EP4291621A1

EP4291621A1 - Hydrotreating process using a sequence of catalysts with a catalyst based on nickel, molybdenum and tungsten

Info

Publication number: EP4291621A1
Application number: EP22702739.8A
Authority: EP
Inventors: Etienne Girard; Anne-Sophie GAY; Isabelle MERDRIGNAC; Antoine Daudin
Original assignee: IFP Energies Nouvelles IFPEN
Current assignee: IFP Energies Nouvelles IFPEN
Priority date: 2021-02-09
Filing date: 2022-02-03
Publication date: 2023-12-20
Also published as: US20240309278A1; FR3119624B1; KR20230143151A; TW202239951A; CN116917446A; WO2022171508A1; JP2024507480A; CA3203989A1; FR3119624A1

Abstract

The subject matter of the invention is a process for the hydrotreating of a hydrocarbon-based feedstock which has a distillation range of between 150°C and 600°C, so as to obtain a hydrotreated effluent, said process comprising the following steps: a) said hydrocarbon-based feedstock is brought into contact, in the presence of hydrogen, with at least one first catalyst occupying a volume V1 and comprising a support based on alumina or on silica or on silica-alumina and an active phase consisting of nickel and of molybdenum, b) the effluent obtained in step a) is brought into contact, in the presence of hydrogen, with at least one second catalyst occupying a volume V2 and comprising a support based on alumina or on silica or on silica-alumina and an active phase consisting of nickel, of molybdenum and of tungsten, and phosphorus, wherein the V1/V2 volume distribution is between 50 vol%/50 vol% and 90 vol%/10 vol% respectively.

Description

HYDROTREATMENT PROCESS USING A SEQUENCING OF CATALYSTS WITH A CATALYST BASED ON NICKEL, MOLYBDENUM AND

TUNGSTEN

Technical area

The invention relates to a process for the hydrotreating of a hydrocarbon feedstock implementing a sequence of at least two catalysts, the second catalyst of which is a catalyst based on nickel, molybdenum and tungsten. The objective of the process is the production of hydrodesulfurized, hydrodenitrogenated and hydrodearomatized hydrocarbon feedstocks.

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 a step of impregnation of metals and phosphorus on the support, followed by drying and 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.

The addition of an organic compound to the hydrotreating catalysts to improve their activity has been recommended by those skilled in the art, in particular for catalysts which have been prepared by impregnation followed by drying without subsequent calcination. These catalysts are often referred to as "additive dried catalysts".

Usually, a catalyst for hydrotreating hydrocarbon cuts aims to eliminate the sulfur, nitrogen or aromatic 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 (automotive fuel, gasoline or diesel, heating oil, jet fuel). Due to the tightening of air quality legislation in many countries, continuous efforts are being made to develop more efficient catalysts and processes for the production of ultra low sulfur fuels, particularly diesel ( USLD). Although great progress has been made in the development of efficient catalysts for these processes, major challenges remain, for example, their modest aromatic hydrocarbon saturation activity. Improving the aromatic saturation activity of hydrotreating catalysts has become a research priority since recent environmental restrictions set minimum values for cetane number and lower limits for polyaromatic contents in diesel cuts. .

The reduction in the sulfur, nitrogen and particularly aromatics content is also sought in the field of pretreatment for a hydrocracking process or for a fluidized bed catalytic cracking process (or FCC process for Fluid Catalytic Cracking according to the English terminology). -Saxon) to improve performance in subsequent hydrocracking or FCC stages. These processes generally treat feedstocks heavily loaded with sulphur, nitrogen and aromatics.

However, a hydrotreating catalyst optimized for hydrodesulfurization (HDS) is not automatically optimized for aromatics saturation (or HDA hydrodearomatization) or for hydrodenitrogenation (HDN) and vice versa. Catalyst sequences are often used in which each catalyst is optimized for a type of hydrotreatment.

Such sequences of supported catalysts are for example described in the documents US2011/0079542, US5068025, CN1176290, FR3013720 or FR3013721.

There are also sequences of unsupported catalysts, also called “bulk” catalysts according to English terminology and known for example from documents US7816299, or CN102851070. However, the chaining of supported catalysts has the advantage of using regenerable catalysts which are also less expensive. (because less loaded with metals) and which are also active with a lower metal content.

Document US2003/0116473 discloses a hydrotreating process using a sequence of a supported catalyst based on molybdenum followed by a supported catalyst based on tungsten. This document does not disclose the volume distribution of the two catalytic zones.

Document CN105435824 discloses a hydrotreating process using a sequence of a CoMoP supported catalyst added to citric acid followed by a supported NiMoWP catalyst. The volume of the first catalyst is between 5 and 95% and the volume of the second catalyst is between 95 and 5%. An increase in HDS and HDN is observed.

Whatever the sequence of catalysts chosen, the modifications induced do not always make it possible to increase the performance of the catalytic system sufficiently to meet the specifications concerning the sulfur, nitrogen and/or aromatic contents of the fuels. Consequently, it is essential for refiners to find new hydrotreating processes with improved performance in terms of activity and stability.

The Applicant has developed a process for the hydrotreating of a hydrocarbon feedstock comprising bringing said feedstock into contact with a specific sequence of catalysts making it possible to increase the overall activity and the overall stability of the process.

Summary

The invention relates to a method for hydrotreating a hydrocarbon feedstock having a distillation range of between 150°C and 600°C, at a temperature of between 180°C and 450°C, a pressure of between 0.5 and 30 MPa, an hourly volumetric speed of between 0.1 and 20 h ^-1 and a hydrogen/charge ratio expressed in volume of hydrogen, measured under normal temperature and pressure conditions, per charge volume liquid comprised between 50 L/L to 5000 L/L, so as to obtain a hydrotreated effluent, said process comprising the following steps: a) a first hydrotreatment step implemented in a first hydrotreatment reaction section, implementing operates at least one catalytic bed comprising at least a first hydrotreating catalyst, said hydrotreating reaction section being supplied with at least said hydrocarbon charge and a gas stream comprising hydrogen, said first catalyst comprising a support based on alumina or silica or silica-alumina and an active phase consisting of nickel and molybdenum, b) a second hydrotreatment stage implemented in a second hydrotreatment reaction section, implementing at least one catalytic bed comprising at at least one second hydrotreating catalyst, said hydrotreating reaction section being supplied with at least part of the effluent obtained in step a), said second catalyst comprising a support based on alumina or silica or silica-alumina and an active phase consisting of nickel, molybdenum and tungsten, and phosphorus, said first hydrotreating reaction section containing the first catalyst occupying a volume V1, and said second hydrotreating reaction section containing the second catalyst occupying a volume V2, the distribution of the volumes V1/V2 being between 50%vol/50%vol and 90%vol/10%vol respectively of said first and second hydrotreating reaction section.

The applicant has surprisingly discovered that a sequence of a first hydrotreatment reaction section containing the first catalyst based on an active phase consisting of nickel and molybdenum and a second hydrotreatment reaction section containing the second catalyst based on an active phase consisting of nickel, molybdenum and tungsten in the presence of phosphorus has a synergistic effect in terms of activity and stability in hydrotreatment, in particular in the hydrogenation of aromatics (HDA) but also in hydrodesulphurization (HDS ) and/or in hydrodenitrogenation (HDN) when the respective volumes of the first and second hydrotreatment reaction section observe a certain distribution, in particular between 50% vol/50% vol and 90% vol/10% vol respectively of said first and second hydrotreatment reaction section.

Indeed, the symbiosis of the first bimetallic catalyst based on an active phase made up of nickel and molybdenum, producing in particular the HDS and part of the HDN, followed by the second trimetallic catalyst based on an active phase made up of nickel, molybdenum and tungsten in the presence of phosphorus, notably performing HDA and HDN, in a certain ratio makes it possible to obtain a highly active and stable catalytic sequence in order to obtain hydrocarbon cuts to specifications.

On the one hand, the second catalyst is very active, in particular in HDA and HDN, which makes it possible to complete the hydrotreatment reactions, in particular HDS and HDN, of the first catalyst necessary to reach the specifications. Typically, thanks to the increase in activity, the temperature necessary to reach a desired sulfur, nitrogen or aromatics content (for example a maximum of 10 ppm of sulfur in the case of a diesel load, in ULSD or Ultra Low mode Sulfur Diesel according to Anglo-Saxon terminology or else a polyaromatic content < 8% by weight and a cetane number > 46 (summer) and 43-46 (winter)) can be lowered. Also, the stability is increased, because the cycle time is extended thanks to the necessary temperature reduction.

On the other hand, the trimetallic catalyst deactivates less quickly than a bimetallic catalyst, which makes it possible all the more to increase the cycle time on a standard load or to allow the treatment of loads heavily loaded with sulphur, nitrogen and/or aromatics.

