HYDROCONVERSION PROCESS IN A DRIVE BED OF HEAVY HYDROCARBONATE FILLERS WITH MOLYBDENNE SULPHIDE-BASED NANOPARTICLES

Abstract

The present invention is a hydroconversion process of a heavy hydrocarbon feed employing at least one entrained bed reactor in the presence of a solid entrained catalyst in the form of bimetallic sulfide MMoS nanoparticles in single sheets, M being a group VIIIB metal such as nickel or cobalt, obtained by an ex-situ preparation process from organosoluble precursors containing metal-sulfur bonds.

Description

Title of the invention: PROCESS FOR HYDROCONVERSION IN A DRIVEBED OF HEAVY HYDROCARBONATE FILLERS WITH NANOPARTICLES BASED ON MOLYBDENNE SULFIDES technical field

[0001] The present invention relates to a process for hydroconversion of heavy hydrocarbon feedstocks in a driven bed, employing a hydroconversion catalyst in the form of bimetallic sulfide nanoparticles MMoS, with M a metal from group VIIIB, obtained by an ex-situ synthesis process from organosoluble precursors comprising metal-sulfur bonds. Previous technique

[0002] The purification and conversion of heavy hydrocarbon feedstocks is well known in the field of petroleum refining and aims to convert heavy fractions into lighter, more valuable fractions, typically as fuels. The treatment of these heavy feedstocks involves reducing their boiling point, increasing the hydrogen-to-carbon ratio, and removing impurities such as metals, sulfur, nitrogen, and high-carbon compounds.

[0003] Catalytic hydroconversion is commonly used for heavy hydrocarbon feedstocks and is generally implemented using three-phase reactors in which the feedstock is brought into contact with hydrogen and a catalyst under high temperature and pressure conditions. In the reactor, the catalyst can be used in the form of a fixed bed, a moving bed, a bubbling bed, or an entrained bed, as described, for example, in Chapter 18, "Catalytic Hydrotreatment and Hydroconversion: Fixed Bed, Moving Bed, Ebullated Bed and Entrained Bed," of the book "Heavy Crude Oils: From Geology to Upgrading, An Overview," published by Technip in 2011. In the case of a bubbling bed or an entrained bed, the reactor includes an upward flow of liquid and gas.The choice of technology generally depends on the nature of the load to be treated and in particular its metal content, its tolerance to impurities and the conversion intended.

[0004] Entrained bed hydroconversion processes use entrained bed technologies, also known as "slurry" technologies, where a dispersed catalyst or catalyst precursor is continuously injected into the heavy hydrocarbon feedstock in the entrained bed reactor, promoting the hydrogenation of radicals formed by thermal cracking reactions, and limiting coke formation. The dispersed catalyst, also called "entrained catalyst" or more commonly "slurry catalyst", provides catalytic activity but also a surface for the deposition of metals and asphaltenes from the feedstock.

[0005] The very small size catalyst (micrometric or nanometric), dispersed in the feed, is carried out of the reactor with the effluents, since the catalyst and the heavy hydrocarbon feed behave as a homogeneous phase.

[0006] Hybrid technologies combining the use of different types of catalyst beds are sometimes used to achieve the hydroconversion of heavy loads, such as hydroconversion processes implementing bubbling-entrained hybrid bed reactors, operating in the presence of hydrogen, with a classically supported solid catalyst of millimeter size maintained as an expanded bed in the reactor and a slurry catalyst exiting with the hydroconverted effluent, as described in US patent 8431016 and application WO2023 / 280624.

[0007] Entrained catalysts are typically unsupported catalysts (also sometimes called "bulk" catalysts according to Anglo-Saxon terminology), although entrained catalysts produced by grinding supported catalysts are known. Entrained (unsupported) catalysts offer several advantages compared to conventional millimeter-sized supported catalysts: they have a high specific surface area (which is greater the smaller the particles), they reduce catalyst deactivation problems, particularly because they do not contain a porous support that is especially susceptible to deactivation by coke and metal deposition, and because their residence time in the reactor is shorter, diffusion problems are reduced or even avoided, and they are less prone to sedimentation.

[0008] Entrained (unsupported) hydroconversion catalysts are typically metal sulfides that can be prepared in various ways.

