Nickel, molybdenum, and tungsten-based ternary metal catalysts and their use in hydrogenation and / or hydrocracking methods.

Abstract

The present invention relates to a catalyst comprising a support, an active phase consisting of nickel, molybdenum, and tungsten, and phosphorus, wherein, relative to the total weight of the catalyst, the amount of nickel, measured in the form of NiO, is 3 to 4 wt. %, the amount of molybdenum, measured in the form of MoO, is 2 to 4 wt. %, the amount of tungsten, measured in the form of WO, is 34 to 40 wt. %, the amount of phosphorus, measured in the form of P2O5, is 3 to 4 wt. %, the WO3 / MoO3 molar ratio is 5.3 to 12.4 mol / mol, the NiO / (WO3 + MoO3) molar ratio is 0.20 to 0.33 mol / mol, and the P2O5 / (WO3 + MoO3) molar ratio is 0.21 to 0.34 mol / mol. The present invention also relates to a method for preparing the catalyst and its use in hydrotreating and / or hydrocracking.

Description

[Technical Field]

[0001] This invention relates to a ternary metal catalyst based on nickel, molybdenum, and tungsten, a method for preparing the same, and its use in the field of hydrogenation and / or hydrocracking. [Background technology]

[0002] Conventional hydrogenation catalysts generally comprise an oxide support and an active phase based on metals from Group VIb and Group VIII in oxide form, and also based on phosphorus. The preparation of these catalysts generally involves impregnation of the support with metal and phosphorus, a subsequent drying step, and a calcination step that allows the active phase to be obtained in their oxide form. Prior to their use in hydrogenation and / or hydrocracking reactions, these catalysts are generally subjected to sulfidation to form the active material.

[0003] The addition of organic compounds to hydrogenation catalysts to improve their activity has been recommended by those skilled in the art, particularly for catalysts prepared by impregnation and subsequent drying, but without subsequent calcination. These catalysts are often called "additive-impregnated dried catalysts."

[0004] Typically, the purpose of catalysts for the hydrogenation of hydrocarbon fractions is to remove sulfur-based compounds, nitrogen-based compounds, or aromatic compounds contained within them, thereby meeting the specifications (sulfur content, aromatic compound content, etc.) required for a given application (automotive fuel, gasoline or gas oil, household fuel oil, jet fuel, etc.).

[0005] Due to tightening of air quality regulations in many countries, ongoing efforts are being made to develop more effective catalysts and low-sulfur fuels, particularly diesel production methods. While significant progress has been made in developing efficient catalysts for these methods, major challenges remain, such as their modest saturation activity for aromatic hydrocarbons. Improving the aromatic saturation activity of hydrogenation catalysts has become a priority research area because recent environmental constraints have established minimum values ​​for cetane numbers and lower limits for polyaromatic compound content in diesel fractions.

[0006] Ternary metal catalysts based on nickel, molybdenum, and tungsten are known to increase not only hydrodesulfurization (HDS) and hydrodenitrification (HDN), but also the hydrogenation of aromatics (HDA).

[0007] For example, there are documents describing bulk NiMoW ternary metal catalysts with low binder content (Patent Documents 1-5). These catalysts, also called "bulk" catalysts, do not contain a support. While these catalysts exhibit high activity in hydrogenation treatments, they have the disadvantages of being very expensive (due to their high metal content) and non-renewable.

[0008] The prior art also refers to supported NiMoW ternary metal catalysts, for example, as described in a publication by Solmanov et al. (Non-Patent Literature 1).

[0009] The document (Patent Document 6) describes a supported NiMoWP catalyst containing 15% to 25% by weight of Mo and / or W expressed as an oxide, 3% to 6% by weight of Ni expressed as an oxide, 0.1% to 1% by weight of P expressed as an oxide, and 0.1 mol% to 0.7 mol% of additives with respect to metal (Group VIb + Group VIII).

[0010] Document (Patent Document 7) discloses a supported NiMoW catalyst containing phosphorus and / or fluorine, with a nickel content of 1 wt% to 10 wt% (expressed as NiO), a total content of molybdenum and tungsten of 10 wt% to 50 wt% (expressed as oxides), fluorine and / or phosphorus in a content of 0.2 wt% to 14 wt% expressed as elements, and a molar ratio of WO3 / Mo3 of 2.6 to 30.

[0011] Regardless of the catalyst selected, it is not always possible to increase the performance quality of the catalyst to fully meet the specifications regarding the sulfur, nitrogen, and / or aromatic compound content of the fuel due to the induced modifications. Moreover, since the implementation of this method is complex, it often becomes very complicated to deploy them industrially.

[0012] As a result, it has become clear that it is essential for catalyst manufacturers to find new hydrotreating and / or hydrocracking catalysts with improved performance quality.

Prior Art Documents

Patent Documents

[0013]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Patent Document 5

Patent Document 6

Patent Document 7

Non-Patent Documents

[0014] [Non-Patent Document 1] Solmanov et al., "Russian Journal of Applied Chemistry," 2018, Vol. 91, No. 8, pp. 1363-1369. [Overview of the Initiative] [Means for solving the problem]

[0015] (overview) The present invention relates to a catalyst comprising an alumina or silica or silica-alumina-based support, an active phase consisting of nickel, molybdenum and tungsten, and phosphorus, characterized by the following: - The nickel content was measured in the form of NiO and was 3% to 4% by weight relative to the total weight of the catalyst. - The molybdenum content was measured in the form of MoO3 and was 2% to 4% by weight relative to the total weight of the catalyst. - The tungsten content was measured in the form of WO3 and was 34% to 40% by weight relative to the total weight of the catalyst. - The phosphorus content was measured in the form of P2O5 and was 3% to 4% by weight relative to the total weight of the catalyst. - The WO3 / MoO3 molar ratio is 5.3 to 12.4 mol / mol. - The molar ratio of NiO / (WO3+MoO3) is 0.20~0.33 mol / mol. - The molar ratio of P2O5 / (WO3+MoO3) is between 0.21 and 0.34 mol / mol.

[0016] The applicant's company has surprisingly discovered that a catalyst based on an active phase consisting of nickel, molybdenum, and tungsten in the presence of phosphorus, deposited on a support and exhibiting a specific ratio between these different metals and / or phosphorus, exhibits, by synergistic effect, better hydrogenation activity compared to catalysts disclosed in the prior art, particularly in the hydrogenation of aromatic compounds (HDA) as well as in the hydrodesulfurization (HDS) and / or hydrodenitrification (HDN). Typically, the increasing force in activity allows for a reduction in the temperature required to achieve the desired sulfur, nitrogen, or aromatic compound content (e.g., in the case of gas oil feedstocks, a maximum of 10 ppm of sulfur in the ULSD, i.e., Ultra Low Sulfur Diesel, or also a polyaromatic compound content <8 wt% and cetane number > 46 (summer) and 43-46 (winter)). Similarly, the reduction in the required temperature increases stability as the cycle time is extended.

[0017] Rather than relying on a single theory, optimizing the content of each metal and phosphorus used in specific ratios will allow for the acquisition of an active phase that leads to improvements in the performance quality of the catalyst. This is because tungsten is known to be more active than molybdenum in the hydrogenation of aromatic compounds; however, its sulfidation is more difficult. By increasing the proximity of molybdenum in the active phase containing tungsten and increasing the WO3 / MoO3 ratio, it is possible to improve the sulfidation ability of tungsten and the observed catalyst performance quality up to a specific WO3 / MoO3 ratio where the molybdenum content is too low to affect the sulfidation ability of tungsten. Therefore, by optimizing the WO3 / MoO3 ratio, in combination with optimized NiO / (WO3+MoO3) and P2O5 / (WO3+MoO3) ratios, it is possible to obtain a catalyst that is highly active in hydrogenation treatments, particularly the hydrogenation of aromatic compounds (HDA).

[0018] According to the alternative form, the catalyst is characterized in the following respects: - The nickel content was measured in the form of NiO and was 3.1% to 3.9% by weight relative to the total weight of the catalyst. - The molybdenum content was measured in the form of MoO3 and was 2.2% to 3.8% by weight relative to the total weight of the catalyst. - The tungsten content was measured in the form of WO3 and was 35% to 39.9% by weight relative to the total weight of the catalyst. - The phosphorus content was measured in the form of P2O5 and was 3.1% to 3.9% by weight relative to the total weight of the catalyst. - The WO3 / MoO3 molar ratio is 5.7 to 11.1 mol / mol. - The molar ratio of NiO / (WO3+MoO3) is 0.21~0.31 mol / mol. - The molar ratio of P2O5 / (WO3+MoO3) is 0.22 to 0.33 mol / mol.

[0019] According to the alternative form, the catalyst is characterized in the following respects: - The nickel content was measured in the form of NiO and was 3.2% to 3.8% by weight relative to the total weight of the catalyst. - The molybdenum content was measured in the form of MoO3 and was 2.5% to 3.5% by weight relative to the total weight of the catalyst. - The tungsten content was measured in the form of WO3 and was 36% to 39% by weight relative to the total weight of the catalyst. - The phosphorus content was measured in the form of P2O5 and was 3.2% to 3.8% by weight relative to the total weight of the catalyst. - The WO3 / MoO3 molar ratio is 6.4 to 9.7 mol / mol. - The molar ratio of NiO / (WO3+MoO3) is 0.22~0.30 mol / mol. - The molar ratio of P2O5 / (WO3+MoO3) is between 0.23 and 0.32 mol / mol.

[0020] In an alternative form, the density of metals from Group VIb exhibited by the catalyst is expressed as the number of metal atoms per unit area of ​​the catalyst, in terms of the area of ​​the catalyst (nm). 2 Each atom contains 5 to 12 metal atoms from Group VIb.

[0021] In an alternative form, the catalyst further contains an organic compound that contains oxygen and / or nitrogen and / or sulfur.

[0022] According to this alternative form, the organic compound is selected from compounds containing one or more chemical functional groups selected from the functional groups of carboxyl, alcohol, thiol, thioether, sulfone, sulfoxide, ether, aldehyde, ketone, ester, carbonate, amine, nitrile, imide, oxime, urea, or amide, or from compounds containing a furan ring, or from sugars.

