Hydrocracking catalysts containing zeolite Y for the production of naphtha.

Abstract

The present invention relates to a hydrogenation-dehydrogenation catalyst comprising at least one hydrogenation-dehydrogenation element selected from the group consisting of elements of Group VIB and non-noble metal elements of Group VIII of the periodic table, either alone or in mixture, and a support comprising at least one porous mineral matrix, zeolite Y, wherein the zeolite Y has an initial lattice parameter a of the unit cell of 24.40 Å to 24.52 Å and a BET specific surface area of ​​850 to 1020 m 2 / g, a micropore volume measured by nitrogen adsorption greater than 0.28 mL / g, and a Bronsted acidity greater than 600 μmol / g.

Description

[Technical Field]

[0001] The present invention relates to a hydrocracking catalyst based on USY zeolite and its use for the production of naphtha by hydrocracking of vacuum distillates and gas oil type petroleum fractions. This type of production method is particularly useful in schemes aimed at the conversion of hydrocarbon feedstocks for the production of petrochemical intermediates and gasoline fuels.

[0002] Hydrocracking catalysts are generally classified based on the nature of their acid functionality into catalysts containing amorphous acid functionality, especially of the silica-alumina type, and catalysts containing zeolitic cracking functionality, such as zeolite Y or zeolite beta.

[0003] Hydrocracking catalysts are also classified according to the main products obtained when they are used in processes for hydrocracking, the two main products being middle distillates and naphtha.

[0004] Naphtha or naphtha fraction is understood to mean a petroleum fraction having a boiling point lower than the middle distillate cut. The middle distillate cut typically has a cut point between 150°C and 370°C to maximize the production of kerosene and diesel. However, for example, in production processes specifically aimed at producing naphtha, the lower cut point of the middle distillate cut can be increased to increase the naphtha yield.

[0005] For this purpose, the boiling point of the naphtha fraction may be between the boiling point of hydrocarbon compounds having 6 carbon atoms per molecule (or the boiling point of 68°C) and 216°C, which includes the gasoline fraction.

[0006] High demand is in the gasoline and naphtha fractions, which is why refiners have been looking for years at hydrocracking catalysts that are selective for naphtha fractions. [Background technology]

[0007] For the production of naphtha fractions, it is known to use catalysts based on FAU type zeolites.

[0008] US Patent No. 7,611,689 (Shell) describes FAU-type zeolite Y, a catalyst containing said zeolite, its preparation, and its use in a process for hydrocracking. In particular, FAU-type zeolite has a lattice parameter of 24.40-24.50 angstroms (Å), a silica-alumina molar ratio (SAR) of 5-10, and a BET specific surface area of ​​650-900 m. 2 / g, and an alkali metal content of less than 0.15 wt. %. Such zeolites have been demonstrated to have high selectivity for naphtha fractions, especially heavy naphtha fractions, when used in processes for hydrocracking.

[0009] Patent application WO 11 / 067258 (Shell) describes a silica-alumina silica having a lattice constant of 24.42 to 24.52 angstroms (Å), a silica-alumina molar ratio (SAR) of 10 to 15, and a BET specific surface area of ​​910 to 1020 m 2 The preparation of FAU-type zeolites with a zeolite content of 0.01g / g has been described. This family teaches that catalysts containing this zeolite are particularly selective for naphtha fractions when used in processes for converting hydrocarbon fractions.

[0010] Patent application WO 04 / 0487988 (Shell) describes a silica-alumina composite with a low lattice constant of 24.10 to 24.40 angstroms (Å), a silica-alumina molar ratio (SAR) greater than 12, preferably 20 to 100, and a silica-alumina molar ratio (SAR) of 850 m 2A process for hydrocracking is described that uses a catalyst comprising zeolite Y having a BET specific surface area greater than 1 / g and a micropore volume greater than 0.28 mL / g. WO 04 / 0487988 teaches that low lattice constant zeolites are known to be selective for middle distillate cuts but less active than high lattice constant zeolites. Nevertheless, catalysts comprising low lattice constant zeolites according to the invention of WO 04 / 0487988 provide high activity coupled with good selectivity for middle distillates.

[0011] Other catalysts based on zeolite Y and zeolite beta can also be used.

[0012] U.S. Patent No. 7,510,645 (UOP) describes a hydrocracking catalyst containing zeolite beta and zeolite Y, where zeolite Y has a lattice parameter of 24.38 to 24.50 angstroms (Å), and the catalyst is characterized by a Y / Beta weight ratio of 5 to 12. The catalyst has a relatively high proportion of zeolite Y compared to the proportion of zeolite Beta. These catalysts have been demonstrated to have improved selectivity and activity compared to conventional commercial catalysts. Also disclosed is a process for hydrocracking using the catalyst at high temperatures and pressures to convert hydrocarbon feedstocks into products with lower boiling points and lower molecular weights. In particular, the resulting products contain a majority of components boiling in the naphtha fraction temperature range (C6 to 216°C). [Prior art documents] [Patent documents]

[0013] [Patent Document 1] U.S. Patent No. 7,611,689 [Patent Document 2] International Publication No. 11 / 067258 [Patent Document 3] International Publication No. 04 / 0487988 [Patent Document 4] U.S. Patent No. 7,510,645 Summary of the Invention [Means for solving the problem]

[0014] While attempting to develop a new hydrocracking catalyst selective for naphtha fractions, the Applicant has surprisingly discovered a catalyst comprising at least one hydrogenation-dehydrogenation element selected from the group formed by the elements of group VIB and the non-noble metal elements of group VIII of the periodic table, and a support comprising at least one porous mineral matrix, zeolite Y, which has an initial lattice parameter a of the unit cell of ≥ 24.40 Å and a BET specific surface area of ​​850-1020 m 2 / g, a micropore volume measured by nitrogen adsorption of more than 0.28 mL / g, and a Brønsted acidity of more than 600 μmol / g, it has been found that it is possible to improve the selectivity to naphtha fractions, in particular, compared to prior art catalysts.

[0015] (Subject of the Invention) More specifically, the present invention provides a hydrocracking catalyst that is selective for naphtha fractions, comprising: The present invention relates to a hydrogenation-dehydrogenation catalyst, comprising at least one hydrogenation-dehydrogenation element selected from the group consisting of elements of Group VIB and non-noble metal elements of Group VIII of the periodic table, either alone or in mixture, and a support comprising at least one porous mineral matrix, zeolite Y, wherein the zeolite Y has an initial lattice parameter a of a unit cell of 24.40 Å to 24.52 Å and a BET specific surface area of ​​850 to 1020 m 2 / g, a micropore volume measured by nitrogen adsorption greater than 0.28 mL / g, and a Bronsted acidity greater than 600 μmol / g.

