FR3104466A1 - Process for preparing a hydrotreatment and / or hydrocracking catalyst by co-mixing in a molten medium - Google Patents

Abstract

The invention relates to a process for the preparation by co-mixing in a molten medium of a catalyst comprising a metal from group VIB and a support comprising alumina, said process comprising the following steps: a) mixing an alumina precursor with an aqueous solution to obtain a paste, b) said paste is brought into contact with a hydrated metal acid comprising at least one metal from group VIB whose melting point of said hydrated solid metal acid is between 20 and 100 ° C, the mass ratio between said metal acid and said support porous being between 0.05 and 2.2, c) the paste is heated with stirring to a temperature between the melting point of said metallic acid and 100 ° C, d) the dough is shaped, e) we dry, f) calcining. The invention also relates to the catalyst and its use in the field of hydrotreatment and / or hydrocracking.

Description

Process for the preparation of a hydrotreating and/or hydrocracking catalyst by co-kneading in a molten medium.

Field of invention

The invention relates to a method for preparing a catalyst for hydrotreating and/or hydrocracking by co-kneading in a molten medium, the catalyst obtained by this method and its use in the field of hydrotreating and/or hydrocracking. .

State of the art

Usually, a catalyst for the hydrotreatment of hydrocarbon cuts aims to eliminate the sulfur or nitrogen compounds contained therein in order to bring, for example, a petroleum product to the required specifications (sulphur content, aromatic content, etc.) for a given application (vehicle fuel, gasoline or diesel, heating oil, jet fuel).

Conventional hydrotreating catalysts generally comprise an oxide support and an active phase based on Group VIB and VIII metals in their oxide forms as well as phosphorus.

The preparation of these catalysts generally includes an impregnation step using an impregnation solution containing metals and phosphorus on the support (also called conventional impregnation thereafter), followed by drying and possibly dipping. calcination to obtain the active phase in their oxide forms. Before their use in a hydrotreating and/or hydrocracking reaction, these catalysts are generally subjected to sulfurization in order to form the active species.

Hydrotreating and/or hydrocracking catalysts based on metals from groups VIB and VIII prepared by a single impregnation step generally make it possible to reach molybdenum and cobalt contents of respectively 30 and 7% by weight expressed as metal to the weight of the catalyst, depending on the pore volume of the support used. When it is desired to prepare catalysts having a higher metal content, several successive impregnations are often necessary to obtain the desired metal content, followed by at least one drying step, then optionally a calcining step between each impregnation. .

The preparation of hydrotreating and/or hydrocracking catalysts based on metals from groups VIB and VIII having a high metal content by the conventional impregnation route thus involves a sequence of numerous steps and the use of a solvent, such as than water, which increases the associated manufacturing costs.

Moreover, even by carrying out several successive impregnations, the maximum achievable molybdenum content is generally around 40% by weight, expressed as molybdenum oxide relative to the weight of the catalyst, higher contents are not accessible with this technique.

Another method of preparation is impregnation in a molten medium. This technique, particularly well described in the publication "Melt Infiltration: an Emerging Technique for the Preparation of Novel Functional Nanostructured Materials", P.E. de Jongh, T.M. Eggenhuisen, Adv. Mater. 2013, 25, 6672-6690 is based on a single-step process based on the infiltration without pressure and by capillarity of a liquid in fusion in a porous body.

Applied to the field of catalysis, impregnation in a molten medium consists of mixing a porous support with a solid metal salt having a relatively low melting point, in particular below its decomposition temperature, then heating the mixture to a temperature above the melting temperature of said metallic salt in order to melt the salt in the support.

This technique is thus distinguished from conventional impregnation by several advantages, in particular by simplified preparation. Indeed, it does not require the preparation of a solution or a solvent because the metal precursors are used in the form of solids. Similarly, the catalyst obtained after heating the solid support/salt mixture does not need additional drying or calcination steps. In addition, a major advantage of impregnation in a molten medium is the fact of being able to obtain a catalyst with a very high metal content in a single step.

This technique has the disadvantage of requiring a metal salt having a relatively low melting temperature, in particular lower than its decomposition temperature. Although such salts exist for Group VIII metals, especially as a hydrated nitrate salt based on nickel or cobalt, there does not appear to be any Group VIB salts that meet these low melting point criteria. Indeed, salts based on a group VIB metal tend to decompose before reaching their melting point.

However, there are hydrated metal acids based on a metal of group VIB which are in the form of powders and which have a low melting point. These acids nevertheless have the particularity of only melting in the presence of a sufficient quantity of water. In other words, it is necessary to keep the water molecules of crystallization to ensure their fusion.

In order to prepare a catalyst heavily loaded with group VIB metals in a few steps, it would be interesting to introduce these acids into a support without the need to moisten the support beforehand.

During the preparation of an alumina-based support from an alumina precursor, a first step is generally shaping, that is to say the transition from a powder state to a millimeter size support. Several shaping techniques exist depending on the application of the catalyst. The technique most commonly used is shaping by mixing/extrusion. Mixing consists of peptizing an alumina precursor (often boehmite), i.e. mixing the alumina precursor with a generally acidic solution in a mixer. The paste obtained is then extruded through a die to form extrudates of variable shape (cylinder, trilobe, quadrilobe, etc.), then the extrudates are dried and then calcined to form the alumina-based support.

The present invention is based on the fact that it is possible to introduce a hydrated metallic acid based on a metal of group VIB in solid form into a paste obtained by kneading and to subsequently heat this mixture in order to melt hydrated metallic acid. Indeed, the kneaded paste contains enough moisture for the hydrated metallic acid to keep the water molecules of crystallization to ensure its fusion. This technique will be called hereafter “co-kneading in a molten medium” or “co-kneading in fusion”. Unlike known conventional co-kneading during which the active phase is provided by one or more solutions containing at least one metal from group VIB, co-kneading in a molten medium thus involves the introduction of the active phase in solid form into the paste followed by 'a heater.

The paste obtained after heating is then treated in a conventional manner by extrusion, drying then calcination in order to obtain an alumina-based catalyst containing at least one group VIB metal.

In this context, one of the objectives of the present invention is to provide a process for the preparation of a hydrotreating and/or hydrocracking catalyst based on a group VIB metal prepared by co-kneading in a molten medium.

Objects of the invention

The invention relates to a process for the preparation of a hydrotreating and/or hydrocracking catalyst comprising at least one group VIB metal and a support comprising alumina, the group VIB metal content being between 5 and 55% by weight expressed as group VIB metal oxide relative to the total weight of the catalyst, said process comprising the following steps:

a) an alumina precursor is mixed with an aqueous solution, optionally containing an inorganic acid, in order to obtain a paste,

b) said paste obtained in step a) is brought into contact with at least one hydrated metallic acid comprising at least one metal from group VIB whose melting point of said hydrated metallic acid is between 20 and 100° C., to form a paste containing the hydrated metallic acid, the mass ratio between said metallic acid and said alumina precursor being between 0.05 and 2.2,

c) the paste containing the hydrated metallic acid obtained at the end of step b) is heated with stirring to a temperature between the melting point of said metallic acid and 100° C.,

c') optionally bringing said paste obtained in step c) into contact with an aqueous solution containing a base,

d) the paste obtained in step c) or in step c′ is shaped,

e) the shaped paste is dried at a temperature below 200° C. to obtain a dried catalyst,

f) the dried catalyst is calcined at a temperature between 200 and 1000°C.

The applicant has in fact found that the use of hydrated metal acid comprising at least one metal from group VIB and having a melting temperature of between 20 and 100° C. makes it possible to introduce a metal from group VIB into a catalyst by co-kneading in a molten medium.

The preparation process according to the invention thus has the advantages of the molten medium, in particular the absence of any preparation of solution or the use of solvent to introduce the active phase based on a group VIB metal.

In addition, the preparation process according to the invention makes it possible to obtain a catalyst heavily loaded with group VIB metal having in particular contents of group VIB metal which are neither attainable by conventional impregnation using a solution of conventional impregnation, or by conventional co-mixing using an impregnating solution.

Thus, the catalyst obtained according to the preparation process according to the invention makes it possible to observe catalytic activity in hydrotreating and/or hydrocracking at least at the same level as a catalyst prepared by conventional comixing using a solution of impregnation with, however, a simplified preparation and the possibility of loading more group VIB metal.

According to a variant, the hydrated metallic acid is chosen from hydrated phosphomolybdic acid, hydrated silicomolybdic acid, hydrated molybdosilicic acid, hydrated phosphotungstic acid and hydrated silicotungstic acid.

According to a variant, in step a) the alumina precursor is boehmite.

According to a variant, in step a) a silicon precursor is also added to the mixture.

According to a variant, in step a) the acid is chosen from nitric acid, hydrochloric acid, sulfuric acid and phosphoric acid.

Alternatively, in step c′) the base is chosen from ammonia, a mono-alkylamine, a di-alkylamine, a tri-alkylamine, a tetra-alkylammonium hydroxide.

According to a variant, step b) further comprises bringing into contact with at least one metal salt comprising at least one group VIII metal whose melting point of said metal salt is between 20 and 100° C., the molar ratio (group VIII metal)/(group VIB metal) being between 0.1 and 0.8.

