WO2022002674A1

WO2022002674A1 - Method for preparing a catalyst obtained from molten salts and a nickel-copper alloy for the hydrogenation of aromatic compounds

Info

Publication number: WO2022002674A1
Application number: PCT/EP2021/066879
Authority: WO
Inventors: Malika Boualleg; Laetitia Jothie
Original assignee: IFP Energies Nouvelles
Priority date: 2020-07-03
Filing date: 2021-06-21
Publication date: 2022-01-06
Also published as: FR3112087B1; FR3112087A1

Abstract

Disclosed is a method for preparing a catalyst for hydrogenating aromatic or polyaromatic compounds, the method including the following steps: – bringing the carrier into contact with an organic additive containing oxygen and/or nitrogen; – bringing the carrier into contact with a nickel metal salt, at a temperature below the melting point of said nickel metal salt, to form a solid mixture; – heating while stirring the solid mixture at a temperature between the melting point of said metal salt and 200°C; – bringing the carrier into contact with a solution containing at least one copper precursor and a nickel precursor at a desired copper concentration to obtain on the final catalyst a content of between 0.5 and 15 wt. % of copper element relative to the total weight of the final catalyst.

Description

PROCESS FOR PREPARING A CATALYST FOR HYDROGENATION OF AROMATIC COMPOUNDS OBTAINED FROM MOLTEN SALTS AND AN ALLOY

NICKEL COPPER

Technical area

The present invention relates to a process for preparing a supported metal catalyst based on nickel intended particularly for the hydrogenation of unsaturated hydrocarbons, and more particularly, for the hydrogenation of aromatic compounds.

State of the art

Many synthesis methods are known from the prior art to improve the reducibility of the metal phase or to control the particle sizes. Among these methods, the use of molten salts as precursors of the active phase of a catalyst or of a capture mass is known from the literature.

For example, document US Pat. No. 5,036,032 discloses a method for preparing a supported cobalt-based catalyst by contacting (of the order of a few tens of seconds) a support in a bath of molten salt of cobalt nitrate, followed by a drying and reduction step without intermediate calcination. This method allows the preferential localization of the cobalt phase on the periphery of the support. However, the method does not allow precise control of the amount of active phase (here cobalt) deposited due to the very short contact time and on the other hand the type of catalyst obtained is not suitable for use. in a reactor operating in the liquid phase with a catalyst in suspension (called a "slurry reactor" or "slurry" according to English terminology) because of the loss of metal by excessive attrition. On the other hand, the absence of a calcination step is risky since the reaction between the reducing element and the nitrates in the solid is very exothermic. Finally, this method requires handling large amounts of cobalt nitrate (toxic) in liquid form and at temperature, with ratios of around 4 grams of active phase precursors per 1 gram of support. The catalysts obtained by this preparation route are used for the synthesis of Fischer-Tropsch hydrocarbons.

He is known to Chem. Mater., 1999, 11, p.1999-2007 to prepare mixed phosphates by a molten salt type route. The reaction mixture contains a metal precursor salt (in particular Ni (NC> ₃ ) ₂ or Co (No ₃ ) ₂ ), a source of phosphorus (NH ₄ HPO ₄ ), and an alkali metal nitrate (Na or K). These preparations are carried out at elevated temperatures of the order of 400 to 450 ° C. Mixed phosphate solids are obtained, for example Na3NII (P207) P04, K2NL (P04) 2P2C> 7 or NagCo3 (PC> 4) 5. These solids can find applications in ion exchange, ionic conduction at high temperature or in catalysis. Document GB 191308864 discloses a method for synthesizing a mass catalyst based on nickel or cobalt for the production of hydrogen by steam reforming (“steam-reforming” according to the English terminology). These catalysts can be obtained by liquefying metal salts at moderate temperature and then poured into a mold before thermal calcination treatment.

The publication of J. -Y. Tilquin entitled “Intercalation of CoCI _å into graphite: Mixing method vs molten sais method” published in Carbon, 35 (2), p. 299-306, 1997, proposes the use in molten salt form of a CoC -NaCl mixture at high temperature (450-580 ° C) for the intercalation between graphite sheets. These graphite intercalation compounds find applications in catalysis for the reduction of oxygen in fuel cells with polymer electrolyte.

Document EP 2921227 discloses a Fischer-Tropsch catalyst based on a metal from group VIIIB deposited on an oxide support comprising alumina, silica, spinel and phosphorus, as well as its manufacturing process. This process comprises the preparation of the oxide support as well as the impregnation of this support with an aqueous solution of a metal precursor followed by drying and calcination. In the case of high metal contents, the impregnation / drying / calcination of the active phase in several stages is preferred.

Objects of the invention

The present invention thus relates to a new process for preparing a catalyst for the hydrogenation of aromatic compounds comprising performance at least as good, or even better than the catalysts according to the prior art, while using an amount of active phase based on nickel at least equal to, or even less than that typically used in the state of the art.

The present invention therefore relates according to a first aspect to a process for preparing a catalyst for the hydrogenation of aromatic and / or polyaromatic compounds comprising an active phase of nickel, a nickel-copper alloy, and an alumina support, said catalyst comprising a nickel content in the active phase being between 20 and 60% by weight of element nickel relative to the total weight of the catalyst, and a copper content being between 0.5 and 15% by weight of copper element relative to the total weight of the catalyst, the size of the nickel particles in the catalyst, measured in oxide form, being less than 18 nm, which process comprising at least the following steps: a) the sequence of the following sub-steps is carried out: a1) the alumina support or the catalyst precursor obtained at the end of step b) is brought into contact with at least one organic additive comprising oxygen and / or nitrogen, the molar ratio between the organic additive and the nickel being greater than 0.05 mol / mol; a2) the alumina support is brought into contact with at least one metal salt of nickel, at a temperature below the melting point of said metal salt of nickel, to form a solid mixture, the mass ratio between said metal salt and the alumina support being between 0.1 and 2.3, steps a1) and a2) being carried out either successively in this order, or simultaneously; a3) the solid mixture obtained at the end of steps a1) and a2) is heated with stirring to a temperature between the melting point of said metal salt and 200 ° C, to obtain a catalyst precursor; a4) optionally, the catalyst precursor is dried at the end of step a3) at a temperature below 250 ° C. to obtain a dried catalyst precursor; b) the following sub-steps are linked together: b1) either the porous support or the catalyst precursor obtained at the end of step a) is impregnated with at least one solution containing at least one precursor of copper and a nickel precursor at a predetermined copper concentration in order to obtain on the final catalyst a content of between 0.5 and 15% by weight of copper element relative to the total weight of the final catalyst; b2) the catalyst precursor obtained at the end of step b1) is dried at a temperature below 250 ° C .; said step b) being carried out, either before step a) or after step a), it being understood that when step b) is carried out before step a), then sub-step a4) is obligatory.