[0016] Another subject of the invention is a process for hydrocracking a hydrocarbon feed in the presence of said catalyst.

[0017] One advantage of the present invention is that it provides a hydrocracking catalyst that has improved selectivity to naphtha fractions compared to prior art catalysts when used in a process for hydrocracking according to the present invention.

[0018] In the present invention, the selectivity of a hydrocracking catalyst for naphtha production is determined during a catalytic test and corresponds to the fraction as a weight percentage of products boiling within the naphtha cut, i.e., between the boiling point of hydrocarbon compounds containing 6 carbon atoms per molecule (or the boiling point of 68°C) and 216°C, relative to the total mass of products obtained in the production process.

[0019] According to an advantageous embodiment, the catalyst according to the invention also comprises beta zeolite.

[0020] An advantage of advantageous embodiments of the present invention is to provide a hydrocracking catalyst comprising the Y zeolite having the specific claimed properties and a Beta zeolite with a specific Y / Beta mass ratio, such that the use of the catalyst in the process for hydrocracking according to the invention allows not only an improved selectivity towards naphtha fractions but also an improved activity compared to prior art catalysts.

[0021] In the present invention, the conversion activity of a hydrocracking catalyst for naphtha production is determined by comparing the temperature at which the catalyst must be used to produce at least 65% by weight of products boiling below 216°C during a catalytic test. The lower the temperature required, the more active the catalyst. This reduction in temperature makes it possible, for example, to limit the energy consumption of the production process, increase the cycle time for using the catalyst, and process less reactive feedstocks without changing the production capacity and scheme.

[0022] Throughout the following text, the term "specific surface area" refers to the BET specific surface area (SBET) determined by nitrogen adsorption according to standard ASTM 4365-19, established from the Brunauer-Emmett-Teller method described in The Journal of the American Chemical Society, 60, 309 (1938). Texture analysis by nitrogen adsorption also makes it possible to determine the micropore volume, i.e., the volume of pores with an opening of less than 2 nm. Before analysis, the zeolite powder is activated at 500°C for 5 hours.

[0023] Similarly, mesopore volume is determined by nitrogen adsorption. Throughout the following text, the term "micropore" means pores with openings less than 2 nm, and "mesopore" means pores with openings greater than 2 nm.

[0024] Throughout the following text, the Bronsted acidity of zeolite Y is measured by pyridine adsorption and subsequent thermal desorption followed by infrared spectroscopy (FTIR). This method is conventionally used to characterize acidic solids such as Y zeolites, as described by CA Emeis, Journal of Catalysis, 141, 347 (1993). Prior to analysis, the zeolite powder is compressed into pellets with a diameter of 16 mm and activated under a secondary vacuum at 450 °C. The introduction of pyridine in the gas phase in contact with the activated pellets and the thermal desorption step are carried out at 150 °C. The concentration of pyridinium ions detected by FTIR after thermal desorption at 150 °C corresponds to the Bronsted acidity of the zeolite and is expressed in micromoles / g.

[0025] For the purposes of the present invention, the various embodiments presented may be used alone or in combination with each other without being limited to combinations.

[0026] For purposes of the present invention, various ranges of parameters for a given step, such as pressure ranges and temperature ranges, may be used alone or in combination. For example, for purposes of the present invention, a preferred range of pressure values ​​may be combined with a more preferred range of temperature values.

[0027] In the remainder of the text, groups of chemical elements are given according to the CAS classification (CRC Handbook of Chemistry and Physics, published by CRC Press, editor DRLide, 81st ed., 2000-2001). For example, group VIII according to the CAS classification corresponds to the metals in rows 8, 9, and 10 according to the new IUPAC classification, and group VIB corresponds to the metals in row 6.

[0028] In the text that follows, the expressions "between ... and ..." and "between ... and ..." are synonymous and mean that the limits of the interval are included in the range of values ​​stated. If this is not the case, and if the limits are not included in the range stated, such clarification is provided by the present invention.

[0029] As used herein, the term "greater than" is understood to mean strictly greater than and is represented by the symbol ">", and the term "less than" is understood to mean strictly less than and is represented by the symbol "<".

[0030] Herein, the overall SiO2 / Al2O3 molar ratio of a zeolite is also referred to as the SAR or silica-alumina ratio. The SiO2 / Al2O3 molar ratio is measured by X-ray fluorescence. DETAILED DESCRIPTION OF THE INVENTION

[0031] (hydrogenation / dehydrogenation function) According to the invention, the catalyst comprises at least one hydrodehydrogenating element selected, alone or in a mixture, from the group formed by the elements of group VIB and the non-noble metal elements of group VIII of the periodic table.

[0032] Preferably, the Group VIII element is selected from iron, cobalt, and nickel, either alone or as a mixture, and more preferably from nickel and cobalt. Preferably, the Group VIB element is selected from tungsten and molybdenum, either alone or as a mixture. The following metal combinations are preferred: nickel-molybdenum, cobalt-molybdenum, nickel-tungsten, cobalt-tungsten, and highly preferably nickel-tungsten. It is also possible to use a combination of three metals, such as nickel-cobalt-molybdenum.

[0033] The content of group VIII elements in the catalyst is advantageously 0.5% to 8% by weight, calculated as oxide, preferably 0.5% to 6% by weight, calculated as oxide, and very preferably 1.0% to 4% by weight, calculated as oxide, relative to the total weight of the catalyst. The content of group VIB elements in the catalyst is advantageously 1% to 30% by weight, calculated as oxide, preferably 2% to 25% by weight, calculated as oxide, and very preferably 5% to 20% by weight, calculated as oxide, and even more preferably 5% to 16% by weight, calculated as oxide, relative to the total weight of the catalyst.

[0034] Preferably, the catalyst used according to the invention may also contain a promoter element selected from phosphorus, boron, silicon, and very preferably phosphorus. When the catalyst contains phosphorus, the phosphorus content is advantageously between 0.5% and 10% by weight, calculated as P2O5 oxide, preferably between 1% and 6% by weight, calculated as P2O5 oxide, and more preferably between 1% and 4% by weight, calculated as P2O5 oxide, relative to the total weight of the catalyst.

[0035] (Carrier) The catalyst according to the present invention comprises a support comprising at least one porous mineral matrix, zeolite Y, preferably dealuminated zeolite USY, which preferably consists of the matrix. The zeolite Y has an initial lattice parameter a of 24.40 Å to 24.52 Å and a BET specific surface area of ​​850 to 1020 m. 2 / g, a micropore volume greater than 0.28 mL / g, and a Bronsted acidity greater than 600 μmol / g.