Alternatively, said metal salt is a hydrated nitrate salt. According to a preferred variant, said metal salt is chosen from nickel nitrate hexahydrate, and cobalt nitrate hexahydrate, taken alone or as a mixture.

According to a variant, step b) further comprises bringing it into contact with phosphoric acid, the phosphorus/(group VIB metal) molar ratio being between 0.08 and 1.

According to a variant, step b) further comprises bringing into contact with an organic compound comprising oxygen and/or nitrogen and/or sulfur whose melting point of said organic compound is between 20 and 100°C, the organic compound/metal molar ratio of group VIB being between 0.01 and 5.

According to this variant, the organic compound is chosen from maleic acid, sorbitol, xylitol, γ-ketovaleric acid, 5-hydroxymethylfurfural and 1,3-dimethyl-2-imidazolidinone.

According to a variant, after step f), an impregnation step g) is carried out using an impregnation solution and in which said catalyst is brought into contact with an impregnation solution comprising a metal from the group VIB and/or a group VIII metal and/or phosphorus and/or an organic compound comprising oxygen and/or nitrogen and/or sulfur, followed by a drying step h) at a temperature below 200° C. and optionally a calcining step i) at a temperature of between 200° C. and 600° C. under an inert atmosphere or under an atmosphere containing oxygen.

According to this variant, the organic compound is chosen from γ-valerolactone, 2-acetylbutyrolactone, triethylene glycol, diethylene glycol, ethylene glycol, ethylenediaminetetraacetic acid (EDTA), maleic acid, malonic acid, citric acid, gluconic acid, dimethyl succinate, glucose, fructose, sucrose, sorbitol, xylitol, γ-ketovaleric acid, dimethylformamide, 1-methyl-2-pyrrolidinone, propylene carbonate, 2-methoxyethyl 3-oxobutanoate, bicine, tricine, 2-furaldehyde (also known as furfural), 5-hydroxymethylfurfural (also known as 5-(hydroxymethyl)-2- furaldehyde or 5-HMF), 2-acetylfuran, 5-methyl-2-furaldehyde, ascorbic acid, butyl lactate, ethyl 3-hydroxybutanoate, ethyl 3-ethoxypropanoate, acetate 2-ethoxyethyl acetate, 2-butoxyethyl acetate, 2-hydroxyethyl acrylate, 1-vinyl-2-pyrrolidinone, 1,3-dimethyl-2-imidazolidinone, 1-(2-hydroxyethyl)- 2-pyrrolidinone, 1-(2-hydroxyethyl)-2,5-pyrrolidinedione, 5-methyl-2(3H)-furanone, 1-methyl-2-piperidinone and 4-aminobutanoic acid.

Alternatively, the catalyst is subjected to a sulfurization step after step f) or after any steps h) or i).

The invention also relates to the catalyst obtained by the preparation process and its use in a hydrotreating and/or hydrocracking process.

Description of the invention

The invention relates to a process for the preparation of a hydrotreating and/or hydrocracking catalyst comprising at least one group VIB metal and a support comprising alumina, the group VIB metal content being between 5 and 55% by weight expressed as group VIB metal oxide relative to the total weight of the catalyst, said process comprising the following steps:

a) an alumina precursor is mixed with an aqueous solution, optionally containing an inorganic acid, in order to obtain a paste,

b) said paste obtained in step a) is brought into contact with at least one hydrated metallic acid comprising at least one metal from group VIB whose melting point of said hydrated metallic acid is between 20 and 100° C., to form a paste containing the hydrated metallic acid, the mass ratio between said metallic acid and said alumina precursor being between 0.05 and 2.2,

c) the paste containing the hydrated metallic acid obtained at the end of step b) is heated with stirring to a temperature between the melting point of said metallic acid and 100° C.,

c') optionally bringing said paste obtained in step c) into contact with an aqueous solution containing a base,

d) the paste obtained in step c) or in step c′ is shaped,

e) the shaped paste is dried at a temperature below 200° C. to obtain a dried catalyst,

f) the dried catalyst is calcined at a temperature between 200 and 1000°C.

Step a) : M mixture of the alumina precursor with an aqueous solution (peptization)

According to step a) of the preparation process according to the invention, an alumina precursor is mixed with an aqueous solution, optionally containing an inorganic acid, in order to obtain a paste.

The alumina precursor, often also called alumina gel, can be chosen from boehmite, gibbsite, bayerite or diaspore, alone or in a mixture. Preferably, the alumina precursor contains at least 50% by weight of boehmite AlOOH relative to the total weight of the alumina precursor. Particularly preferably, the alumina precursor consists of boehmite.

The alumina precursor used in step a) can be obtained according to different embodiments. Synthesis by precipitation and by sol-gel process are the most common methods used to produce boehmite.

The alumina precursor used in step a) may contain an inorganic acid. The quantity of acid contained in the alumina precursor is between 0 and 6%, expressed as mass of acid/mass of Al ₂ O ₃ .

The alumina precursor, which comes in powder form, is mixed with an aqueous solution optionally containing an inorganic acid. The inorganic acid can be chosen from nitric acid, hydrochloric acid, sulfuric acid and phosphoric acid. Preferably nitric acid is used.

The quantity of inorganic acid added is between 0 and 20%, preferably 0 and 10%, expressed as mass of acid/mass of Al ₂ O ₃ .

Step a) of mixing is advantageously carried out by kneading. Step a) advantageously takes place in a mixer, for example a Z-arm mixer well known to those skilled in the art. The alumina precursor is placed in the mixer tank. Then the aqueous solution possibly containing the inorganic acid is added to the syringe.

The speed of rotation of said mixer is generally between 0.5 and 200 revolutions per minute, preferably between 5 and 100 revolutions per minute.

The mixing time is generally between 2 minutes and 180 minutes, preferably between 5 minutes and 90 minutes.

Step a) of mixing can be carried out at a temperature between 5°C and 100°C, preferably between 15°C and 60°C. It is preferably carried out at room temperature.

Any other element, for example silica in the form of a silicic precursor solution or emulsion, can be introduced at the time of this step a). Silicon sources are well known to those skilled in the art. Mention may be made, by way of example, of silicic acid, silica in powder form or in colloidal form (silica sol), tetraethylorthosilicate Si(OEt) ₄ . The introduction of a silica precursor makes it possible to obtain a silica-alumina support.

Similarly, all sources of zeolite can be incorporated. Preferably, the zeolite is chosen from the group FAU, BEA, ISV, IWR, IWW, MEI, UWY and preferably, the zeolite is chosen from the group FAU and BEA, such as Y and/or beta zeolite, and particularly preferably such as USY and/or beta zeolite.

Step b) : Contacting the metallic acid with l a dough obtained in step a)

According to step b) of the preparation process according to the invention, said paste obtained in step a) is brought into contact with at least one hydrated metallic acid comprising at least one group VIB metal whose melting temperature of said acid hydrated metal is between 20 and 100° C., to form a paste containing the hydrated metal acid, the mass ratio between said metal acid and said alumina precursor being between 0.05 and 2.2.

The hydrated metallic acid must have a relatively low melting temperature, in particular lower than its decomposition temperature. The melting point of the hydrated metallic acid is between 20 and 100°C, and preferably between 50 and 90°C.

The hydrated metal acid includes at least one Group VIB metal. The group VIB metal present in the acid is preferably chosen from molybdenum and tungsten.

The hydrated metallic acid may additionally include phosphorus and silicon.

The metallic acid can be an acid of a Keggin type heteropolyanion.

The hydrated metallic acid is preferably chosen from hydrated phosphomolybdic acid (H ₃ PMo ₁₂ O ₄₀ , 28H ₂ O, melting point T= 85° C.), hydrated silicomolybdic acid (H ₄ SiMo ₁₂ O ₄₀ , xH ₂ O, melting point T= 47-55°C), hydrated molybdosilicic acid (H ₆ Mo ₁₂ O ₄₁ Si, xH ₂ O, melting point T= 45-70°C), phosphotungstic acid hydrated (H ₃ PW ₁₂ O ₄₀ , 28H ₂ O, melting point T= 89°C), hydrated silicotungstic acid (H ₄ SiW ₁₂ O ₄₀ , xH ₂ O, melting point T= 53°C).

The mass ratio between said hydrated metal acid and said alumina precursor is between 0.05 and 2.2, preferably between 0.1 and 2.0.

In this step, the hydrated metal acid is in solid form, that is to say that the hydrated metal acid is brought into contact with the paste of step a) at a temperature below the melting point of said hydrated metallic acid. Step b) is preferably carried out at ambient temperature.

According to step b), the contacting of said paste and the hydrated metallic acid can be done by any method known to those skilled in the art. Preferably, the contacting is carried out by adding the hydrated metallic acid to the said paste in a mixer as described in step a).

The speed of rotation of said mixer is generally between 0.5 and 200 rpm, preferably between 5 and 100 rpm. It can be the same or different from the speed used in step a). Generally it is the same.

The mixing time is generally between 2 and 180 minutes, preferably between 2 and 90 minutes. It can be identical or different to the mixing time of step a).