The volume distribution of the two catalysts, in particular the fact that the second reaction section containing the second catalyst occupies a smaller volume than the first reaction section containing the first catalyst, makes it possible to optimize the reactions of HDS, HDN and HDA carried out in the first or second reaction section in order to obtain hydrocarbon cuts to specifications while increasing the activity and the stability of the catalytic system compared to a system containing only one of the catalysts or a system containing the two catalysts with a volume distribution outside the distribution between 50%vol/50%vol and 90 %vol/10%vol. Another advantage of the hydrotreating process according to the invention is the fact that both light feedstocks (diesel) and heavier feedstocks (vacuum distillate) can be treated. The hydrotreating process according to the invention is also particularly suitable for the hydrotreating of feedstocks comprising high nitrogen and aromatics contents, such as feedstocks resulting from catalytic cracking, coker or visbreaking. The process according to the present invention makes it possible to produce a hydrotreated hydrocarbon fraction, that is to say freed from nitrogen compounds, sulfur compounds and aromatic compounds. Preferably, according to the process according to the invention, the conversion to hydrodesulphurization (HDS) is greater than 95%, preferably greater than 98%. Preferably, according to the process according to the invention, the conversion to hydrodenitrogenation (HDN) is greater than 90%, preferably greater than 95%. Preferably, according to the process according to the invention, the conversion into hydrogenation of the aromatics (HDA) is greater than 70%, preferably greater than 80%.

According to a variant, the distribution of the volumes V1/V2 is between 60% vol/40% vol and 85% vol/15% vol respectively of said first and second hydrotreatment reaction section.

According to a variant, the distribution of the volumes V1/V2 is between 70% vol/30% vol and 80% vol/20% vol respectively of said first and second hydrotreatment reaction section.

According to a variant, the second catalyst is characterized in that: - the nickel content, measured in NiO form, is between 1 and 4% by weight relative to the total weight of the catalyst, - the molybdenum content, measured in MoO ₃ form, is between 2 and 9% by weight relative to the total weight of the catalyst,

- the tungsten content, measured in WO ₃ form, is between 18 and 40% by weight relative to the total weight of the catalyst,

- the phosphorus content, measured in P ₂ O ₅ form, is between 0.5 and 4% by weight relative to the total weight of the catalyst.

According to a variant, the second catalyst is characterized in that:

- the nickel content, measured in NiO form, is between 3 and 4% by weight relative to the total weight of the catalyst,

- the molybdenum content, measured in MoO ₃ form, is between 2 and 9% by weight relative to the total weight of the catalyst,

- the tungsten content, measured in WO ₃ form, is between 29 and 40% by weight relative to the total weight of the catalyst,

- the phosphorus content, measured in P ₂ O ₅ form, is between 3 and 4% by weight relative to the total weight of the catalyst.

According to a variant, the second catalyst is further characterized in that:

- the WO ₃ /MoO ₃ molar ratio is between 2 and 12.4 mol/mol,

- the NiO/(WO ₃ +MoO ₃ ) molar ratio is between 0.20 and 0.33 mol/mol,

- the P ₂ O /(WO ₃ +MoO ₃ ) molar ratio is between 0.21 and 0.34 mol/mol.

According to a variant, the first catalyst has a molybdenum content of between 5 and 40% by weight, expressed as MoO ₃ , relative to the total weight of the catalyst and a nickel content of between 1 and 10% by weight, expressed as NiO, per relative to the total weight of the catalyst.

According to a variant, the first catalyst also comprises phosphorus at a content of between 0.1 and 20% by weight, expressed as P ₂ O ₅ relative to the total weight of the catalyst.

According to a variant, the first and/or the second catalyst additionally contains an organic compound containing oxygen and/or nitrogen and/or sulphur. According to a variant, the organic compound is chosen from a compound comprising one or more chemical functions chosen from a carboxylic, alcohol, thiol, thioether, sulphone, sulphoxide, ether, aldehyde, ketone, ester, carbonate, amine, nitrile, imide, oxime, urea, amide or compounds including a furan ring or a sugar, and preferably it is chosen from γ-valerolactone, 2-acetylbutyrolactone, triethylene glycol, diethylene glycol, ethylene glycol, ethylenediaminetetra- acetic acid (EDTA), maleic acid, malonic acid, citric acid, acetic acid, oxalic acid, gluconic acid, glucose, fructose, sucrose, sorbitol, xylitol, g-ketovaleric acid, a C1-C4 dialkyl succinate and more particularly dimethyl succinate, dimethylformamide, 1-methyl-2-pyrrolidinone, propylene carbonate, 2-methoxyethyl 3-oxobutanoate, bicine , tricine, 2-furaldehyde (also co nnu under the name furfural), 5-hydroxymethylfurfural, 2-acetylfuran, 5-methyl-2-furaldehyde, ascorbic acid, butyl lactate, ethyl lactate, butyl butyryllactate, 3- ethyl hydroxybutanoate, ethyl 3-ethoxypropanoate, 2-ethoxyethyl acetate, 2-butoxyethyl acetate, 2-hydroxyethyl acrylate, 1-vinyl-2-pyrrolidinone, 1,3 -dimethyl-2-imidazolidinone, 1,5-pentanediol, 1-(2-hydroxyethyl)-2-pyrrolidinone, 1-(2-hydroxyethyl)-2,5-pyrrolidinedione, 5-methyl-2(3H) -furanone, 1-methyl-2-piperidinone, 4-aminobutanoic acid, butyl glycolate, ethyl 2-mercaptopropanoate, ethyl 4-oxopentanoate, diethyl maleate, dimethyl maleate, dimethyl fumarate, diethyl fumarate, dimethyl adipate and dimethyl 3-oxoglutarate.

According to a variant, the content of organic compound is between 1 and 30% by weight relative to the total weight of the catalyst.

According to a variant, the first and/or the second catalyst is at least partially sulfurized.

According to a variant, the hydrotreatment process is a hydrodesulfurization process (HDS) of a gas oil cut. Alternatively, the hydrotreating process is implemented as a pretreatment in a fluidized bed catalytic cracking process.

Alternatively, the hydrotreating process is implemented as a pretreatment in a hydrocracking process.

Detailed description of the invention

Definitions

In the following, the groups of chemical elements are given according to the CAS classification (CRC Handbook of Chemistry and Physics, publisher CRC press, editor-in-chief DR 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.

By specific surface area is meant the BET specific surface area (S _BET in m ² /g) determined by nitrogen adsorption in accordance with the ASTM D 3663-78 standard established from the BRUNAUER-EMMETT-TELLER method described in the periodical " The Journal of American Society", 1938, 60, 309.

By total pore volume of the catalyst or of the support used for the preparation of the catalyst is meant the volume measured by intrusion with a mercury porosimeter according to standard ASTM D4284-83 at a maximum pressure of 4000 bar (400 MPa), using a surface tension of 484 dyne/cm and a contact angle of 140°. The wetting angle was taken as equal to 140° by following the recommendations of the work “Engineering techniques, treatise on analysis and characterization”, pages 1050-1055, written by Jean Charpin and Bernard Rasneur. In order to obtain better precision, the value of the total pore volume corresponds to the value of the total pore volume measured by intrusion with a mercury porosimeter measured on the sample minus the value of the total pore volume measured by intrusion with a mercury porosimeter measured on the same sample for a pressure corresponding to 30 psi (about 0.2 MPa).

The contents of group VIII and group VIB metals are measured by X-ray fluorescence. The group VIB metal, group VIII metal and phosphorus contents in the catalyst are expressed as oxides after correction for 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.

By hydrotreating we mean reactions including in particular hydrodesulphurization (HDS), hydrodenitrogenation (HDN) and the hydrogenation of aromatics (HDA).

Load

The hydrocarbon feedstock to be treated according to the hydrotreatment process of the invention has a distillation range of between 150°C and 600°C, preferably between 180°C and 580°C.

The hydrocarbon feed may be of any chemical nature, that is to say possess, apart from the aromatics content described below, any distribution between the different chemical families chosen from paraffins, olefins and naphthenes.

The feedstocks used in the hydrotreating process are, for example, 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 aromatics content in the filler is greater than or equal to 20% by weight, preferably it is between 25 and 90% by weight, more preferably between 30 and 80% by weight. The aromatics content is determined according to the method described in the publication Burdett R.A, Taylor LW and Jones LC, Journal of Molecular Spectroscopy, Rept. Conf., Inst. Petroleum, London 1954, 30-41 (Publ. 1955).

The nitrogen content in the charge is greater than or equal to 150 ppm, preferably it is between 200 and 10,000 ppm by weight, more preferably between 300 and 4,000 ppm by weight.

The sulfur content in the charge is generally between 0.01 and 5% by weight, preferably between 0.2 and 4% by weight and even more preferably between 0.25 and 3% by weight.

Said hydrocarbon charge may optionally contain metals, in particular nickel and vanadium. The cumulative nickel and vanadium content of said hydrocarbon charge is preferably less than 50 ppm by weight, preferably less than 25 ppm, even more preferably less than 10 ppm.

Said hydrocarbon charge may optionally contain asphaltenes. The asphaltene content of said hydrocarbon charge is generally less than 3000 ppm, preferably less than 1000 ppm, even more preferably less than 200 ppm.