[0036] The porous mineral matrix used as the catalyst carrier, also called binder, advantageously consists of at least one refractory oxide, preferably selected from the group formed by alumina, silica-alumina, clay, titanium oxide, boron oxide, and zirconia, either alone or as a mixture. Preferably, the porous mineral matrix is ​​selected from alumina and silica-alumina, either alone or as a mixture. More preferably, the porous mineral matrix is ​​alumina. Advantageously, the alumina may be in any of its forms known to those skilled in the art. Highly preferably, the alumina is gamma alumina, such as boehmite.

[0037] Preferably, the carrier comprises 15% to 55% by weight, preferably 25% to 50% by weight, very preferably 25% to 40% by weight of binder relative to the total weight of the carrier.

[0038] According to the present invention, the support comprises zeolite Y having an initial lattice parameter a0 of the unit cell of 24.40 Å to 24.52 Å.

[0039] Preferably, the initial lattice parameter a0 of the unit cell of the zeolite Y used is between 24.40 and 24.51 Å, preferably between 24.43 and 24.51 Å, very preferably between 24.45 and 24.48 Å.

[0040] The initial lattice parameter a0 of the unit cell of zeolite Y given is the value of the initial lattice parameter a0 of the zeolite Y used in the synthesis of the catalyst according to the invention.

[0041] The initial lattice parameter a0 of the unit cell of zeolite Y is measured by X-ray diffraction according to the ASTM D3942-80 standard.

[0042] According to the present invention, the zeolite Y has a molecular weight of 850 to 1020 m 2 / g, preferably 875 to 995 m 2 / g, preferably 900 to 970 m 2 / g specific surface area measured by nitrogen physisorption using the BET method.

[0043] According to the invention, the zeolite Y has a micropore volume determined by nitrogen adsorption of more than 0.28 mL / g, preferably more than 0.30 mL / g, advantageously more than 0.31 mL / g and advantageously less than 0.34 mL / g.

[0044] According to the invention, the zeolite Y has a Brønsted acidity of more than 600 μmol / g, preferably more than 650 μmol / g, preferably more than 700 μmol / g, very preferably more than 760 μmol / g. Preferably, the Brønsted acidity of the zeolite Y is less than 1000 μmol / g.

[0045] Preferably, the zeolite Y has a silica-alumina molar ratio (SAR) of 5-50, preferably 5-20, more preferably 5-10.

[0046] Preferably, the zeolite Y has a mesopore volume of greater than or equal to 0.18 mL / g, preferably between 0.18 and 0.27 mL / g, preferably between 0.20 and 0.26 mL / g, very preferably between 0.22 and 0.25 mL / g.

[0047] Preferably, the support has a content of zeolite Y, preferably dealuminated zeolite USY, of 15% to 80% by weight, preferably 20% to 75% by weight, preferably 40% to 75% by weight, relative to the total weight of the support.

[0048] Said zeolites are advantageously defined in the classification "Atlas of Zeolite Framework Types, 6th revised edition", Ch. Baerlocher, LBMcCusker, DH Olson, 6th Edition, Elsevier, 2007, Elsevier.

[0049] According to a preferred embodiment of the present invention, zeolite Y, having the specific combination of properties defined above and suitable for use as a catalyst support in the process according to the present invention, is advantageously prepared according to a preparation method known to those skilled in the art. Advantageously, zeolite Y, having the specific combination of properties defined above and suitable for use as a catalyst support in the process according to the present invention, is obtained according to a preparation method comprising several steps. Among these steps, a homogeneous mixture, called a precursor gel, is obtained by mixing at least one alkali metal, at least one organic compound R (where R is a quaternary ammonium salt formed by a carbon-based chain containing 1 to 4 carbon atoms), at least one silicon source SiO2, and at least one aluminum source Al2O3 in an aqueous medium. This precursor gel may undergo an optional aging step and optional steps, including the addition of FAU-structural-type zeolite seeds. After these optional steps are completed, the precursor gel is subjected to a hydrothermal treatment until the zeolite Y is formed.

[0050] Therefore, the obtained zeolite Y has an initial lattice constant a of 24.40 Å to 24.52 Å, and a specific surface area of ​​850 to 1020 m2 measured by nitrogen physical adsorption using the BET method. 2 / g, a micropore volume determined by nitrogen adsorption greater than 0.28 mL / g, and a Bronsted acidity greater than 600 μmol / g.

[0051] The support may also advantageously comprise zeolite beta.

[0052] Zeolite beta is generally synthesized from a reaction mixture containing a structuring agent. The use of structuring agents is well known to those skilled in the art; for example, U.S. Patent No. 3,308,069 describes the use of tetraethylammonium hydroxide, and U.S. Patent No. 5,139,759 describes the use of tetraethylammonium cations derived from tetraethylammonium halide compounds. Another standard method for preparing zeolite beta is shown in the book "Verified Synthesis of Zeolitic Materials."

[0053] The zeolite beta used in the support according to the invention preferably has an overall SAR atomic ratio of 10 to 100, preferably 20 to 50, more preferably 20 to 30. The zeolite beta used in the support according to the invention advantageously has an SAR of 400 to 800 m, measured by nitrogen physisorption according to the BET method. 2 / g, preferably 500 to 750m 2 / g, preferably 550 to 700m 2 / g specific surface area.

[0054] When the support comprises zeolite beta, it advantageously has a zeolite beta content of between 2% and 40% by weight, preferably between 5% and 35% by weight, preferably between 10% and 35% by weight, relative to the total weight of the support.

[0055] When the carrier contains zeolite beta, the weight ratio of the zeolite Y to the zeolite beta in the catalyst is 1-40.

[0056] Preferably, the weight ratio of the zeolite Y to the zeolite beta in the catalyst is 1-20, preferably 1.2-15, more preferably 1.2-8.

[0057] This weight ratio is calculated from the dry mass of the zeolite, ie the mass of the zeolite (dry mass) corrected for its water content determined by measuring the loss on ignition at 1000°C.

[0058] When the support comprises only zeolite USY (no zeolite beta), it preferably consists of: - 15% to 80%, preferably 20% to 70%, more preferably 40% to 70% by weight of zeolite Y, preferably dealuminated zeolite USY, with an initial lattice parameter a of the unit cell between 24.40 Å and 24.52 Å, relative to the total weight of the support; - 20% to 85% by weight, preferably 20% to 60% by weight, very preferably 20% to 50% by weight of at least one porous mineral matrix relative to the total weight of the support.