According to a first variant, step b) consists of bringing said paste obtained in step a) into contact with at least one hydrated metal acid comprising at least one group VIB metal whose melting point of said hydrated metal acid is between 20 and 100° C., to form a paste containing the hydrated metallic acid, the mass ratio between said metallic acid and said alumina precursor being between 0.05 and 2.2.

Although the addition of other solid compounds to the catalyst obtained according to the preparation process of the invention after step f) is not necessary to obtain a catalytic activity close to that of catalysts according to the state of the art (prepared by co-mixing using a solution), it may be advantageous in certain cases to add other solid compounds to the solid mixture obtained in step b). Such compounds may in particular be a metal salt comprising at least one group VIII metal, phosphoric acid or even an organic compound.

Thus, according to a second variant, step b) further comprises bringing into contact with at least one metal salt comprising at least one group VIII metal whose melting point of said metal salt is between 20 and 100° C., the molar ratio (group VIII metal)/(group VIB metal) being between 0.1 and 0.8.

The metal salt must have a relatively low melting temperature, in particular lower than its decomposition temperature. The melting point of the metal salt is between 20 and 100°C, and preferably between 40 and 60°C.

The metal salt includes at least one Group VIII metal. The group VIII metal present in the salt is preferably chosen from nickel and cobalt.

Preferably the metal salt is hydrated. Preferably, the metal salt is a hydrated nitrate salt. Preferably, the metal salt is chosen from nickel nitrate hexahydrate (Ni(NO ₃ ) ₂ .6H ₂ O, melting point T= 56.7° C.) and cobalt nitrate hexahydrate (Co(NO ₃ ) _{2.6H 2} O, melting point T=55.0° C.), taken alone or as a mixture.

The molar ratio (group VIII metal)/(group VIB metal) is generally between 0.1 and 0.8, preferably between 0.15 and 0.6.

Preferably, the combination of nickel-molybdenum, cobalt-molybdenum, nickel-tungsten, nickel-molybdenum-tungsten and nickel-cobalt-molybdenum metals is chosen, and very preferably the active phase consists of cobalt and molybdenum, nickel and molybdenum, nickel and tungsten or a nickel-molybdenum-tungsten combination.

It is well known that it is advantageous to add phosphorus to hydrotreating and/or hydrocracking catalysts. Indeed, phosphorus has no catalytic character but increases the catalytic activity of the active phase by the formation of heteropolyanions which increases the dispersion of the elements in the support.

When the hydrated metal acid used is hydrated phosphomolybdic acid or hydrated phosphotungstic acid, phosphorus is introduced into the catalyst together with the hydrated metal acid. In the case of hydrated phosphomolybdic acid, the P/Mo ratio is 0.08. In the case of hydrated phosphotungstic acid, the P/W molar ratio is 0.08.

When it is desired to increase the P/(group VIB metal) molar ratio in order ultimately to increase the catalytic activity, it is possible to add to the paste obtained in step a) a phosphorus compound in solid form, in particular the acid phosphoric. Phosphoric acid has a melting point of 42°C. Thus, according to a third variant, step b) further comprises bringing into contact with phosphoric acid.

The phosphorus/(group VIB metal) molar ratio is generally between 0.08 and 1, preferably between 0.1 and 0.9, and very preferably between 0.15 and 0.8.

The addition of an organic compound to the hydrotreating and/or hydrocracking catalysts to improve their activity has been recommended by those skilled in the art, in particular for catalysts which have been prepared by impregnation using an impregnation solution followed by drying without subsequent calcination. These catalysts are often referred to as "additive dried catalysts". The introduction of an organic compound makes it possible to increase the dispersion of the active phase. The addition of an organic compound can also be carried out in the preparation process according to the invention when the organic compound is in solid form.

Thus, according to a fourth variant, step b) further comprises bringing into contact with an organic compound comprising oxygen and/or nitrogen and/or sulfur whose melting point of said organic compound is comprised between 20 and 100°C.

Generally, the organic compound is chosen from a compound comprising one or more chemical functions chosen from a carboxylic function, alcohol, thiol, thioether, sulphone, sulphoxide, ether, aldehyde, ketone, ester, carbonate, amine, nitrile, imide, oxime, urea and amide or even compounds including a furan ring or even sugars.

Among the organic compounds comprising oxygen and/or nitrogen and/or sulfur and having a melting point of between 20 and 100° C., preference will be given to maleic acid, sorbitol, xylitol , γ-ketovaleric acid, 5-hydroxymethylfurfural (also known as 5-(hydroxymethyl)-2-furaldehyde or 5-HMF), 1,3-dimethyl-2-imidazolidinone.

The organic compound/metal molar ratio of group VIB (contained in the hydrated metallic acid) is between 0.01 and 5 mol/mol, preferably between 0.05 and 3 mol/mol, preferably between 0 0.05 and 2 mol/mol and very preferably between 0.1 and 1.5 mol/mol.

After step b), a paste is thus obtained which comprises at least one group VIB metal in the form of hydrated metal acid and an alumina precursor. It may also additionally contain at least one group VIII metal in the form of a metal salt and/or phosphoric acid and/or an organic compound comprising oxygen and/or nitrogen and/or sulfur.

Step c) : Heating with stirring

According to step c) of the preparation process according to the invention, the paste containing the hydrated metal acid obtained at the end of step b) is heated with stirring to a temperature between the melting point of said metal acid and 100°C.

Step c) is advantageously carried out at atmospheric pressure. Step c) is generally carried out between 5 minutes and 12 hours, preferably between 5 minutes and 4 hours.

According to step c), the stirring (mechanical homogenization) of the mixture can be done by any method known to those skilled in the art. Preferably, convective mixers, drum mixers or static mixers can be used. Very preferably, step c) is carried out in a mixer as described in step a). The speed of rotation of said mixer is generally between 0.5 and 200 rpm, preferably between 5 and 100 rpm. It can be the same or different from the speed used in step a). Generally it is the same.

Step c') : Addition of a basic solution (optional)

According to step c′) of the preparation process according to the invention, said paste obtained in step c) is optionally brought into contact with an aqueous solution containing a base.

The base is chosen from ammonia, a mono-alkylamine, a di-alkylamine, a tri-alkylamine, a tetra-alkylammonium hydroxide.

The amount of base added is such that it partially or totally neutralizes the paste. The molar ratio: "number of moles of base added in step c') divided by number of moles of acid present in step a)" is generally between 0.1 and 2, preferably between 0.4 and 1.

The contacting can be done by any method known to those skilled in the art. Preferably, convective mixers, drum mixers or static mixers can be used. Very preferably, step c′) is carried out in a mixer as described in step a). The speed of rotation of said mixer is generally between 0.5 and 200 rpm, preferably between 5 and 100 rpm. It can be the same or different from the speed used in step a) or c). Generally it is the same.

Step c′) can be carried out at a temperature between 5°C and 100°C, preferably between 15°C and 60°C. It is preferably carried out at ambient temperature.

Step d) : Formatting

According to step d) of the process according to the invention, the paste obtained in step c) or optionally in step c′) is shaped.

The shaping can be carried out using any technique known to those skilled in the art. It is generally carried out by extrusion.

Preferably, said paste obtained in step c) is shaped by extrusion in the form of extrudates with a diameter generally between 0.5 and 10 mm and preferably 0.8 and 3.2 mm and in a particularly preferably between 1.0 and 2.5 mm.

The shape of the extrudates can be cylindrical, trilobe or quadrilobe.

In a preferred embodiment, the catalyst is composed of trilobal or quadrilobal extrudates of size between 1.0 and 2.5 mm in diameter.

Stage e ) : Drying

According to step e) of the process according to the invention, the shaped paste is dried at a temperature below 200° C. to obtain a dried catalyst.

Step e) of drying is carried out at a temperature below 200°C, advantageously between 100°C and below 200°C, preferably between 50°C and 180°C, more preferably between 70°C and 150°C, very preferably between 75°C and 130°C.

The drying temperature in step e) is generally higher than the heating temperature in step c). Preferably, the drying temperature of step e) is at least 10°C higher than the heating temperature of step c).

The drying step is preferably carried out under an inert atmosphere or under an atmosphere containing oxygen.

The drying step can be carried out by any technique known to those skilled in the art. It is advantageously carried out at atmospheric pressure or at reduced pressure. Preferably, this step is carried out at atmospheric pressure. It is advantageously carried out in a traversed bed using air or any other hot gas. Preferably, when the drying is carried out in a fixed bed, the gas used is either air or an inert gas such as argon or nitrogen. Very preferably, the drying is carried out in a traversed bed in the presence of nitrogen and/or air. Preferably, the drying step lasts between 5 minutes and 4 hours, preferably between 30 minutes and 4 hours and very preferably between 1 hour and 3 hours.

Stage f ) : calcination

According to step f) of the process according to the invention, the dried catalyst is calcined at a temperature of between 200 and 1000°C.

Calcination step f) is carried out at a temperature of between 200 and 1000°C, preferably between 300 and 900°C and even more preferably between 500°C and 850°C.

Preferably, the calcination step lasts between 0.5 hours and 16 hours, preferably between 1 hour and 5 hours.