[0023] According to alternative forms, organic compounds include γ-valerolactone, 2-acetylbutyrolactone, triethylene glycol, diethylene glycol, ethylene glycol, ethylenediaminetetraacetic acid (EDTA), maleic acid, malonic acid, citric acid, acetic acid, gluconic acid, glucose, fructose, sucrose, sorbitol, xylitol, γ-ketovaleric acid, di(C1-C4 alkyl) succinate, more specifically dimethyl succinate, dimethylformamide, 1-methyl-2-pyrrolidinone, propylene carbonate, 2-methoxyethyl 3-oxobutanoate, bicine, tricine, 2-flualdehyde (also known under the name furfural), and 5-hydroxymethylfurfural (also known under the names 5-(hydroxymethyl)-2-flualdehyde or 5-HMF). , 2-acetylfuran, 5-methyl-2-flualdehyde, ascorbic acid, butyl lactate, ethyl lactate, butyl butyryl lactate, ethyl 3-hydroxybutanoate, ethyl 3-ethoxypropanoate, 2-ethoxyethyl acetate, 2-butoxyethyl acetate, 2-hydroxyethyl acrylate, 1-vinyl-2-pyrrolidinone, 1,3-dimethyl-2-imidasolidinone, 1,5-pentanediol, 1-(2-hydroxyethyl)-2-pyrrolidinone, Selected from 1-(2-hydroxyethyl)-2,5-pyrrolidinedione, 5-methyl-2(3H)-furanone, 1-methyl-2-piperidinone, 4-aminobutanoic acid, butyl glycolate, ethyl 2-mercaptopropanoate, ethyl 4-oxopentanoate, diethyl maleate, dimethyl maleate, dimethyl fumarate, diethyl fumarate, dimethyl adipate, and dimethyl 3-oxoglutarate.

[0024] According to alternative forms, the content of organic compounds is 1% to 30% by weight relative to the total weight of the catalyst.

[0025] According to one alternative form, the catalyst is at least partially sulfidized.

[0026] The present invention also relates to a method for preparing a catalyst according to the present invention, the method comprising the following steps: a) A step of obtaining a catalyst precursor by contacting at least one nickel precursor, at least one molybdenum precursor, at least one tungsten precursor, and phosphorus with an alumina, silica, or silica-alumina based support, b) A step of drying the catalyst precursor derived from step a) at a temperature of less than 200°C.

[0027] In an alternative embodiment, the preparation method further comprises step c), in which the catalyst obtained in step b) is calcined at a temperature of 200°C to 550°C.

[0028] In an alternative embodiment, the preparation method further comprises step d), in which step d) the catalyst obtained in step b) or step c) is sulfurized.

[0029] The present invention also relates to the use of catalysts according to the present invention in methods for the hydrogenation and / or hydrocracking of hydrocarbon fractions. [Modes for carrying out the invention]

[0030] (Detailed description of the invention) (definition) The following groups of chemical elements are given according to the CAS classification (CRC Handbook of Chemistry and Physics, published by CRC Press, Editor-in-Chief DR. Lide, 81st edition, 2000-2001). For example, Group VIII according to the CAS classification corresponds to the metals in columns 8, 9, and 10 of the new IUPAC classification.

[0031] The term "specific surface area" refers to the BET specific surface area (S) determined by nitrogen adsorption according to the standard ASTM D 3663-78, which was established from the Brunauer-Emmett-Teller method described in the periodical "The Journal of the American Chemical Society," 1938, 60, 309. BET (m 2 It is understood to mean / g)).

[0032] The total pore volume of a catalyst or carrier used for catalyst preparation is understood to mean the volume measured by mercury intrusion porosimetry according to standard D4284-83, at a maximum pressure of 4000 bar (400 MPa), with a surface tension of 484 dynes / cm and a contact angle of 140°. The wetting angle was set to 140° in accordance with the recommendation on pages 1050-1055 of the publication "Techniques de l'ingenieur, traite analyze et caracterisation" [Techniques of the Engineer, Analysis and Characterization Treatise] written by Jean Charpin and Bernard Rasneur. For greater accuracy, the total pore volume value corresponds to the total pore volume value measured by mercury intrusion porosimetry on the same sample minus the total pore volume value measured by mercury intrusion porosimetry on the same sample at a pressure corresponding to 30 psi (approximately 0.2 MPa).

[0033] The metal and phosphorus content from Groups VIII and VIb is measured by X-ray fluorescence.

[0034] The content of metals from Group VIb, Group VIII, and phosphorus in the catalyst is expressed as oxides after correction for ignition loss of the catalyst sample in a muffle furnace at 550°C for 2 hours. Ignition loss is due to water loss, which is determined according to ASTM D7348.

[0035] Hydrogenation is understood to refer to reactions that specifically include hydrogenated desulfurization (HDS), hydrogenated denitrification (HDN), and hydrogenation of aromatic compounds (HDA).

[0036] (catalyst) The present invention relates to a catalyst comprising an alumina or silica or silica-alumina-based support, an active phase consisting of nickel, molybdenum and tungsten, and phosphorus, characterized in the following respects: - The nickel content was measured in the form of NiO and was 3% to 4% by weight relative to the total weight of the catalyst. - The molybdenum content was measured in the form of MoO3 and was 2% to 4% by weight relative to the total weight of the catalyst. - The tungsten content was measured in the form of WO3 and was 34% to 40% by weight relative to the total weight of the catalyst. - The phosphorus content was measured in the form of P2O5 and was 3% to 4% by weight relative to the total weight of the catalyst. - The WO3 / MoO3 molar ratio is 5.3 to 12.4 mol / mol. - The molar ratio of NiO / (WO3+MoO3) is 0.20~0.33 mol / mol. - The molar ratio of P2O5 / (WO3+MoO3) is between 0.21 and 0.34 mol / mol.

[0037] The hydrogenation functional group of the catalyst is also known as the active phase, and it is composed of nickel, molybdenum, and tungsten.

[0038] The nickel content is measured in the form of NiO and is 3% to 4% by weight, preferably 3.1% to 3.9% by weight, and more preferably 3.2% to 3.8% by weight, relative to the total weight of the catalyst.

[0039] The molybdenum content is measured in the form of MoO3 and is 2% to 4% by weight, preferably 2.2% to 3.8% by weight, and more preferably 2.5% to 3.5% by weight, relative to the total weight of the catalyst.

[0040] The tungsten content is measured in the form of WO3 and is 34% to 40% by weight, preferably 35% to 39.9% by weight, and more preferably 36% to 39% by weight, relative to the total weight of the catalyst.

[0041] The WO3 / MoO3 molar ratio is 5.3 to 12.4 mol / mol, preferably 5.7 to 11.1 mol / mol, and more preferably 6.4 to 9.7 mol / mol.

[0042] The NiO / (WO3+MoO3) molar ratio is 0.20 to 0.33 mol / mol, preferably 0.21 to 0.31 mol / mol, and more preferably 0.22 to 0.30 mol / mol.

[0043] The catalyst according to the present invention also contains phosphorus as a dopant. A dopant is an additive element that does not exhibit catalytic properties on its own, but enhances the catalytic activity of the active phase.

[0044] The phosphorus content in the catalyst is measured in the form of P2O5 and is preferably 3% to 4% by weight, preferably 3.1% to 3.9% by weight, and very preferably 3.2% to 3.8% by weight, relative to the total weight of the catalyst.

[0045] The P2O5 / (WO3+MoO3) molar ratio is 0.21 to 0.34 mol / mol, preferably 0.22 to 0.33 mol / mol, and more preferably 0.23 to 0.32 mol / mol.

[0046] In addition, the density of metals (Mo+W) from Group VIb exhibited by the catalyst is expressed as the number of metal atoms per unit area of ​​the catalyst, and the area of ​​the catalyst (nm) 2) There are 5 to 12, preferably 6 to 11, more preferably 7 to 10 atoms of a metal from Group VIb per hit. The number of metal atoms from Group VIb per unit area of the catalyst (the number of metal atoms from Group VIb per hit of the catalyst area (nm 2 ) The density of the metal from Group VIb, expressed as the number of metal atoms from Group VIb, is calculated, for example, from the following relational expression:

[0047]

Number

[0048] In the formula: X Mo = weight % of molybdenum; X W = weight % of tungsten; N A = Avogadro's number, equal to 6.022×10 23 ; S = specific surface area of the catalyst (m 2 / g), measured according to standard ASTM D3663; M Mo = molar mass of molybdenum; M W = molar mass of tungsten.

[0049] As an example, if the catalyst contains 3 wt% molybdenum oxide MoO3 (i.e., 2.0 wt% Mo) and 29.3 wt% tungsten oxide and has a specific surface area of 122 m 2 / g, the density d(Mo+W) is equal to the following formula:

[0050]

Number

[0051] The catalyst according to the present invention can advantageously also contain at least one dopant selected from boron, fluorine, and a mixture of boron and fluorine. <00OO286> If the catalyst contains boron, fluorine, or a mixture of boron and fluorine, the content of boron, fluorine, or a mixture of the two, expressed as boron oxide and / or fluorine, is preferably 0.1% to 10% by weight, preferably 0.2% to 7% by weight, and very preferably 0.2% to 5% by weight, relative to the total weight of the catalyst.

[0053] The pore volume of a catalyst is generally 0.1 cm³. 3 / g~1.5cm 3 / g, preferably 0.15cm 3 / g~1.1cm 3 The total pore volume is measured by mercury porosimetry in accordance with standard ASTM D4284, at a wetting angle of 140°, as described in "Adsorption by Powders & Porous Solids: Principle, Methodology and Applications" by Rouquerol F., Rouquerol J., and Singh K., Academic Press, 1999, for example, using an Autopore III® model instrument of the Micromeritics® brand.

[0054] The catalyst is 5-350m 2 / g, preferably 10-330m 2 / g, preferably 40-320m 2 / g, very preferably 50-300m 2 It is characterized by its specific surface area per gram. In this invention, the specific surface area is determined by the BET method in accordance with standard ASTM D3663, which is described in the same publication as above.

[0055] The catalyst support comprises, and preferably consists of, alumina, silica, or silica-alumina.

[0056] If the catalyst support is alumina-based, it contains more than 50% by weight of alumina relative to the total weight of the support, and generally contains only alumina or silica-alumina as defined below.