Said hydrocarbon charge may optionally contain resins. The resin content may be greater than 1% by weight, in particular greater than 5% by weight. The resin content is measured according to the ASTM D 2007-11 standard. The hydrocarbon charge may also contain very few resins (less than 1% by weight).

According to one embodiment, said hydrocarbon charge is advantageously chosen from LCO (Light Cycle Oil according to the Anglo-Saxon terminology or light gas oils from a catalytic cracking unit), atmospheric distillates, for example gas oils from the direct distillation of crude or conversion units such as fluidized catalytic cracking, coker or visbreaking, or distillates from desulphurization or hydroconversion in a fixed bed or in an ebullating bed of atmospheric residues, or a mixture of the aforementioned feedstocks.

According to another embodiment, said hydrocarbon charge is advantageously chosen from HCO (Heavy Cycle Oil according to the Anglo-Saxon terminology (heavy gas oils from a catalytic cracking unit)), vacuum distillates, for example gas oils from the distillation directly from crude or from conversion units such as catalytic cracking, coker or visbreaking, feeds from aromatics extraction units, lubricating oil bases or from solvent dewaxing of oil bases lubricating oil, distillates from fixed bed or bubbling bed desulphurization or hydroconversion processes of atmospheric residues and/or vacuum residues and/or deasphalted oils, or else the feed may be a deasphalted oil or comprise vegetable oils or even come from the conversion of feedstocks from biomass. Said hydrocarbon feedstock treated according to the hydrocracking process of the invention may also be a mixture of said feedstocks mentioned above.

Implementation of the process and operating conditions

The process according to the invention can be carried out in one, two or more reactors. It is usually performed in a fixed bed.

When the process according to the invention is carried out in two reactors, step a) can be carried out in the first reactor containing the first reaction section through which the charge passes, then step b) can be carried out in the second reactor containing the second reaction section, placed downstream of the first reactor. Optionally, the effluent from stage a) leaving the first reactor can be subjected to a separation stage making it possible to separate a light fraction containing in particular the H ₂ S and the NH ₃ formed during the hydrotreatment in stage a ) of a heavy fraction containing partially hydrotreated hydrocarbons. The heavy fraction obtained after the separation step is then introduced into the second reactor allowing step b) to be carried out. of the process according to the invention. The separation step can be carried out by distillation, flash separation or any other method known to those skilled in the art.

When the process is carried out in a single reactor, step a) is carried out in a first zone containing the first reaction section, and step b) is carried out in a second zone containing the second reaction section downstream of the first zone .

Said first hydrotreatment reaction section containing the first catalyst occupies a volume V1, and said second hydrotreatment reaction section containing the second catalyst occupies a volume V2, the distribution of the volumes V1/V2 being between 50% vol/50% vol and 90%vol/10%vol, preferably between 60%vol/40%vol and 85%vol/15%vol and particularly preferably between 70%vol/30%vol and 80%vol/20%vol , respectively of said first and second hydrotreating reaction section.

The volume distribution of the two catalysts, in particular the fact that the second reaction section containing the second catalyst occupies a smaller volume than the first reaction section containing the first catalyst, makes it possible to optimize the reactions of HDS, HDN and HDA carried out in the first or second reaction section. Indeed, a volume of the second catalyst that is too large does not allow the quantitative reduction of nitrogen compounds, thus resulting in an inhibition of the HDA reaction. Conversely, too small a volume of second catalyst does not maximize the HDA reaction.

The operating conditions used in steps a) or b) of the hydrotreatment process according to the invention are generally the following: 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 . The hourly volume velocity (WH) is defined here as the ratio between the hourly volume flow of the hydrocarbon charge by the volume of catalyst(s). 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. The operating conditions may be identical or different in steps a) and b). Preferably, they are identical.

Composition of the catalysts used in the invention

In accordance with the invention, the hydrotreatment process implements a sequence of a first catalyst comprising a support based on alumina or silica or silica-alumina and an active phase consisting of nickel and molybdenum, and a second catalyst comprising a support based on alumina or silica or silica-alumina and an active phase consisting of nickel, molybdenum and tungsten, and phosphorus.

First catalyst

The first catalyst comprises a support based on alumina or silica or silica-alumina and an active phase consisting of nickel and molybdenum. It may also comprise phosphorus, an organic compound, and optionally boron and/or fluorine.

The hydrogenating function of said first catalyst, also called active phase, is ensured by nickel and molybdenum.

Preferably, the total content of nickel and molybdenum is advantageously greater than 6% by weight, expressed as oxide relative to the total weight of the catalyst.

Preferably, the molybdenum content, measured in MoO ₃ form, is between 5 and 40% by weight, preferably between 8 and 39% by weight, and more preferably between 10 and 38% by weight relative to the total weight of the catalyst. . Preferably, the nickel content, measured in NiO form, is between 1 and 10% by weight, preferably between 1.5 and 9% by weight, and more preferably between 2 and 8% by weight relative to the total weight of the catalyst.

Preferably, the nickel to molybdenum molar ratio in the first catalyst is preferably between 0.1 and 0.8, preferably between 0.15 and 0.6 and even more preferably between 0.2 and 0, 5.

The first catalyst may also include phosphorus as a dopant. The dopant is an added element which in itself has no catalytic character but which increases the catalytic activity of the active phase.

The phosphorus content in said catalyst, measured in P ₂ O ₅ form, is between 0.1 and 20% by weight relative to the total weight of the catalyst, preferably between 0.2 and 15% by weight, and very preferably between 0.3 and 11% by weight expressed as P ₂ O ₅ .

The phosphorus to molybdenum molar ratio in the first catalyst is greater than or equal to 0.05, preferably greater than or equal to 0.07, preferably between 0.08 and 1, preferably between 0.1 and 0.9 and very preferably between 0.15 and 0.8.

The first catalyst may advantageously also contain at least one dopant chosen from boron, fluorine and a mixture of boron and fluorine.

When the catalyst contains boron or fluorine or a mixture of boron and fluorine, the content of boron or fluorine or a mixture of the two is preferably between 0.1 and 10% by weight expressed as boron oxide and/or in fluorine element relative to the total weight of the catalyst, preferably between 0.2 and 7% by weight, and very preferably between 0.2 and 5% by weight.

The pore volume of said 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”, Academie Press, 1999, for example by means of an Autopore III™ model apparatus from the Micromeritics™ brand.

The first catalyst is characterized by a specific surface of between 5 and 400 m ² /g, preferably between 10 and 350 m ² /g, preferably between 40 and 350 m ² /g, very preferably between 50 and 300 m ² /g. The specific surface is determined in the present invention by the BET method according to standard ASTM D3663, method described in the same work cited above.

The support for the first catalyst comprises, and preferably consists of, an alumina or a silica or a silica-alumina.

When the support of said catalyst is based on alumina, it contains more than 50% by weight of alumina relative to the total weight of the support and, in general, it contains only alumina or silica-alumina such as defined below.

Preferably, the support comprises alumina, and preferably extruded alumina. Preferably, the support is made of gamma alumina.

The alumina support advantageously has a total pore volume of between 0.1 and 1.5 cm ³ . g ^-1 , preferably between 0.4 and 1.1 cm ³ .g ^-1 . 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”, Academie Press, 1999, for example by means of an Autopore III™ model apparatus from the Micromeritics™ brand.

The specific surface of the alumina support is advantageously between 5 and 400 m ² . g ^-1 , preferably between 10 and 350 m ² .g ^-1 , more preferably between 40 and 350 m ² .g ^-1 . The specific surface is determined in the present invention by the BET method according to standard ASTM D3663, method described in the same work cited above. In another preferred case, the support of said catalyst 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%.

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 .

When the support of said catalyst is based on silica, it contains more than 50% by weight of silica relative to the total weight of the support and, in general, it contains only silica.

According to a particularly preferred variant, the support consists of alumina, silica or silica-alumina.

The support may also advantageously additionally contain a zeolite. 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. When the zeolite is present, its content is between 0.1 and 50% by weight relative to the total weight of the support.

The support 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.

The first catalyst may further comprise an organic compound or a group of organic compounds known for their role as additives. The function of additives is to increase catalytic activity compared to non-additive catalysts. More particularly, the catalyst may further comprise one or more organic compounds containing oxygen and/or one or more organic compounds containing oxygen. nitrogen and/or one or more sulfur-containing organic compounds. Preferably, the catalyst may further comprise one or more organic compounds containing oxygen and/or one or more organic compounds containing nitrogen. Preferably, the organic compound contains at least 2 carbon atoms and at least one oxygen and/or nitrogen atom, without containing other heteroatoms.

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 compounds including a furan ring or a sugar.

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. Here, an organic compound containing oxygen is understood to mean a compound not comprising any other heteroatom. 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, oxalic acid, maleic acid, malic acid, malonic acid, gluconic acid, tartaric acid, citric acid, g-ketovaleric acid, a succinate of C1-C4 dialkyl 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, y-valerolacton e, 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, ethyl lactate, butyl butyryllactate, ethyl 3-hydroxybutanoate, ethyl 3-ethoxypropanoate, methyl 3-methoxypropanoate, 2-ethoxyethyl acetate, l 2-butoxyethyl acetate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,5-hexanediol, 3-ethyl -1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 5-methyl-2(3H)-furanone, butyl glycolate, ethyl 4-oxo-pentanoate, ethyl maleate diethyl, dimethyl maleate, dimethyl fumarate, diethyl fumarate, dimethyl adipate, dimethyl 3-oxoglutarate, dimethyl tartrate, diethyl tartrate, diisopropyl tartrate, di- tert-butyl, dimethyl malate, diethyl malate, diisopropyl malate and dibutyl malate.