The process for preparing the catalyst according to the invention results in a catalyst having a nickel particle size of less than 18 nm, conferring significant intrinsic activity of the active nickel phase. Also, the process for preparing the catalyst implemented in the context of the present invention allows the introduction of the precursor of the active phase of nickel without adding solvent and therefore allows, in a very limited and above all lower number of steps the conventional preparation process (ie by impregnation standard of the precursor of the active phase on the support), obtaining a catalyst whose catalytic performance is at least as good or even superior to conventional catalysts. In addition, the presence on the catalyst of a NiCu alloy allows said catalyst to be reduced in situ in the reactor before hydrogenation and this at very low temperatures compared to the conventional reduction temperature which thus takes place ex situ and which therefore requires a step in addition to passivation.

In one embodiment according to the invention, said process comprises a step c) in which the catalyst precursor resulting from the sequence of steps a) + b), or b) + a) is reduced, by contacting said catalyst precursor with a reducing gas at a temperature greater than or equal to 150 ° C and less than 250 ° C.

Advantageously, the copper precursor is chosen from copper acetate, copper acetylacetonate, copper nitrate, copper sulfate, copper chloride, copper bromide, copper iodide and fluoride. copper.

In one embodiment according to the invention, said method further comprises a step c5) in which the catalyst obtained at the end of step c4) is calcined at a temperature between 250 ° C and 600 ° C.

Advantageously, the melting point of said metal salt is between 20 ° C and 150 ° C.

Advantageously, the molar ratio between said organic additive introduced in step a1) and the element nickel introduced in step a2) is between 0.1 and 5.0 mol / mol.

Advantageously, steps a1) and a2) are carried out simultaneously.

Advantageously, the organic additive of step a1) is chosen from aldehydes containing 1 to 14 carbon atoms per molecule, ketones or polyketones containing 3 to 18 carbon atoms per molecule, ethers and esters containing 2 to 14 carbon atoms per molecule, alcohols or polyalcohols containing 1 to 14 carbon atoms per molecule and carboxylic acids or polycarboxylic acids containing 1 to 14 carbon atoms per molecule, or a combination of the various compounds referred to above.

Advantageously, said organic additive of step a1) is chosen from formic acid, formaldehyde, acetic acid, citric acid, oxalic acid, glycolic acid, malonic acid, acid levulinic acid, ethanol, methanol, ethyl formate, methyl formate, paraldehyde, acetaldehyde, gamma-valerolactone acid, glucose and sorbitol. Advantageously, the organic additive is chosen from citric acid, formic acid, glycolic acid, levulinic acid and oxalic acid.

Preferably, the organic additive is citric acid.

Advantageously, step a3) is carried out by means of a drum operating at a speed of between 4 and 70 revolutions per minute.

Advantageously, in step a2), the mass ratio between said metal salt and the alumina support is between 0.2 and 2.

Advantageously, the nickel precursor content supplied in step b1) is at a predetermined concentration in order to obtain on the catalyst a nickel content of between 0.5 and 15% by weight of the nickel element in the copper-nickel alloy. relative to the total weight of the catalyst.

Another object according to the invention relates to a process for the hydrogenation of at least one aromatic or polyaromatic compound contained in a hydrocarbon feedstock having a final boiling point less than or equal to 650 ° C, said process being carried out in phase gas or in liquid phase, at a temperature between 30 and 350 ° C, at a pressure between 0.1 and 20 MPa, at a hydrogen / (aromatic compounds to be hydrogenated) molar ratio between 0.1 and 10 and at a hourly volume speed VVH of between 0.05 and 50 h ¹ , in the presence of a catalyst prepared according to the process according to the first aspect.

Detailed description of the invention

1. Definitions

In the following, the groups of chemical elements are given according to the CAS classification (CRC Handbook of Chemistry and Physics, editor CRC press, editor-in-chief D.R. Lide, 81st edition, 2000-2001). For example, group VIII according to the CAS classification corresponds to the metals of columns 8, 9 and 10 according to the new IUPAC classification.

In the present description, according to the IUPAC convention, micropores are understood to mean pores whose diameter is less than 2 nm, ie 0.002 μm; by mesopores the pores whose diameter is greater than or equal to 2 nm, i.e. 0.002 μm and less than or equal to 50 nm, i.e. 0.05 μm and by macropores the pores whose diameter is greater than 50 nm, i.e. 0.05 µm. The total pore volume is measured by mercury porosimetry according to standard ASTM D4284-92 with a wetting angle of 140 °, for example by means of an Autopore III ™ model device from the Microméritics ™ brand.

The BET specific surface is measured by physisorption with nitrogen according to standard ASTM D3663-03, method described in the work Rouquerol F .; Rouquerol J .; Singh K. “Adsorption by Powders & Porous Solids: Principle, methodology and applications”, Academie Press, 1999.

The mesoporous median diameter is also defined as being the diameter such that all the pores, among all the pores constituting the mesoporous volume, of size less than this diameter constitute 50% of the total mesoporous volume determined by intrusion with a mercury porosimeter.

The term “size of the nickel particles” is understood to mean the diameter of the nickel crystallites included in the active phase of the catalyst in oxide form. The diameter of the crystallites of nickel in oxide form is determined by X-ray diffraction, from the width of the diffraction line located at the angle 2theta = 43 ° (that is to say according to the crystallographic direction [200 ]) using the Scherrer relation. This method, used in X-ray diffraction on powders or polycrystalline samples which relates the width at mid-height of the diffraction peaks to the size of the particles, is described in detail in the reference: Appl. Cryst. (1978), 11, 102-113 “Scherrer after sixty years: A survey and some new results in the determination of crystallite size”, J. I. Langford and A. J. C. Wilson.

The nickel and copper content is measured by X-ray fluorescence.

2. Process for preparing the catalyst The stages of said preparation process are described in detail below.

Step a) consists of the following substeps.

According to step a1) of the process for preparing the catalyst, the porous support or the catalyst precursor obtained at the end of step b) is brought into contact with at least one organic additive comprising oxygen and / or nitrogen, preferably chosen from aldehydes containing from 1 to 14 carbon atoms per molecule (preferably from 2 to 12), ketones or polyketones containing from 3 to 18 (preferably from 3 to 12) atoms of carbon per molecule, ethers or esters containing from 2 to 14 (preferably from 3 to 12) carbon atoms per molecule, alcohols or polyalcohols containing from 1 to 14 (preferably from 2 to 12) carbon atoms per molecule and carboxylic acids or polycarboxylic acids containing from 1 to 14 (preferably from 1 to 12) carbon atoms per molecule. The organic additive can be composed of a combination of the different compound groups mentioned above.

Preferably, the organic additive is chosen from formic acid HCOOH, formaldehyde CH ₂ 0, acetic acid CH ₃ COOH, citric acid, oxalic acid, glycolic acid (HOOC-CH2-OH ), malonic acid (HOOC-CH ₂ -COOH), levulinic acid (CH ₃ CCH2CH2CO2H), ethanol, methanol, ethyl formate HCOOC2H5, methyl formate HCOOCH ₃ , paraldehyde (CH ₃ -CHO) ₃ , acetaldehyde C2H4O, gamma-valerolactone acid (C5H8O2), glucose and sorbitol.

