusive), the organic cations containing the nitrogen (among which there are the alkylammoniums and the aryl ammoniums and 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 greater than 0 and lower or equal to 2, and «^ represents an octahedral cavity.

The diffraction diagram of the X-rays is characterized by the presence of the following rays: a line corresponding to a value of d,,, equal to 1.49 + 0.01 10 ~ 10 m; - two other stripes different from the values of d ,,, equal to 4.46 + 0.02 10 ~ 10 m and 2.56 + 0.015 10 ~ 10m; - at least one reflection 001 such that dnn? is equal to 12.5 + 3 10 m s e g u n the nature of the compensation cation and its hydration status to the moisture considered.

Preferably, the fluorine content is such that the ratio, molar F / Si, is between 0.1 and 4. The dioctahedral 2: 1 phyllosilicate also has at least one signal at -133 ppm (+ _5 ppm) in NMR, rotation 19F . to the magical angle, of the said phyllosilicates are synthesized in a fluorinated medium in the presence of the HF acid and at a pH lower than 9, and preferably comprised between 0.5 and 6.5. The preparation of this type of solids in a fluorinated medium and their characterization are described in patent FR-A-2, 673, 930 and in a publication of 202 / a. meeting of the American Chemical Society (ACS) of New York in August 1991 whose content has been published in Synthesis of Microporus Materials, Extended Clays and other Microporous Solids (1992). The teaching of these references is included in the present description. The invention also covers any type of dioctahedral 2: 1 phyllosilicate containing fluorine. This fluoride can be introduced in the synthesis or after the synthesis. Any method of preparation is convenient, and that described above will be used very advantageously. These dioctahedral 2: 1 phyllosilicates can be provided with bridges by any of the techniques known to the person skilled in the art but more particularly by the bridging provisioning process 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 polycations and the phyllosilicate to which it is going to provide bridges, comprising interchangeable cations, which thus form the reaction mixture.; then a second stage where the exchange between the polycations and the interchangeable cations of the phyllosilicate is allowed: and finally a third stage where the product obtained by filtration is separated and where it is 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 lasts between 1 minute and 3 hours, the separation time of the third stage is comprised between 20 seconds and 60 minutes per liter of 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 1"0, (OH)", (H-0), 2] still called Keggin ions, or polycations containing at least one element selected from the group consisting of zirconium, titanium, molybdenum and vanadium, such as title 8+ of non-limiting examples: [Zr, (OH) "(H" 0),,], or else [Zr0Cl2Alg (0H) 20] 4+. The catalyst of the present invention can thus contain a Y zeolite of the faujasite structure (Molecular Zéolite Sieves Structure, chemistry and uses, D.W. BREC, J. WILLEY and Sons 1973). Among the zeolites And that they can be used, a stabilized Y zeolite, commonly called ultrastable 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 metals of the rare earths of the 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 SiO ^ / A ^ O ,, comprised between approximately 8 and 70 and preferably between approximately 12 and 40: a sodium content lower than 0.15% in weight determined on 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 or replacement of sodium ions, expressed in grams of Na per 100 grams of modified zeolite, neutralized then calcined, greater than about 0.85; a specific surface determined by the method B.E.T. greater than about 400 m / g and preferably greater than 550 m2 / 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 partition porous comprising between 1 and 20% and preferably between 3 and 15% of the pore volume contained in the pores of diameter located between 20 x 10 m and 80 x 10 m, the rest of the pore volume is contained in the pores of smaller diameter 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, zirconia, 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 thus contains: a) from 20 to 90%, or even from 30 to 96%, preferably from 40 to 90% and even more preferably from 50 to 85% by weight of the matrix (matrices), b) from 1 to 80%, or even from 4 to 70%, preferably from 10 to 60% and even more preferably from 15 to 50% by weight of the ) 2: 1 phyllosilicate (s) dioctahedral (s) synthesized in a fluoride medium, optionally bridged, c) from 0 to at most 30%, or even from 0.1 to 30%, preferably from 0 to at most 20% or even from 0.1 to 20% and even more preferably from 0 to 10% or even from 0.1 to 10% of zeolite (s). And from the structure of faujasite, it forms hydrogen, which has preference the characteristics given above.