[0059] When the support comprises zeolite USY and zeolite beta, it preferably consists of: - 15% to 80%, preferably 20% to 70%, more preferably 40% to 70% by weight of zeolite Y, preferably dealuminated zeolite USY, with an initial lattice parameter a of the unit cell between 24.40 Å and 24.52 Å, relative to the total weight of the support; - 2% to 40% by weight, preferably 5% to 35% by weight, or 10% to 35% by weight, of zeolite beta relative to the total weight of the support; and - 5% to 83% by weight, preferably 15% to 40% by weight, very preferably 20% to 40% by weight, of at least one porous mineral matrix relative to the total weight of the support.

[0060] Preferably, the catalyst has a content of zeolite Y of between 7% and 78% by weight relative to the total weight of the catalyst.

[0061] Preferably, when zeolite beta is present in the catalyst formulation, the catalyst has a zeolite beta content of between 2% and 39% by weight, based on the total weight of the catalyst.

[0062] Preferably, the catalyst has a content of at least one porous mineral matrix of between 4% and 81% by weight relative to the total weight of the catalyst.

[0063] Advantageously, a hydrocracking catalyst having a Y / Beta ratio within these ranges makes it possible to obtain not only an improved selectivity for naphtha fractions when said catalyst is used in the process for hydrocracking according to the invention, but also an improved activity compared to prior art catalysts.

[0064] (Catalyst Preparation) The catalyst is advantageously prepared according to conventional methods used in the prior art.

[0065] In particular, the catalyst - preparing a carrier, - at least one porous mineral matrix with a unit cell initial lattice parameter a0 between 24.40 Å and 24.52 Å and a specific surface area between 850 and 1020 m2, as measured by nitrogen physisorption using the BET method; 2 / g, a micropore volume measured by crude adsorption greater than 0.28 mL / g, and a Bronsted acidity greater than 600 μmol / g, and optionally zeolite beta, wherein the weight ratio of the zeolite Y to the zeolite beta, when present, in the catalyst is from 1 to 40; forming said mixture; preparing a carrier; at least one hydrodehydrogenating element selected from the group formed by elements of group VIB of the periodic table, preferably nickel and cobalt, non-noble metal elements of group VIII of the periodic table, preferably iron, cobalt, nickel and mixtures thereof, preferably nickel and cobalt, and mixtures thereof; - adding at least one precursor of said element during its formation to introduce at least a portion of said element, - impregnating the support with at least one precursor of the element, - optionally, at the end of the preparation of the support, a step of drying and / or calcining and / or a step of introducing at least one hydrogenation-dehydrogenation element. introducing the compound onto the carrier by It is prepared according to a preparation method comprising:

[0066] More particularly, the catalyst comprises the steps of: a) preparing zeolite Y according to the above method, having the specific crystallographic properties claimed, b) preparing zeolite beta if it is present in the catalyst formulation according to the invention, c) mixing with a porous mineral matrix and forming to obtain a carrier; d) adding at least one hydrodehydrogenating element to the catalyst by the following method: - adding at least one precursor of said element during the formation to introduce at least a portion of said element; - impregnating the support with at least one precursor of said hydrodehydrogenating element; - optionally drying and / or calcining the product obtained at the end of each of the preparation steps a) or b) or c) or d). introducing the carrier onto the carrier by at least one of It is prepared according to a preparation method comprising:

[0067] The carrier may be advantageously formed by any technique known to those skilled in the art, for example by extrusion, by pelletizing, by the drop congealing (oil drop) method, by granulation on a rotating plate, or by any other method known to those skilled in the art.

[0068] The carriers are preferably formed into particles of various shapes and sizes. They are generally used in the form of cylindrical pellets with a linear or twisted shape or multi-shaped pellets such as trilobal, tetralobal, or multi-shaped pellets, but can also be manufactured and used in the form of crushed powder, lozenges, rings, beads, or wheels. However, the carriers are advantageously in the form of pellets with a diameter of 0.5 to 5 mm, more specifically 0.7 to 3 mm, and even more specifically 1.0 to 2.5 mm. The shape can be cylindrical (which may or may not be hollow), twisted cylindrical, multi-lobed (e.g., 2, 3, 4, or 5 lobes), or annular. Other shapes can also be used.

[0069] One of the preferred shaping methods consists in co-kneading the zeolite with a binder, preferably alumina, in wet gel form for a few tens of minutes, preferably between 10 and 40 minutes, and then forcing the paste thus obtained through a die to form extrudates with a diameter preferably between 0.5 and 5 mm.

[0070] According to another preferred method of formation, the zeolite can be introduced during the synthesis of the porous mineral matrix. For example, according to this preferred embodiment of the present invention, the zeolite Y and Beta are added during the synthesis of a porous mineral matrix, for example a silica-alumina matrix. In this case, the zeolite can be advantageously added to a mixture consisting of an alumina compound in an acidic medium containing a completely soluble silica compound.

[0071] The group VIB and / or group VIII elements may optionally be introduced during the shaping step by adding at least one compound of said element to introduce at least a portion of said element.

[0072] The introduction of at least one hydrogenation-dehydrogenation element may advantageously be accompanied by the introduction of at least one promoter element selected from phosphorus, boron, silicon and preferably phosphorus, optionally an element of group VIIA and / or VB. The shaped solid is optionally dried at a temperature between 60°C and 250°C and optionally calcined at a temperature between 250°C and 800°C for a duration between 30 minutes and 6 hours.

[0073] The step of introducing at least one hydrogenation-dehydrogenation element is advantageously carried out by methods known to those skilled in the art, in particular by one or more operations of impregnating the shaped, calcined or dried, preferably calcined, support with a solution containing precursors of elements of groups VIB and / or VIII, optionally precursors of at least one promoter element, and optionally precursors of at least one element of groups VIIA and / or VB.

[0074] Preferably, said step d) is carried out by dry impregnation with a solution containing precursors of the hydrogenation / dehydrogenation functions, i.e., group VIB and / or group VIII elements, optionally followed by a drying step, preferably without a calcination step.

[0075] When the catalyst of the present invention contains a non-noble Group VIII metal, the Group VIII metal is preferably introduced after the Group VIB metal or simultaneously with the latter, by one or more impregnation operations of the formed and calcined support.

[0076] The introduction of at least one hydrogenation-dehydrogenation element can optionally be followed by drying at a temperature between 60°C and 250°C, followed by calcination, optionally at a temperature between 250°C and 800°C.

[0077] The sources of molybdenum and tungsten are advantageously selected from oxides and hydroxides, molybdic acid and tungstic acid and their salts, in particular ammonium salts such as ammonium molybdate, ammonium heptamolybdate and ammonium tungstate, phosphomolybdic acid, phosphotungstic acid and their salts, silicomolybdic acid, silicotungstic acid and their salts. Oxides and ammonium salts, such as ammonium molybdate, ammonium heptamolybdate and ammonium tungstate, are preferably used.