Particularly preferably, the organic additive is selected from citric acid, formic acid, glycolic acid, levulinic acid and oxalic acid.

In one embodiment according to the invention, said step a1) is carried out by bringing the support into contact with at least one organic additive in the form of a powder.

In another embodiment according to the invention, said step a1) is carried out by bringing the support into contact with at least one organic additive in the form of a powder dissolved in a minimum amount of water. The term “minimum quantity of water” is understood to mean the quantity of water allowing at least partial dissolution of said organic additive in water. This minimum quantity of water cannot be assimilated to a solvent. In this case, and, when the step of introducing the additive is carried out separately from the introduction of the precursor of the active phase of the catalyst (ie steps a1) and a2) are carried out separately) the step of placing in contact with the support with the organic additive is advantageously followed by drying at a temperature below 250 ° C, preferably between 15 and 240 ° C, more preferably between 30 and 220 ° C.

The contacting according to step a1) is generally carried out at a temperature between 0 and 70 ° C, preferably between 10 and 60 ° C, and particularly preferably at room temperature.

According to step a1), the bringing into contact of said porous support or of the catalyst precursor obtained at the end of step b) with the organic additive can be carried out by any method known to those skilled in the art. Preferably, convective mixers, drum mixers or static mixers can be used. Step a1) is carried out advantageously for a period of between 5 minutes to 5 hours depending on the type of mixer used, preferably between 10 minutes and 4 hours.

According to the invention, the molar ratio between the organic additive and the nickel is greater than 0.05 mol / mol, preferably between 0.1 and 5 mol / mol, more preferably between 0.12 and 3 mol / mol, and even more preferably between 0.15 and 2.5 mol / mol.

Step a2)

According to step a2), the alumina support, optionally obtained at the end of step a1), is brought into contact with at least one metal salt of nickel, at a temperature below the melting temperature of the salt. metallic, optionally for a period of between 5 minutes to 5 hours, to form a solid mixture, the mass ratio between said metallic salt and the alumina support being between 0.1 and 2.3, preferably between 0.2 and 2.

Preferably, the melting point of said metal salt is between 20 ° C and 150 ° C. Preferably, the metal salt is hydrated. Preferably, the metal salt is nickel nitrate hexahydrate (Ni (NC> 3) 2, 6H ₂ O, T _fusion = 56.7 ° C).

According to step a2), the contacting of said porous alumina support and the nickel metal salt can be done by any method known to those skilled in the art. Preferably, convective mixers, drum mixers or static mixers can be used. Step a2) is advantageously carried out for a period of between 5 minutes to 5 hours depending on the type of mixer used, preferably between 10 minutes and 4 hours.

Implementation of steps a1) and a2)

According to the invention:

- steps a1) a2) are carried out successively in this order, or

- Steps a) and a2) are carried out simultaneously.

In a preferred embodiment, step a1) is performed before performing step a2).

Step a3)

According to step a3), the mixture obtained at the end of steps a1) and a2) is heated with stirring to a temperature between the melting point of the metal salt and 200 ° C., and optionally at atmospheric pressure. Preferably, the temperature is between 50 and 100 ° C. Advantageously, step a3) is carried out for a period of between 5 minutes and 12 hours, preferably between 5 minutes and 4 hours.

According to step a3), the mechanical homogenization of the mixture can be carried out by any method known to those skilled in the art. Preferably, convective mixers, drum mixers or static mixers can be used. Even more preferably, step a3) is carried out by means of a drum mixer, the speed of rotation of which is between 4 and 70 revolutions / minute, preferably between 10 and 60 revolutions / minute. Indeed, if the rotation of the drum is too high, the active phase of the catalyst may not be distributed as a crust on the periphery of the support, but can be distributed homogeneously throughout the support, which is less desirable.

In one embodiment according to the invention, the drying step a4) is advantageously carried out at a temperature below 250 ° C, preferably between 15 and 180 ° C, more preferably between 30 and 160 ° C, even more preferably between 50 and 150 ° C, and even more preferably between 70 and 140 ° C, optionally for a period of between 0.5 to 12 hours, and even more preferably for a period of 0.5 to 5 hours . Longer durations are not excluded, but do not necessarily bring improvement.

The drying step can be carried out by any technique known to those skilled in the art. It is advantageously carried out under an inert atmosphere or under an atmosphere containing oxygen or under a mixture of inert gas and oxygen. It is advantageously carried out at atmospheric pressure or at reduced pressure. Preferably, this step is carried out at atmospheric pressure and in the presence of air or nitrogen.

Calcination step a5) can be carried out after step a3) or after optional step a4) at a temperature between 250 ° C and 600 ° C, preferably between 350 ° C and 550 ° C, for a period of time. period typically between 0.5 to 24 hours, preferably for a period of 0.5 to 12 hours, and even more preferably for a period of 0.5 to 10 hours, preferably under an inert atmosphere or under an atmosphere containing oxygen. Longer durations are not excluded, but do not necessarily bring improvement. Step b) comprises the following sub-steps.

During step b1) of the process, either the porous support or the catalyst precursor obtained at the end of step a) is impregnated with at least one solution containing at least one copper precursor and one nickel precursor. at a predetermined copper concentration to obtain on the final catalyst a content of between 0.5 and 15% by weight of copper element relative to the total weight of the final catalyst.

The pH of said solution comprising at least one nickel precursor and one impregnated copper precursor can be modified by the optional addition of an acid or a base.

Preferably, said nickel precursor and the copper precursor are introduced in aqueous solution.

When the nickel precursor is introduced in aqueous solution, a nickel precursor is advantageously used in the form of nitrate, carbonate, acetate, chloride, hydroxide, hydroxycarbonate, oxalate, sulfate, formate. , of complexes formed by a polyacid or an acid-alcohol and its salts, of complexes formed with acetylacetonates, of tetrammine or hexammine complexes, or even of any other inorganic derivative soluble in aqueous solution, which is brought into contact with said precursor of catalyst. Preferably, nickel precursor, nickel nitrate, nickel hydroxide, nickel carbonate, nickel chloride or nickel hydroxycarbonate are advantageously used. Very preferably, the nickel precursor is nickel nitrate, nickel carbonate or nickel hydroxide.

When the copper precursor is introduced in aqueous solution, a copper precursor in mineral or organic form is advantageously used. In mineral form, the copper precursor can be chosen from copper acetate, copper acetylacetonate, copper nitrate, copper sulfate, copper chloride, copper bromide, copper iodide or copper fluoride. Very preferably, the copper precursor salt is copper nitrate.

Preferably, the nickel precursor is supplied to step b1) at a predetermined concentration in order to obtain a nickel content on the final catalyst (ie obtained at the end of steps a) + b) or b) + a)) included in the copper-nickel alloy between 0.5 and 15% by weight of nickel element relative to the total weight of the catalyst, preferably between 1 and 12% by weight, and more preferably between 1 and 10% by weight.