[0057] Preferably, the carrier contains alumina, preferably extruded alumina. Preferably, the alumina is γ-alumina.

[0058] The total pore volume of the alumina support is preferably 0.1 to 1.5 cm³. 3 ·g -1 Preferably 0.4 to 1.1 cm 3 ·g -1 The total pore volume is measured by mercury porosimetry in accordance with standard ASTM D4284, at a wetting angle of 140°, as described in "Adsorption by Powders & Porous Solids: Principle, Methodology and Applications" by Rouquerol F., Rouquerol J., and Singh K., Academic Press, 1999, for example, using an Autopore III® model instrument of the Micromeritics® brand.

[0059] The specific surface area of ​​the alumina support is advantageously 5 to 400 m². 2 ·g -1 Preferably 10-350m 2 ·g -1 More preferably 40-350m 2 ·g -1 The specific surface area is determined in this invention by the BET method in accordance with standard ASTM D3663, and this method is described in the same publication as above.

[0060] In another preferred case, the catalyst support is silica-alumina containing at least 50% by weight of alumina relative to the total weight of the support. The silica content in the support is at most 50% by weight, generally 45% by weight or less, and preferably 40% by weight or less, relative to the total weight of the support.

[0061] Sources of silicon are well known to those skilled in the art. Examples include silicic acid, silica in powder or colloidal form (silica sol), or tetraethyl orthosilicate Si(OEt)4.

[0062] If the support for the catalyst is silica-based, it contains more than 50% by weight of silica relative to the total weight of the support, and generally, it contains only silica.

[0063] In a particularly preferred alternative form, the carrier consists of alumina, silica, or silica-alumina.

[0064] In addition, the carrier may also advantageously contain zeolite. In this case, any source of zeolite known to those skilled in the art and any related preparation method may be incorporated. Preferably, the zeolite is selected from the group FAU, BEA, ISV, IWR, IWW, MEI, UWY, preferably the zeolite is selected from the group FAU and BEA, for example, zeolite Y and / or beta-zeolite, and particularly preferably, for example, USY and / or beta-zeolite. If zeolite is present, its content is 0.1% to 50% by weight relative to the total weight of the carrier.

[0065] The carrier is advantageously provided in the form of beads, extruded materials, pellets, or irregular and non-spherical aggregates, the specific shape of which may originate from the crushing stage.

[0066] The catalyst according to the present invention may further contain one or a group of organic compounds known for their role as additives. The function of the additives is to increase catalytic activity compared to the unadded impregnated catalyst. More specifically, the catalyst according to the present invention may further contain one or more oxygen-containing organic compounds and / or one or more nitrogen-containing organic compounds and / or one or more sulfur-containing organic compounds. Preferably, the catalyst according to the present invention may further contain one or more oxygen-containing organic compounds and / or one or more nitrogen-containing organic compounds. Preferably, the organic compounds contain at least two carbon atoms and at least one oxygen and / or nitrogen atom, but do not contain other heteroatoms.

[0067] Generally, organic compounds are selected from compounds containing one or more chemical functional groups selected from carboxyl, alcohol, thiol, thioether, sulfone, sulfoxide, ether, aldehyde, ketone, ester, carbonate, amine, nitrile, imide, oxime, urea, and amide functional groups, or compounds containing a furan ring, or sugars.

[0068] Oxygen-containing organic compounds may be compounds containing one or more chemical functional groups selected from carboxyl, alcohol, ether, aldehyde, ketone, ester, or carbonate functional groups, or compounds containing a furan ring, or one or more selected from sugars. Here, oxygen-containing organic compounds are understood to mean compounds that do not contain any other heteroatoms. For example, oxygen-containing organic compounds include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol (molecular weight 200-1500 g / mol), propylene glycol, 2-butoxyethanol, 2-(2-butoxyethoxy)ethanol, 2-(2-methoxyethoxy)ethanol, triethylene glycol dimethyl ether, glycerol, acetophenone, 2,4-pentanedione, pentanone, acetic acid, oxalic acid, maleic acid, malic acid, malonic acid, oxalic acid, gluconic acid, tartaric acid, citric acid, γ-ketovaleric acid, di(C1-C4 alkyl) succinate, more specifically dimethyl succinate, methyl acetoacetate, ethyl acetoacetate, 2-methoxyethyl 3-oxobutanoate, 2-methacryloyloxyethyl 3-oxobutanoate, dibenzofuran, crown ether, orthophthalic acid, glucose, fructose, sucrose, sorbitol, xylitol, and γ-valerola. Cthone, 2-acetylbutyrolactone, propylene carbonate, 2-flualdehyde (also known as furfural), 5-hydroxymethylfurfural (also known as 5-(hydroxymethyl)-2-flualdehyde or 5-HMF), 2-acetylfuran, 5-methyl-2-flualdehyde, methyl 2-fluate, furfuryl alcohol (also known as furfuranol), furfuryl acetate, ascorbyl Bic acid, butyl lactate, ethyl lactate, butyl butyryl lactate, ethyl 3-hydroxybutanoate, ethyl 3-ethoxypropanoate, methyl 3-methoxypropanoate, 2-ethoxyethyl acetate, 2-butoxyethyl acetate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,5-hexanediol, 3-ethyl-1,5-pentanediol, 2,4-diethyl-1,It may be one or more selected from the group consisting of 5-pentanediol, 5-methyl-2(3H)-furanone, butyl glycolate, ethyl 4-oxopentanoate, diethyl maleate, dimethyl maleate, dimethyl fumarate, diethyl fumarate, dimethyl adipate, dimethyl 3-oxoglutarate, dimethyl tartrate, diethyl tartrate, diisopropyl tartrate, di(tert-butyl) tartrate, dimethyl malate, diethyl malate, diisopropyl malate, and dibutyl malate.

[0069] Nitrogen-containing organic compounds may be one or more compounds selected from those containing one or more chemical functional groups selected from amine or nitrile functional groups. Here, nitrogen-containing organic compounds are understood to mean compounds that do not contain any other heteroatoms. For example, nitrogen-containing organic compounds may be one or more compounds selected from the group consisting of ethylenediamine, diethylenetriamine, hexamethylenediamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, acetonitrile, octylamine, guanidine, and carbazole.

[0070] Organic compounds containing oxygen and nitrogen can be one or more compounds selected from those containing one or more chemical functional groups selected from carboxylic acids, alcohols, ethers, aldehydes, ketones, esters, carbonates, amines, nitriles, imides, amides, ureas, or oximes. Here, organic compounds containing oxygen and nitrogen are understood to mean compounds that do not contain another heteroatom. Examples of organic compounds containing oxygen and nitrogen include 1,2-cyclohexanediaminetetraacetic acid, monoethanolamine (MEA), 1-methyl-2-pyrrolidinone, dimethylformamide, ethylenediaminetetraacetic acid (EDTA), alanine, glycine, nitrilotriacetic acid (NTA), N-(2-hydroxyethyl)ethylenediamine-N,N',N'-triacetic acid (HEDTA), and diethylenetriaminepentaacetic acid. The acid may be one or more selected from the group consisting of DTPA, tetramethylurea, glutamic acid, dimethylglyoxime, bicine, tricine, 2-methoxyethyl cyanoacetate, 1-ethyl-2-pyrrolidinone, 1-vinyl-2-pyrrolidinone, 1,3-dimethyl-2-imidazolidinone, 1-(2-hydroxyethyl)-2-pyrrolidinione, 1-(2-hydroxyethyl)-2,5-pyrrolidinone, 1-methyl-2-piperidinone, 1-acetyl-2-azepanone, 1-vinyl-2-azepanone, and 4-aminobutanoic acid.

[0071] The sulfur-containing organic compound may be one or more compounds selected from those containing one or more chemical functional groups selected from thiol, thioether, sulfone, or sulfoxide functional groups. For example, the sulfur-containing organic compound may be one or more compounds selected from the group consisting of thioglycolic acid, 2,2'-thiodiethanol, 2-hydroxy-4-methylthiobutanoic acid, sulfone derivatives or sulfoxide derivatives of benzothiophene, ethyl 2-mercaptopropanoate, methyl 3-(methylthio)propanoate, and ethyl 3-(methylthio)propanoate.

[0072] Preferably, the organic compound contains oxygen; preferably, it is γ-valerolactone, 2-acetylbutyrolactone, triethylene glycol, diethylene glycol, ethylene glycol, ethylenediaminetetraacetic acid (EDTA), maleic acid, malonic acid, citric acid, acetic acid, oxalic acid, gluconic acid, glucose, fructose, sucrose, sorbitol, xylitol, γ-ketovaleric acid, di(C1-C4 alkyl) succinate, more specifically, dimethyl succinate, dimethylformamide, 1-methyl-2-pyrrolidinone, propylene carbonate, 2-methoxyethyl 3-oxobutanoate, bicine, tricine, 2-flualdehyde (also known under the name furfural), 5-hydroxymethylfurfural (also known under the name 5-(hydroxymethyl)-2-flualdehyde or 5-HMF), 2-acetate Selected from tilfuran, 5-methyl-2-flualdehyde, ascorbic acid, butyl lactate, ethyl lactate, butyl butyryl lactate, ethyl 3-hydroxybutanoate, ethyl 3-ethoxypropanoate, 2-ethoxyethyl acetate, 2-butoxyethyl acetate, 2-hydroxyethyl acrylate, 1-vinyl-2-pyrrolidinone, 1,3-dimethyl-2-imidasolidinone, 1,5-pentanediol, 1-(2-hydroxyethyl)-2-pyrrolidinone, 1-(2-hydroxyethyl)-2,5-pyrrolidinidione, 5-methyl-2(3H)-furanone, 1-methyl-2-piperidinone, 4-aminobutanoic acid, butyl glycolate, ethyl 2-mercaptopropanoate, ethyl 4-oxopentanoate, diethyl maleate, dimethyl maleate, dimethyl fumarate, diethyl fumarate, dimethyl adipate, and dimethyl 3-oxoglutarate.

[0073] If present, the total content of oxygen-containing and / or nitrogen-containing and / or sulfur-containing organic compounds (one or more) in the catalyst is generally 1% to 30% by weight, preferably 1.5% to 25% by weight, and more preferably 2% to 20% by weight, relative to the total weight of the catalyst.