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. Here, an organic compound containing nitrogen is understood to mean a compound containing no other heteroatom. By way of example, the organic compound containing nitrogen can be one or more chosen 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, alcohol, ether, aldehyde, ketone, ester, carbonate, amine, nitrile, imide, amide, urea or oxime. Here, an organic compound containing oxygen and nitrogen is understood to mean a compound not comprising any other heteroatom. 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'-triacetic acid (HEDTA), diethylenetriaminepentaacetic 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, ethyl 2-mercaptopropanoate, 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, ethylenediaminetetra-acetic acid (EDTA), l maleic acid, malonic acid, citric acid, acetic acid, oxalic acid, gluconic acid, glucose, fructose, sucrose, sorbitol, xylitol, y-ketovaleric acid , a C1-C4 dialkyl succinate and more particularly dimethyl succinate, 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 lactate, butyl butyryllactate, ethyl 3-hydroxybutanoate, 3 - ethyl ethoxypropanoate, 2-ethoxyethyl acetate, 2-butoxyethyl acetate, 2-hydroxyethyl acrylate, 1-vinyl-2-pyrrolidinone, 1,3-dimethyl-2-imidazolidinone, 1,5-pentanediol, 1-(2-hydroxyethyl)-2-pyrrolidinone, 1-(2-hydroxyethyl)-2,5-pyrrolidinedione, 5-methyl-2(3H)-furanone, 1-methyl -2-piperidinone, 4-aminobutanoic acid, butyl glycolate, ethyl 2-mercaptopropanoate, ethyl 4-oxopentanoate, diethyl maleate, dimethyl maleate, dimethyl fumarate, diethyl fumarate, dimethyl adipate and 3-oxoglutarate of dimethyl.

When present, the total content of organic compound(s) containing oxygen and/or nitrogen and/or sulfur present in the catalyst 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.

During the preparation of the catalyst requiring a drying step, the drying step(s) following the introduction of the organic compound is (are) carried out at a temperature below 200° C. so as to retain preferably at least 30%, preferably at least 50%, and very preferably at least 70% of the amount of organic compound introduced calculated on the basis of the carbon remaining on the catalyst. The remaining carbon is measured by elemental analysis according to ASTM D5373.

Second catalyst In accordance with the invention, the second catalyst comprises a support based on alumina or silica or silica-alumina and an active phase consisting of nickel, molybdenum and tungsten. The second catalyst according to the invention also comprises phosphorus as a dopant. It may also comprise an organic compound, and/or optionally boron and/or fluorine. The hydrogenating function of said second catalyst, also called active phase, consists of nickel, molybdenum and tungsten.

The second catalyst is characterized in that:

- the nickel content, measured in NiO form, is between 1 and 4% by weight relative to the total weight of the catalyst, - the molybdenum content, measured in MoO ₃ form, is between 2 and 9% by weight relative to the total weight of the catalyst,

Preferably, the second catalyst is characterized in that:

- the nickel content, measured in NiO form, is between 3 and 4% by weight relative to the total weight of the catalyst, preferably between 3.1 and 3.9% by weight, and more preferably between 3.2 and 3.8% by weight,

- the molybdenum content, measured in MoO ₃ form, is between 2 and 9% by weight relative to the total weight of the catalyst, preferably between 2 and 4% by weight, preferably between

2.2 and 3.8% by weight, and more preferably between 2.5 and 3.5% by weight,

- the tungsten content, measured in WO ₃ form, is between 29 and 40% by weight relative to the total weight of the catalyst, preferably between 34 and 40% by weight, preferably between 35 and 39.9% by weight, and more preferably between 36 and 39% by weight,

- the phosphorus content, measured in P ₂ O ₅ form, is preferably between 3 and 4% by weight relative to the total weight of the catalyst, preferably between 3.1 and 3.9% by weight, and very preferably between 3.2 and 3.8% by weight.

Preferably, the WO ₃ /MoO ₃ molar ratio is between 2 and 12.4 mol/mol, preferably

5.3 and 12.4 mol/mol, preferably between 5.7 and 11.1 mol/mol and even more preferably between 6.4 and 9.7 mol/mol.

Preferably, the NiO/(WO ₃ +MoO ₃ ) molar ratio is between 0.20 and 0.33 mol/mol, preferably between 0.21 and 0.31 mol/mol and even more preferably between between 0.22 and 0.30 mol/mol. Preferably, the P ₂ O /(WO ₃ +MoO ₃ ) molar ratio is between 0.21 and 0.34 mol/mol, preferably between 0.22 and 0.33 mol/mol and even more preferably between 0.23 and 0.32 mol/mol.

The catalyst based on an active phase consisting of nickel, molybdenum and tungsten in the presence of phosphorus, deposited on a support, and having the specific ratios between the various metals and/or phosphorus described above, presents by effect synergistically excellent activity and stability in hydrotreating, and in particular in the hydrogenation of aromatics (HDA) but also in hydrodesulfurization (HDS) and/or hydrodenitrogenation (HDN).

Without wishing to be bound by any theory, an optimization of the content of each metal and of phosphorus by using specific ratios would make it possible to obtain an active phase inducing an improvement in catalytic performance. Indeed, tungsten is known to be more active in the hydrogenation of aromatics than molybdenum, however its sulfurization is more difficult. The proximity of molybdenum in the active phase containing tungsten and the increase in the WO ₃ /MoO ₃ ratio make it possible to improve the sulfurability of tungsten and the catalytic performances observed, up to a certain WO ₃ /MoO ₃ ratio where the content in molybdenum is too low to influence the sulfurability of tungsten. Thus, the optimization of the WO ₃ /MoO ₃ ratio in combination with the optimized NiO/(WO ₃ +MoO ₃ ) and R ₂ O ₅ /(WO ₃ +MoO ₃ ) ratios makes it possible to obtain a very active and stable catalyst. in hydrotreating, and in particular in the hydrogenation of aromatics (HDA).

The trimetallic catalyst having the specific ratios mentioned above is therefore particularly preferred during a sequence with said first bimetallic catalyst upstream.

In addition, the catalyst has a density of group VIB metals (Mo+W), expressed as the number of atoms of said metals per unit area of the catalyst, which is between 5 and 12 atoms of group VIB metals per nm ² of catalyst, preferably between 6 and 11, even more preferably between 7 and 10. The density of group VIB metals, expressed as the number of atoms of the group VIB metals per surface unit of the catalyst (number of group VIB metal atoms per nm² of catalyst) is calculated for example from the following relationship: with: X _Mo = % weight of molybdenum; X _W = % weight of tungsten; N _A = Avogadro's number equal to 6.022.10 ²³ ; S = Specific surface of the catalyst (m²/g), measured according to standard ASTM D3663; M _Mo = Molar mass of molybdenum; M _W = Molar mass of tungsten. For example, if the catalyst contains 3% by weight of molybdenum oxide MoO ₃ (i.e. 2.0% by weight of Mo) and 29.3% by weight of tungsten oxide and has a specific surface of 122 m²/ g, the density d(Mo+W) is equal to: The second catalyst can advantageously also contain at least one dopant chosen from boron, fluorine and a mixture of boron and fluorine. When this dopant is present, its content is as described for the first catalyst. The pore volume of the second 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”, Academie Press, 1999, for example by means of an Autopore III™ model apparatus from the Micromeritics™ brand.

The second catalyst is characterized by a specific surface of between 5 and 400 m ² /g, preferably between 10 and 350 m ² /g, preferably between 40 and 350 m ² /g, very preferably between 50 and 300 m ² /g. The specific surface is determined in the present invention by the BET method according to standard ASTM D3663, method described in the same work cited above.

The support for the second catalyst comprises, and preferably consists of, an alumina or a silica or a silica-alumina. The support is a support as described for the first catalyst. It may also comprise a zeolite as described for the first catalyst. It may be identical to or different from the support of the first catalyst.

The first catalyst according to the invention may also comprise an organic compound or a group of organic compounds whose nature and the quantities used are described in the part for the first catalyst. When the two catalysts comprise one or more organic compounds, these may be identical or different.