The quantities of the copper precursor (s) introduced into the solution according to step b1) are chosen such that the total copper content is between 0.5 and 15% by weight of copper element relative to the total weight of the catalyst final (ie obtained at the end of steps a) + b) or b) + a)), preferably between 0.5 and 12% by weight, preferably between 0.75 and 10% by weight, and again more preferably between 1 and 9% by weight.

Step b2)

A step b2) of drying the catalyst precursor obtained at the end of step b1) is carried out. Step b2) of drying is advantageously carried out at a temperature below 250 ° C, preferably between 15 and 180 ° C, more preferably between 30 and 160 ° C, even more preferably between 50 and 150 ° C, and even more preferably between 70 and 140 ° C, optionally for a period of between 0.5 hour to 12 hours, and even more preferably for a period of 0.5 hour to 5 hours. Longer durations are not excluded, but do not necessarily bring improvement.

Step b2 ’)

In one embodiment according to the invention, a step b2 ′) of calcination of the catalyst precursor obtained at the end of step b2) is carried out at a temperature between 250 ° C and 600 ° C. Calcination step b2 ′) can be carried out at a temperature between 250 ° C and 600 ° C, preferably between 350 ° C and 550 ° C, optionally for a period of between 0.5 to 24 hours, so preferred for a period of 0.5 to 12 hours, and even more preferably for a period of 0.5 to 10 hours, preferably under an inert atmosphere or under an oxygen-containing atmosphere. Longer durations are not excluded, but do not necessarily bring improvement. Implementation of steps a) and b)

The process for preparing the catalyst comprises several modes of implementation. They are distinguished in particular by the order of introduction of the solution comprising the precursor of the active phase of nickel and the solution based on nickel and copper to obtain the NiCu alloy.

Step b) can be carried out either before step a) or after step a) of the preparation process.

When performing step b) before step a), then substep a4) is mandatory. Preferably, steps a5) and / or b2 ′) are also carried out.

Step c) Reduction by reducing gas

Prior to the use of the catalyst in the catalytic reactor and the implementation of a hydrogenation process, a reducing treatment step c) is carried out in the presence of a reducing gas so as to obtain a catalyst comprising nickel in less partially in metallic form. This step is advantageously carried out in-situ, that is to say after loading the catalyst into a hydrogenation reactor. This treatment makes it possible to activate said catalyst and to form metal particles, in particular nickel in the zero valent state. Carrying out in situ the reducing treatment of the catalyst eliminates the need for an additional step of passivation of the catalyst with an oxygen-containing compound or with CO2, which is necessarily the case when the catalyst is prepared by carrying out a reducing treatment ex -situ, that is to say outside the reactor used for the hydrogenation of aromatic or polyaromatic compounds. In fact, when the reducing treatment is carried out ex-situ, it is necessary to carry out a passivation step in order to preserve the metallic phase of the catalyst in the presence of air (during the operations of transporting and loading the catalyst into the reactor d. 'hydrogenation), then to carry out a new step of reduction of the catalyst.

The reducing gas is preferably hydrogen. The hydrogen can be used pure or as a mixture (for example a mixture of hydrogen / nitrogen, hydrogen / argon, hydrogen / methane). In the case where the hydrogen is used as a mixture, all the proportions can be envisaged.

According to one or more embodiments of the preparation process according to the invention, said reducing treatment is carried out at a temperature greater than or equal to 150 ° C and less than 250 ° C, preferably between 160 and 230 ° C, and more preferably between 170 and 220 ° C. The duration of the reducing treatment is between 5 minutes and less than 5 hours, preferably between 10 minutes and 4 hours, and even more preferably between 10 minutes and 110 minutes.

The presence of the nickel-copper alloy at least partially in reduced form makes it possible to use operating conditions for reducing the active phase of nickel which are less severe than in the prior art and thus makes it possible to carry out the reduction step directly. within the reactor in which it is desired to carry out the hydrogenation of unsaturated or aromatic compounds.

Furthermore, the presence of copper in the catalyst makes it possible to maintain good catalyst activity and good catalyst life when the latter is brought into contact with a hydrocarbon feed comprising sulfur. In fact, compared to nickel, the copper present in the catalyst more easily captures the sulfur compounds included in the feed, which limits the irreversible poisoning of the active sites. The temperature rise to the desired reduction temperature is generally slow, for example set between 0.1 and 10 ° C / min, preferably between 0.3 and 7 ° C / min.

The hydrogen flow rate, expressed in L / hour / gram of catalyst precursor is between 0.01 and 100 L / hour / gram of catalyst, preferably between 0.05 and 10 L / hour / gram of catalyst precursor , even more preferably between 0.1 and 5 L / hour / gram of catalyst precursor.

The process according to the invention can advantageously comprise a step of passivation by a sulfur compound which makes it possible to improve the selectivity of the catalysts and to avoid thermal runaways during the start-up of new catalysts (“run-away” according to the English terminology). Saxon). Passivation generally consists in irreversibly poisoning with the sulfur compound the most virulent active sites of nickel which exist on the new catalyst and therefore in attenuating the activity of the catalyst in favor of its selectivity. The passivation step is carried out by implementing methods known to those skilled in the art.

The passivation step with a sulfur compound is generally carried out at a temperature between 20 and 350 ° C, preferably between 40 and 200 ° C, for 10 to 240 minutes. The sulfur compound is, for example, chosen from the following compounds: thiophene, thiophane, alkylmonosulfides such as dimethylsulfide, diethylsulfide, dipropylsulfide and propylmethylsulfide or else an organic disulfide of formula HO-R ₁ -S- SR ₂ -OH such as di-thio -di-ethanol of the formula HO-C ₂ H ₄ -SSC ₂ H ₄ -OH (often called DEODS). The sulfur content is generally between 0.1 and 2% by weight of said element relative to the total weight of the catalyst.

In one embodiment according to the invention, the preparation of the catalyst is carried out ex situ, that is to say before loading the catalyst into the reaction unit of the process for selective hydrogenation or hydrogenation of aromatics.

Catalyst

The nickel content included in the active phase of the catalyst obtained according to the preparation process according to the invention is between 20 and 60% by weight of nickel element relative to the total weight of the catalyst, more preferably between 20 and 50% by weight and again more preferably between 20 and 45% by weight relative to the total weight of the catalyst.

The copper content included in the alloy of the catalyst obtained according to the preparation process according to the invention is between 0.5 and 15% by weight of copper element relative to the total weight of the catalyst, preferably between 0.5 and 12% by weight, preferably between 0.75 and 10% by weight, and even more preferably between 1 and 9% by weight.

Part of the nickel and copper included in the catalyst is in the form of a nickel-copper alloy, advantageously corresponding to the formula Ni _x Cu _y with x ranging between 0.1 and 0.9 and including between 0 , 1 and 0.9. Preferably, the nickel content included in the copper-nickel alloy obtained by the preparation process according to the invention is between 0.5 and 15% by weight of nickel element relative to the total weight of the catalyst, preferably between 1 and 12% by weight, and more preferably between 1 and 10% by weight.