It is generally carried out under an inert atmosphere (nitrogen for example) or under an atmosphere containing oxygen (air for example).

It can be carried out in the presence of an air flow containing up to 60% volume of water. If water is added, the contact with the water vapor can take place at atmospheric pressure (also called steaming according to the Anglo-Saxon terminology). In the case of steaming, the water content is preferably between 150 and 900 grams per kilogram of dry air, and even more preferably between 250 and 650 grams per kilogram of dry air.

Said calcination step f) allows the transition from the alumina precursor to the final alumina. After this treatment, the active phase is thus in oxide form, the heteropolyanions are thus transformed into oxides. Similarly, the catalyst no longer contains or contains very little organic compound when it has been calcined. However, the introduction of the organic compound during its preparation made it possible to increase the dispersion of the active phase, thus leading to a more active catalyst.

Stage g) impregnation using an impregnating solution via p ost-impregnation (optional)

According to a variant, it may be advantageous in certain cases to add to the catalyst obtained according to step f) of the preparation process according to the invention, at least one of the additional metal precursors by impregnation using a solution of impregnation (classic post-impregnation). One can also add phosphorus or an organic compound.

This classic impregnation step has the advantage of being able to use metallic precursors or organic compounds that are not accessible via the molten medium technique (because they are in liquid form or have a melting temperature that is too high).

Thus, according to a variant, step f) of calcination can be followed by an impregnation step g) using an impregnation solution and in which said catalyst is brought into contact with a solution of impregnation comprising a metal from group VIB and/or a metal from group VIII and/or phosphorus and/or an organic compound comprising oxygen and/or nitrogen and/or sulphur.

In this case, the group VIB metal, when it is introduced, is preferably chosen from molybdenum and tungsten. When the group VIII metal is introduced, it is preferably chosen from cobalt, nickel and a mixture of these two metals. Preferably, the combination of nickel-molybdenum, cobalt-molybdenum, nickel-tungsten, nickel-molybdenum-tungsten and nickel-cobalt-molybdenum metals is chosen, and very preferably the active phase consists of cobalt and molybdenum, nickel and molybdenum, nickel and tungsten or a nickel-molybdenum-tungsten combination.

The group VIB metal introduced and/or the group VIII metal introduced may or may not be identical to the metals already present in the catalyst from step f).

By way of example, among the sources of molybdenum, use may be made of oxides and hydroxides, molybdic acids and their salts, in particular ammonium salts such as ammonium molybdate, ammonium heptamolybdate, phosphomolybdic acid (H ₃ PMo ₁₂ O ₄₀ ), and their salts, and optionally silicomolybdic acid (H ₄ SiMo ₁₂ O ₄₀ ) and its salts. The sources of molybdenum can also be any heteropolycompound of Keggin, lacunary Keggin, substituted Keggin, Dawson, Anderson, Strandberg type, for example. Preferably, molybdenum trioxide and the heteropolycompounds of Keggin, lacunary Keggin, substituted Keggin and Strandberg type are used.

The tungsten precursors which can be used are also well known to those skilled in the art. For example, among the sources of tungsten, it is possible to use oxides and hydroxides, tungstic acids and their salts, in particular ammonium salts such as ammonium tungstate, ammonium metatungstate, phosphotungstic acid and their salts, and optionally silicotungstic acid (H ₄ SiW ₁₂ O ₄₀ ) and its salts. The tungsten sources can also be any heteropolycompound of Keggin, lacunary Keggin, substituted Keggin, Dawson type, for example. Preferably, ammonium oxides and salts are used, such as ammonium metatungstate or heteropolyanions of Keggin, lacunary Keggin or substituted Keggin type.

The cobalt precursors which can be used are advantageously chosen from oxides, hydroxides, hydroxycarbonates, carbonates and nitrates, for example. Cobalt hydroxide and cobalt carbonate are preferably used.

The nickel precursors which can be used are advantageously chosen from oxides, hydroxides, hydroxycarbonates, carbonates and nitrates, for example. Nickel hydroxide and nickel hydroxycarbonate are preferably used.

In this case, the molar ratio (group VIII metal)/(group VIB metal) is generally between 0.1 and 0.8, preferably between 0.15 and 0.6.

Phosphorus can also be introduced into the impregnation solution.

The preferred phosphorus precursor is orthophosphoric acid H ₃ PO ₄ , but its salts and esters such as ammonium phosphates are also suitable. The phosphorus can also be introduced at the same time as the group VIB metal(s) in the form of heteropolyanions of Keggin, lacunary Keggin, substituted Keggin or of the Strandberg type.

In this case, the molar ratio of added phosphorus per group VIB metal is between 0.1 and 2.5 mol/mol, preferably between 0.1 and 2.0 mol/mol, and even more preferably between 0.1 and 1.0 mol/mol.

It is also possible to introduce an organic compound comprising oxygen and/or nitrogen and/or sulfur into the impregnation solution.

The function of additives or organic compounds is to increase the catalytic activity compared to catalysts without additives. Said organic compound is preferentially impregnated on said catalyst after solubilization in aqueous or non-aqueous solution.

Generally, the organic compound is chosen from a compound comprising one or more chemical functions chosen from a carboxylic function, alcohol, thiol, thioether, sulphone, sulphoxide, ether, aldehyde, ketone, ester, carbonate, amine, nitrile, imide, oxime, urea and amide or even compounds including a furan ring or even sugars.

The organic compound containing oxygen can be one or more chosen from compounds comprising one or more chemical functions chosen from a carboxylic, alcohol, ether, aldehyde, ketone, ester or carbonate function or else compounds including a furan cycle. or sugars. By way of example, the organic compound containing oxygen can be one or more chosen from the group consisting of ethylene glycol, diethylene glycol, triethylene glycol, a polyethylene glycol (with a molecular weight of between 200 and 1500 g /mol), propylene glycol, 2-butoxyethanol, 2-(2-butoxyethoxy)ethanol, 2-(2-methoxyethoxy)ethanol, triethyleneglycoldimethylether, glycerol, acetophenone, 2,4-pentanedione, pentanone, acetic acid, maleic acid, malic acid, malonic acid, oxalic acid, gluconic acid, tartaric acid, citric acid, γ-ketovaleric acid, a succinate of dialkyl C1-C4, and more particularly dimethyl succinate, methyl acetoacetate, ethyl acetoacetate, 2-methoxyethyl 3-oxobutanoate, 2-methacryloyloxyethyl 3-oxobutanoate, dibenzofuran, a crown ether, orthophthalic acid, glucose, fructose, sucrose, sorbitol, xylitol, γ-valerolactone, 2-acetylbutyrolactone, propylene carbonate, 2-furaldehyde (also known as furfural), 5 -hydroxymethylfurfural (also known as 5-(hydroxymethyl)-2-furaldehyde or 5-HMF), 2-acetylfuran, 5-methyl-2-furaldehyde, methyl 2-furoate, furfuryl alcohol (also known as furfuranol), furfuryl acetate, ascorbic acid, butyl lactate, butyl butyryllactate, ethyl 3-hydroxybutanoate, ethyl 3-ethoxypropanoate, methyl 3-methoxypropanoate , 2-ethoxyethyl acetate, 2-butoxyethyl acetate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, and 5-methyl-2(3H)-furanone.

The organic compound containing nitrogen can be one or more chosen from compounds comprising one or more chemical functions chosen from an amine or nitrile function. By way of example, the organic compound containing nitrogen can be one or more selected from the group consisting of ethylenediamine, diethylenetriamine, hexamethylenediamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, acetonitrile , octylamine, guanidine or a carbazole.

The organic compound containing oxygen and nitrogen can be one or more chosen from compounds comprising one or more chemical functions chosen from a carboxylic acid, alcohol, ether, aldehyde, ketone, ester, carbonate, amine, nitrile, imide, amide, urea or oxime. By way of example, the organic compound containing oxygen and nitrogen can be one or more chosen from the group consisting of 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 acid ′-triacetic acid (HEDTA), diethylene-triaminepentaacetic acid (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-pyrrolidinone, 1-(2-hydroxyethyl)-2,5-pyrrolidinedione, 1- methyl-2-piperidinone, 1-acetyl-2-azepanone, 1-vinyl-2-azepanone and 4-aminobutanoic acid.

The organic compound containing sulfur can be one or more chosen from compounds comprising one or more chemical functions chosen from a thiol, thioether, sulphone or sulphoxide function. By way of example, the organic compound containing sulfur can be one or more selected from the group consisting of thioglycolic acid, 2,2'-thiodiethanol, 2-hydroxy-4-methylthiobutanoic acid, a sulfonated derivative of a benzothiophene or a sulfoxide derivative of a benzothiophene, methyl 3-(methylthio)propanoate and ethyl 3-(methylthio)propanoate.