[0078] Sources of non-noble Group VIII elements that can be used are well known to those skilled in the art, for example, for non-noble metals, nitrates, sulfates, hydroxides, phosphates, halides such as chlorides, bromides and fluorides, carboxylates such as acetates and carbonates are used.

[0079] The preferred source of phosphorus is orthophosphoric acid H3PO4, but its salts and esters, such as ammonium phosphate, are also suitable.Phosphorus can be introduced, for example, in the form of a mixture of phosphoric acid with nitrogen-containing basic organic compounds, such as aqueous ammonia, primary and secondary amines, cyclic amines, compounds of the pyridine and quinoline families, and compounds of the pyrrole family.Tungsten phosphate or tungsten molybdate can be used.

[0080] The phosphorus content is adjusted to form mixed compounds, such as tungsten-phosphorus, molybdenum-phosphorus, or molybdenum-tungsten-phosphorus, in the solution and / or on the support, without limiting the scope of the present invention. These mixed compounds may be heteropolyanions. These compounds may be, for example, Anderson heteropolyanions.

[0081] The boron source may be boric acid, preferably orthoboric acid H3BO3, ammonium diborate or ammonium pentaborate, boron oxide, or boric acid ester. Boron can be introduced, for example, in the form of a mixture of boric acid, aqueous hydrogen peroxide, and nitrogen-containing basic organic compounds, such as aqueous ammonia, primary and secondary amines, cyclic amines, compounds of the pyridine and quinoline families, and compounds of the pyrrole family. Boron can be introduced, for example, by a solution of boric acid in a water / alcohol mixture.

[0082] Many silicon sources can be used. Thus, ethyl orthosilicate Si(OEt)4, siloxane, polysiloxane, silicone, silicone emulsion, halide silicates such as ammonium fluorosilicate (NH4)2SiF6 or sodium fluorosilicate Na2SiF6 can be used. Silicomolybdic acid and its salts, silicotungstic acid and its salts can also be advantageously used. Silicon can be added, for example, by impregnation with ethyl silicate in solution in a water / alcohol mixture. Silicon can be added, for example, by impregnation with a silicon compound of silicone or silicic acid type suspended in water.

[0083] Usable sources of Group VB elements are well known to those skilled in the art. For example, among niobium sources, oxides such as diniobium pentoxide Nb2O5, niobate Nb2O5·H2O, niobium hydroxide and polyoxyniobic acid, niobium alkoxide of the formula Nb(OR1)3 (wherein R1 is an alkyl radical), niobium oxalate NbO(HC2O4)5, or ammonium niobate may be used. Preferably, niobium oxalate or ammonium niobate is used.

[0084] Sources of Group VIIA elements that can be used are well known to those skilled in the art. For example, fluoride anions can be introduced in the form of hydrofluoric acid or its salts. These salts are formed with alkali metals, ammonium, or organic compounds. In the latter case, the salt is advantageously formed in the reaction mixture by the reaction between the organic compound and hydrofluoric acid. It is also possible to use hydrolyzable compounds that can release fluoride anions in water, such as ammonium silicofluoride (NH4)2SiF6in, silicon tetrafluoride SiF4, or sodium silicofluoride Na2SiF6. Fluorine can be introduced, for example, by impregnation with an aqueous solution of hydrofluoric acid or ammonium fluoride.

[0085] (Process for Hydrocracking) The catalyst according to the invention is then advantageously used in a process for hydrocracking, in particular for the production of naphtha. The catalyst used in a process for hydrocracking, such as the process according to the invention, can advantageously be in sulfide form. Thus, the Group VIB metal and / or the non-noble Group VIII metal of the catalyst are present in sulfide form.

[0086] Consequently, it is advantageous to subject the catalyst used in the process according to the invention to a sulfurization treatment in advance, before contacting it with the feedstock to be treated, in order to convert at least part of the metal species into the sulfide form. This activation treatment by sulfurization can be carried out either in situ (i.e. in the reactor) or ex situ, by any of the methods known to those skilled in the art and already described in the literature.

[0087] Conventional sulfurization processes well known to those skilled in the art consist of heating the catalyst in the presence of sulfide (neat or in a stream of, for example, a hydrogen / sulfide mixture) at temperatures between 150°C and 800°C, preferably between 250°C and 600°C, generally in a fluidized bed reaction zone.

[0088] Another subject of the present invention is a process for hydrocracking at least one hydrocarbon feedstock, preferably in liquid form, in the presence of a catalyst according to the invention, wherein at least 50% by weight of the compounds of the at least one hydrocarbon feedstock have an initial boiling point above 300°C and a final boiling point below 650°C, at a temperature between 200°C and 480°C, a total pressure between 1 MPa and 25 MPa, a ratio of the volume of hydrogen per volume of hydrocarbon feedstock of between 80 and 5000 liters / liter, and an hourly space velocity (HSV), defined by the ratio of the volumetric flow rate of the preferably liquid hydrocarbon feedstock per volume of catalyst packed in the reactor, of between 0.1 and 50 h -1 That is the method.

[0089] Advantageously, the catalyst according to the invention is used in the process for hydrocracking according to the invention after a pretreatment section, which may be any catalyst known to those skilled in the art and which contains one or more hydrotreating catalysts making it possible to reduce the content of certain pollutants in the feedstock (see below), such as nitrogen, sulfur or metals. The operating conditions of this pretreatment section (HSV, temperature, pressure, hydrogen flow rate, liquid, reaction configuration, etc.) can vary widely according to the knowledge of those skilled in the art.

[0090] (raw materials) A wide variety of feedstocks can be processed by the process for hydrocracking according to the invention. The feedstock used in the process for hydrocracking according to the invention is a hydrocarbon feedstock in which at least 50% by weight of the compounds have an initial boiling point above 300°C and a final boiling point below 650°C, preferably at least 60% by weight, preferably at least 75% by weight, more preferably at least 80% by weight of the compounds have an initial boiling point above 300°C and a final boiling point below 650°C.

[0091] The feedstocks are advantageously selected, alone or in mixtures, from LCO (light cycle oil, light diesel oil from catalytic cracking units), atmospheric distillates, vacuum distillates, e.g., diesel obtained from direct distillation of crude oil or from conversion units such as FCC, coking, or visbreaking units, feedstocks derived from units for extracting aromatic compounds from lubricating oil bases or from solvent dewaxing of lubricating oil bases, distillates obtained from fixed-bed or evaporative bed desulfurization or hydroconversion processes for atmospheric residues (AR) and / or vacuum residues (VR) and / or deasphalted oils, and paraffins obtained from Fischer-Tropsch processes. Feedstocks of renewable origin (e.g., vegetable oils, animal fats, oils from the hydrothermal conversion or pyrolysis of lignocellulosic biomass) and plastic pyrolysis oils may also be mentioned. The above list is not limiting. The feedstock preferably has a boiling point T5 above 300°C, preferably above 340°C, i.e. 95% of the compounds present in the feedstock have a boiling point above 300°C, preferably above 340°C.