Preferably, the molar ratio between the nickel of the alloy and the copper is between 0.5 and 5, preferably between 0.7 and 4.5, more preferably between 0.9 and 4.

Advantageously, the catalyst does not comprise a metal from group VIB. In particular, it does not include molybdenum or tungsten.

The size of the nickel particles in the catalyst, measured in oxide form, is less than 18 nm, preferably less than 15 nm, more preferably between 0.5 and 12 nm, more preferably between 1 and 8 nm, from even more preferably between 1 and 6 nm, and even more preferably between 1 and 5 nm. Said catalyst is generally presented in all the forms known to those skilled in the art, for example in the form of balls (generally having a diameter of between 1 and 8 mm), extrudates, tablets, hollow cylinders. Preferably, it consists of extrudates with a diameter generally between 0.5 and 10 mm, preferably between 0.8 and 3.2 mm and very preferably between 1.0 and 2.5 mm and of average length. between 0.5 and 20 mm. The term “average diameter” of the extrudates is understood to mean the average diameter of the circle circumscribing the cross section of these extrudates. The catalyst can advantageously be presented in the form of cylindrical, multilobed, trilobal or quadrilobed extrudates. Preferably its shape will be trilobed or quadrilobed. The shape of the lobes can be adjusted according to all the methods known from the prior art.

The specific surface of the catalyst is generally greater than or equal to 30 m ² / g, preferably greater than or equal to 50 m ² / g, more preferably between 60 m ² / g and 500 m ² / g, and even more preferably between between 70 m ² / g and 400 m ² / g.

The total pore volume of the catalyst is generally between 0.1 and 1.5 cm ³ / g, preferably between 0.35 and 1.2 cm ³ / g, and even more preferably between 0.4 and 1, 0 cm ³ / g, and even more preferably between 0.45 and 0.9 cm ³ / g.

The catalyst advantageously has a macroporous volume less than or equal to 0.6 mL / g, preferably less than or equal to 0.5 mL / g, more preferably less than or equal to 0.4 ml / g, and even more preferably less than or equal to equal to 0.3 mL / g.

The mesoporous volume of the catalyst is generally at least 0.10 ml / g, preferably at least 0.20 ml / g, more preferably between 0.25 ml / g and 0.80 ml / g, more preferably between 0.30 and 0.65 mL / g.

The mesoporous median diameter of the catalyst is advantageously between 3 nm and 25 nm, and preferably between 6 and 20 nm, and particularly preferably between 8 and 18 nm.

The catalyst advantageously has a macroporous median diameter of between 50 and 1500 nm, preferably between 80 and 1000 nm, even more preferably between 250 and 800 nm. Preferably, the catalyst has a microporosity of less than 0.05 ml / g, very preferably it has no microporosity.

Support

According to the invention, the support is an alumina, that is to say that the support comprises at least 95%, preferably at least 98%, and particularly preferably at least 99% by weight of alumina relative to the weight of the support. Alumina generally has a crystallographic structure of the delta, gamma or theta alumina type, alone or as a mixture. According to the invention, the alumina support may comprise impurities such as oxides of metals from groups I IA, INB, IVB, II B, II IA, IVA according to the CAS classification, preferably silica, sodium dioxide. titanium, zirconium dioxide, zinc oxide, magnesium oxide and calcium oxide, or even alkali metals, preferably lithium, sodium or potassium, and / or alkaline earth metals, preferably magnesium, calcium, strontium or barium or else sulfur.

The specific surface of the support is generally greater than or equal to 30 m ² / g, preferably greater than or equal to 50 m ² / g, more preferably between 60 m ² / g and 500 m ² / g, and even more preferably between between 70 m ² / g and 400 m ² / g.

The total pore volume of the support is generally between 0.1 and 1.5 cm ³ / g, preferably between 0.35 and 1.2 cm ³ / g, and even more preferably between 0.4 and 1, 0 cm ³ / g, and even more preferably between 0.45 and 0.9 cm ³ / g.

The support advantageously has a macroporous volume less than or equal to 0.6 mL / g, preferably less than or equal to 0.5 mL / g, more preferably less than or equal to 0.4 mL / g, and even more preferably less than or equal to or equal to 0.3 mL / g.

The mesoporous volume of the support is generally at least 0.10 mL / g, preferably at least 0.20 mL / g, preferably between 0.25 mL / g and 0.80 mL / g, more preferably between 0.30 and 0.65 mL / g.

The mesoporous median diameter of the support is advantageously between 3 nm and 25 nm, and preferably between 6 and 20 nm, and particularly preferably between 8 and 18 nm. The support advantageously has a macroporous median diameter of between 50 and 1500 nm, preferably between 80 and 1000 nm, even more preferably between 250 and 800 nm.

Preferably, the catalyst has a microporosity of less than 0.05 ml / g, very preferably it has no microporosity.

Aromatics hydrogenation process

A subject of the present invention is also a process for the hydrogenation of at least one aromatic or polyaromatic compound contained in a hydrocarbon feedstock having a final boiling point less than or equal to 650 ° C, generally between 20 and 650 ° C. , and preferably between 20 and 450 ° C, in the presence of the catalyst obtained by the preparation process as described above in the description. Said hydrocarbon feedstock containing at least one aromatic or polyaromatic compound can be chosen from the following petroleum or petrochemical cuts: reformate from catalytic reforming, kerosene, light gas oil, heavy gas oil, cracked distillates, such as fluidized bed catalytic cracking recycling oil (FCC, “Fluid Catalytic Cracking”), coking unit gas oil, hydrocracking distillates. The content of aromatic or polyaromatic compounds contained in the hydrocarbon feedstock treated in the hydrogenation process according to the invention is generally between 0.1 and 80% by weight, preferably between 1 and 50% by weight, and particularly preferably between 2 and 35% by weight, the percentage being based on the total weight of the hydrocarbon feed. The aromatic compounds present in said hydrocarbon feed are, for example, benzene or alkylaromatics such as toluene, ethylbenzene, Go-xylene, m-xylene, or p-xylene, or else aromatics having several aromatic rings. (polyaromatics) such as naphthalene.

The sulfur or chlorine content of the feed is generally less than 5000 ppm by weight of sulfur or chlorine, preferably less than 100 ppm by weight, and particularly preferably less than 10 ppm by weight.

The technological implementation of the process for the hydrogenation of aromatic or polyaromatic compounds is for example carried out by injection, in an ascending or descending current, of the hydrocarbon feed and of the hydrogen into at least one fixed bed reactor. Said reactor may be of the isothermal type or of the adiabatic type. An adiabatic reactor is preferred. The hydrocarbon feed can advantageously be diluted by one or more re-injection (s) of the effluent, coming from said reactor where the aromatics hydrogenation reaction takes place, at various points of the reactor, located between the inlet and the outlet of the reactor in order to limit the gradient of temperature in the reactor. The technological implementation of the aromatics hydrogenation process according to the invention can also be advantageously carried out by implanting the catalyst in a reactive distillation column or in reactors - exchangers or in a reactor in which the catalyst is in suspension. ("Slurry" according to Anglo-Saxon terminology). The hydrogen stream can be introduced at the same time as the feed to be hydrogenated and / or at one or more different points of the reactor.