According to a preferred embodiment, the hydrotreatment process implements a sequence of a first hydrotreatment reaction section containing the first catalyst based on nickel and molybdenum in the presence of phosphorus and a second reaction section of hydrotreating containing the second catalyst based on nickel, molybdenum and tungsten in the presence of phosphorus, said first hydrotreating reaction section containing the first catalyst occupying a volume V1 , and said second hydrotreating reaction section containing the second catalyst occupying a volume V2, the distribution of the volumes V1/V2 being between 50%vol/50%vol and 90%vol/10%vol respectively of said first and second hydrotreating reaction section, said second catalyst being characterized by: - a nickel content, measured in NiO form, of between 3 and 4% by weight relative to the total weight of the catalyst, preferably between 3.1 and 3.9% by weight, and more preferably between 3.2 and 3 .8% by weight;

- a molybdenum content, measured in MoO ₃ form, of between 2 and 9% by weight relative to the total weight of the catalyst, preferably between 2 and 4% by weight, preferably between 2.2 and 3.8% by weight, and more preferably between 2.5 and 3.5% by weight;

- a tungsten content, measured in WO ₃ form, of between 29 and 40% by weight relative to the total weight of the catalyst, preferably between 34 and 40% by weight, preferably between 35 and 39.9% by weight, and so more preferably between 36 and 39% by weight;

- a phosphorus content in said catalyst, measured in P ₂ O ₅ form, preferably between 3 and 4% by weight relative to the total weight of the catalyst, preferably between 3.1 and 3.9% by weight, and so very preferably between 3.2 and 3.8% by weight;

- a WO ₃ /MoO ₃ molar ratio of between 2 and 12.4 mol/mol, preferably 5.3 and 12.4 mol/mol, preferably between 5.7 and 11.1 mol/mol and so even more preferably between 6.4 and 9.7 mol/mol;

- a NiO/(WO ₃ +MoO ₃ ) molar ratio of between 0.20 and 0.33 mol/mol, preferably between 0.21 and 0.31 mol/mol and even more preferably between 0, 22 and 0.30 mol/mol;

- a P ₂ O ₅ /(WO ₃ +MoO ₃ ) molar ratio comprised between 0.21 and 0.34 mol/mol, preferably comprised between 0.22 and 0.33 mol/mol and even more preferably comprised between 0.23 and 0.32 mol/mol.

According to this preferred embodiment, the first and/or the second catalyst further comprises at least one organic compound containing oxygen and/or nitrogen and/or sulfur. According to this mode, the organic compound is preferably chosen from γ-valerolactone, 2-acetylbutyrolactone, triethylene glycol, diethylene glycol, ethylene glycol, ethylenediaminetetraacetic acid (EDTA), maleic acid, acid malonic acid, citric acid, acetic acid, gluconic acid, glucose, fructose, sucrose, sorbitol, xylitol, g-ketovaleric acid, a C1-C4 dialkyl succinate and more particularly the dimethyl succinate, 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, lactate ethyl ester, butyl butyryllactate, ethyl 3-hydroxybutanoate, ethyl 3-ethoxypropanoate, 2-ethoxyethyl acetate hyle, 2-butoxyethyl acetate, 2-hydroxyethyl acrylate, 1-vinyl-2-pyrrolidinone, 1,3-dimethyl-2-imidazolidinone, 1,5-pentanediol, 1-(2- hydroxyethyl)-2-pyrrolidinone, 1-(2-hydroxyethyl)-2,5-pyrrolidinedione, 5-methyl-2(3H)-furanone, 1-methyl-2-piperidinone, 4-aminobutanoic acid, butyl glycolate, ethyl 2-mercaptopropanoate, ethyl 4-oxopentanoate, diethyl maleate, dimethyl maleate, dimethyl fumarate, diethyl fumarate, dimethyl adipate and 3- dimethyl oxoglutarate.

Preparation process

The first and the second catalysts can be prepared according to any mode of preparation of a supported catalyst known to those skilled in the art.

The first and the second catalysts can be prepared according to a preparation process comprising the following steps: i) bringing into contact a nickel precursor, a molybdenum precursor, a tungsten precursor when it is present, and phosphorus when it is present, with a support based on alumina or silica or silica-alumina, so as to obtain a catalyst precursor, ii) said catalyst precursor from step i) is dried at a temperature below 200° C., iii) optionally, the catalyst precursor obtained in step ii) is calcined at a temperature between 200° C. and 550° C., iv) optionally, the catalyst obtained in stage ii) or in stage iii) is sulfurized.

During the contacting of step i), the first and the second catalysts can be prepared by impregnation of metals and phosphorus on the selected support. The impregnation can for example be carried out according to the mode known to those skilled in the art under the terminology of dry impregnation, in which just the quantity of desired elements is introduced in the form of salts soluble in the chosen solvent, for example demineralised water, so as to fill the pores of the support as exactly as possible.

The precursors of the active phase can be introduced simultaneously or successively. The impregnation of each precursor can advantageously be carried out in at least two stages. The different precursors can thus be advantageously impregnated successively with a different impregnation and maturation time. One of the precursors can also be impregnated several times.

Preferably, the precursors of the active phase are introduced simultaneously.

The nickel precursors which can be used are advantageously chosen from nickel oxides, hydroxides, hydroxycarbonates, carbonates and nitrates, for example nickel hydroxycarbonate, nickel carbonate or hydroxide are used so favourite.

The molybdenum precursors which can be used are well known to those skilled in the art. For example, among the sources of molybdenum, it is possible to use oxides and hydroxides, molybdic acids and their salts, in particular ammonium salts such as ammonium molybdate, ammonium heptamolybdate, phosphomolybdic acid ( H3PM012O40) and their salts, and possibly silicomolybdic acid (H ₄ SiMo ₁₂ O ₄₀ ) and its salts. The sources of molybdenum can also be heteropoly compounds of the Keggin, lacunary Keggin, substituted Keggin, Dawson, Anderson, Strandberg type, for example. Preferably, molybdenum trioxide and heteropolyanions of the Strandberg, Keggin, lacunary Keggin or substituted Keggin 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 sources of tungsten can also be heteropolycompounds 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 phosphorus can be introduced in whole or in part by impregnation. Preferably, it is introduced by impregnation, preferably dry, using a solution containing the precursors of nickel, molybdenum and tungsten.

Said phosphorus can advantageously be introduced alone or mixed with the active phase, and this during any of the steps of impregnation of the hydrogenating function if the latter is introduced several times. Said phosphorus can also be introduced, in whole or in part, during the impregnation of an organic compound containing oxygen and/or nitrogen and/or sulfur if the latter is introduced separately from the hydrogenating function ( case of post- and pre-impregnation described later). It can also be introduced from the synthesis of the support, at any stage of the synthesis of the latter. It can thus be introduced before, during or after the kneading of the chosen alumina gel matrix, such as for example and preferably aluminum oxyhydroxide (boehmite) precursor of alumina. 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 element(s) of group VIB in the form of heteropolyanions of Keggin, lacunary Keggin, substituted Keggin or of the Strandberg type.

Any impregnation solution described in the present invention can comprise any polar solvent known to those skilled in the art. Said polar solvent used is advantageously chosen from the group formed by methanol, ethanol, water, phenol, cyclohexanol, taken alone or as a mixture. Preferably, a polar protic solvent is used. A list of the usual polar solvents as well as their dielectric constant can be found in the book “Solvents and Solvent Effects in Organic Chemistry”, C. Reichardt, Wiley-VCH, 3rd edition, 2003, pages 472-474. Very preferably, the solvent used is water or ethanol, and particularly preferably, the solvent is water. In a possible embodiment, the solvent may be absent in the impregnation solution.

When the first or the second catalyst also comprises a dopant chosen from boron, fluorine or a mixture of boron and fluorine, the introduction of this (these) dopant(s) can be done in the same way as the introduction of phosphorus described above at various stages of preparation and in various ways.

The boron precursors can be boric acid, orthoboric acid H ₃ BO ₃ , ammonium biborate or pentaborate, boron oxide, boric esters. The boron can be introduced for example by a solution of boric acid in a water/alcohol mixture or else in a water/ethanolamine mixture. Preferably the boron precursor, if boron is introduced, is orthoboric acid.

The fluorine precursors which can be used are well known to those skilled in the art. For example, the fluoride anions can be introduced in the form of hydrofluoric acid or its salts. These salts are formed with alkali metals, ammonium or an organic compound. In the latter case, the salt is advantageously formed in the reaction mixture by reaction between the organic compound and hydrofluoric acid. Fluoride can be introduced for example by impregnation with an aqueous solution of hydrofluoric acid, or ammonium fluoride or ammonium bifluoride.

When the first or the second catalyst also comprises an organic compound containing oxygen and/or nitrogen and/or sulfur, the latter is introduced before the drying stage ii). The organic compound is generally introduced by impregnation, in the presence or absence of the active phase and phosphorus and in the presence or absence of a solvent.

The introduction of the organic compound comprises several modes of implementation which are distinguished in particular by the moment of the introduction of the organic compound compared to the introduction of the metals. It can be carried out either at the same time as the impregnation of the metals (co-impregnation), or after the impregnation of the metals (post-impregnation), or finally before the impregnation of the metals (pre-impregnation) in particular during the preparation of the support, and preferably during shaping or by impregnation on an already formed support. Each mode, taken alone or in combination, can take place in one or more stages.