[0074] During the preparation of the catalyst requiring a drying step, the drying step (one or more times) following the introduction of the organic compound is carried out at a temperature below 200°C and retains, preferably at least 30%, preferably at least 50%, and very preferably at least 70% of the amount of introduced organic compound, calculated based on the carbon remaining on the catalyst. The residual carbon is measured by elemental analysis according to ASTM D5373.

[0075] According to one embodiment, the catalyst according to the present invention comprises, preferably composed of, an alumina or silica or silica-alumina-based support, an active phase consisting of nickel, molybdenum and tungsten, and phosphorus, and is characterized in the following respects: - The nickel content is measured in the form of NiO and is 3% to 4% by weight, preferably 3.1% to 3.9% by weight, and more preferably 3.2% to 3.8% by weight, relative to the total weight of the catalyst. - The molybdenum content was measured in the form of MoO3 and was 2% to 4% by weight, preferably 2.2% to 3.8% by weight, and more preferably 2.5% to 3.5% by weight, relative to the total weight of the catalyst. - The tungsten content was measured in the form of WO3 and was 34% to 40% by weight, preferably 35% to 39.9% by weight, and more preferably 36% to 39% by weight, relative to the total weight of the catalyst. - The phosphorus content was measured in the form of P2O5 and was 3% to 4% by weight, preferably 3.1% to 3.9% by weight, and more preferably 3.2% to 3.8% by weight, relative to the total weight of the catalyst. - The WO3 / MoO3 molar ratio is 5.3 to 12.4 mol / mol, preferably 5.7 to 11.1 mol / mol, and more preferably 6.4 to 9.7 mol / mol. - The NiO / (WO3+MoO3) molar ratio is 0.20-0.33 mol / mol, preferably 0.21-0.31 mol / mol, and more preferably 0.22-0.30 mol / mol. - The P2O5 / (WO3+MoO3) molar ratio is 0.21 to 0.34 mol / mol, preferably 0.22 to 0.33 mol / mol, and more preferably 0.23 to 0.32 mol / mol.

[0076] According to another embodiment, the catalyst according to the present invention comprises, preferably, an alumina or silica or silica-alumina-based support, an active phase consisting of nickel, molybdenum and tungsten, phosphorus and an oxygen-containing and / or nitrogen-containing and / or sulfur-containing organic compound, and is characterized in the following respects: - The nickel content is measured in the form of NiO and is 3% to 4% by weight, preferably 3.1% to 3.9% by weight, and more preferably 3.2% to 3.8% by weight, relative to the total weight of the catalyst. - The molybdenum content was measured in the form of MoO3 and was 2% to 4% by weight, preferably 2.2% to 3.8% by weight, and more preferably 2.5% to 3.5% by weight, relative to the total weight of the catalyst. - The tungsten content was measured in the form of WO3 and was 34% to 40% by weight, preferably 35% to 39.9% by weight, and more preferably 36% to 39% by weight, relative to the total weight of the catalyst. - The phosphorus content was measured in the form of P2O5 and was 3% to 4% by weight, preferably 3.1% to 3.9% by weight, and more preferably 3.2% to 3.8% by weight, relative to the total weight of the catalyst. - The WO3 / MoO3 molar ratio is 5.3 to 12.4 mol / mol, preferably 5.7 to 11.1 mol / mol, and more preferably 6.4 to 9.7 mol / mol. - The NiO / (WO3+MoO3) molar ratio is 0.20-0.33 mol / mol, preferably 0.21-0.31 mol / mol, and more preferably 0.22-0.30 mol / mol. - The P2O5 / (WO3+MoO3) molar ratio is 0.21 to 0.34 mol / mol, preferably 0.22 to 0.33 mol / mol, and more preferably 0.23 to 0.32 mol / mol.

[0077] According to this embodiment, the organic compound is preferably γ-valerolactone, 2-acetylbutyrolactone, triethylene glycol, diethylene glycol, ethylene glycol, ethylenediaminetetraacetic acid (EDTA), maleic acid, malonic acid, citric acid, acetic acid, gluconic acid, glucose, fructose, sucrose, sorbitol, xylitol, γ-ketovaleric acid, di(C1-C4 alkyl) succinate, more specifically dimethyl succinate, dimethylformamide, 1-methyl-2-pyrrolidinone, propylene carbonate, 2-methoxyethyl 3-oxobutanoate, bicine, tricine, 2-flualdehyde (also known under the name furfural), 5-hydroxymethylfurfural (also known under the names 5-(hydroxymethyl)-2-flualdehyde or 5-HMF), 2-acetylfuran, 5 Selected from -methyl-2-flualdehyde, ascorbic acid, butyl lactate, ethyl lactate, butyl butyryl lactate, ethyl 3-hydroxybutanoate, ethyl 3-ethoxypropanoate, 2-ethoxyethyl acetate, 2-butoxyethyl acetate, 2-hydroxyethyl acrylate, 1-vinyl-2-pyrrolidinone, 1,3-dimethyl-2-imidazolidinone, 1,5-pentanediol, 1-(2-hydroxyethyl)-2-pyrrolidinone, 1-(2-hydroxyethyl)-2,5-pyrrolidinidione, 5-methyl-2(3H)-furanone, 1-methyl-2-piperidinone, 4-aminobutanoic acid, butyl glycolate, ethyl 2-mercaptopropanoate, ethyl 4-oxopentanoate, diethyl maleate, dimethyl maleate, dimethyl fumarate, diethyl fumarate, dimethyl adipate, and dimethyl 3-oxoglutarate.

[0078] (Preparation method) The catalyst according to the present invention can be prepared by any method for preparing supported catalysts known to those skilled in the art.

[0079] The catalyst according to the present invention can be prepared by a preparation method comprising the following steps: a) A step of obtaining a catalyst precursor by contacting at least one nickel precursor, at least one molybdenum precursor, at least one tungsten precursor, and phosphorus with an alumina, silica, or silica-alumina based support, b) A step of drying the catalyst precursor derived from step a) at a temperature of less than 200°C. c) Depending on the case, the catalyst precursor obtained in step b) is calcined at a temperature of 200°C to 550°C. d) Depending on the case, a step of sulfurizing the catalyst obtained in step b) or step c).

[0080] During the contact operation of step a), the catalyst according to the present invention may be prepared by impregnating a selected carrier with nickel, molybdenum, and tungsten metals and phosphorus. The impregnation may be carried out, for example, by a method known to those skilled in the art under the term dry impregnation, in which exactly an amount of the desired element in the form of a soluble salt is introduced into a selected solvent, for example, demineralized water, to fill the porous portions of the carrier as precisely as possible.

[0081] The nickel, molybdenum, and tungsten-based precursors of the active phase and phosphorus can be introduced simultaneously or sequentially. The impregnation of each precursor can be advantageously carried out at least twice. Therefore, different precursors can be advantageously impregnated sequentially with different numbers of impregnations and maturations. One type of precursor can even be impregnated multiple times.

[0082] Preferably, the nickel, molybdenum, and tungsten-based precursors of the active phase and phosphorus are introduced simultaneously.

[0083] The nickel precursors that can be used are advantageously selected from nickel oxides, hydroxides, hydroxycarbonates, carbonates, and nitrates; for example, nickel hydroxycarbonate, nickel carbonate, or nickel hydroxide are preferably used.

[0084] The molybdenum precursors that can be used are well known to those skilled in the art. Among the sources of molybdenum that may be used are, for example, oxides and hydroxides, molybdic acid and its salts, in particular ammonium salts, such as ammonium molybdate and ammonium heptamolybdate, phosphomolybdic acid (H3PMo 12 O 40 ) and their salts, and in some cases, silicic acid (H4SiMo 12 O 40 ) and their salts. Sources of molybdenum can also be heteropoly compounds, such as those of the Keggin, Lachnarikegin, substituted Keggin, Dawson, Anderson, or Strandberg types. Preferably used are molybdenum trioxide and heteropoly anions of the Strandberg, Keggin, Lachnarikegin, or substituted Keggin types.

[0085] The tungsten precursors that can be used are also well known to those skilled in the art. For example, among the sources of tungsten that may be used are oxides and hydroxides, tungstic acids and their salts, in particular ammonium salts, such as ammonium tungstate and ammonium metatungstate, phosphotungstic acids and their salts, and optionally tungstosilicic acid (H4SiW). 12 O 40 ) and its salts. The source of tungsten may also be heteropoly compounds, such as those of the type of Keggin, Lachnarikegin, substituted Keggin, or Dawson. Preferably used are oxides and ammonium salts, such as ammonium metatungstate, or heteropolyanions of the type of Keggin, Lachnarikegin, or substituted Keggin.

[0086] Phosphorus can be introduced completely or partially by impregnation. Preferably, it is introduced by impregnation, preferably by dry impregnation, using a solution containing nickel, molybdenum, and tungsten precursors.

[0087] The phosphorus may be introduced advantageously alone or as a mixture with nickel, molybdenum, and / or tungsten, which may be done during any of these impregnation steps if the hydrogenation group precursor is introduced multiple times. The phosphorus may also be introduced during these impregnations, in whole or in part, if an oxygen-containing and / or nitrogen-containing and / or sulfur-containing organic compound is introduced separately from the hydrogenation group precursor (in the case of post-impregnation and pre-impregnation described later). It may also be introduced from the synthesis of the support, at any stage of the synthesis of the support. Thus, it may be introduced before, during, or after the kneading of a selected alumina gel matrix, for example, and preferably, an alumina precursor, aluminum oxyhydroxide (boehmite).

[0088] A suitable phosphorus precursor is orthophosphate H3PO4, but its salts and esters, such as ammonium phosphate, are also suitable. Phosphorus can be introduced simultaneously with one or more elements from Group VIb, as well as in the form of heteropolyanions of the type Keggin, lachnarikeggin, substituted Keggin, or Strandberg.