The hydrogenation of the aromatic or polyaromatic compounds can be carried out in the gas phase or in the liquid phase, preferably in the liquid phase. In general, the hydrogenation of aromatic or polyaromatic compounds is carried out at a temperature between 30 and 350 ° C, preferably between 50 and 325 ° C, at a pressure between 0.1 and 20 MPa, from preferably between 0.5 and 10 MPa, at a hydrogen / (aromatic compounds to be hydrogenated) molar ratio between 0.1 and 10 and at an hourly volume speed VVH of between 0.05 and 50 h ¹ , preferably between 0.1 and 10 h ^-1 of a hydrocarbon feed containing aromatic or polyaromatic compounds and having a final boiling point less than or equal to 650 ° C, generally between 20 and 650 ° C, and preferably between 20 and 450 ° vs.

The hydrogen flow rate is adjusted in order to have enough of it to theoretically hydrogenate all of the aromatic compounds and to maintain an excess of hydrogen at the reactor outlet.

The conversion of the aromatic or polyaromatic compounds is generally greater than 20 mol%, preferably greater than 40 mol%, more preferably greater than 80 mol%, and particularly preferably greater than 90 mol% of the aromatic compounds. or polyaromatics contained in the hydrocarbon feed. The conversion is calculated by dividing the difference between the total moles of the aromatic or polyaromatic compounds in the hydrocarbon feed and in the product by the total moles of the aromatic or polyaromatic compounds in the hydrocarbon feed.

According to a particular variant of the process according to the invention, a process is carried out for the hydrogenation of benzene from a hydrocarbon feedstock, such as the reformate obtained from a catalytic reforming unit. The benzene content in said hydrocarbon feedstock is generally between 0.1 and 40% by weight, preferably between 0.5 and 35% by weight, and particularly preferably between 2 and 30% by weight, the percentage by weight being based on the total weight of the oil charge. The sulfur or chlorine content of the feed is generally less than 10 ppm by weight of sulfur or chlorine respectively, and preferably less than 2 ppm by weight.

The hydrogenation of the benzene contained in the hydrocarbon feed can be carried out in the gas phase or in the liquid phase, preferably in the liquid phase. When it is carried out in the liquid phase, a solvent may be present, such as cyclohexane, heptane, octane. In general, the hydrogenation of benzene is carried out at a temperature between 30 and 250 ° C, preferably between 50 and 200 ° C, and more preferably between 80 and 180 ° C, at a pressure of between 0.1 and 10 MPa, preferably between 0.5 and 4 MPa, at a hydrogen / (benzene) molar ratio between 0.1 and 10 and at an hourly volume speed VVH of between 0.05 and 50 h ¹ , preferably between 0.5 and 10 h ¹ .

The conversion of benzene is generally greater than 50 mol%, preferably greater than 80 mol%, more preferably greater than 90 mol% and particularly preferably greater than 98 mol%.

The invention will now be illustrated via the examples below which are in no way limiting.

Examples

For all the catalysts mentioned in the examples mentioned below, the support is an AL-1 alumina having a specific surface area of 80 m ² / g, a pore volume of 0.7 mL / g.

Example 1: Preparation of an aqueous solution of the precursors of the NiCu alloy (5% Ni)

The aqueous solution of Ni precursors (used for the preparation of catalysts containing NiCu is prepared by dissolving 14.5 g of nickel nitrate (N1NO ₃ , supplier Strem Chemicals®) in a volume of 13 mL of distilled water. A solution is obtained with a Ni concentration of 116.6 g of Ni per liter of solution.The copper nitrate precursor is then added in order to have a Ni / Cu molar ratio of 1 (catalysts A to E). the solution S is obtained. It makes it possible to introduce the precursors of the NiCu alloy with a mass content of Ni relative to the final catalyst of about 5% by weight.

Example 2 (compliant, 25% by weight of molten salt nickel + citric acid (Ac) + NiCu in pre-impregnation, Ac / Ni ratio = 0.2)

The solution prepared in Example 1 is added to 10 grams (g) of AL-1 alumina. The Ni / Cu ratio is 1. The Ni content at the end of this step is 5% by weight relative to the total catalyst weight. The solid thus obtained is then dried in an oven overnight at 120 ° C., then calcined under an air flow of 1 L / h / g of catalyst at 450 ° C. for 2 hours. 10 g of the alumina impregnated with the NiCu are brought into contact with 3.98 g of citric acid dissolved in 5.4 g of water. The solid thus obtained is then dried in an oven for 2 hours at 60 ° C. then 12 hours at 120 ° C.

Then, the support is contacted with 19.95 g of hydrated hexa nickel nitrate in a drum at 25 ° C which rotates at a speed of 40 to 50 revolutions per minute. The drum is then heated to 62 ° C and rotates at a speed of 40 to 50 rpm for 15 minutes. The molar ratio of citric acid to nickel is 0.2.

The nickel content targeted in this second impregnation step is 25% by weight of Ni relative to the weight of the final catalyst. The solid thus obtained is then dried in an oven overnight at 120 ° C, then calcined under an air flow of 1 L / h / g of catalyst at 450 ° C for 2 hours.

Catalyst A is obtained containing 30% by weight of the element nickel relative to the total weight of the catalyst (25% by weight of Ni in the active phase and 5% by weight of Ni in the nickel-copper alloy). The characteristics of catalyst A thus obtained are reported in Table 1 below.

Example 3 (compliant, 25% by weight of Ni SF + citric acid (Ac) + NiCu in post impregnation, Ac / Ni ratio = 0.2)

10 g of AL-1 alumina are contacted with 3.98 g of citric acid dissolved in 5.4 g of water. The solid thus obtained is then dried in an oven for 2 hours at 60 ° C. then 12 hours at 120 ° C.

Then, the support is contacted with 18.95 g of hydrated nickel nitrate hexa in a drum at 25 ° C which rotates at a speed of 40 to 50 revolutions per minute. The drum is then heated to 62 ° C and rotates at a speed of 40 to 50 rpm for 15 minutes. The molar ratio by weight of citric acid to nickel is 0.2.

The nickel content targeted in this step is 25% by weight of Ni relative to the weight of the final catalyst. The solid thus obtained is then dried in an oven overnight at 120 ° C, then calcined under an air flow of 1 L / h / g of catalyst at 450 ° C for 2 hours.

The solution prepared in Example 1 is added to 10 g of the catalyst precursor prepared above. The Ni / Cu ratio is 1. The Ni content at the end of this step is 5% by weight relative to the weight of the final catalyst. The solid thus obtained is then dried in an oven overnight at 120 ° C., then calcined under an air flow of 1 L / h / g of catalyst at 450 ° C. for 2 hours. Catalyst B is obtained containing 30% by weight of the element nickel relative to the total weight of the catalyst. The characteristics of catalyst B thus obtained are reported in Table 1 below. Example 4 (compliant. 25% by weight of molten nickel salt + citric acid (Ac) + NiCu in pre-impregnation, Ac / Ni ratio = 0.4)

The solution prepared in Example 1 is added to 10 g of AL-1 alumina. The Ni / Cu ratio is 1. The Ni content at the end of this step is 5% by weight relative to the weight of the final catalyst. The solid thus obtained is then dried in an oven overnight at 120 ° C, then calcined under an air flow of 1 L / h / g of catalyst at 450 ° C for 2 hours.