In addition, the contacting step can combine at least two modes of implementation, for example co-impregnation and post-impregnation. According to an alternative embodiment, the contacting according to step i) combines at least two modes of contacting, for example the co-impregnation of the active phase and of the phosphorus with an organic compound, followed by drying at a temperature below 200° C., followed by post-impregnation with an organic compound which may be identical to or different from that used for the co-impregnation. Each mode, taken alone or in combination, can take place in one or more stages.

The organic compound(s) is (are) advantageously introduced into an impregnation solution which, depending on the method of preparation, can be the same solution or a different solution from that containing the precursors of the active phase and phosphorus, in an amount corresponding to: - at a molar ratio of the organic compound to the sum of the group VIB element(s) of the catalyst precursors (Mo for the first catalyst or (Mo and W) for the second catalyst) of between 0.01 and 5 mol/mol, preferably between 0.05 and 3 mol/mol, preferably between 0.05 and 1.5 mol/mol and very preferably between 0.1 and 1.2 mol/mol, calculated on the base of the components introduced into the impregnation solution(s), and

- at a molar ratio of the organic compound to nickel of between 0.02 and 17 mol/mol, preferably between 0.1 and 10 mol/mol, preferably between 0.15 and 8 mol/mol and so very preferred, between 0.6 and 5 mol/mol, calculated on the basis of the components introduced into the impregnation solution(s).

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

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 five hours, is sufficient. Longer durations are not excluded, but do not necessarily bring improvement.

In accordance with step ii) of the preparation process according to the invention, the catalyst precursor obtained in step i), optionally matured, is subjected to a drying step at a temperature below 200° C., preferably between 50 and 180°C, preferably between 70 and 150°C and very preferably between 75 and 130°C.

The drying step is advantageously carried out by any technique known to those skilled in the art. It is advantageously carried out at atmospheric pressure or at pressure reduced, and preferably 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 has a short duration of 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 drying is then carried out so as to preferably retain at least 30% of the organic compound introduced, preferably this quantity is greater than 50% and even more preferably, greater than 70%, calculated on the carbon base remaining on the catalyst. At the end of the drying step b), a dried catalyst is obtained.

Optionally, the drying step ii) can be followed by a calcination step iii).

According to this variant, at the end of step ii) of drying, a calcination step c) is carried out at a temperature 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 this heat treatment is generally between 0.5 hours and 16 hours, preferably between 1 hour and 5 hours. 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 was introduced. 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.

When an organic compound is present, the catalyst is preferably not subjected to calcination. Here, calcination means a heat treatment under a gas containing air or oxygen at a temperature greater than or equal to 200°C.

However, the catalyst precursor can undergo a calcination step before the introduction of the organic compound, in particular after the impregnation of the active phase, and of the phosphorus. The first or the second catalyst can be a fresh catalyst, that is to say a catalyst which has not been used as a catalyst before in a catalytic unit and in particular in hydrotreating.

The first or the second catalyst according to the invention can also be a regenerated and/or rejuvenated catalyst. A regenerated and/or rejuvenated catalyst is understood to mean a catalyst which has been used as a catalyst in a catalytic unit and in particular in hydrotreating and/or hydrocracking and which has been subjected to at least one stage of partial or total removal of the coke for example by calcination (regeneration). The regeneration can be carried out by any means known to those skilled in the art. Regeneration is generally carried out by calcination at temperatures between 350 and 550°C, and most often between 400 and 520°C, or between 420 and 520°C, or even between 450 and 520°C, lower temperatures at 500° C. being often advantageous.

When the regenerated catalyst no longer comprises enough active phase and/or phosphorus or it has a ratio or ratios outside the preferred ratios described above, the regenerated catalyst can be rejuvenated by introducing one or more precursors of the active phase and/or phosphorus in the regenerated catalyst. It is also possible to introduce at least one organic compound simultaneously with the metals and the phosphorus or separately. The organic compound introduced may or may not be identical to the organic compound of the fresh catalyst when this catalyst included such an organic compound. The operating conditions described above concerning the maturation, the drying and the optional calcination and the optional sulfurization are of course applicable in the context of this last embodiment.

Before its use for the hydrotreating reaction, it is advantageous to transform the first and/or the second catalyst 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 sulphur-reducing atmosphere in the presence of hydrogen and hydrogen sulphide. According to a variant, the first or the second catalyst is advantageously subjected to a sulfurization stage after the drying stage ii) or the optional calcination stage iii).

Said catalyst is advantageously sulfurized ex situ or in situ. 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.

Application of the process according to the invention in a ULSD process of a diesel fraction

According to a first mode of use, said hydrotreating process according to the invention is a hydrotreating process, and in particular hydrodesulfurization (HDS) of a diesel fraction carried out in the presence of said sequence of catalysts. Said hydrotreating process according to the invention 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 significantly reduce the aromatics and nitrogen contents of the gas oil cut to be hydrotreated.

Said gas oil cut to be hydrotreated according to the process of the invention 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). Saxony), a steam cracking unit (steam cracking according to the Anglo- Saxon), a unit for the hydrotreating and/or hydrocracking of heavier feedstocks and/or a catalytic cracking unit (Fluid Catalytic Cracking according to the Anglo-Saxon terminology). Said gas oil fraction preferably has at least 90% of the compounds whose boiling point is between 250° C. and 400° C. at atmospheric pressure.

The method for hydrotreating said diesel fraction according to the invention is implemented under the following operating conditions: a temperature between 200°C and 400°C, preferably between 300°C and 380°C, a total pressure 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, between 100 and 600 liters per liter and more preferably between 200 and 400 liters per liter and an hourly volume rate (WH) between 0.5 and 10 h ^-1 , preferably between 0.7 and 8 h ^-1 . The WH 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 diesel fraction according to the invention is preferably operated in a fixed bed.

Application of the process according to the invention in a hydrocracking process

According to a second variant, the hydrotreatment process according to the invention is advantageously implemented as a pretreatment in a hydrocracking process, and more particularly in a so-called "one-step" hydrocracking process or in a hydrocracking process. said in "two stages". The hydrocracking process makes it possible to convert petroleum fractions, in particular vacuum distillates (DSV) into lighter and more recoverable products (gasoline, middle distillates). The hydrotreatment process according to the invention aims to eliminate the sulphurous, nitrogenous or aromatic compounds present in the said vacuum distillate cut. A wide variety of loads can be processed. 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.

A so-called "one-step" hydrocracking process firstly and generally comprises extensive hydrotreating, the purpose of which is to carry out extensive HDN, HDS and HDA of the feedstock before it is sent to the hydrocracking catalysts. Said one-step hydrocracking process is particularly advantageous when said hydrocracking catalyst(s) comprise(s) a support comprising zeolite crystals. This extensive hydrotreating of the feed only results in a limited conversion of the feed, into lighter fractions, which remains insufficient and must therefore be supplemented on the more active hydrocracking catalyst(s). However, it should be noted that no separation of the effluents occurs between the different catalytic beds: all of the effluent leaving the hydrotreatment catalytic bed is injected onto the catalytic bed(s) containing the said hydrocracking catalyst(s) then a separation of the products formed is carried out. This version of hydrocracking has a variant which presents recycling of the unconverted fraction to at least one of the catalytic beds. hydrocracking for further feed conversion. Advantageously, the hydrotreatment process according to the invention comprising the specific sequence according to the invention, is implemented upstream of a hydrocracking catalyst in a one-step hydrocracking process. It also makes it possible to limit the nitrogen content at the end of the pretreatment stage in order to protect the hydrocracking catalyst based on zeolite which is very sensitive to nitrogen.

A so-called "two-stage" hydrocracking process comprises a first stage whose objective, as in the "one-stage" process, is to carry out the hydrotreating of the feed, but also to achieve a conversion of the latter of 'order in general from 40 to 60%. The effluent from the first stage then undergoes separation, generally by distillation, most often called intermediate separation, the purpose of which is to separate the conversion products from the unconverted fraction. In the second stage of the two-stage hydrocracking process according to the invention, only the fraction of the feed not converted during the first stage is treated. This separation allows the two-step hydrocracking process according to the invention to be more selective in middle distillate (kerosene+diesel) than the one-step process according to the invention. Indeed, the intermediate separation of the conversion products avoids their “over-cracking” into naphtha and gas in the second stage on the hydrocracking catalyst(s). Furthermore, it should be noted that the unconverted fraction of the feed treated in the second stage generally contains very low levels of NH ₃ as well as organic nitrogen compounds, generally less than 20 ppm by weight or even less than 10 ppm. weight.

Said first stage is implemented in the presence of the specific sequence of catalysts according to the invention, and of a hydrocracking catalyst in order to carry out a hydrotreatment and a conversion of the order in general of 40 to 60%. The catalytic beds of the specific sequence of catalysts according to the invention are advantageously located upstream of the hydrocracking catalyst. Said second stage is generally implemented in the presence of a hydrocracking catalyst of different composition from that present for the implementation of said first stage. The hydrocracking processes are generally carried out at a temperature of between 250 and 480° C., advantageously between 320 and 450° C., preferably between 330 and 435° C., under a pressure of between 2 and 25 MPa, preferably between 3 and 20 MPa, the hourly volume rate of the feed relative to the volume of each catalyst (WH) is advantageously between 0.1 and 40 h ^-1 , preferably between 0.2 and 12 h ^-1 , so very preferably between 0.4 and 6 h ^-1 and the hydrogen/charge ratio expressed in normal cubic meters (Nm ³ ) of hydrogen per cubic meter (m ³ ) of hydrocarbon charge is advantageously between 80 NL/L and 5000 NL /L, preferably between 100 and 2000 NL/L. Vacuum distillate hydrocracking processes cover pressure and conversion ranges 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.