Preferably, the organic compound contains oxygen, preferably it is chosen from γ-valerolactone, 2-acetylbutyrolactone, triethylene glycol, diethylene glycol, ethylene glycol, ethylenediaminetetraacetic acid (EDTA), l maleic acid, malonic acid, citric acid, gluconic acid, dimethyl succinate, glucose, fructose, sucrose, sorbitol, xylitol, γ-ketovaleric acid, dimethylformamide, 1-methyl-2-pyrrolidinone, propylene carbonate, 2-methoxyethyl 3-oxobutanoate, bicine, tricine, 2-furaldehyde (also known as furfural), 5-hydroxymethylfurfural (also known as name 5-(hydroxymethyl)-2-furaldehyde or 5-HMF), 2-acetylfuran, 5-methyl-2-furaldehyde, ascorbic acid, butyl lactate, ethyl 3-hydroxybutanoate, 3 -ethyl ethoxypropanoate, 2-ethoxyethyl acetate, 2-butoxyethyl acetate, 2-hydroxyethyl acrylate, 1-vinyl-2-pyrrolidinone, 1,3-dimethyl-2-imidazolidinone, 1-(2-hydroxyethyl)-2-pyrrolidinone, 1-(2-hydroxyethyl)-2,5-pyrrolidinedione, 5-methyl-2(3H)-furanone, 1-methyl-2-piperidinone and l 4-aminobutanoic acid.

In this case, the molar ratio of the organic compound added per group VIB metal is between 0.01 and 5 mol/mol, preferably between 0.05 and 3 mol/mol, preferably between 0.05 and 2 mol/mol and very preferably between 0.1 and 1.5 mol/mol.

When more than one organic compound is present, the different molar ratios apply for each of the organic compounds present.

The impregnation step g) using an impregnation solution and in which said catalyst is brought into contact with an impregnation solution comprising a metal from group VIB and/or a metal from group VIII and/ or phosphorus and/or an organic compound comprising oxygen and/or nitrogen and/or sulfur can be produced either by impregnation in excess, or by dry impregnation, or by any other means known to the Man of the trade.

Impregnation at equilibrium (or in excess), consists in immersing the support or the catalyst in a volume of solution (often largely) greater than the pore volume of the support or the catalyst while maintaining the system under agitation to improve the exchanges between the solution and the support or catalyst. An equilibrium is finally reached after diffusion of the different species in the pores of the support or catalyst. The control of the quantity of deposited elements is ensured by the prior measurement of an adsorption isotherm which links the concentration of the elements to be deposited contained in the solution to the quantity of the elements deposited on the solid in equilibrium with this solution.

Dry impregnation consists of introducing a volume of impregnation solution equal to the pore volume of the support or catalyst. Dry impregnation makes it possible to deposit all the metals and additives contained in the impregnation solution on a given support or catalyst.

Any impregnation solution described above can comprise any polar protic solvent known to those skilled in the art. Preferably, a polar protic solvent is used, for example chosen from the group formed by methanol, ethanol and water. Preferably, the impregnation solution comprises a water-ethanol or water-methanol mixture as solvents in order to facilitate the impregnation of the compound containing a group VIB metal (and optionally of the compound containing a group VIII metal and/or or phosphorus and/or organic compound) on the catalyst. Preferably, the solvent used in the impregnation solution consists of water or a water-ethanol or water-methanol mixture.

In a possible embodiment, the solvent may be absent in the impregnation solution. In this case, phosphoric acid also acts as a solvent.

The impregnation step g) using an impregnation solution can be advantageously carried out by one or more impregnations in excess of solution or preferably by one or more dry impregnations and very preferably by a single dry impregnation of said catalyst, using the impregnation solution.

The impregnation step using an impregnation solution includes several modes of implementation. They are distinguished in particular by the moment of the introduction of the organic compound when it is present and which can be carried out either at the same time as the impregnation of the group VIB metal (co-impregnation), or after (post-impregnation) , or before (pre-impregnation). In addition, the modes of implementation can be combined. Preferably, a co-impregnation is carried out.

Advantageously, after each impregnation step, the impregnated support is allowed to mature. Curing allows the impregnation solution to disperse evenly within the support.

Any maturation step described in the present invention is advantageously carried out at atmospheric pressure, in an atmosphere saturated with water and at a temperature between 17° C. and 50° C., and preferably at room temperature. Generally, a maturation period of between ten minutes and forty-eight hours, and preferably between thirty minutes and six hours, is sufficient.

When performing several impregnation steps, each impregnation step is followed by an intermediate drying step and optionally a calcination step as described below.

After the impregnation step g), a drying step h) is carried out. The drying step h) is carried out at a temperature below 200°C, advantageously between 100°C and below 200°C, preferably between 50°C and 180°C, more preferably between 70°C and 150°C, very preferably between 75°C and 130°C.

The drying step is preferably carried out under an inert atmosphere or under an atmosphere containing oxygen.

The drying step can be carried out by any technique known to those skilled in the art. It is advantageously carried out at atmospheric pressure or at reduced pressure. Preferably, this step is carried out at atmospheric pressure. It is advantageously carried out in a traversed bed using air or any other hot gas. Preferably, when the drying is carried out in a fixed bed, the gas used is either air or an inert gas such as argon or nitrogen. Very preferably, the drying is carried out in a traversed bed in the presence of nitrogen and/or air. Preferably, the drying step lasts between 5 minutes and 4 hours, preferably between 30 minutes and 4 hours and very preferably between 1 hour and 3 hours.

When an organic compound is present, the catalyst is preferably dried without a subsequent calcination step. In this case, the drying is preferably carried out so as to preferably retain at least 30% by weight of the organic compound introduced, preferably this quantity is greater than 50% by weight and even more preferably, greater than 70% by weight, calculated based on the carbon remaining on the catalyst. The remaining carbon is measured by elemental analysis according to ASTM D5373.

According to a variant, at the end of the drying step, a dried catalyst is then obtained, which will preferably be subjected to an optional activation step (sulfidation) for its subsequent implementation in a hydrotreatment process and/or or hydrocracking.

According to another variant, the dried catalyst can be subjected to a calcination step i). The calcination step i) is carried out at a temperature of between 200° C. and 600° C., preferably between 250° C. and 550° C., under an inert atmosphere (nitrogen for example) or under an atmosphere containing oxygen (air for example). The duration of the calcination is generally between 0.5 hours and 16 hours, preferably between 1 hour and 5 hours.

Stage of the ulfidation (optional step)

Before its use for the hydrotreating and/or hydrocracking reaction, it is advantageous to convert the catalyst obtained according to the process according to the invention into a sulphide catalyst in order to form its active species. This activation or sulfurization step is carried out by methods well known to those skilled in the art, and advantageously under a sulfo-reducing atmosphere in the presence of hydrogen and hydrogen sulfide. This sulfurization can be carried out in situ or ex situ (inside or outside the reactor) of the reactor of the process according to the invention at temperatures between 200 and 600° C., and more preferably between 300 and 500° C.

The catalyst obtained at the end of step f), or optionally from step h) of drying or from step i) of calcination, is therefore advantageously subjected to a sulfurization step.

Sulfurizing agents are H ₂ S gas, elemental sulphur, CS ₂ , mercaptans, sulphides and/or polysulphides, hydrocarbon cuts with a boiling point below 400°C containing sulfur compounds or any other compound containing sulfur used for the activation of the hydrocarbon charges in order to sulfurize the catalyst. Said compounds containing sulfur are advantageously chosen from alkyl disulphides such as for example dimethyl disulphide (DMDS), alkyl sulphides, such as for example dimethyl sulphide, thiols such as for example n- butyl mercaptan (or 1-butanethiol) and polysulphide compounds of the tertiononylpolysulphide type. The catalyst can also be sulfurized by the sulfur contained in the charge to be desulfurized. Preferably, the catalyst is sulfurized in situ in the presence of a sulfurizing agent and a hydrocarbon charge. Very preferably, the catalyst is sulfurized in situ in the presence of a hydrocarbon feed containing dimethyl disulfide.

Catalyst

After step f), the hydrotreating and/or hydrocracking catalyst is obtained which comprises at least one group VIB metal and a support comprising alumina. It may additionally comprise at least one group VIII metal and/or phosphorus, and/or an organic compound comprising oxygen and/or nitrogen and/or sulfur.

The total content of group VIB metal (introduced by the hydrated metallic acid and optionally supplemented by impregnation using an impregnation solution comprising a group VIB metal in post-impregnation) present in the catalyst is between 5 and 55% by weight, preferably between 10 and 50% by weight, and more preferably between 25 and 45% by weight expressed as group VIB metal oxide relative to the total weight of the catalyst.

The total content of Group VIII metal, when present, (introduced by the metal salt or by impregnation using an impregnation solution comprising a Group VIII metal in post-impregnation) present in the catalyst is between 1 and 23% by weight, preferably between 2 and 18% by weight, and more preferably between 5 and 15% by weight, expressed as group VIII metal oxide relative to the total weight of the catalyst.

The molar ratio of group VIII metal to group VIB metal of the catalyst is generally between 0.1 and 0.8, preferably between 0.15 and 0.6.

Optionally, the catalyst may also have a total phosphorus content (introduced by phosphoric acid in step b) or by impregnation using an impregnation solution comprising phosphoric acid in post- impregnation) present in the catalyst generally between 0.1 and 20% by weight of P ₂ O ₅ relative to the total weight of catalyst, preferably between 0.2 and 15% by weight of P ₂ O ₅ , very preferably between 0.3 and 11% by weight of P ₂ O ₅ . For example, the phosphorus present in the catalyst is combined with the group VIB metal and possibly also with the group VIII metal in the form of heteropolyanions.