10 g of the alumina impregnated with the NiCu are contacted with 7.96 g of citric acid dissolved in 10 g of water. The solid thus obtained is then dried in an oven for 2 hours at 60 ° C. then 12 hours at 120 ° C. Then, the support is contacted with 18.95 g of hydrated nickel nitrate hexa in a drum at 25 ° C which rotates at a speed of 40 to 50 revolutions per minute. The drum is then heated to 62 ° C and rotates at a speed of 40 to 50 rpm for 15 minutes. The citric acid to Ni molar ratio is 0.4.

Catalyst C is obtained containing 30% by weight of the element nickel relative to the total weight of the catalyst. The characteristics of catalyst C thus obtained are reported in Table 1 below.

Example 5 (conforms 25% by weight of nickel molten salt + alcoholic acid (Aq) + NiCu in post impregnation, Ag / Ni ratio = 0.2)

10 g of AL-1 alumina support are brought into contact with 1.73 g of glycolic acid dissolved in 5.4 g of water. The solid thus obtained is then dried in an oven for 2 hours at 60 ° C. then 12 hours at 120 ° C.

Then, the support is contacted with 18.95 g of hydrated nickel nitrate hexa in a drum at 25 ° C which rotates at a speed of 40 to 50 revolutions per minute. The drum is then heated to 62 ° C and rotates at a speed of 40 to 50 rpm for 15 minutes. The glycolic acid to Ni molar ratio is 0.2.

The Ni content targeted in this step is 25% by weight of Ni relative to the weight of the final catalyst. The solid thus obtained is then dried in an oven overnight at 120 ° C, then calcined under an air flow of 1 L / h / g of catalyst at 450 ° C for 2 hours.

The solution prepared in Example 1 is added to 10 g of the catalyst precursor prepared above. The Ni / Cu ratio is 1. The Ni content at the end of this stage is 5% relative to the total weight of the catalyst. The solid thus obtained is then dried in an oven. overnight at 120 ° C, then calcined under an air flow of 1 L / h / g of catalyst at 450 ° C for 2 hours.

Catalyst D is obtained containing 30% by weight of the element nickel relative to the total weight of the catalyst. The characteristics of catalyst D thus obtained are reported in Table 1 below.

Example 6 (non-compliant without citric acid but with NiCu in post impregnation)

10 g of AL-1 alumina support are dry impregnated with 18.95 g of hydrated hexa nickel nitrate in a drum at 25 ° C which rotates at a speed of 40 to 50 revolutions per minute. The drum is then heated to 62 ° C and rotates at a speed of 40 to 50 rpm for 15 minutes.

The solution prepared in Example 1 is then added to 10 g of the catalyst precursor prepared above. The Ni / Cu ratio is 1. The Ni content at the end of this step is 5% by weight. The solid thus obtained is then dried in an oven overnight at 120 ° C, then calcined under an air flow of 1 L / h / g of catalyst at 450 ° C for 2 hours.

Catalyst E is obtained containing 30% by weight of the element nickel relative to the total weight of the catalyst. The characteristics of catalyst E thus obtained are reported in Table 1 below.

Example 7 (non-compliant. 25% by weight of molten salt nickel +

+ NiCu-free, Ac / Ni ratio = 0.2)

The nickel content targeted in this step is 15% by weight of Ni relative to the weight of the final catalyst. The solid thus obtained is then dried in an oven overnight at 120 ° C., then calcined under an air flow of 1 L / h / g of catalyst at 450 ° C. for 2 hours. Catalyst F is obtained containing 25% by weight of the element nickel relative to the total weight of the catalyst. The characteristics of catalyst F thus obtained are reported in Table 1 below.

Example 8: Characterization

All the catalysts contain the target contents during the impregnation, i.e. 30% by weight of nickel element for catalysts A to E and 25% by weight for catalyst F (characterized by Fluorescence X) relative to the total weight of the catalyst, and the% Copper added (characterized by Fluorescence X).

The amount of alloy obtained after the calcination then reduction step was determined by X-ray diffraction (XRD) analysis on samples of the catalyst in powder form.

The amount of nickel in metallic form obtained after the reduction step was determined by X-ray diffraction (XRD) analysis on samples of the catalyst in powder form. Between the reduction step and throughout the duration of the XRD characterization, the catalysts are never vented. The diffraction patterns are obtained by radiocrystallographic analysis using a diffractometer using the classical powder method with the Ka1 radiation of copper (l = 1.5406

AT).

The reduction rate was calculated by calculating the area of the Ni ^{0 line} located around 52 ° 2Q, on all the diffractograms of each sample of catalyst analyzed, then by subtracting the signal present from ambient temperature under the line. at 52 ° and which is due to the alumina.

Table 1 below collates the reduction rates or even the metallic nickel content Ni ° (expressed in% by weight relative to the total weight of “active” Ni which does not make up the alloy) for all the catalysts A to F characterized by DRX after a reduction step at 170 ° C for 90 minutes under a flow of hydrogen. These values were also compared with the reduction rate obtained for catalyst A (Ni alone) after a conventional reduction step (that is to say at a temperature of 400 ° C for 15 hours under a flow of hydrogen) .

At room temperature on all catalysts, after calcination, containing copper and nickel, we detect alumina in delta and theta form, and large lines of NiO and CuO.

We also detect after reduction a line corresponding to the alloy in the form

In order to evaluate the rate of reducibility and therefore the formation of Ni ⁰ , we measure the area of the line of Ni ⁰ located around 52 ° 2Q, on all the diffractograms, by subtracting the signal present from room temperature under the line at 52 ° and which is due to the alumina. It is thus possible to determine the relative percentage of Ni ⁰ crystallized after the reduction.

Table 1 below summarizes the reducibility rates or the Ni ° content for all the catalysts characterized by DRX after reduction at 170 ° C for 90 minutes under a flow of hydrogen. These values were also compared with the reduction rate obtained for catalyst F (Ni alone) after a conventional reduction step (that is to say at a temperature of 400 ° C for 15 hours under a flow of hydrogen) .

Table 1

Example 9 The catalysts A to F described in the examples above are tested against the reaction of hydrogenation of toluene.