[0092] The nitrogen content of the feedstock treated in the process according to the invention is advantageously greater than 500 ppm by weight, preferably between 500 and 10,000 ppm by weight, more preferably between 700 and 4,000 ppm by weight, and even more preferably between 1,000 and 4,000 ppm by weight. The sulfur content of the feedstock treated in the process according to the invention is advantageously between 0.01 and 5% by weight, preferably between 0.2 and 4% by weight, and even more preferably between 0.5 and 3% by weight.

[0093] The feedstock may optionally contain metals. The cumulative content of nickel and vanadium in the feedstock treated with the method according to the invention is preferably less than 1 ppm by weight.

[0094] The feedstock may optionally contain asphaltenes, which generally have an asphaltene content of less than 3000 ppm by weight, preferably less than 1000 ppm by weight, and even more preferably less than 200 ppm by weight.

[0095] Advantageously, when the catalyst according to the invention is used after the hydrotreating section as described above, the nitrogen, sulfur, metal or asphaltenes content in the liquid injected into the production process according to the invention using the catalyst according to the invention is reduced. Preferably, the organic nitrogen content in the feedstock to be treated in the process for hydrocracking according to the invention is 0 to 200 ppm, preferably 0 to 50 ppm, even more preferably 0 to 30 ppm after hydrotreating. The sulfur content is preferably less than 1000 ppm, the asphaltene content is preferably less than 200 ppm, while the metal (Ni or V) content is less than 1 ppm.

[0096] The process for hydrocracking according to the invention may include a fractionation step between pretreatment of the feedstock and the one or more hydrocracking reactors using the catalyst according to the invention. In the preferred case where the process for hydrocracking is carried out without splitting (gas and liquid) between pretreatment and the one or more hydrocracking reactors using the catalyst according to the invention, the nitrogen and sulfur removed from the liquid after pretreatment are injected in the form of NH3 and HS into the one or more reactors containing the catalyst according to the invention.

[0097] According to the present invention, the method for hydrocracking a hydrocarbon feedstock according to the present invention is carried out at a temperature of 200°C to 480°C, a total pressure of 1 MPa to 25 MPa, a ratio of the volume of hydrogen per volume of hydrocarbon feedstock of 80 to 5000 liters / liter, and an hourly space velocity (HSV), defined as the ratio of the volumetric flow rate of the hydrocarbon feedstock per volume of catalyst packed in the reactor, of 0.1 to 50 h -1 It is executed in

[0098] Preferably, the process for hydrocracking according to the invention is carried out in the presence of hydrogen at a temperature of 250°C to 480°C, preferably 320°C to 450°C, very preferably 330°C to 435°C, under a pressure of 2 to 25 MPa, very preferably 3 to 20 MPa, for 0.1 to 20 hours. -1 , preferably 0.1 to 6 hours -1 , preferably 0.2 to 3 hours -1The amount of hydrogen introduced is such that the volume ratio of liters of hydrogen to liters of hydrocarbon is 100 to 2000 L / L.

[0099] The process can be carried out in one or two stages, depending on the desired degree of feedstock conversion, with or without recycling of the unconverted fraction. The catalyst according to the present invention can be used, without limitation, alone or in combination with another hydrocracking catalyst in a one-stage or two-stage hydrocracking process.

[0100] These operating conditions used in the process according to the invention generally make it possible to obtain a conversion per pass of more than 15% by weight, more preferably between 20% and 100% by weight, to products having a boiling point below 340° C., and even better below 370° C.

[0101] The examples illustrate the invention without limiting its scope.

[0102] (Example) Example 1 - Preparation of Comparative Catalyst A The support of catalyst A has a lattice constant of 24.53 Å, a silica-alumina molar ratio (SAR) of 9, and a specific surface area of ​​925 m2 measured by nitrogen physisorption using the BET method. 2 The support is prepared by kneading and extruding 70 wt. % USY zeolite, which has a molecular weight of 0.32 mL / g, a micropore volume determined by nitrogen adsorption of 0.12 mL / g, a mesopore volume determined by nitrogen adsorption of 0.12 mL / g, and a Bronsted acidity of 852 μmol / g, in the presence of commercial boehmite (Pural SB3, Sasol). The resulting pellets are dried at 80°C and then calcined at 600°C in moist air (5 wt. % water per kg dry air). The calcined support contains, on a dry basis, 70 wt. % zeolite and 30 wt. % alumina.

[0103] Catalyst A is prepared by dry impregnation of the resulting support with an aqueous solution containing the elements Ni and Mo. This solution is obtained by dissolving the following precursors in water: nickel nitrate and ammonium heptamolybdate. The amount of precursor in the solution is adjusted depending on the desired concentration of the final catalyst. After dry impregnation, the catalyst is dried in air at 120 °C.

[0104] The mass percentages in the catalyst are 15.1 wt. % molybdenum (in the form of MoO3) and 3.3 wt. % nickel (in the form of NiO) on a dry basis.

[0105] Example 2 - Preparation of Comparative Catalyst B The support of catalyst B has a lattice constant of 24.48 Å, a silica-alumina molar ratio (SAR) of 6, and a specific surface area of ​​827 m2 measured by nitrogen physisorption using the BET method. 2 The support is prepared by kneading and extruding 70 wt. % zeolite USY, which has a molecular weight of 0.27 mL / g, a micropore volume determined by nitrogen adsorption of 0.27 mL / g, a mesopore volume determined by nitrogen adsorption of 0.16 mL / g, and a Bronsted acidity of 614 μmol / g, in the presence of commercial boehmite (Pural SB3, Sasol). The resulting pellets are dried at 80°C and then calcined at 600°C in moist air (5 wt. % water per kg dry air). The calcined support contains, on a dry basis, 70 wt. % zeolite USY and 30 wt. % alumina.

[0106] Catalyst B is prepared by dry impregnation of the resulting support with an aqueous solution containing the elements Ni and Mo. This solution is obtained by dissolving the following precursors in water: nickel nitrate and ammonium heptamolybdate. The amount of precursor in the solution is adjusted depending on the desired concentration of the final catalyst. After dry impregnation, the catalyst is dried in air at 120 °C.

[0107] The mass percentages in the catalyst are 15.1 wt. % molybdenum (in the form of MoO3) and 3.3 wt. % nickel (in the form of NiO) on a dry basis.