[0089] Any impregnation solution described in the present invention may contain any polar solvent known to those skilled in the art. The polar solvent used is advantageously selected from the group formed by methanol, ethanol, water, phenol, and cyclohexanol, and is used alone or in mixtures. Preferably, a polar protic solvent is used. A list of common polar solvents and their dielectric constants can be found in the book "Solvents and Solvent Effects in Organic Chemistry," C. Reichardt, Wiley-VCH, 3rd edition, 2003, pp. 472-474. Much preferably, the solvent used is water or ethanol, and particularly preferably, the solvent is water.

[0090] If the catalyst further contains a dopant selected from boron, fluorine, or a mixture of boron and fluorine, the introduction of these dopants may be carried out in various stages and in various ways at the same stage as the introduction of phosphorus described above.

[0091] The boron precursor may be boric acid, orthoborate H3BO3, ammonium diborate or ammonium pentaborate, boron oxide, or a boric acid ester. Boron can be introduced, for example, by a solution of boric acid in a water / alcohol mixture or a water / ethanolamine mixture. Preferably, the boron precursor is orthoborate, if boron is to be introduced.

[0092] The fluorine precursors 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 a salt thereof. These salts are formed from alkali metals, ammonium, or organic compounds. In the case of organic compounds, the salt is advantageously formed in a reaction mixture by a reaction between the organic compound and hydrofluoric acid. Fluorine can be introduced, for example, by impregnation with an aqueous solution of hydrofluoric acid, ammonium fluoride, or ammonium difluoride.

[0093] If the catalyst further contains oxygen-containing and / or nitrogen-containing and / or sulfur-containing organic compounds, these are introduced before drying step b). Organic compounds are generally introduced by impregnation, in the presence or absence of nickel, molybdenum, tungsten, and phosphorus, and in the presence or absence of the solvent.

[0094] The introduction of organic compounds includes several embodiments that differ particularly in their timing compared to the introduction of metals. It can be carried out simultaneously with metal impregnation (co-impregnation), after metal impregnation (post-impregnation), or finally, before metal impregnation (pre-impregnation), particularly during the preparation of the carrier, preferably during shaping, or by impregnation on a pre-formed carrier. Each embodiment can be carried out individually or in combination, in one or more steps.

[0095] Furthermore, the contact step can be a combination of at least two embodiments, e.g., co-impregnation and post-impregnation. According to an alternative embodiment, the contact operation in step a) combines at least two embodiments of contact, e.g., co-impregnation with an organic compound of nickel, molybdenum, tungsten, and phosphorus, followed by drying at a temperature below 200°C, and then post-impregnation with an organic compound that may be the same as or different from the one used for co-impregnation. Each embodiment can be used alone or in combination and can be carried out in one or more steps.

[0096] The organic compound(s) are advantageously introduced into the impregnation solution, which may be the same as or different from the solution containing nickel, molybdenum, and tungsten precursors and phosphorus in the following amounts, depending on the embodiment of the preparation: - The molar ratio of the organic compound to the total precursor of elements (Mo and W) from Group VIb of the catalyst is calculated based on the components introduced into the impregnation solution (one or more) and is 0.01 to 5 mol / mol, preferably 0.05 to 3 mol / mol, preferably 0.05 to 1.5 mol / mol, and very preferably 0.1 to 1.2 mol / mol, and - The molar ratio of the organic compound to the catalyst precursor (one or more elements) from Group VIII (Ni) is calculated based on the components introduced into the impregnation solution (one or more elements) and is 0.02 to 17 mol / mol, preferably 0.1 to 10 mol / mol, preferably 0.15 to 8 mol / mol, and very preferably 0.6 to 5 mol / mol.

[0097] When several organic compounds are present, various molar ratios are applied to each of the organic compounds present.

[0098] Advantageously, after each impregnation step, the impregnated carrier is allowed to mature. This maturation process allows the impregnation solution to diffuse and the precursor to be uniformly distributed within the carrier.

[0099] All maturation steps described in this invention are advantageously carried out at atmospheric pressure, in a water-saturated atmosphere, and at a temperature of 17°C to 50°C, preferably at ambient temperature. Generally, a maturation time of 10 minutes to 48 hours, preferably 30 minutes to 5 hours, is sufficient. Longer periods are not considered non-standard, but they do not necessarily contribute to improvement.

[0100] According to step b) of the preparation method according to the present invention, the catalyst precursor obtained in step a) and optionally aged is subjected to a drying step at a temperature of less than 200°C, preferably 50°C to 180°C, more preferably 70°C to 150°C, and most preferably 75°C to 130°C.

[0101] The drying step is carried out by any technique known to those skilled in the art, preferably by atmospheric pressure or under reduced pressure. It is carried out preferably on a transverse bed using hot air or any other hot gas. Preferably, when drying is carried out on a fixed bed, the gas used is either air or an inert gas, such as argon or nitrogen. Much preferably, drying is carried out on a transverse bed in the presence of nitrogen and / or air. Preferably, the drying step has a short duration of 5 minutes to 4 hours, preferably 30 minutes to 4 hours, much preferably 1 hour to 3 hours. If organic compounds are present, drying is carried out so as to preferentially retain at least 30% of the introduced organic compounds; preferably, this amount is greater than 50%, more preferably greater than 70%, calculated based on the carbon remaining on the catalyst. At the end of drying step b), the dried catalyst is obtained.

[0102] In some cases, the firing step c) may be performed after the drying step b).

[0103] According to this alternative configuration, at the completion of drying step b), the calcination step c) is carried out at a temperature of 200°C to 600°C, preferably 250°C to 550°C, under an inert atmosphere (e.g., nitrogen) or an oxygen-containing atmosphere (e.g., air). The duration of this heat treatment is generally 0.5 to 16 hours, preferably 1 to 5 hours. After this treatment, the active phase is therefore generally found in the form of oxides; thus, heteropolyanions are converted to oxides. Similarly, the catalyst no longer contains or contains little to no organic compounds when organic compounds are introduced. However, the introduction of organic compounds during its preparation makes it possible to increase the dispersion of the active phase, thus resulting in a more active catalyst.

[0104] If organic compounds are present, the catalyst is preferably not subjected to calcination. Calcination is understood here to mean heat treatment at a temperature of 200°C or higher under air or an oxygen-containing gas.

[0105] However, the catalyst precursor may undergo a calcination step before the introduction of the organic compound, particularly after impregnation with nickel, molybdenum, and tungsten, and phosphorus.

[0106] The catalyst according to the present invention may be a fresh catalyst, that is, a catalyst in a catalyst unit that has not been previously used as a catalyst, particularly in hydrogenation and / or hydrocracking.

[0107] The catalyst according to the present invention may also be a rejuvenated catalyst. A rejuvenated catalyst is understood to mean a catalyst used as a catalyst in a catalyst unit, particularly in hydrogenation and / or hydrocracking, and subjected to at least one step (rejuvenation) of partial or complete removal of coke, for example, by calcination. Rejuvenation can be carried out by any means known to those skilled in the art. Rejuvenation is generally carried out by calcination at temperatures of 350°C to 550°C, generally 400°C to 520°C, or 420°C to 520°C, with temperatures below 500°C often being advantageous.

[0108] If the regenerated catalyst no longer contains sufficient active phase or phosphorus, or if it exhibits a ratio of one or more components other than those described, the regenerated catalyst may be restored to activity by introducing one or more precursors of the active phase and / or phosphorus into the regenerated catalyst. It is also possible to introduce at least one organic compound simultaneously with or separately from the metal and phosphorus. The introduced organic compound may be identical to or different from the organic compound that the fresh catalyst contained. The above operating conditions relating to aging, drying and optionally calcination and optionally sulfidation are, of course, applicable in the context of this last embodiment.

[0109] Prior to its use for hydrogenation and / or hydrocracking reactions, it is advantageous to convert the catalyst obtained by any one of the introduction methods described in the present invention into a sulfidation catalyst to form its active form. This activation or sulfidation step is advantageously carried out in a sulfo-reducing atmosphere in the presence of hydrogen and hydrogen sulfide, by methods well known to those skilled in the art.

[0110] In an alternative configuration, the catalyst is advantageously subjected to a sulfidation step after a drying step (b) or, in the case, a calcination step (c).

[0111] The catalyst is preferably sulfided ex situ or in situ. The sulfiding agent is H2S gas, elemental sulfur, CS2, thiols, sulfides and / or polysulfides, hydrocarbon fractions having a boiling point below 400°C and containing sulfur compounds, or any other sulfur-containing compound used to activate the hydrocarbon feedstock with the aim of sulfiding the catalyst. The sulfur-containing compound is preferably selected from alkyl disulfides, e.g., dimethyl disulfide (DMDS), alkyl sulfides, e.g., dimethyl sulfide, thiols, e.g., n-butylthiol (or 1-butanethiol), and tert-nonyl polysulfide type polysulfide compounds. The catalyst may also be sulfided by sulfur contained in the feedstock to be desulfurized. Preferably, the catalyst is sulfided in situ in the presence of the sulfiding agent and the hydrocarbon feedstock. More preferably, the catalyst is sulfurized in situ in the presence of a hydrocarbon feedstock to which dimethyl disulfide has been added.

[0112] (Methods of hydrogenation and / or hydrocracking) Finally, another subject of the present invention is the use of catalysts according to the present invention or catalysts prepared by preparation methods according to the present invention in methods for the hydrogenation and / or hydrocracking of hydrocarbon fractions.

[0113] The catalyst according to the present invention, preferably one that has been pre-sulfurized, is advantageously used for the hydrogenation and / or hydrocracking reactions of a hydrocarbon feedstock, and more specifically for the hydrogenation, hydrodenitrification, hydrodesaromatherapy, hydrodesulfurization, hydrodesoxidation, hydrodemetallation or hydroconversion reactions of a hydrocarbon feedstock, the hydrocarbon feedstock being, for example, hydrocarbons derived from petroleum fractions, coal fractions, or natural gas, and in some cases, these being mixtures, or the hydrocarbon feedstock being hydrocarbon fractions derived from biomass.

[0114] In these uses, the catalyst according to the present invention, preferably one that has been pre-treated in a sulfidation step, exhibits improved activity compared to catalysts of the prior art. This catalyst can also be advantageously used in the pretreatment of feedstock for catalytic cracking or hydrocracking, or during the hydrodesulfurization of residues or the forced hydrodesulfurization of gaseous oil (ULSD: ultra-low-sulfur diesel).