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 2: 1 dioctahedral phyllosilicate synthesized in a fluorinated medium and optionally bridged, and eventually 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 pieces 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-desi-drogenating 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 of at least one metal or metal compound of group VIII (especially cobalt or nickel) of the periodic classification may be used. of the elements. 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 -30%, and the weight ratio expressed in metal oxide in the metal (or metals) of group VI on the metal (or metals) of group VIII is between 1.25 and 20 and preferably between 2 and 10. In addition, this catalyst can contain phosphorus. The content of phosphorus, expressed in the concentration of phosphorus oxide P "0_, 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 part only (in the case, for example, associations of groups VI and VIII) or in its entirety at the time of kneading the 2: 1 dioctahedral phyllosilicate synthesized in a fluorinated medium and optionally provided with bridges with the gel of the oxide chosen as the matrix. It can be introduced by one or several ion exchange operations on the calcined support based on the 2: 1 dioctahedral 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 the groups VIII (especially the cobalt and the nickel) at the moment in which the precursors of the oxides of group VI metals (especially molybdenum or tungsten) have been introduced before the kneading of the support, it can finally be introduced by one or several impregnation operations of the support, advantageously in the form pre-heating, calcined, based on a 2: 1 phyllosilicate dioctahedral synthesized in a fluorinated medium and optionally provided with bridges and matrix, by one of the solutions containing the precursors of the oxides of 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 than the latter. In the case where the oxides of the metals are introduced into several impregnations of the corresponding precursor salts, an intermediate calcination step of the catalyst should be carried out at a temperature between 250 and 600 ° C. Impregnation of molybdenum can be facilitated by the addition of phosphoric acid in 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, gasoils, vacuum distillates, gasoils under vacuum, deasphalted or hydrotreated residues 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 and nitrogen. The nitrogen content is usually between 1 and 500 ppm by weight and the sulfur content between 0.01 and 5% by weight. Hydrocracking conditions such as temperature, pressure, hydrogen recycling 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 the disposition of the refiner. 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 generally greater than 3 MPa, inclusive 10 MPa, and less than 30 MPa. The amount of hydrogen is generally at a minimum of 100 1/1 of the charge and frequently comprises between 260 and 3,000 liters of hydrogen per liter of charge. The volumetric speed per hour is generally comprised between 0.2 and 10 h-1 The results that matter to the refiner are the activity and the selectivity in the intermediate distillates. The objectives set must be carried out in conditions compatible with economic reality. So the refiner will look 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 the hydrogen, but this to the detriment of the economy of the process. This type of catalyst makes it possible to achieve, under conventional operating conditions, selectivities in intermediate distillates of boiling point between 150 ° C and 380 ° C higher than 65%, and this for the conversion levels, in knitted products. of boiling below 380 ° C, greater than 55% by volume. In the less severe conditions of mild or tempered 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 very frequently less than 55%. This catalyst also has a 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 foregoing.