[0108] Example 3 - Preparation of Comparative Catalyst C The support of catalyst C has a lattice constant of 24.48 Å, a silica-alumina molar ratio (SAR) of 6, and a specific surface area of ​​847 m2 measured by nitrogen physisorption using the BET method. 2 The support is prepared by kneading and extruding 70 wt. % zeolite USY, which has a molecular weight of 0.29 mL / g, a micropore volume determined by nitrogen adsorption of 0.11 mL / g, a mesopore volume determined by nitrogen adsorption of 0.11 mL / g, and a Bronsted acidity of 420 μmol / g, in the presence of commercial boehmite (Pural SB3, Sasol). The resulting pellets are dried at 80°C and then calcined at 600°C in moist air (5 wt. % water per kg dry air). The calcined support contains, on a dry basis, 70 wt. % zeolite USY and 30 wt. % alumina.

[0109] Catalyst C is prepared by dry impregnation of the resulting support with an aqueous solution containing the elements Ni and Mo. This solution is obtained by dissolving the following precursors in water: nickel nitrate and ammonium heptamolybdate. The amount of precursor in the solution is adjusted depending on the desired concentration of the final catalyst. After dry impregnation, the catalyst is dried in air at 120 °C.

[0110] The mass percentages in the catalyst are 15.1 wt. % molybdenum (in the form of MoO3) and 3.3 wt. % nickel (in the form of NiO) on a dry basis.

[0111] Example 4 - Preparation of Catalyst D according to the invention The support of catalyst D has a lattice constant of 24.47 Å, a silica-alumina molar ratio (SAR) of 9, and a specific surface area of ​​931 m2 measured by nitrogen physisorption using the BET method. 2% of zeolite USY, having a micropore volume of 0.31 mL / g, a mesopore volume of 0.24 mL / g, and a Brønsted acidity of 698 μmol / g, as determined by nitrogen adsorption, and formed by kneading extrusion in the presence of commercial boehmite, Pural SB3.

[0112] The resulting pellets are dried at 80° C. and then calcined in moist air (5% by weight water per kg of dry air) at 600° C. The calcined support contains, on a dry basis, 70% by weight zeolite USY and 30% by weight alumina.

[0113] Catalyst D is prepared by dry impregnation of the resulting support with an aqueous solution containing the elements Ni and Mo. This solution is obtained by dissolving the following precursors in water: nickel nitrate and ammonium heptamolybdate. The amount of precursor in the solution is adjusted depending on the desired concentration of the final catalyst. After dry impregnation, the catalyst is dried in air at 120 °C.

[0114] The mass percentages in the catalyst are 15.0 wt. % molybdenum (in the form of MoO3) and 3.2 wt. % nickel (in the form of NiO) on a dry basis.

[0115] Example 5 - Preparation of Catalyst E according to the invention The support of catalyst E has a lattice constant of 24.47 Å, a silica-alumina molar ratio (SAR) of 9, and a specific surface area of ​​931 m2 measured by nitrogen physisorption using the BET method. 2 / g, a micropore volume measured by nitrogen adsorption of 0.31 mL / g, a mesopore volume measured by nitrogen adsorption of 0.24 mL / g, a Brønsted acidity of 698 μmol / g, and a zeolite USY 60 wt % with a SiO2 / Al2O3 molar ratio of 25 and a specific surface area of ​​670 m2 measured by nitrogen physical adsorption by the BET method. 2% of commercially available zeolite beta (CP814E, Zeolyst) at 0.1 wt. / g in the presence of commercially available boehmite (pure SB3, Sasol) formed by kneading extrusion.

[0116] The pellets obtained are dried at 80°C and then calcined in moist air (5% by weight of water per kg of dry air) at 600°C. The calcined support contains, on a dry basis, 60% by weight of zeolite USY, 10% by weight of zeolite Beta and 30% by weight of alumina, i.e., a Y / Beta weight ratio in the catalyst of 6. After dry impregnation, the catalyst is dried in air at 120°C.

[0117] Catalyst E is prepared by dry impregnation of the resulting support with an aqueous solution containing the elements Ni and Mo. This solution is obtained by dissolving the following precursors in water: nickel nitrate and ammonium heptamolybdate. The amount of precursor in the solution is adjusted depending on the desired concentration of the final catalyst.

[0118] The mass percentages in the catalyst are 15.0 wt. % molybdenum (in the form of MoO3) and 3.2 wt. % nickel (in the form of NiO) on a dry basis.

[0119] Example 6 - Preparation of Comparative Catalyst F according to Shell U.S. Patent No. 7,611,689 The support of catalyst F has a lattice constant of 24.46 Å, a silica-alumina molar ratio (SAR) of 8.1, and a specific surface area of ​​810 m2 measured by nitrogen physisorption using the BET method. 2The support is prepared by kneading and extruding 70 wt. % zeolite USY, which has a molecular weight of 0.27 mL / g, a micropore volume determined by nitrogen adsorption of 0.27 mL / g, a mesopore volume determined by nitrogen adsorption of 0.14 mL / g, and a Bronsted acidity of 510 μmol / g, in the presence of commercial boehmite (Pural SB3, Sasol). The resulting pellets are dried at 80°C and then calcined at 600°C in moist air (5 wt. % water per kg dry air). The calcined support contains, on a dry basis, 70 wt. % zeolite USY and 30 wt. % alumina.

[0120] Catalyst F is prepared by dry impregnation of the resulting support with an aqueous solution containing the elements Ni and Mo. This solution is obtained by dissolving the following precursors in water: nickel nitrate and ammonium heptamolybdate. The amount of precursor in the solution is adjusted depending on the desired concentration of the final catalyst.

[0121] The mass percentages in the catalyst are 15.0 wt. % molybdenum (in the form of MoO3) and 3.2 wt. % nickel (in the form of NiO) on a dry basis.

[0122] Example 7 The performance of the aforementioned catalysts is evaluated in one step in the hydrocracking of feedstocks containing vacuum distillate and gas oil fractions using an isothermal test pilot unit in downflow configuration.

[0123] The test feed undergoes hydrotreating (HDT). After the hydrotreating step, the test feed has a density of 0.8755 g / mL at 15°C, a residual nitrogen content of 23 ppm by weight, and a residual sulfur content of 16 ppm by weight. The initial point of the simulated distillation of this test feed after hydrotreating is 163.3°C, and the final point is 578.7°C. The 50% point by weight of the simulated distillation is 391.7°C. To simulate the partial pressures of hydrogen sulfide and ammonia produced in the HDT step of the manufacturing process, DMDS and aniline, respectively, are added to the test feed to achieve 8820 ppm by weight of sulfur and 1900 ppm by weight of nitrogen in the final added feed.