Furthermore, the phosphorus/(group VIB metal) molar ratio is generally between 0.08 and 1, preferably between 0.1 and 0.9, and very preferably between 0.15 and 0.8 .

The contents of group VIB metal, group VIII metal and phosphorus in the catalyst are expressed in oxides after correction of the loss on ignition of the catalyst sample at 550°C for two hours in a muffle furnace. Loss on ignition is due to moisture loss. It is determined according to ASTM D7348.

The total content of organic compound(s) containing oxygen and/or nitrogen and/or sulfur present in the catalyst after drying is generally between 1 and 30% by weight, preferably between 1.5 and 25% by weight, and more preferably between 2 and 20% by weight relative to the total weight of the catalyst.

The support comprises alumina. Preferably, it contains more than 50% by weight of alumina relative to the total weight of the support and, in general, it contains only alumina. Preferably, the alumina is gamma alumina. According to a particularly preferred variant, the support consists of gamma alumina.

In another preferred case, the support is a 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 relative to the total weight of the support, usually less than or equal to 45% by weight, preferably less than or equal to 40%. The silica can be introduced in the form of precursors during stage a) of mixing (mixing). According to another particularly preferred variant, the support consists of silica-alumina.

The support comprising alumina can also advantageously also contain from 0.1 to 80% by weight, preferably from 0.1 to 49% by weight of zeolite relative to the total weight of the support. In this case, all the sources of zeolite and all the methods of associated preparations known to those skilled in the art can be incorporated. Preferably, the zeolite is chosen from the group FAU, BEA, ISV, IWR, IWW, MEI, UWY and preferably, the zeolite is chosen from the group FAU and BEA, such as Y and/or beta zeolite, and particularly preferably such as USY and/or beta zeolite.

The pore volume of the catalyst is generally between 0.1 cm ³ /g and 1.5 cm ³ /g, preferably between 0.15 cm ³ /g and 1.1 cm ³ /g. The total porous volume is measured by mercury porosimetry according to the ASTM D4284 standard with a wetting angle of 140°, as described in the work Rouquerol F.; Rouquerol J.; Singh K. “Adsorption by Powders & Porous Solids: Principle, methodology and applications”, Academic Press, 1999, for example by means of an Autopore III™ model apparatus from the Micromeritics™ brand.

The catalyst is characterized by a specific surface comprised between 5 and 400 m²/g, preferably comprised between 10 and 350 m²/g, preferably comprised between 40 and 350 m²/g, very preferably comprised between 50 and 300 m²/g. g. The specific surface is determined in the present invention by the B.E.T method according to standard ASTM D3663, method described in the same work cited above.

The catalyst is advantageously in the form of beads, extrudates, pellets or irregular and non-spherical agglomerates, the specific shape of which may result from a crushing step. Preferably, it is in the form of extrudates, particularly preferably in the form of trilobe or quadrilobe extrudates.

Hydrotreating and/or hydrocracking process

Finally, another subject of the invention is the use of the catalyst prepared by the preparation process according to the invention in processes for the hydrotreating and/or hydrocracking of hydrocarbon cuts.

The process for hydrotreating and/or hydrocracking hydrocarbon cuts can be carried out in one or more reactors in series of the fixed bed type or of the bubbling bed type.

The process for hydrotreating and/or hydrocracking hydrocarbon cuts is carried out in the presence of the catalyst prepared by the preparation process according to the invention. It can also be carried out in the presence of a mixture of the catalyst prepared by the preparation process according to the invention and of a catalyst prepared by conventional impregnation, using an impregnation solution, and this whether a fresh, regenerated or rejuvenated catalyst.

When the catalyst prepared by impregnation using an impregnating solution is present, it comprises at least one group VIIl metal, at least one group VIB metal and an oxide support, and optionally phosphorus and / or an organic compound as described above.

The active phase and the support of the catalyst prepared by impregnation using an impregnation solution may or may not be identical to the active phase and the support of the catalyst prepared by the preparation process according to the invention.

When the process for hydrotreating and/or hydrocracking hydrocarbon cuts is carried out in the presence of a catalyst prepared by the preparation process according to the invention and of a catalyst prepared by conventional impregnation, it can be carried out in a reactor of the fixed bed type containing several catalytic beds.

In this case, and according to a first variant, a catalytic bed containing the catalyst prepared by the preparation process according to the invention can precede a catalytic bed containing the catalyst prepared by conventional impregnation in the direction of the flow of the charge.

In this case, and according to a second variant, a catalytic bed containing the catalyst prepared by conventional impregnation can precede a catalytic bed containing the catalyst prepared by the preparation process according to the invention in the direction of the flow of the charge.

In this case, and according to a third variant, a catalytic bed may contain a mixture of a catalyst prepared by the preparation process according to the invention and of a catalyst by conventional impregnation.

In these cases, the operating conditions are those described below. They are generally identical in the different catalytic beds with the exception of the temperature which generally increases in a catalytic bed following the exothermicity of the hydrodesulphurization reactions.

When the process for hydrotreating and/or hydrocracking hydrocarbon cuts is carried out in the presence of a catalyst prepared by the preparation process according to the invention and of a catalyst prepared by conventional impregnation in several reactors in series of the bed type fixed or of the bubbling bed type, a reactor can comprise a catalyst prepared by the preparation process according to the invention while another reactor can comprise a catalyst prepared by conventional impregnation, or a mixture of a catalyst prepared by the process of preparation according to the invention and a catalyst prepared by conventional impregnation, and this in any order. Provision may be made for a device for removing the H ₂ S from the effluent from the first hydrodesulphurization reactor before treating said effluent in the second hydrodesulphurization reactor. In these cases, the operating conditions are those described above and may or may not be identical in the different reactors.

The catalyst prepared according to the preparation process according to the invention and having preferably previously undergone a sulfurization stage is advantageously used for the hydrotreating and/or hydrocracking reactions of hydrocarbon feedstocks such as petroleum cuts, cuts from coal or hydrocarbons produced from natural gas, optionally in mixtures or even from a hydrocarbon fraction derived from biomass and more particularly for hydrogenation, hydrodenitrogenation, hydrodearomatization, hydrodesulphurization, hydrodeoxygenation, hydrodemetallization or hydroconversion of hydrocarbon feedstocks.

In these uses, the catalyst having preferably undergone a sulfurization step beforehand has an activity at least as good as the catalysts of the prior art. This catalyst can also advantageously be used during the pretreatment of catalytic cracking or hydrocracking feeds, or the hydrodesulfurization of residues or the extensive hydrodesulfurization of gas oils (ULSD Ultra Low Sulfur Diesel according to the Anglo-Saxon terminology).

The feedstocks used in the hydrotreating process are, for example, gasolines, gas oils, vacuum gas oils, atmospheric residues, vacuum residues, atmospheric distillates, vacuum distillates, heavy fuel oils, oils, waxes and paraffins, waste oils, residues or deasphalted crudes, fillers from thermal or catalytic conversion processes, lignocellulosic fillers or more generally fillers from biomass such as vegetable oils, taken alone or in a mixture. The fillers which are treated, and in particular those cited above, generally contain heteroatoms such as sulphur, oxygen and nitrogen and, for heavy fillers, they most often also contain metals.

The operating conditions used in the processes implementing the hydrocarbon feedstock hydrotreating reactions described above are generally as follows: the temperature is advantageously between 180 and 450° C., and preferably between 250 and 440° C., the pressure is advantageously between 0.5 and 30 MPa, and preferably between 1 and 18 MPa, the hourly volume velocity is advantageously between 0.1 and 20 h ^-1 and preferably between 0.2 and 5 h ^-1 , and the hydrogen/feed ratio expressed as volume of hydrogen, measured under normal temperature and pressure conditions, per volume of liquid feed is advantageously between 50 l/l to 5000 l/l and preferably 80 to 2000 l/l.

According to a first mode of use, said hydrotreating process is a hydrotreating process, and in particular hydrodesulfurization (HDS) of a gas oil cut carried out in the presence of at least one catalyst prepared according to the invention. Said hydrotreatment process aims to eliminate the sulfur compounds present in said gas oil cut so as to achieve the environmental standards in force, namely an authorized sulfur content of up to 10 ppm. It also makes it possible to reduce the aromatic and nitrogen contents of the gas oil cut to be hydrotreated.

Said gas oil cut to be hydrotreated contains from 0.02 to 5.0% by weight of sulphur. It is advantageously derived from direct distillation (or straight run gas oil according to Anglo-Saxon terminology), from a coking unit (coking according to Anglo-Saxon terminology), from a visbreaking unit (visbreaking according to Anglo-Saxon terminology). Saxon), a steam cracking unit (steam cracking according to the Anglo-Saxon terminology), a hydrotreating and/or hydrocracking unit for heavier loads and/or a catalytic cracking unit (Fluid Catalytic Cracking according to Anglo-Saxon terminology). Said diesel fraction preferably has at least 90% of the compounds whose boiling point is between 250° C. and 400° C. at atmospheric pressure.