Example 1: Preparation of 2: 1 dioctahedral phyllosilicate provided with bridges PPl that enter the composition of the catalyst Cl according to the invention For this preparation, to 36 g of distilled water, they are added successively and according to the indications provided: 0. 31 g of NaF salt (Prolabo) under moderate agitation, - 0.66 g of 40% HF acid (Fluka), 2.35 g of A100H oxide (Catapal B Vista) under vigorous stirring, 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 SiO 2 oxide is: 1. 0 SiO, 0.382 A1203: 0.177 NaF; 0.20 HF: 48 H20 or in terms of the molar ratio Yes / Al 1,309 Na + / Si 0.177 F / Yes 0.497 HF / Yes 0.32 H20 / Si 48 This composition has not taken into account the water contributed by the aluminum source and by the HF acid. The hydrogel thus obtained is matured 4 hours at room temperature (20 ° C) under moderate agitation. The pH is then close to 5. The crystallization is then carried out in a steel autoclave, clad with a Teflon coating, of a capacity of 120 ml, at 220 ° C, under autogenous pressure for 168 hours under agitation. The autoclave is cooled immediately exposed to the ambient air. The pH at the end of the synthesis is approximately 4. The product is recovered immediately, filtered and washed abundantly in distilled water. It is then dried at 40-50 ° C for 24 hours. After 24 hours, the product obtained, at 50% relative humidity, is characterized by its X-ray diffraction diagram indicated hereinafter: hkl (A) I / I 12. 42 100 6.22 6 4.46 55 2.55 21 2.48 15 2.25 2 2.22 3.5 1.74 5 1.73 6 1.69 13 1.66 7 1.62 2 1.48 20 This diffractogram is characteristic of the dioctahedral 2: 1 phyllosilicates according to the invention. The inflating or swelling properties of the obtained phyllosilicate are reported in the following table: HR 50% HR 80% 14% glycerol in ethanol hkl (A) 12.4 15.5 17.6 HR: relative humidity The fluorine weight content of the obtained silicate is 3.15%. A signal at -133 ppm is present in the NMR spectrum, rotation at the magical angle, of the 19F of the phyllosilicate prepared according to this example. The 2: 1 dioctahedral 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 dioctahedral 2: 1 phyllosilicate thus prepared and named Pl are directly placed in solution in 148 ml of a Keggin ion solution [Al, -O, (OH) 2 »(H20), 2] whose concentration is _3 of the order of 9.10 mol / 1 and the pH is 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 54 g / 1. The ratio R, defined as the ratio between the number of polycations taken, multiplied by the charge of the polycation and the amount of sodium present in the beideli-ta, is 1. After an exchange duration of 7 minutes under agitation at temperature environment and a filtration step of 1 minute, the product is washed with distilled water, for 2 minutes, then dried at 90 ° C overnight (about 15 hours). The phyllosilicate mass provided with bridges after ion exchange and drying at 60 ° C is 0.85 g. The reticular distance nr) is of the order of 1.92 nm and the specific surface area measured 2 by the BET method is of the order of 265 m / g. After hours of calcination at 550 ° C under air, the clay provided with bridges thus prepared has a reticular distance d. ,,,. of the order of 1.83 nm and a specific surface BET of the order of 230 m / g. The 2: 1 dioctahedral phyllosilicate provided with bridges by the polycations [Al. -0, (OH) 2 - (H20) .2] thus prepared is termed PPl.

Example 2 Preparation of the catalyst Cl (according to the invention) The dioctahedral phyllosilicate 2: 1 PP1, such as that 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 where they are located. in the form 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 ^ O 15% by weight of molybdenum oxide Mo0"5% by weight of NiO nickel oxide The clay content provided with bridges in the catalyst assembly is 40%.

Example 3 Preparation of catalyst C2 (not according to the invention).

The dioctahedral phyllosilicate 2: 1 PP1 as described in Example 1 and a zeolite H-Y of the mesh parameter 24.30A are kneaded with 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 by 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 they find in the form 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 Po0_ 15% by weight of molybdenum oxide Mo0"5% by weight of NiO nickel oxide The clay content 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 SIO2 and 75% by weight of Al ^ 0- is used. 3% by weight of pure nitric acid at 67% is added with respect to the dry weight of the silica-alumina powder 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 weight) 930 The catalytic test unit comprises a fixed bed, upwardly flowing ("upstream") reactor, into which 80 ml of the catalyst are introduced. 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 cost of hydrogen is 1000 liters of hydrogen gas per liter of injected load, the volumetric velocity per hour is 1.0 h. The catalytic operations are expressed by the temperature that allows to achieve a level of gross conversion 70% and for gross selectivity. 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 is taken as equal to: CB = weight 380- effluents 100 The gross selectivity SB is taken or valued as equal to: B = r Weight 150/380 ~ effluents -. ^. nf) weight 380 - effluents Example No. T (° C) SB (70% CB) (70% CB) Catalyst Cl 419 72.1 according to Catalyst C2 410 71.8 according to Catalyst C3 438 74 non-compliant The use of a dioctahedral 2: 1 phyllosilicate provided with bridges by the polycations [AloO, (OH) 2, (H20), 2] allows to reduce the CB crude conversion temperature in a substantial way since a gain of 19 ° C is observed between the catalyst with the 2: 1 dioctahedral phyllosilicate provided with bridges by the polycations [Al, 0, (OH) 2, (H20) -2] (catalyst Cl) and the catalyst that does not contain them (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 2: 1 dioctyl-bridged phyllosilicates with bridges thus allows a substantial temperature gain of the iso-conversion without this being to the detriment of the selectivity of the intermediate distillates. The use of a dioctahedral 2: 1 phyllosilicate provided with bridges together with a zeolite HY (catalyst C2) thus allows to obtain a reduction in the crude conversion temperature CB, (gain of 9 ° C) with respect to the nonconforming catalyst C3, without that it 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 sweet or soft 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, an upward flow 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 0.5 h. The catalytic operations are expressed for the crude conversion obtained at a given temperature (here, 400 ° C) and for the gross selectivity, for a gross conversion equal to 50%. These catalytic performances 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 or valued as equal to: "R _% by weight 380-» effluents 100 The gross selectivity SB is taken or valued as equal to • Weight 150/380 - effluents i # i weight 380 - effluents CB SB No. example at 400 ° C (50% CB) Catalyst Cl 42.2 81.4 according to Catalyst C3 38.3 81.0 nonconforming The use of a 2: 1 dioctahedral phyllosilicate provided with bridges (catalyst Cl of example 2), allows a gain in the conversion of 3.9% at approximately 400 ° C with respect to the catalyst that does not contain them (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, at the selectivity recorded in the case of the silica-alumina-based catalyst (catalyst C3 of example 4). These results show that the catalyst containing the 2: 1 dioctahedral phyllosilicate provided with bridges has 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 aforementioned invention, is that which is clear from the present description of the invention.