[0124] Each catalyst was evaluated separately and sulfided prior to hydrocracking tests under SRGO (straight run gas oil) feed, i.e., gas oil obtained from direct distillation of crude oil added with 4 wt.% dimethyl sulfide (DMDS) and 2 wt.% aniline. The sulfidation was carried out for 2 h. -1 (HSV = space velocity), H2 / feed volume ratio of 1000 NL / L, total pressure of 140 bar (i.e., 14.0 MPa) and holding temperature of 350°C for 6 hours.

[0125] After sulfurization, the operating conditions are adjusted to those used in the hydrocracking test: 1.5 h -1 HSV of 1000 NL / L, H2 / feed volume ratio of 1000 NL / L, total pressure of 140 bar (i.e., 14.0 MPa). The reactor temperature is adjusted so that after 150 hours with the feed, the net conversion of the 216°C+ fraction is 65 wt%.

[0126] Net conversion is defined as the yield of the cut (or fraction) boiling below 216°C minus the yield of the cut (or fraction) boiling below 216°C present in the test feed.

[0127] The performance of the catalysts is compared to that of Catalyst D as a reference and is reported in Table 1. The relative activity (in degrees Celsius (°C)) is obtained from the temperature difference between the temperatures obtained for the catalyst being evaluated and the reference catalyst D to obtain a net conversion of 65%. Similarly, the relative yield for the 68-216°C fraction is determined as the difference between the yields obtained at 216°C + 65% net conversion by weight of the fraction. Positive values ​​indicate higher activity or yield.

[0128] [Table 1]

[0129] The results reported in Table 1 show a lattice constant of 24.47 Å, a lattice constant of 931 m 2 This shows that catalyst D according to the invention, consisting of zeolite USY having a BET surface area of ​​0.25 mL / g, a micropore volume of 0.31 mL / g and an acidity of 698 μmol / g, shows a systematic gain in activity compared to comparative catalysts B and C without a loss in yield, and also shows a gain in selectivity to naphtha fractions without a loss in activity compared to comparative catalyst A.

[0130] More specifically, it is found that comparative catalyst A, which has the acidity according to the invention but whose lattice constant is not according to the invention, shows a clear decrease in yield for naphtha fraction compared to catalyst D according to the invention.

[0131] Furthermore, the addition of zeolite Beta to the zeolite USY according to the invention demonstrates that in the presence of Beta, the zeolite USY used in the catalyst according to the invention also achieves high performance in terms of both activity and selectivity towards naphtha fractions, higher than those obtained with prior art catalysts.

[0132] Comparative Catalyst F, which has an acidity, micropore volume and SBET not in accordance with the invention, was found to have a lower activity compared to the activity of Catalyst D in accordance with the invention.

Claims

1. The present invention relates to a hydrogenation-dehydrogenation system comprising at least one hydrogenation-dehydrogenation element selected from the group formed by the elements of Group VIB and the non-noble metal elements of Group VIII of the periodic table, alone or in mixture, and a support comprising at least one porous mineral matrix, zeolite Y, wherein zeolite Y has an initial lattice constant a of the unit cell. ０ is 24.40 Å to 24.52 Å, and the BET specific surface area is 850 to 1020 m ２ / g, a micropore volume measured by nitrogen adsorption greater than 0.28 mL / g, and a Bronsted acidity greater than 600 μmol / g.

2. 2. The catalyst according to claim 1, wherein the Group VIII element is selected from iron, cobalt, nickel, preferably from nickel and cobalt, alone or in mixture, and the content of the Group VIII element is between 0.5% and 8% by weight, calculated as oxide, preferably between 0.5% and 6% by weight, calculated as oxide, very preferably between 1.0% and 4% by weight, calculated as oxide, relative to the total weight of the catalyst.

3. 3. The catalyst according to claim 1 or 2, wherein the Group VIB element is selected from tungsten and molybdenum, alone or in mixture, and the content of the Group VIB element is from 1% to 30% by weight, calculated as oxide, preferably from 2% to 25% by weight, calculated as oxide, very preferably from 5% to 20% by weight, calculated as oxide, and even more preferably from 5% to 16% by weight, calculated as oxide, relative to the total weight of the catalyst.

4. Catalyst according to any one of claims 1 to 3, wherein the zeolite Y has a Brønsted acidity of more than 650 μmol / g, preferably more than 700 μmol / g, very preferably more than 760 μmol / g, preferably the zeolite Y has a Brønsted acidity of less than 1000 μmol / g.

5. The initial lattice constant a of the unit cell of the zeolite Y ０ 5. The catalyst according to claim 1, wherein the SiO2 content is 24.40 to 24.51 Å, preferably 24.43 to 24.51 Å, very preferably 24.45 to 24.48 Å.

6. The zeolite Y has a viscosity of 875 to 995 m ２ / g, preferably 900 to 970 m ２ 6. The catalyst according to claim 1, having a specific surface area of ​​0.1 wt % or less, as measured by nitrogen physisorption using the BET method, of 0.1 wt % or less.

7. 7. The catalyst according to claim 1, wherein the zeolite Y has a micropore volume, determined by nitrogen adsorption, of more than 0.30 mL / g, advantageously more than 0.31 mL / g, and advantageously less than 0.34 mL / g.

8. 8. The catalyst according to any one of claims 1 to 7, wherein the zeolite Y has a silica-alumina molar ratio (SAR) of 5 to 50, preferably 5 to 20, more preferably 5 to 10.

9. 9. The catalyst according to any one of claims 1 to 8, wherein the zeolite Y has a mesopore volume of at least 0.18 mL / g, preferably between 0.18 and 0.27 mL / g, preferably between 0.20 and 0.26 mL / g, very preferably between 0.22 and 0.25 mL / g.

10. Catalyst according to any one of claims 1 to 9, wherein the catalyst also comprises zeolite beta.

11. 11. A process for hydrocracking of at least one hydrocarbon feedstock carried out in the presence of a catalyst according to any one of claims 1 to 10, wherein at least 50 wt. % of the compounds of said at least one hydrocarbon feedstock have an initial boiling point above 300°C and a final boiling point below 650°C, and the process is carried out at a temperature of 200°C to 480°C, a total pressure of 1 MPa to 25 MPa, a ratio of the volume of hydrogen per volume of said hydrocarbon feedstock of 80 to 5000 L / L, and an hourly space velocity (HSV), defined by the ratio of the volumetric flow rate of the hydrocarbon feedstock per volume of catalyst loaded in the reactor, of 0.1 to 50 h －１ That's the method.

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