Hydrocracking catalysts are of the bifunctional type: they combine an acid function with a hydro-dehydrogenating function. The acid function is provided by porous supports, the surfaces of which generally vary from 150 to 800 m ² .g ^-1 and exhibit surface acidity, such as halogenated aluminas (chlorinated or fluorinated in particular), combinations of boron oxides and aluminium, amorphous or crystallized mesoporous aluminosilicates and zeolites dispersed in an oxide binder. The hydro-dehydrogenating function is provided by the presence of an active phase based on at least one metal from group VIB and optionally at least one metal from group VIII of the periodic table of the elements. The most common formulations are of the nickel-molybdenum (NiMo) and nickel-tungsten (NiW) type and more rarely of the cobalt-molybdenum (CoMo) type. After preparation, the hydro-dehydrogenating function is often in the form of an oxide. The usual methods leading to the formation of the hydro-dehydrogenating phase of hydrocracking catalysts consist of depositing molecular precursor(s) of at least one metal from group VIB and optionally at least one metal from group VIII on an acid oxide support by the so-called "dry impregnation" technique followed by maturation, drying and calcination stages leading to the formation of the oxidized form of said metal(s) employed. Since the active and stable form for hydrocracking processes is the sulfurized form, these catalysts must undergo a sulfurization step. This can be carried out in the unit of the associated process (we then speak of in-situ sulfurization) or prior to loading the catalyst into the unit (we then speak of ex-situ sulfurization).

Application of the method according to the invention in an FCC method

According to a third variant, the hydrotreatment process according to the invention 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 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 (whose first industrial implementation dates back to 1936 (HOUDRY process) or in 1942 for the use of fluidized bed catalyst) can be found in ULLMANS ENCYCLOPEDIA OF INDUSTRIAL CHEMISTRY VOLUME A 18, 1991, pages 61 to 64.

A conventional catalyst comprising a matrix, optionally an additive and at least one zeolite is usually used in the FCC process. The quantity of zeolite is variable but usually from 3 to 60% by weight, often from 6 to 50% by weight and most often from 10 to 45% by weight relative to the weight of the catalyst. The zeolite is usually dispersed in the matrix. The amount of additive is usually 0 to 30% by weight and often 0 to 20% by weight based on the weight of the catalyst. The amount of matrix represents the complement to 100% by weight. The additive is generally chosen from the group formed by the oxides of the metals of group MA of the periodic table of the elements such as, for example, magnesium oxide or calcium oxide, the oxides of the rare earths and the titanates of the metals of the MA group. The matrix is most often a silica, an alumina, a silica-alumina, a silica-magnesia, a clay or a mixture of two or more of these products. The most commonly used zeolite is zeolite Y. The cracking is carried out in a substantially vertical reactor either in ascending mode (riser) or in descending mode (dropper). The choice of the catalyst and of the operating conditions are functions of the desired products as a function of the feedstock treated, as is for example described in the article by M. MARCILLY pages 990-991 published in the review of the French Petroleum Institute Nov. -dec. 1975 pp. 969-1006. The operation is usually carried out at a temperature of 450 to 600° C. and residence times in the reactor of less than 1 minute, often 0.1 to 50 seconds.

The pretreatment also makes it possible to limit the nitrogen content at the end of the pretreatment step in order to protect the catalytic cracking catalyst based on zeolite, which is very sensitive to nitrogen.

EXAMPLES

The following examples demonstrate the significant gain in activity in HDA and HDN using the specific sequence according to the invention.

Examples 1 to 3 describe the preparation of catalysts C1 to C3. The final metal and phosphorus composition of each catalyst, expressed in the form of oxides and related to the weight of the catalyst, as well as the ratios WO ₃ /MoO ₃ , NiO/(WO ₃ +MoO ₃ ) and P ₂ O ₅ / (WO ₃ +MoO ₃ ) are shown in the table below.

Examples 4 to 7 describe the evaluation in hydrogenation of aromatics (HDA) and in hydrodenitrogenation (HDN) of diesel fuel of different sequences of catalysts C1, C2 and C3.

Example 1: Preparation of the NiMoP catalyst on C1 alumina

On 100 grams of an A1 alumina support having a loss on ignition of 4.9% by weight, a BET surface of 230 m ² /g, a porous volume measured by mercury porosimetry of 0.78 ml/g and a average pore diameter of 11.5 nm defined as the median diameter by volume by mercury porosimetry and which is in the “extruded” form, nickel, molybdenum and phosphorus are added. Support A1 has a water uptake volume of 0.77 mL/g. The impregnation solution is prepared by dissolution at 90°C of 37.41 grams of molybdenum oxide (Merck™, purity > 99.5% by weight), 11.96 grams of nickel hydroxycarbonate (Merck™, purity 99.9% by weight) and 14.53 grams of a solution of orthophosphoric acid (Merck™, 85 wt% in water) in 67.2 mL of distilled water. After dry impregnation, the extrudates are left to mature in an atmosphere saturated with water for 24 h at room temperature, then they are dried at 90° C. for 16 h. The dried support impregnated with catalyst C1 is then additived by dry impregnation with a solution containing a mixture of dimethyl succinate (DMSU) and acetic acid (at 75% purity). The molar ratios are as follows: DMSU/Mo=0.85 mol/mol, DMSU/acetic acid=0.5 mol/mol. The catalyst further undergoes a maturation step of 3 h at 20° C. in air then drying in a traversed bed type oven at 120° C. for 3 h. The dried catalyst thus obtained is denoted C1. The final composition of catalyst C1 expressed in the form of oxides is then as follows: MoO ₃ = 25.1 +/- 0.2 (% by weight), NiO = 5.1 +/- 0.1 (% by weight ) and P ₂ O ₅ = 6.0 +- 0.1 (% by weight).

Example 2: Preparation of the NiMoWP catalyst on C2 alumina

On the same support A1 as presented in Example 1, nickel, molybdenum, tungsten and phosphorus are added. The impregnation solution is prepared by dissolving at 90°C molybdenum oxide (Merck™, purity > 99.5% by weight, 6.12 g), hydrated ammonium metatungstate (Merck™, ≥ 85, 0% by weight WO ₃ , 74.74 g), nickel nitrate hexahydrate (Merck™, purity 99.999% by weight, 26.07 g) and a solution of orthophosphoric acid (Merck™, 85% by weight in the water, 10.24 grams) in 68.3 mL of distilled water. After dry impregnation of 100 grams of support A1, the extrudates are left to mature in an atmosphere saturated with water for 24 hours at ambient temperature, then they are dried at 90° C. for 16 hours. The dried catalyst thus obtained is denoted C2.

The final composition of catalyst C2 expressed in the form of oxides is then the following: MoO ₃ = 3.4 +/- 0.1 (% by weight), WO ₃ = 36.6 +/- 0.2 (% by weight), NiO = 3.7 +/- 0.1 (% by weight) and P ₂ O ₅ = 3.5 +- 0.1 (% by weight). Example 3: Preparation of the NiMoWP catalyst on C3 alumina by post-additivation of an organic compound (ascorbic acid).

100 g of catalyst precursor C2 described above in Example 2 and which is in the "extruded" form are impregnated with an aqueous solution containing 28.78 g of ascorbic acid (Merck™, 100% purity) and whose volume is equal to the pore volume of catalyst precursor C2. The quantities involved are such that the quantity of ascorbic acid is 0.5 mole per mole of molybdenum and tungsten (corresponding to 1.9 moles per mole of nickel). The extrudates are left to mature in an atmosphere saturated with water for 16 h at room temperature. The precursor of catalyst C3 is then dried at 120° C. for 2 hours to give catalyst C3.

The final composition of catalyst C3 expressed in the form of oxides is then the following: MoO ₃ = 3.4 +/- 0.1 (% by weight), WO ₃ = 36.6 +/- 0.2 (% by weight), NiO = 3.7 +/- 0.1 (% by weight) and P ₂ O ₅ = 3.5 +- 0.1 (% by weight).

[Table 1] Table 1: Composition of catalysts C1, C2 and C3.

Examples 4 to 7: Evaluation in hydrogenation of aromatics (HDA) and hydrodenitrogenation (HDN) of gas oil of sequences of catalysts C1, C2 and, C3

The sequences of catalysts taken from catalysts C1, C2, C3 were tested in the hydrogenation of aromatics (HDA) of diesel fuel. The charge is a mixture of 30% volume of gas oil from atmospheric distillation (also called straight-run according to Anglo-Saxon terminology) and 70% volume of light gas oil from a catalytic cracking unit (also called LCO for light cycle oil according to Anglo-Saxon terminology). The characteristics of the test load used are as follows: density at 15°C= 0.8994 g/cm ³ (NF EN ISO 12185), refractive index at 20°C = 1.5143 (ASTM D1218-12), sulfur content = 0.38% by weight, nitrogen content = 0.05% by weight.