The process for hydrotreating said diesel fraction is implemented under the following operating conditions: a temperature of between 200 and 400° C., preferably between 300 and 380° C., a total pressure of between 2 MPa and 10 MPa and more preferably between 3 MPa and 8 MPa with a ratio of volume of hydrogen per volume of hydrocarbon charge, expressed in volume of hydrogen, measured under normal temperature and pressure conditions, per volume of liquid charge, of between 100 and 600 liters per liter and more preferentially between 200 and 400 liters per liter and an hourly volume velocity (VVH) comprised between 1 and 10 h ^-1 , preferentially between 2 and 8 h ^-1 . The VVH corresponds to the inverse of the contact time expressed in hours and is defined by the ratio of the volume flow rate of liquid hydrocarbon feedstock to the volume of catalyst loaded into the reaction unit implementing the hydrotreatment process according to the invention. . The reaction unit implementing the process for hydrotreating said gas oil fraction is preferably operated in a fixed bed, in a moving bed or in an ebullated bed, preferably in a fixed bed.

According to a second mode of use, said hydrotreating and/or hydrocracking process is a hydrotreating process (in particular hydrodesulphurization, hydrodenitrogenation, hydrogenation of aromatics) and/or hydrocracking of a vacuum distillate cut produced in the presence of at least one catalyst prepared according to the preparation process according to the invention. Said hydrotreating and/or hydrocracking process, otherwise called hydrocracking or hydrocracking pretreatment process, aims, depending on the case, at eliminating the sulfur, nitrogen or aromatic compounds present in said distillate cut so as to carry out a pretreatment before conversion in catalytic cracking or hydroconversion processes, or in hydrocracking the distillate cut which may have been pretreated beforehand if necessary.

A wide variety of feedstocks can be processed by the vacuum distillate hydrotreating and/or hydrocracking processes described above. Generally they contain at least 20% volume and often at least 80% volume of compounds boiling above 340° C. at atmospheric pressure. The feedstock can be, for example, vacuum distillates as well as feedstocks from aromatics extraction units from lubricating oil bases or from solvent dewaxing of lubricating oil bases, and/or deasphalted oils. , or else the filler can be a deasphalted oil or paraffins resulting from the Fischer-Tropsch process or even any mixture of the aforementioned fillers. In general, the fillers have a boiling point T5 greater than 340°C at atmospheric pressure, and better still greater than 370°C at atmospheric pressure, that is to say that 95% of the compounds present in the filler have a point boiling point higher than 340°C, and better still higher than 370°C. The nitrogen content of the feeds treated in the processes according to the invention is usually greater than 200 ppm by weight, preferably between 500 and 10,000 ppm by weight. The sulfur content of the feeds treated in the processes according to the invention is usually between 0.01 and 5.0% by weight. The filler may optionally contain metals (for example nickel and vanadium). The asphaltene content is generally less than 3000 ppm by weight.

The catalyst prepared according to the preparation process according to the invention is generally brought into contact, in the presence of hydrogen, with the fillers described above, at a temperature above 200° C., often between 250° C. and 480° C., advantageously between 320°C and 450°C, preferably between 330°C and 435°C, under a pressure greater than 1 MPa, often between 2 and 25 MPa, preferably between 3 and 20 MPa, the volumetric speed being between 0.1 and 20.0 h ^-1 and preferably 0.1-6.0 h ^-1 , preferably 0.2-3.0 h ^-1 , and the quantity of hydrogen introduced is such that the ratio volume liter of hydrogen/liter of hydrocarbon, expressed in volume of hydrogen, measured under normal conditions of temperature and pressure, per volume of liquid charge, i.e. between 80 and 5,000 l/l and most often between 100 and 2000 l/l. These operating conditions used in the processes according to the invention generally make it possible to achieve conversions per pass, into products having boiling points below 340° C. at atmospheric pressure, and better still below 370° C. at atmospheric pressure, above to 15% and even more preferably between 20 and 95%.

The vacuum distillate hydrotreating and/or hydrocracking processes using the catalysts prepared according to the preparation process according to the invention cover the pressure and conversion ranges ranging from mild hydrocracking to high pressure hydrocracking. . By mild hydrocracking is meant hydrocracking leading to moderate conversions, generally less than 40%, and operating at low pressure, generally between 2 MPa and 6 MPa.

The catalyst prepared according to the preparation process according to the invention can be used alone, in a single or several fixed-bed catalytic beds, in one or more reactors, in a so-called one-step hydrocracking scheme, with or without liquid recycling. of the unconverted fraction, or alternatively in a so-called two-stage hydrocracking scheme, optionally in combination with a hydrorefining catalyst located upstream of the catalyst prepared according to the preparation process according to the invention.

According to a third mode of use, said hydrotreating and/or hydrocracking process is advantageously implemented as pretreatment in a fluidized bed catalytic cracking process (or FCC process for Fluid Catalytic Cracking according to the English terminology) . The pretreatment operating conditions in terms of temperature range, pressure, hydrogen recycling rate, hourly volume rate are generally identical to those described above for the hydrotreatment and/or hydrocracking processes of vacuum distillates. The FCC process can be carried out in a conventional manner known to those skilled in the art under the appropriate cracking conditions in order to produce lower molecular weight hydrocarbon products. For example, a summary description of catalytic cracking can be found in ULLMANS ENCYCLOPEDIA OF INDUSTRIAL CHEMISTRY VOLUME A 18, 1991, pages 61 to 64.

According to a fourth mode of use, said hydrotreating and/or hydrocracking process according to the invention is a process for hydrotreating (in particular hydrodesulfurization) a gasoline cut in the presence of at least one catalyst prepared according to the preparation process according to the invention.

Unlike other hydrotreating processes, the hydrotreating (in particular hydrodesulfurization) of gasolines must make it possible to respond to a double antagonistic constraint: ensuring deep hydrodesulfurization of gasolines and limiting the hydrogenation of the unsaturated compounds present in order to limit the loss of octane number.

The feed is generally a hydrocarbon cut having a distillation range of between 30 and 260°C. Preferably, this hydrocarbon cut is a cut of the gasoline type. Very preferably, the gasoline cut is an olefinic gasoline cut resulting for example from a catalytic cracking unit (Fluid Catalytic Cracking according to the Anglo-Saxon terminology).

The hydrotreating process consists in bringing the hydrocarbon cut into contact with the catalyst prepared according to the preparation process according to the invention and hydrogen under the following conditions: at a temperature between 200 and 400° C., from preferably between 230 and 330°C, at a total pressure between 1 and 3 MPa, preferably between 1.5 and 2.5 MPa, at an Hourly Volume Velocity (VVH), defined as being the reported load volume flow rate to the volume of catalyst, between 1 and 10 h^-1, preferably between 2 and 6 hours^-1and at a hydrogen/gasoline feedstock ratio of between 100 and 600 Nl/l, preferably between 200 and 400 Nl/l.

The process for the hydrotreatment of gasolines can be carried out in one or more reactors in series of the fixed bed type or of the bubbling bed type. If the method is implemented by means of at least two reactors in series, it is possible to provide a device for removing H ₂ S from the effluent from the first hydrodesulphurization reactor before treating said effluent in the second hydrodesulfurization reactor.

Examples

Example 1 : Preparation of the reference comixed catalyst C1

25.7 g of boehmite powder (loss on ignition of this powder: 32%) are introduced into the tank of a Z-arm mixer. The rotation of the arms, at a speed of 15 revolutions per minute, is started while 26.1 g of a solution of phosphomolybdic acid (concentration of the solution: 122 g of Mo/kg) and 170 mg of nitric acid diluted in 2.1 mL of water are added over two minutes. The speed of rotation is then set at 25 revolutions per minute for 30 minutes.

The paste obtained is collected and extruded through a cylindrical die with a diameter of 2 mm. The rods obtained are dried in an oven at 80° C. for 4 hours then calcined in a muffle furnace at 540° C. for 4 hours. Catalyst C1 is thus obtained, which contains 22% by weight of MoO ₃ .

Example 2 : Preparation of the comixed catalyst C2 in accordance with the invention

27.81 g of boehmite powder (loss on ignition of this powder: 32%) are introduced into the tank of a Z-arm mixer. The rotation of the arms, at a speed of 15 revolutions per minute, is started while 189 mg of nitric acid diluted in 16.9 mL of water is added in two minutes. The rotation speed is then set at 25 revolutions per minute, which allows the dough to pass.

After 10 minutes of mixing, 7.19 g of hydrated phosphomolybdic acid H ₃ PMo ₁₂ O _{40.28H 2} O (PMA), whose melting point is 85° C., are added to the tank. The heating of the mixer tank is started with the set temperature of 85° C. and the mixing is continued for an additional 30 minutes.

The paste obtained is collected and extruded through a cylindrical die with a diameter of 2 mm. The rods obtained are dried in an oven at 80° C. for 4 hours then calcined in a muffle furnace at 540° C. for 4 hours. Catalyst C2 is thus obtained, which contains 22% by weight of MoO ₃ .