[0115] The feedstocks used in the hydrogenation process include, for example, gasoline, gas oil, vacuum gas oil, atmospheric residue, vacuum residue, atmospheric distillates, vacuum distillates, heavy fuel oil, oils, waxes and paraffins, waste oil, de-asphalt residue or crudes, feedstocks originating from thermal or decomposition conversion methods, lignocellulose feedstocks, or more generally, feedstocks derived from biomass, such as vegetable oils, which are used individually or in mixtures. The feedstocks to be processed, in particular those mentioned above, generally contain heteroatoms, such as sulfur, oxygen and nitrogen, and in the case of heavy feedstocks, they usually also contain metals.

[0116] The operating conditions used in the method for carrying out the reaction for the hydrogenation treatment of the above-mentioned hydrocarbon feedstock are generally as follows: temperature is advantageously 180°C to 450°C, preferably 250°C to 440°C; pressure is advantageously 0.5 to 30 MPa, preferably 1 to 18 MPa; and space velocity per hour is advantageously 0.1 to 20 h. -1 Preferably 0.2 to 5 hours -1 The hydrogen / supply ratio is expressed as the volume of hydrogen / volume of liquid supplying material measured under standard temperature and pressure conditions, and is advantageously 50 L / L to 5000 L / L, preferably 80 L / L to 2000 L / L.

[0117] According to the first mode of use, the hydrogenation method according to the present invention is a method for hydrogenating a gas oil fraction, in particular for hydrodesulfurization (HDS), carried out in the presence of at least one catalyst according to the present invention. The hydrogenation method according to the present invention aims to remove sulfur-based compounds present in the gas oil fraction to meet effective environmental standards, namely, an acceptable sulfur content: up to 10 ppm. This also makes it possible to reduce the content of aromatic compounds and nitrogen in the gas oil fraction to be hydrogenated.

[0118] The gas oil fraction to be hydrogenated by the method of the present invention contains 0.02% to 5.0% by weight of sulfur. It is advantageously derived from straight-run distillation (or straight-run gas oil), coking units, bisque breaking units, steam cracking units, units for hydrogenation and / or hydrocracking of heavier feedstocks, and / or catalytic cracking units (fluid catalytic cracking). The gas oil fraction preferably contains at least 90% compounds with a boiling point of 250°C to 400°C at atmospheric pressure.

[0119] The method for hydrogenating the gas oil fraction according to the present invention is carried out under the following operating conditions: the temperature is 200°C to 400°C, preferably 300°C to 380°C; the total pressure is 2 MPa to 10 MPa, more preferably 3 MPa to 8 MPa; the volume-to-hydrogen ratio per volume of hydrocarbon feedstock is 100 to 600 liters / liter, more preferably 200 to 400 liters / liter, as measured under standard temperature and pressure conditions, and the space velocity per hour (HSV) is 0.5 to 10 h -1 Prioritizing 0.7-8 hours -1 That is the case.

[0120] HSV corresponds to the reciprocal of the contact time expressed in time and is defined by the ratio of the volumetric flow rate of the liquid hydrocarbon feedstock to the volume of the catalyst loaded into the reaction unit carrying out the hydrogenation method according to the present invention. The reaction unit carrying out the method for hydrogenating the gas oil fraction according to the present invention is preferably operated as a fixed bed, a moving bed, or a boiling bed.

[0121] According to a second mode of use, the hydrogenation and / or hydrocracking method according to the present invention is a method for hydrogenation (particularly hydrodesulfurization, hydrodenitrification, and hydrogenation of aromatic compounds) and / or hydrocracking of a vacuum distillate fraction, carried out in the presence of at least one catalyst according to the present invention. The hydrogenation and / or hydrocracking method, also known separately as a hydrocracking or hydrocracking pretreatment method according to the present invention, is targeted to remove sulfur-based compounds, nitrogen-based compounds, or aromatic compounds present in the distillate fraction to be pretreated before conversion in a catalytic cracking or hydroconversion method, or to hydrocracking a distillate fraction that may be pretreated as needed.

[0122] A wide variety of feedstocks can be processed by the hydrogenation and / or hydrocracking methods for the vacuum distillates described above. Generally, they contain at least 20% by volume, often at least 80% by volume, of compounds that boil above 340°C at atmospheric pressure. The feedstocks may be, for example, vacuum distillates and also feedstocks originating from units for the extraction of aromatic compounds from lubricating oil bases or feedstocks derived from solvent dewaxing oils and / or deasphalting oils of lubricating oil bases, or the feedstocks may be paraffins derived from deasphalting oils or the Fischer-Tropsch process, or any mixture of the feedstocks mentioned above. Generally, the T5 boiling point of the feedstocks is above 340°C at atmospheric pressure, and more preferably above 370°C at atmospheric pressure, meaning that 95% of the compounds present in the feedstocks have a boiling point above 340°C, and more preferably above 370°C. The nitrogen content of the feed material processed in the method according to the present invention is typically greater than 200 ppm by weight, preferably 500 to 10,000 ppm by weight. The sulfur content of the feed material processed in the method according to the present invention is typically 0.01% to 5.0% by weight. The feed material may optionally contain metals (e.g., nickel and vanadium). The asphaltene content is generally less than 3,000 ppm by weight.

[0123] The catalyst for hydrogenation and / or hydrocracking is generally brought into contact with the above-mentioned feedstock in the presence of hydrogen at a temperature greater than 200°C, often 250°C to 480°C, preferably 320°C to 450°C, and more preferably 330°C to 435°C, under a pressure greater than 1 MPa, often 2 to 25 MPa, and more preferably 3 to 20 MPa, with a space velocity of 0.1 to 20.0 h. -1 Preferably 0.1 to 6.0 hours -1 Preferably 0.2 to 3.0 hours -1The amount of hydrogen introduced is such that the volume ratio of hydrogen volume (liters) / hydrocarbon volume (liters), measured under standard temperature and pressure conditions, is 80 to 5000 L / L, generally 100 to 2000 L / L. These operating conditions used in the method according to the present invention generally make it possible to obtain a conversion rate per pass of more than 15%, more preferably 20% to 95%, to a product having a boiling point of less than 340°C at atmospheric pressure, and more preferably less than 370°C at atmospheric pressure.

[0124] The method for hydrogenation and / or hydrocracking of vacuum distillates employing the catalyst according to the present invention covers a range of pressures and conversions ranging from mild to high-pressure hydrocracking. Mild hydrocracking is understood to mean hydrocracking that results in moderate conversion, generally less than 40%, and is operated at low pressures, generally between 2 MPa and 6 MPa.

[0125] The catalyst according to the present invention may be used alone, in a single or several fixed-bed catalyst bed, in one or more reactors, in a "one-stage" hydrocracking scheme with or without liquid recycling of unconverted fractions, or in a "two-stage" hydrocracking scheme, and optionally in combination with a hydropurification catalyst placed upstream of the catalyst of the present invention.

[0126] According to a third mode of use, the hydrogenation and / or hydrocracking method according to the present invention is advantageously employed as a pretreatment in a fluid-bed catalytic cracking (or FCC) method. The operating conditions for the pretreatment, with respect to the range of temperature, pressure, hydrogen recycling rate and space velocity per hour, are generally the same as those described above for methods for hydrogenation and / or hydrocracking of vacuum distillates. The FCC method can be carried out under appropriate cracking conditions for the purpose of producing hydrocarbon products with lower molecular weights in conventional methods known to those skilled in the art. An overview of catalytic cracking can be found, for example, in Ullmann's Encyclopedia of Industrial Chemistry, Volume A18, 1991, pages 61 to 64.

[0127] According to the fourth mode of use, the hydrogenation and / or hydrocracking method according to the present invention is a method for hydrogenation (particularly hydrodesulfurization) of a gasoline fraction in the presence of at least one catalyst according to the present invention.

[0128] Unlike other hydrogenation methods, the hydrogenation of gasoline (particularly hydrodesulfurization) must be able to address two conflicting constraints: providing extreme hydrodesulfurization of gasoline and limiting the hydrogenation of present unsaturated compounds to limit the loss of octane.

[0129] The feedstock is generally a hydrocarbon fraction having a distillation range of 30°C to 260°C. Preferably, this hydrocarbon fraction is a gasoline type fraction. More preferably, the gasoline fraction is an olefin-based gasoline fraction, for example, derived from a fluid catalytic cracking unit.

[0130] The hydrogenation treatment method involves contacting a hydrocarbon fraction with the catalyst and hydrogen according to the present invention under the following conditions: the temperature is 200-400°C, preferably 230-330°C; the total pressure is 1-3 MPa, preferably 1.5-2.5 MPa; and the space velocity per hour (HSV) is defined as the volumetric flow rate of the feed material relative to the volume of the catalyst, and the treatment is performed for 1-10 hours. -1 Preferably 2-6 hours -1 The volume ratio of hydrogen / gasoline supply raw materials in this case is 100 to 600 SL / L, preferably 200 to 400 SL / L.

[0131] Methods for the hydrogenation of gasoline can be carried out in one or more series-connected reactors of the fixed-bed or boiling-bed type. If the method is carried out by at least two series-connected reactors, it is possible to provide a device for removing H2S from the effluent generated from the first hydrogenation reactor before the effluent is treated in the second hydrogenation reactor.

[0132] (Examples) The following examples demonstrate a significant increase in the activity of the catalyst according to the present invention compared with conventional catalysts.

[0133] Examples 1 to 10 describe the preparation of catalysts C1 to C10. The final composition of each catalyst in oxide form, with respect to the weight of the catalyst and the metal and phosphorus, as well as the ratios of WO3 / MoO3, NiO / (WO3+MoO3), and P2O5 / (WO3+MoO3), are shown in Table 1 below.

[0134] Examples 1 to 6 describe the preparation of catalysts C1 to C6 that do not conform to the present invention, in which the ratios of WO3 / MoO3, NiO / (WO3+MoO3), or P2O5 / (WO3+MoO3) are below or above the claims, respectively.

[0135] Examples 7 to 10 describe the preparation of catalysts C7 to C10 whose ratios of WO3 / MoO3, NiO / (WO3+MoO3), or P2O5 / (WO3+MoO3) are in accordance with the claims of the present invention.