Catalysts A to F described in the examples above are also tested against the reaction of hydrogenation of toluene. 214 mL of n-heptane (supplier VWR®, purity> 99% chromanorm HPLC) and a quantity of 3 mL of catalyst are added in an autoclave. The autoclave is closed and purged. Then the autoclave is pressurized under 35 bar (3.5 MPa) of hydrogen. The catalyst is first reduced in situ, at 170 ° C for 90 minutes under a hydrogen flow of 1 L / h / g (temperature rise ramp of 1 ° C / min) for catalysts A to F ( which corresponds here to step g) of the preparation process according to the invention according to one embodiment). After the addition of 216 mL of n-heptane (supplier VWR®, purity> 99% chromanorm HPLC), the autoclave is closed, purged, then pressurized under 35 bar (3.5 MPa) of hydrogen, and brought to the test temperature equal to 80 ° C. At time t = 0, approximately 26 g of toluene (supplier SDS®, purity> 99.8%) are introduced into the autoclave (the initial composition of the reaction mixture is then toluene 6% wt / n-heptane 94% wt) and agitation is started at 1600 rpm. The pressure is kept constant at 35 bar (3.5 MPa) in the autoclave using a reservoir bottle located upstream of the reactor.

The progress of the reaction is followed by taking samples of the reaction medium at regular time intervals: the toluene is completely hydrogenated to methylcyclohexane. The hydrogen consumption is also monitored over time by the decrease in pressure in a reservoir bottle located upstream of the reactor. Catalytic activity is expressed in moles of H2 consumed per minute and per gram of Ni.

The catalytic activities measured for catalysts A to F are reported in Table 2 below. They are related to the catalytic activity (A _HYD 2) measured for catalyst F prepared under conventional reduction conditions (at a temperature of 400 ° C. for 15 hours under a flow of hydrogen). Table 2

Catalysts A, B, C and D according to the invention lead to very high selective hydrogenation activities. In Example 6, the additive was not added which leads to catalyst E with a very low activity due to the size of the nickel particles of 20 nm, ie 10 times greater than for the catalysts, In Example 7, the NiCu was not added which leads, after reduction at 170 ° C., to a catalyst exhibiting only Ni atoms in the oxide form which is not active in hydrogenation.

Claims

1. Process for preparing a catalyst for the hydrogenation of aromatic and / or polyaromatic compounds comprising an active phase of nickel, a nickel-copper alloy, and an alumina support, said catalyst comprising a nickel content in the active phase being between 20 and 60% by weight of element nickel relative to the total weight of the catalyst, and a copper content being between 0.5 and 15% by weight of element copper relative to the total weight of the catalyst, the size of the nickel particles in the catalyst, measured in oxide form, being less than 18 nm, which process comprising at least the following steps: a) the following sub-steps are linked together: a1) the support of alumina or the catalyst precursor obtained at the end of step b) with at least one organic additive comprising oxygen and / or nitrogen, the molar ratio between the organic additive and the nickel being greater than 0.05 mol / mol; a2) the alumina support is brought into contact with at least one metal salt of nickel, at a temperature below the melting point of said metal salt of nickel, to form a solid mixture, the mass ratio between said metal salt and the alumina support being between 0.1 and 2.3, steps a1) and a2) being carried out either successively in this order, or simultaneously; a3) the solid mixture obtained at the end of steps a1) and a2) is heated with stirring to a temperature between the melting point of said metal salt and 200 ° C, to obtain a catalyst precursor; a4) optionally, the catalyst precursor is dried at the end of step a3) at a temperature below 250 ° C. to obtain a dried catalyst precursor; b) the sequence of the following sub-steps is carried out: b1) either the alumina support or the catalyst precursor obtained at the end of step a) is impregnated with at least one solution containing at least one copper precursor and a nickel precursor at a predetermined copper concentration in order to obtain on the final catalyst a content of between 0.5 and 15% by weight of copper element relative to the total weight of the final catalyst; b2) the catalyst precursor obtained at the end of step b1) is dried at a temperature below 250 ° C .; said step b) being carried out, either before step a) or after step a), it being understood that when step b) is carried out before step a), then sub-step a4) is obligatory.

2. Method according to claim 1, characterized in that it comprises a step c) in which the catalyst precursor resulting from the sequence of steps a) + b), or b) + a) is reduced, by placing contacting said catalyst precursor with a reducing gas at a temperature greater than or equal to 150 ° C and less than 250 ° C.

3. Method according to one of claims 1 or 2, wherein the copper precursor is chosen from copper acetate, copper acetylacetonate, copper nitrate, copper sulfate, copper chloride, copper. copper bromide, copper iodide and copper fluoride.

4. Method according to any one of claims 1 to 3, characterized in that it further comprises a step a5) in which the catalyst obtained at the end of step a4) is calcined at a temperature of between 250 ° C and 600 ° C.

5. A method according to any one of claims 1 to 4, wherein the melting temperature of said metal salt is between 20 ° C and 150 ° C.

6. Method according to any one of claims 1 to 5, wherein the molar ratio between said organic additive introduced in step a1) and the element nickel introduced in step a2) is between 0.1 and 5. , 0 mol / mol.

7. Method according to any one of claims 1 to 6, wherein steps a1) and a2) are performed simultaneously.

8. Method according to any one of claims 1 to 7, wherein the organic additive of step a1) is chosen from aldehydes containing 1 to 14 carbon atoms per molecule, ketones or polyketones containing 3 to 18 atoms. carbon per molecule, ethers and esters containing 2 to 14 carbon atoms per molecule, alcohols or polyalcohols containing 1 to 14 carbon atoms per molecule and carboxylic acids or polycarboxylic acids containing 1 to 14 carbon atoms per molecule, or a combination of the various compounds referenced above.

9. Method according to any one of claims 1 to 8, wherein said organic additive of step a1) is chosen from formic acid, formaldehyde, acetic acid, citric acid, oxalic acid. , glycolic acid, malonic acid, levulinic acid, ethanol, methanol, ethyl formate, methyl formate, paraldehyde, acetaldehyde, gamma-valerolactone acid, glucose and sorbitol.

10. The method of claim 9, wherein the organic additive is selected from citric acid, formic acid, glycolic acid, levulinic acid and oxalic acid.

11. The method of claim 10, wherein the organic additive is citric acid.

12. A method according to any one of claims 1 to 11, wherein step a3) is carried out by means of a drum operating at a speed of between 4 and 70 revolutions per minute.

13. A method according to any one of claims 1 to 12, wherein in step a2) the mass ratio between said metal salt and the alumina support is between 0.2 and 2.

14. A method according to any one of claims 1 to 13, wherein the nickel precursor content supplied in step b1) is at a desired concentration to obtain on the catalyst a nickel content included in the copper alloy. nickel between 0.5 and 15% by weight of nickel element relative to the total weight of the catalyst.

15. Process for hydrogenating at least one aromatic or polyaromatic compound contained in a hydrocarbon feedstock having a final boiling point less than or equal to 650 ° C, said process being carried out in gas phase or in liquid phase, at a temperature between 30 and 350 ° C, at a pressure between 0.1 and 20 MPa, at a hydrogen / (aromatic compounds to be hydrogenated) molar ratio between 0.1 and 10 and at an hourly volume speed VVH between 0 , 05 and 50 h ¹ , in the presence of a catalyst prepared according to the process according to any one of claims 1 to 14.