• Simulated Distillation (ASTM D2887):

- IP: 133°C; - 10%: 223°C;

- 50%: 285°C;

-90%: 357°C;

- MP: 419°C.

The test is carried out in an isothermal pilot reactor with a traversed fixed bed, the fluids circulating from bottom to top. The reactor comprises two catalytic zones making it possible to evaluate different sequences of catalysts C1, C2 and C3. The charge first passes through the first zone charged with the first catalyst, then the second zone charged with the second catalyst.

According to Example 4 (in accordance with the invention), the first zone is loaded with catalyst C1 (75% of the volume), then the second with catalyst C2 (25% of the volume).

According to Example 5 (in accordance with the invention), the first zone is loaded with catalyst C1 (75% of the volume), then the second with catalyst C3 (25% of the volume).

According to Example 6 (not in accordance with the invention), the first zone is loaded with catalyst C1 (40% by volume), then the second with catalyst C2 (60% by volume). According to Example 7 (not in accordance with the invention), the first zone is loaded with catalyst C1 (95% by volume), then the second with catalyst C2 (5% by volume). The catalysts are previously sulfurized in situ at 350°C in the pressurized reactor by means of an atmospheric distillation gas oil charge (straight run according to Anglo-Saxon terminology) (density at 15°C= 0.8491 g/cm ³ (NF EN ISO 12185) and initial sulfur content = 0.42% by weight), to which is added 2% by weight of dimethyldisulphide.

The catalytic tests were carried out under the following operating conditions: a total pressure of 8 MPa, a total volume of the two catalytic zones of 4 cm ³ , a temperature of 330° C., with a hydrogen flow rate of 3.0 L/ h and with a charge rate of 4.5 cm ³ /h.

The characteristics of the effluents are analysed: density at 15°C (NF EN ISO 12185), refractive index at 20°C (ASTM D1218-12), simulated distillation (ASTM D2887), sulfur content and nitrogen content. The residual aromatic carbon contents are calculated by the n-d-M method (ASTM D3238). The rate of hydrogenation of the aromatics is calculated as the ratio of the aromatic carbon content in the feed from which that of the effluents is subtracted, to that of the test feed. The rate of hydrodenitrogenation is calculated as the ratio of the nitrogen content in the load, from which that of the effluents is subtracted, to that of the test load.

The catalytic performances of the sequences of catalysts tested are given in Table 2. They are expressed in relative volume activity (RVA) with respect to the sequence of 95% vol catalyst C1 (first zone of the reactor) + 5% vol catalyst C2 (second reactor zone) chosen as reference (Example 7), assuming an order of 1.7 for the HDA reaction and an order of 1 for the HDN reaction.

Table 2 clearly shows the gain in the catalytic effect provided by the specific sequences according to the invention. Indeed, the sequences of catalysts according to the invention make it possible to significantly increase the volume activities in the hydrodearomatization (HDA) and hydrodenitrogenation (HDN) reaction of gas oils. [Table 2]

Table 2: Relative activities HDA and HDN for the specific sequences according to the invention (examples 4 and 5) and non-compliant (examples 6 and 7).

Claims

1. Process for hydrotreating a hydrocarbon charge having a distillation range of between 150°C and 600°C, at a temperature of between 180°C and 450°C, a pressure of between 0.5 and 30 MPa, an hourly volume rate of between 0.1 and 20 h ^-1 and a hydrogen/charge ratio expressed in volume of hydrogen, measured under normal temperature and pressure conditions, per liquid charge volume of between 50 L/L to 5000 L/L, so as to obtain a hydrotreated effluent, said method comprising the following steps: a) a first hydrotreatment step implemented in a first hydrotreatment reaction section, implementing at least one catalytic bed comprising at least a first hydrotreating catalyst, said hydrotreating reaction section being supplied with at least said hydrocarbon charge and a gas stream comprising hydrogen, said first catalyst comprising a support based on alumina or silica or silica-alumina and an active phase consisting of nickel and molybdenum, b) a second hydrotreatment stage implemented in a second hydrotreatment reaction section, implementing at least one catalytic bed comprising at least one second catalyst hydrotreatment, said hydrotreatment reaction section being supplied with at least a portion of the effluent obtained in step a), said second catalyst comprising a support based on alumina or silica or silica-alumina and a active phase consisting of nickel, molybdenum and tungsten, and phosphorus, said first hydrotreating reaction section containing the first catalyst occupying a volume V1, and said second hydrotreating reaction section containing the second catalyst occupying a volume V2, the distribution of volumes V1/V2 being between 50%vol/50%vol and 90%vol/10%vol respectively of said first and second hydrotra reaction section item.

2. Hydrotreatment process according to claim 1, in which the distribution of the volumes V1/V2 is between 60% vol/40% vol and 85% vol/15% vol respectively of said first and second hydrotreatment reaction section.

3. Hydrotreatment process according to claim 2, in which the distribution of the volumes V1/V2 is between 70% vol/30% vol and 80% vol/20% vol respectively of said first and second hydrotreatment reaction section.

4. Hydrotreating process according to one of the preceding claims, in which the second catalyst is characterized in that:

- the nickel content, measured in NiO form, is between 1 and 4% by weight relative to the total weight of the catalyst,

5. Hydrotreating process according to the preceding claim, in which the second catalyst is characterized in that:

6. Hydrotreating process according to claim 5, in which the second catalyst is further characterized in that:

- the WO ₃ /MoO ₃ molar ratio is between 2 and 12.4 mol/mol,

- the NiO/(WO ₃ +MoO ₃ ) molar ratio is between 0.20 and 0.33 mol/mol,

- the P ₂ O ₅ /(WO ₃ +MoO ₃ ) molar ratio is between 0.21 and 0.34 mol/mol.

7. Hydrotreating process according to one of the preceding claims, in which the first catalyst has a molybdenum content of between 5 and 40% by weight, expressed as MoO ₃ , relative to the total weight of the catalyst and a nickel content of between between 1 and 10% by weight, expressed as NiO, relative to the total weight of the catalyst.

8. Hydrotreating process according to one of the preceding claims, in which the first catalyst further comprises phosphorus at a content of between 0.1 and 20% by weight, expressed as P ₂ O ₅ relative to the total weight of the catalyst.

9. Hydrotreating process according to one of the preceding claims, in which the first and/or the second catalyst additionally contains an organic compound containing oxygen and/or nitrogen and/or sulphur.

10. Hydrotreatment process according to claim 9, in which 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, amide or compounds including a furan ring or a sugar.

11. Hydrotreating process according to claim 10, in which the organic compound is chosen from γ-valerolactone, 2-acetylbutyrolactone, triethylene glycol, diethylene glycol, ethylene glycol, ethylenediaminetetra-acetic acid (EDTA), l maleic acid, malonic acid, citric acid, acetic acid, oxalic acid, gluconic acid, glucose, fructose, sucrose, sorbitol, xylitol, y-ketovaleric acid , a C1-C4 dialkyl succinate and more particularly dimethyl succinate, dimethylformamide, 1-methyl-2-pyrrolidinone, propylene carbonate, 2-methoxyethyl 3-oxobutanoate, bicine, tricine, 2-furaldehyde (also known as furfural), 5-hydroxymethylfurfural, 2-acetylfuran, 5-methyl-2-furaldehyde, ascorbic acid , butyl lactate, ethyl lactate, butyl butyryllactate, ethyl 3-hydroxybutanoate, ethyl 3-ethoxypropanoate, 2-ethoxyethyl acetate, 2-butoxyethyl acetate, l 2-hydroxyethyl acrylate, 1-vinyl-2-pyrrolidinone, 1,3-dimethyl-2-imidazolidinone, 1,5-pentanediol, 1-(2-hydroxyethyl)-2-pyrrolidinone, 1-( 2-hydroxyethyl)-2,5-pyrrolidinedione, 5-methyl-2(3H)-furanone, 1-methyl-2-piperidinone, 4-aminobutanoic acid, butyl glycolate, 2-mercaptopropanoate ethyl, ethyl 4-oxopentanoate, diethyl maleate, dimethyl maleate, dimethyl fumarate, diethyl fumarate, dimethyl adipate and dimethyl 3-oxoglutarate.

12. Hydrotreating process according to one of claims 9 to 11, in which the organic compound content is between 1 and 30% by weight relative to the total weight of the catalyst.

13. Hydrotreating process according to one of the preceding claims, in which the first and/or the second catalyst is at least partially sulfurized.

14. Hydrotreatment process according to one of the preceding claims, which is a process for the hydrodesulphurization of a gas oil cut.

15. Hydrotreating process according to one of claims 1 to 13, which is implemented as pretreatment in a fluidized bed catalytic cracking process.

16. Hydrotreating process according to one of claims 1 to 13, which is implemented as pretreatment in a hydrocracking process.