[0136] (Example 1: Preparation of alumina-supported catalyst NiMoWP (C1; not conforming to the present invention)) Nickel, molybdenum, tungsten, and phosphorus are added to 100 g of alumina support A1. The ignition loss of alumina support A1 is 4.9% by weight, and the BET specific surface area is 230 m². 2 The volume is 0.78 mL / g, measured by mercury porosimetry, and the average pore diameter, defined as the median diameter by mercury porosimetry, is 11.5 nm, which is supplied in the form of "extruded material". The impregnation solution is prepared by dissolving 10.2 g of an 85 wt% solution of molybdenum oxide (16.5 g), ammonium metatungstate (55.9 g), nickel nitrate (25.8 g), and orthophosphoric acid in 78 mL of distilled water at 90°C. After dry impregnation, the extruded material is allowed to stand and mature in a water-saturated atmosphere at ambient temperature for 24 hours, and then dried at 90°C for 16 hours. The dried catalyst thus obtained is denoted as C1.

[0137] (Example 2: Preparation of alumina-supported catalyst NiMoWP (C2; not conforming to the present invention)) Nickel, molybdenum, tungsten, and phosphorus are added to the same carrier A1 provided in Example 1. The impregnation solution is prepared by dissolving 10.2 grams of an 85 wt% solution of molybdenum oxide (1.9 g), ammonium metatungstate (82.5 g), nickel nitrate (25.8 g), and orthophosphoric acid in 78 mL of distilled water at 90°C. After dry impregnation, the extruded materials are allowed to mature in a water-saturated atmosphere at ambient temperature for 24 hours, and then dried at 90°C for 16 hours. The dried catalyst thus obtained is denoted as C2.

[0138] (Example 3: Preparation of alumina-supported catalyst NiMoWP (C3; not conforming to the present invention)) Nickel, molybdenum, tungsten, and phosphorus are added to the same carrier A1 prepared in Example 1. The impregnation solution is prepared by dissolving 10.2 grams of an 85 wt% solution of molybdenum oxide (6.1 g), ammonium metatungstate (74.8 g), nickel nitrate (18.2 g), and orthophosphoric acid in 78 mL of distilled water at 90°C. After dry impregnation, the extruded material is allowed to stand and mature in a water-saturated atmosphere at ambient temperature for 24 hours, and then dried at 90°C for 16 hours. The dried catalyst thus obtained is denoted as C3.

[0139] (Example 4: Preparation of alumina-supported catalyst NiMoWP (C4; not conforming to the present invention)) Nickel, molybdenum, tungsten, and phosphorus are added to the same carrier A1 provided in Example 1. The impregnation solution is prepared by dissolving 10.2 grams of an 85 wt% solution of molybdenum oxide (6.1 g), ammonium metatungstate (74.8 g), nickel nitrate (35.4 g), and orthophosphoric acid in 78 mL of distilled water at 90°C. After dry impregnation, the extruded materials are allowed to stand and mature in a water-saturated atmosphere at ambient temperature for 24 hours, and then dried at 90°C for 16 hours. The dried catalyst thus obtained is denoted as C4.

[0140] (Example 5: Preparation of alumina-supported catalyst NiMoWP (C5; not conforming to the present invention)) Nickel, molybdenum, tungsten, and phosphorus are added to the same carrier A1 provided in Example 1. The impregnation solution is prepared by dissolving 7.2 grams of an 85 wt% solution of molybdenum oxide (6.1 g), ammonium metatungstate (74.8 g), nickel nitrate (25.8 g), and orthophosphoric acid in 78 mL of distilled water at 90°C. After dry impregnation, the extruded materials are allowed to stand and mature in a water-saturated atmosphere at ambient temperature for 24 hours, and then dried at 90°C for 16 hours. The dried catalyst thus obtained is denoted as C5.

[0141] (Example 6: Preparation of alumina-supported catalyst NiMoWP (C6; not conforming to the present invention)) Nickel, molybdenum, tungsten, and phosphorus are added to the same carrier A1 provided in Example 1. The impregnation solution is prepared by dissolving 14.0 grams of an 85 wt% solution of molybdenum oxide (6.1 g), ammonium metatungstate (74.8 g), nickel nitrate (25.8 g), and orthophosphoric acid in 78 mL of distilled water at 90°C. After dry impregnation, the extruded materials are allowed to stand and mature in a water-saturated atmosphere at ambient temperature for 24 hours, and then dried at 90°C for 16 hours. The dried catalyst thus obtained is denoted as C6.

[0142] (Example 7: Preparation of alumina-supported catalyst NiMoWP (C7; conforming to the present invention)) Nickel, molybdenum, tungsten, and phosphorus are added to the same carrier A1 provided in Example 1. The impregnation solution is prepared by dissolving 10.2 grams of an 85 wt% solution of molybdenum oxide (6.1 g), ammonium metatungstate (74.8 g), nickel nitrate (25.8 g), and orthophosphoric acid in 78 mL of distilled water at 90°C. After dry impregnation, the extruded materials are allowed to stand and mature in a water-saturated atmosphere at ambient temperature for 24 hours, and then dried at 90°C for 16 hours. The dried catalyst thus obtained is denoted as C7.

[0143] (Example 8: Preparation of alumina-supported catalyst NiMoWP (C8; consistent with the present invention) by co-impregnation with an organic compound (oxalic acid)) Nickel, molybdenum, tungsten, and phosphorus are added to an alumina support. This alumina support is the one described in Example 1 above and is provided in the form of an "extruded" material. The impregnation solution is prepared by dissolving 9.3 grams of an 85 wt% solution of molybdenum oxide (4.3 g), ammonium metatungstate (70.5 g), nickel nitrate (21.8 g), and orthophosphoric acid in 78 mL of distilled water at 90°C. After homogenization of the above mixture, 6.7 g of oxalic acid is added, and then the volume of the solution is adjusted to the pore volume of the support by adding water. The molar ratio of (oxalic acid) / (Mo+W) is equal to 0.25 mol / mol, and the molar ratio of (oxalic acid) / Ni is equal to 1 mol / mol. After dry impregnation, the extruded materials are allowed to mature in a water-saturated atmosphere at ambient temperature for 24 hours, and then dried at 120°C for 16 hours. The catalyst obtained in this manner, to which oxalic acid has been added and dried, is denoted as C8.

[0144] (Example 9: Preparation by post-addition of an organic compound (ascorbic acid) to an alumina-supported catalyst NiMoWP (C9; consistent with the present invention)) In Example 3, 100 g of the catalyst C7 precursor, provided in the form of an "extruded" as described above, is impregnated with an aqueous solution containing 28.8 g of ascorbic acid, the volume of which is equal to the pore volume of the catalyst C7 precursor. The amount of ascorbic acid is such that it is 0.5 mol per mole of molybdenum and tungsten (corresponding to 1.9 mol per mole of nickel). The extruded is allowed to stand and mature in a water-saturated atmosphere at ambient temperature for 16 hours. The catalyst C9 precursor is then dried at 120°C for 2 hours to give catalyst C9.

[0145] (Example 10: Preparation of silica-alumina supported catalyst NiMoWP (C10; conforming to the present invention) by post-addition of an organic compound (1-methyl-2-pyrrolidinone)) Nickel, molybdenum, tungsten, and phosphorus are added to a silica-alumina support containing 10% by weight of silicon. The ignition loss of this silica-alumina support is 0.7% by weight, and the BET specific surface area is 249 m². 2 The pore volume is 0.45 mL / g, measured by mercury porosimetry, and the average pore diameter, defined as the median diameter by mercury porosimetry, is 7.3 nm. This is provided in the form of an "extruded" material. The impregnation solution is prepared by dissolving 11.1 g of an 85 wt% solution of molybdenum oxide (4.6 g), ammonium metatungstate (75.8 g), nickel nitrate (25.3 g), and orthophosphoric acid in 55.7 mL of distilled water at 90°C. After dry impregnation, the extruded materials are allowed to stand and mature in a water-saturated atmosphere at ambient temperature for 24 hours, and then dried at 90°C for 16 hours. The catalyst precursor is then impregnated with an aqueous solution containing 25.9 g of 1-methyl-2-pyrrolidinone. The volume of this aqueous solution is equal to the pore volume of the catalyst C7 precursor. The amounts included are such that the amount of 1-methyl-2-pyrrolidinone is 0.8 mol per mole of molybdenum and tungsten (corresponding to 3.0 mol per mole of nickel). The extruded material is allowed to stand and mature in a water-saturated atmosphere at ambient temperature for 16 hours. The catalyst C10 precursor is then dried at 120°C for 2 hours to give catalyst C10.

[0146] (Example 11: Preparation of alumina-supported catalyst NiMoWP(C11; comparison)) Nickel, molybdenum, tungsten, and phosphorus are added to the same carrier A1 provided in Example 1. The impregnation solution is prepared by dissolving 7.5 grams of an 85 wt% solution of molybdenum oxide (7.7 g), ammonium metatungstate (85.3 g), nickel nitrate (37.6 g), and ruthric acid in 78 mL of distilled water at 90°C. After dry impregnation, the extruded materials are allowed to stand and mature in a water-saturated atmosphere at ambient temperature for 24 hours, and then dried at 90°C for 16 hours. The dried catalyst thus obtained is denoted as C11.

[0147] (Example 12: Preparation of alumina-supported catalyst NiMoWP (C12; comparative) by post-addition of an organic compound (citric acid)) 100 g of catalyst C11 precursor, provided in the form of an "extruded" material, is impregnated with an aqueous solution containing 7.8 g of citric acid. The volume of this aqueous solution is equal to the pore volume of the catalyst C11 precursor. The amount is such that the molar ratio of (citric acid) / (NiO + MoO3 + WO3) is 0.08. The extruded material is allowed to mature in a water-saturated atmosphere at ambient temperature for 16 hours. The catalyst C12 precursor is then dried at 120°C for 2 hours to obtain catalyst C12.