Example 3 : Preparation of the catalyst C3 in accordance with the invention

26.5 g of boehmite powder (loss on ignition of this powder: 32%) are introduced into the tank of a Z-arm mixer. The rotation of the arms, at a speed of 15 revolutions per minute, is started while 180 mg of nitric acid diluted in 16.1 mL of water is added in two minutes. The rotation speed is then set at 25 revolutions per minute, which allows the dough to pass.

After 10 minutes of mixing, 8.53 g of PMA are added to the tank. The heating of the mixer tank is started with the set temperature of 85° C. and the mixing is continued for an additional 30 minutes.

The paste obtained is collected and extruded through a cylindrical die with a diameter of 2 mm. The rods obtained are dried in an oven at 80° C. for 4 hours then calcined in a muffle furnace at 540° C. for 4 hours. Catalyst C3 is thus obtained, which contains 26% by weight of MoO ₃ .

Example 4 : Preparation of the C4 catalyst according to the invention

18.96 g of boehmite powder (loss on ignition of this powder: 32%) are introduced into the tank of a Z-arm mixer. The rotation of the arms, at a speed of 15 revolutions per minute, is started while 129 mg of nitric acid diluted in 12.4 mL of water is added in two minutes. The rotation speed is then set at 25 revolutions per minute, which allows the dough to pass.

After 10 minutes of mixing, 16.04 g of PMA are added to the tank. The heating of the mixer tank is started with the set temperature of 85° C. and the mixing is continued for an additional 30 minutes.

The paste obtained is collected and extruded through a cylindrical die with a diameter of 2 mm. The rods obtained are dried in an oven at 80° C. for 4 hours then calcined in a muffle furnace at 540° C. for 4 hours. Catalyst C4 is thus obtained, which contains 48% by weight of MoO ₃ .

Example 5 : Preparation of the C5 catalyst according to the invention

24.30 g of boehmite powder (loss on ignition of this powder: 32%) are introduced into the tank of a Z-arm mixer. The rotation of the arms, at a speed of 15 revolutions per minute, is started while 165 mg of nitric acid diluted in 15.5 mL of water is added in two minutes. The rotation speed is then set at 25 revolutions per minute, which allows the dough to pass.

After 10 minutes of mixing, 6.68 g of PMA and 4.02 g of cobalt nitrate hexahydrate are added to the tank. The heating of the mixer tank is started with the set temperature of 85° C. and the mixing is continued for an additional 30 minutes.

The paste obtained is collected and extruded through a cylindrical die with a diameter of 2 mm. The rods obtained are dried in an oven at 80° C. for 4 hours then calcined in a muffle furnace at 540° C. for 4 hours. Catalyst C5 is thus obtained, which contains 22% by weight of MoO ₃ and 4.6% by weight of CoO.

Example 6 : Evaluation of catalysts C1 to C6 in the hydrogenation of toluene

The catalysts were evaluated in the hydrogenation of toluene under sulpho-reducing conditions. The feed consists of dimethyldisulphide (5.9% by weight) and toluene (20% by weight) mixed in cyclohexane. The catalysts are pre-sulphured in situ with the test charge at an hourly volume rate (VVH) of 4 h ^-1 , a hydrogen to charge ratio of 450 L/L and a pressure of 6 MPa (60 bar). The temperature is increased from ambient conditions to 350° C. with a ramp of 2° C. min ^-1 . The catalytic test is then carried out under the following conditions: a temperature of 350°C, a pressure of 6 MPa (60 bar), an hourly volume velocity (VVH) of 2 h ^-1 , and a hydrogen to charge ratio of 450 L /I. The reaction products are analyzed online by gas chromatography. The hydrogenation activity of toluene (A Hydro) is expressed by considering an order 1 according to the following equation and relative to the activity of catalyst C1, 22% by weight MoO ₃ prepared by conventional co-mixing.

with X _Toluene , conversion of toluene by hydrogenation

The activity results are given in the following table. These results show that a catalyst prepared by melt co-kneading with the same molybdenum oxide content at 22 wt% is more active than the reference catalyst prepared by conventional co-kneading with an activity of 117.

Increasing the amount of molybdenum oxide by melt co-mixing to 26 wt% gives an activity of 143.

Increasing the amount of molybdenum oxide by melt comixing to 48 wt%, which would not be possible by conventional comixing, gives an activity of 235.

The catalyst prepared by co-mixing in fusion with cobalt and molybdenum gives an activity of 538.

Catalyst Mixing %MoO ₃
weight %CoO
weight A-Hydro C1 Reference classic 22 0 100 C2 Invention merger 22 0 117 C3 Invention merger 26 0 143 C4 Invention merger 48 0 235 C5 Invention merger 22 4.6 538

Claims (15)

Process for the preparation of a hydrotreating and/or hydrocracking catalyst comprising at least one group VIB metal and a support comprising alumina, the group VIB metal content being between 5 and 55% by weight expressed as group VIB metal oxide based on total catalyst weight, said process comprising the following steps:
a) an alumina precursor is mixed with an aqueous solution, optionally containing an inorganic acid, in order to obtain a paste,
b) said paste obtained in step a) is brought into contact with at least one hydrated metallic acid comprising at least one metal from group VIB whose melting point of said hydrated metallic acid is between 20 and 100° C., to form a paste containing the hydrated metallic acid, the mass ratio between said metallic acid and said alumina precursor being between 0.05 and 2.2,
c) the paste containing the hydrated metallic acid obtained at the end of step b) is heated with stirring to a temperature between the melting point of said metallic acid and 100° C.,
c′) optionally bringing said paste obtained in step c) into contact with an aqueous solution containing a base,
d) the paste obtained in step c) or in step c′ is shaped,
e) the shaped paste is dried at a temperature below 200° C. to obtain a dried catalyst,
f) the dried catalyst is calcined at a temperature between 200 and 1000°C. Process according to the preceding claim, in which in step b) the hydrated metallic acid is chosen from hydrated phosphomolybdic acid, hydrated silicomolybdic acid, hydrated molybdosilicic acid, hydrated phosphotungstic acid and silicotungstic acid hydrate. Process according to one of the preceding claims, in which in step a) the alumina precursor is boehmite. Method according to one of the preceding claims, in which in step a) a silicon precursor is also added to the mixture. Process according to one of the preceding claims, in which in step a) the inorganic acid is chosen from nitric acid, hydrochloric acid, sulfuric acid and phosphoric acid. Process according to one of the preceding claims, in which in step c′) the base is chosen from ammonia, a mono-alkylamine, a di-alkylamine, a tri-alkylamine, a tetra-alkylammonium hydroxide. Process according to one of the preceding claims, in which step b) further comprises bringing into contact with at least one metal salt comprising at least one group VIII metal whose melting point of said metal salt is between 20 and 100° C., the molar ratio (group VIII metal)/(group VIB metal) being between 0.1 and 0.8. Process according to the preceding claim, wherein said metal salt is a hydrated nitrate salt. Process according to the preceding claim, in which the said metal salt is chosen from nickel nitrate hexahydrate, and cobalt nitrate hexahydrate, taken alone or as a mixture. Process according to one of the preceding claims, in which step b) further comprises contacting with phosphoric acid, the phosphorus/(group VIB metal) molar ratio being between 0.08 and 1. Process according to one of the preceding claims, in which step b) further comprises bringing into contact with an organic compound comprising oxygen and/or nitrogen and/or sulfur whose melting point of said organic compound is between 20 and 100°C, the organic compound/group VIB metal molar ratio being between 0.01 and 5. Process according to the preceding claim, in which the organic compound is chosen from maleic acid, sorbitol, xylitol, γ-ketovaleric acid, 5-hydroxymethylfurfural and 1,3-dimethyl-2-imidazolidinone. Process according to one of the preceding claims, in which, after step f), an impregnation step g) is carried out using an impregnation solution and in which the said catalyst is brought into contact with a solution of impregnation comprising a group VIB metal and/or a group VIII metal and/or phosphorus and/or an organic compound comprising oxygen and/or nitrogen and/or sulfur, followed by a step drying h) at a temperature below 200° C. and optionally a calcining step i) at a temperature between 200° C. and 600° C. under an inert atmosphere or under an atmosphere containing oxygen. Process according to the preceding claim, in which the organic compound is chosen from γ-valerolactone, 2-acetylbutyrolactone, triethylene glycol, diethylene glycol, ethylene glycol, ethylenediaminetetra-acetic acid, maleic acid, malonic acid , citric acid, gluconic acid, dimethyl succinate, glucose, fructose, sucrose, sorbitol, xylitol, γ-ketovaleric acid, dimethylformamide, 1-methyl-2-pyrrolidinone, propylene carbonate, 2-methoxyethyl 3-oxobutanoate, bicine, tricine, 2-furaldehyde, 5-hydroxymethylfurfural, 2-acetylfuran, 5-methyl-2-furaldehyde, ascorbic acid, butyl 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-(2-hydroxyethyl)-2-pyrrolidinone, 1-(2-hydroxyethyl)-2,5-pyrrolidinedione, 5-methyl-2(3H )-furanone, 1-methyl-2-piperidinone and 4-aminobutanoic acid. Process according to one of the preceding claims, in which the catalyst is subjected to a sulfurization step after step f) or after any steps h) or i).