Having described the invention as above, as property contained in the following

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 one 2: 1 phyllosilicate dioctahedral containing fluorine, and 0-30% by weight of minus one zeolite And, and at least one catalytic element.

2. The catalyst according to claim 1, characterized in that the catalytic element is chosen between 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 155 phosphorus.

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

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

7. The catalyst according to one of the preceding claims, characterized in that the 2: 1 dioctahedral phyllosilicate has: a) the approximate general chemical formula below (for a semi-mesh): m + M x /, m ((Si (4, -?.) Tx) (t2 Qs - "*., 1) or? 1n0 (OH., .F)) x- (2-y) y wherein T represents an element chosen from the group consisting of IIIA of the periodic classification of the elements and the iron, where M is at least one compensation cation from 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 periodic classification of the elements, the proton, the organic cations containing the nitrogen, the cation of ammonium, 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 greater than 0 and less than or equal to 2 and L_J. represents an octahedral cavity. an X-ray diffraction pattern characterized by the presence of the following stripes: - a line corresponding to a value of d, h.kl, equal to: 1.49 + 0.01 10 ~ 10m - other strips to the values of d, h.k, l equal to: 4.46 + 0.02 10 ~ 10m and 2.56 + 0.015 10 ~ 10 m - at least one reflection 001 in such a way that dn (,. is equal to: 12.5 + 3 10 m depending on the nature of the compensation cation and its hydration status at the moisture considered. c) a fluorine content such that the molar ratio F / Si is between 0.1 and 4; d) at least one signal at - 133 ppm (+ 5ppm) of NMR, rotation at the magic angle, of 19F. said phyllosilicates have been synthesized in a fluorinated medium in the presence of HF acid and at a pH lower than 9.

8. The catalyst according to claim 7, characterized in that the pH of the synthesis is between 0.5 and 6.5.

9. The catalyst according to one of the preceding claims, characterized in that the 2: 1 dioctahedral phyllosilicate is provided with bridges.

10. The catalyst according to claim 9, wherein the dioctahedral 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 that is going to provide bridges, comprising 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 which bridges are to be supplied, 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 three hours, - the separation times of the third stage are comprised between 20 seconds and 60 minutes per liter of solution containing in suspension the product to be separated.

11. The catalyst according to one of claims 9 or 10, characterized in that the polycations used are the polycations [Al, "0, (OH) 2, (HO) 12] or the polycations containing at least one element selected from the group formed by zirconium, titanium, molybdenum and vanadium, or polycations [Zr (OH) g (H20) 16] 8+ polycations [ZrOCl2 Alg (OH) 20] 4+

12. 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 phosphorylate ( s) 2: 1 dioctahedral (s), and from 0 to 30% by weight of zeolite (s) Y.

13. 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 dioctahedral (s) and from 0 to 20% of zeolite (s) Y.

14. 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 2: 1 phyllosilicate (s). dioctahedral (s) and 0 to 10% zeolite (s) Y.

15. The catalyst according to 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, and 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 the final calcination.

17. The hydrocracking process of heavy cuts 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 of 0.2-10 h, characterized in that carried out with a catalyst according to one of claims 1 to 16. R E I V I N D I C A C I O N S 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 dioctahedral 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.