[0148] (Example 13: Preparation of alumina-supported catalyst NiMoWP (C13; conforming to the present invention) by post-addition of an organic compound (citric acid)) 100 g of the catalyst C7 precursor of this application, provided in the form of an "extruded product," is impregnated with an aqueous solution containing 6.4 g of citric acid. The volume of this aqueous solution is equal to the pore volume of the catalyst C7 precursor. The amount is adjusted so that the molar ratio of (citric acid) / (NiO+MoO3+WO3) is 0.08. The extruded product is allowed to mature in a water-saturated atmosphere at ambient temperature for 16 hours. Then, the catalyst C13 precursor is dried at 120°C for 2 hours to give catalyst C13.

[0149] (Example 14: Evaluation of catalysts C1, C2, C3, C4, C5, C6, C11 and C12 (not conforming to the present invention) and catalysts C7, C8, C9, C10 and C13 (conforming to the present invention) in the hydrogenation (HDA) of aromatic compounds in gas oil) Catalysts C1, C2, C3, C4, C5, C6, C11, and C12 (not conforming to the present invention) and catalysts C7, C8, C9, C10, and C13 (conforming to the present invention) were tested in the hydrogenation (HDA) of aromatic compounds in gas oil.

[0150] The feedstock is a mixture of 30% by volume of gas oil produced from atmospheric distillation (also called straight-run distillation) and 70% by volume of light gas oil (also called Light Cycle Oil (LCO)) produced from a catalytic cracking unit. The characteristics of the test feedstock used are as follows: Density at 15°C = 0.8994 g / cm³ 3 (NF EN ISO 12185), refractive index at 20°C = 1.5143 (ASTM D1218-12), sulfur content = 0.38 wt%, nitrogen content = 0.05 wt%. • Simulated distillation (ASTM D2887): - IP: 133℃ - 10% : 223℃ - 50% : 285℃ - 90% : 357℃ - FP: 419℃ The test was conducted in an isothermal test-scale reactor with a transverse fixed bed, and the fluid was circulated upwards from the bottom.

[0151] The catalyst is sulfurized in-situ beforehand in a reactor under pressure at 350°C, producing atmospheric pressure (straight-run) distilled gas oil feedstock (density at 15°C = 0.8491 g / cm³). 3 This is done using (NF EN ISO 12185) and by adding 2% by weight of dimethyl disulfide to an initial sulfur content of 0.42% by weight.

[0152] Hydrogenation tests of aromatic compounds were conducted under the following operating conditions: total pressure 8 MPa, catalyst volume 4 cm³. 3 Temperature 330°C, hydrogen flow rate 3.0 L / h, and raw material flow rate 4.5 cm 3 / h.

[0153] The characteristics of the effluent are analyzed as follows: density at 15°C (NF EN ISO 12185), refractive index at 20°C (ASTM D1218-12), simulated distillation (ASTM D2887), sulfur content, and nitrogen content. The residual aromatic carbon content is calculated by the ndM method (ASTM D3238). The degree of hydrogenation of aromatic compounds is calculated as the ratio of the aromatic carbon content in the effluent to the content in the test feedstock. The catalytic performance quality of the tested catalysts is given in Table 1. These are expressed as relative volume activity (RVA) relative to catalyst C7, which was selected as the baseline, assuming a 1.7th order reaction for the relevant reaction.

[0154] Table 1 clearly shows the gains related to the catalytic effect contributed by specific formulations according to the present invention. This is because catalysts C1, C2, C3, C4, C5, C6, C11, and C12 (not conforming to the present invention) exhibit lower activity than catalyst C7 (conforming to the present invention). Catalysts C8, C9, C10, and C13 (conforming to the present invention) also exhibit higher activity than catalyst C7.

[0155] Table 1 clearly shows the gains related to the catalytic effect contributed by specific formulations according to the present invention. This is because the non-additive catalyst C11 (comparative) exhibits lower activity than the activity obtained with the non-additive catalyst C7 (compliant with the present invention). Similarly, the added catalyst C12 (comparative) exhibits lower activity than the activity obtained with the added catalyst C13 (compliant with the present invention). For the two comparisons, only the content and ratio of metal and phosphorus were modified.

[0156] Therefore, the advantages of the catalysts according to the present invention are significant, regardless of their preparation method, and thus they have greater efficacy than other compounds of the existing prior art.

[0157] [Table 1]

Claims

1. A catalyst for the hydrogenation and / or hydrocracking of hydrocarbon fractions, comprising an alumina or silica or silica-alumina based support, an active phase consisting of nickel, molybdenum and tungsten, and phosphorus, and characterized by the following: - The nickel content is measured in the form of NiO and is 3% to 4% by weight relative to the total weight of the catalyst. - Molybdenum content is MoO ３ It is measured in a form that is 2% to 4% by weight relative to the total weight of the catalyst. - The tungsten content is WO ３ It is measured in this form and is 34% to 40% by weight relative to the total weight of the catalyst. - The phosphorus content is P ２ O ５ It is measured in this form and is 3% to 4% by weight relative to the total weight of the catalyst. - WO ３ / MoO ３ The molar ratio is 5.3 to 12.4 mol / mol. - NiO / (WO ３ +MoO ３ The molar ratio is 0.20 to 0.33 mol / mol. -P ２ O ５ / (WO ３ +MoO ３ ) The molar ratio is 0.21 to 0.34 mol / mol.

2. The catalyst according to claim 1, characterized by the following: - The nickel content, measured in the form of NiO, is 3.1% to 3.9% by weight relative to the total weight of the catalyst. - Molybdenum content is MoO ３ It is measured in this form and is 2.2% to 3.8% by weight relative to the total weight of the catalyst. - The tungsten content is WO ３ It is measured in this form and is 35% to 39.9% by weight relative to the total weight of the catalyst. - The phosphorus content is P ２ O ５ It is measured in this form and is 3.1% to 3.9% by weight relative to the total weight of the catalyst. - WO ３ / MoO ３ The molar ratio is 5.7 to 11.1 mol / mol. - NiO / (WO ３ +MoO ３ The molar ratio is 0.21 to 0.31 mol / mol. - P ２ O ５ / (WO ３ +MoO ３ The molar ratio is 0.22 to 0.33 mol / mol.

3. The catalyst according to claim 2, characterized by the following: - The nickel content, measured in the form of NiO, is 3.2% to 3.8% by weight relative to the total weight of the catalyst. - Molybdenum content is MoO ３ It is measured in this form and is 2.5% to 3.5% by weight relative to the total weight of the catalyst. - The tungsten content is WO ３ It is measured in this form and is 36% to 39% by weight relative to the total weight of the catalyst. - The phosphorus content is P ２ O ５ It is measured in this form and is 3.2% to 3.8% by weight relative to the total weight of the catalyst. - WO ３ / MoO ３ The molar ratio is 6.4 to 9.7 mol / mol. - NiO / (WO ３ +MoO ３ The molar ratio is 0.22 to 0.30 mol / mol. - P ２ O ５ / (WO ３ +MoO ３ The molar ratio is 0.23 to 0.32 mol / mol.

4. The density of metals from Group VIB is expressed as the number of atoms of the metal per unit area of ​​the catalyst, where the area of ​​the catalyst is (nm). ２ The catalyst according to any one of claims 1 to 3, wherein each atom contains 5 to 12 metal atoms from Group VIb.

5. The catalyst according to any one of claims 1 to 4, further comprising an organic compound containing oxygen and / or nitrogen and / or sulfur.

6. The catalyst according to claim 5, wherein the organic compound is a compound comprising one or more chemical functional groups selected from the functional groups of carboxyl, alcohol, thiol, thioether, sulfone, sulfoxide, ether, aldehyde, ketone, ester, carbonate, amine, nitrile, imide, oxime, urea, or amide, or a compound comprising a furan ring, or a sugar.

7. The organic compounds include γ-valerolactone, 2-acetylbutyrolactone, triethylene glycol, diethylene glycol, ethylene glycol, ethylenediaminetetraacetic acid (EDTA), maleic acid, malonic acid, citric acid, acetic acid, oxalic acid, gluconic acid, glucose, fructose, sucrose, sorbitol, xylitol, γ-ketovaleric acid, and di(C) succinate. １ -C ４ Alkyl), especially dimethyl succinate, dimethylformamide, 1-methyl-2-pyrrolidinone, propylene carbonate, 2-methoxyethyl 3-oxobutanoate, bicine, tricine, 2-flualdehyde (also known as furfural), 5-hydroxymethylfurfural, 2-acetylfuran, 5-methyl-2-flualdehyde, ascorbic acid, butyl lactate, ethyl lactate, butyl butyryl lactate, ethyl 3-hydroxybutanoate, ethyl 3-ethoxypropanoate, 2-ethoxyethyl acetate, 2-butoxyethyl acetate, 2-hydroxyethyl acrylate, 1-bicine The catalyst according to claim 6, selected from nyl-2-pyrrolidinone, 1,3-dimethyl-2-imidazolidinone, 1,5-pentanediol, 1-(2-hydroxyethyl)-2-pyrrolidinone, 1-(2-hydroxyethyl)-2,5-pyrrolidinedione, 5-methyl-2(3H)-furanone, 1-methyl-2-piperidinone, 4-aminobutanoic acid, butyl glycolate, ethyl 2-mercaptopropanoate, ethyl 4-oxopentanoate, diethyl maleate, dimethyl maleate, dimethyl fumarate, diethyl fumarate, dimethyl adipate, and dimethyl 3-oxoglutarate.

8. The catalyst according to any one of claims 5 to 7, wherein the content of the organic compound is 1% by weight to 30% by weight relative to the total weight of the catalyst.

9. The catalyst according to any one of claims 1 to 8, which is at least partially sulfurized.

10. A method for preparing a catalyst according to any one of claims 1 to 9, comprising the following steps: a) A step of obtaining a catalyst precursor by contacting at least one nickel precursor, at least one molybdenum precursor, and at least one tungsten precursor and phosphorus with an alumina, silica, or silica-alumina based support, b) A step of drying the catalyst precursor produced in step a) at a temperature of less than 200°C.

11. The method for preparing a catalyst according to claim 10, further comprising step c), wherein in step c), the catalyst obtained in step b) is calcined at a temperature of 200°C to 550°C.

12. A method for preparing a catalyst according to claim 10 or 11, further comprising step d), wherein in step d), the catalyst obtained in step b) or step c) is sulfurized.

13. Use of the catalyst according to any one of claims 1 to 9 in a method for the hydrogenation and / or hydrocracking of hydrocarbon fractions.

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