[0009] The solid particles of the entrained catalyst containing the metal sulfides can be formed after mixing catalyst precursors with the feed to be treated upstream of the hydroconversion reactor or within the hydroconversion reactor. This is a formation of the entrained catalyst that can be described as in-situ, in which the active form of the entrained catalyst, i.e., the metal sulfides, is obtained during the hydroconversion process. For example, nanoparticulate catalysts (which can also be called colloidal or molecular) formed in-situ from organosoluble metallic compounds (i.e., soluble in an organic substance or solvent), precursors of the driven catalyst, such as molybdenum naphthenate or molybdenum octoate (molybdenum 2-ethylhexanoate, also called Mo-octoate in Anglo-Saxon terminology), are disclosed in patents US4244839, US2005 / 0241991, US2014 / 0027344 and WO2013 / 034642. Patent application US2005 / 0241991 describes, for example, a hydroconversion process for heavy hydrocarbon feedstocks employing one or more hybrid bubbling-linked bed reactors, operating with a supported solid catalyst and a dispersed entrained solid catalyst within the feedstock formed by the addition of an organosoluble metallic precursor. The addition of a dispersed organosoluble catalyst precursor, typically molybdenum 2-ethylhexanoate, which is pre-diluted in vacuum gas oil (VGO), is carried out in an intimate mixing step with the feedstock to prepare a conditioned feedstock before its introduction into the reactor. The catalyst precursor forms a colloidal or molecular catalyst (e.g. dispersed molybdenum sulfide) when heated, by reaction with H2S from the hydrodesulfurization of the feed.Water-soluble metallic compounds, such as phosphomolybdic acid cited in US patents 3231488, 4637870, and 4637871, ammonium heptamolybdate cited in US patent 6043182, or salts of a heteropolyanion as cited in EP3723903, can also be used as entrained catalyst precursors. In the case of water-soluble compounds, the entrained catalyst precursor is generally mixed with the feedstock to form an emulsion. The dissolution of the entrained catalyst precursor (usually molybdenum), optionally activated by cobalt or nickel, in acidic media (in the presence of H3PO4) or basic media (in the presence of NH4OH), has been the subject of numerous studies and patents.Patent application EP3723903 describes, for example, a hybrid bed hydroconversion process for heavy hydrocarbon feedstocks, in which the dispersed solid catalyst is obtained from at least one salt of a heteropolyanion combining molybdenum with at least one metal selected from cobalt and nickel in a Strandberg, Keggin, vacancy Keggin, or substituted vacancy Keggin structure. The entrained molybdenum sulfide-based catalyst, promoted by nickel and / or cobalt, is obtained by decomposition of the precursor in the presence of sulfur, either in the hydroconversion reactor by reaction with H2S from the hydrodesulfurization of the feedstock, or during a heat treatment of the emulsion containing the precursor injected into the feedstock upstream of the hydroconversion reactor.

[0010] The solid particles of the entrained catalyst containing the metal sulfides can also be formed before any mixing or contact with the feedstock to be treated. Such a formation of the solid entrained catalyst can thus be described as ex-situ. Documents WO2006 / 031575, WO2006 / 031543 and WO2006 / 031570 describe, for example, this type of ex-situ preparation of entrained catalysts, and more particularly the dissolving of a VIB group oxide with an aqueous ammonia solution to form a solution which is then sulfided, possibly promoted by the addition of a VIB group metal after said sulfidation, and mixed with the feed in the last step.

[0011] Another example of ex-situ catalyst synthesis is given in the publication by Scott et al. 2015 (Preparation of NiMoS nanoparticles for hydrotreating, Catalysis Today, 250, pp. 21–27), which discloses the preparation of NiMoS nanoparticles for hydrotreating reactions (hydrodesulfurization, commonly referred to as “HDS,” and hydrodeazotation, commonly referred to as “HDN”) of VGO in a reactor operated solely with the nanoparticle catalyst. This preparation involves the precipitation of water-in-oil microemulsions using hydrated ammonium heptamolybdate and nickel nitrate in aqueous solution as molybdenum and nickel precursors, respectively. A sulfidation step with CS2 carbon disulfide in decahydronaphthalene and under hydrogen is carried out before injecting the catalyst into the reactor containing the VGO feedstock to test the catalyst's catalytic activity.

[0012] Yet another example of ex-situ catalyst synthesis is provided in the publication by Guo et al. 2018 (One-step synthesis of ultrafine MoNiS and MoCoS monolayers as highperformance catalysts for hydrodesulfurization and hydrodenitrogenation, Applied Catalysis B: Environmental, 239, pp. 433-440), which discloses the preparation of MoNiS and MoCoS nanoparticles in the form of monolayers for hydrotreating reactions (HDS and HDN) of a feed containing thiophene and pyridine in a reactor operated with the nanoparticle catalyst alone. The preparation of the nanoparticles is carried out in one step by thermal decomposition of organometallic complexes, in particular molybdenum hexacarbonyl Mo(CO)6 and nickel(II) acetylacetonate or cobalt(III) acetylacetonate, in the presence of a sulfurizing agent which is elemental sulfur and in the presence of oleylamine.

[0013] In the context of ex-situ syntheses of entrained solid catalysts, sulfidation of the catalyst is generally necessary and carried out using a sulfurizing agent (H₂S, elemental sulfur, C₂S, etc.) during the catalyst synthesis or the hydroconversion process, before its injection into the hydroconversion reactor, for example, during a dedicated sulfidation step. This sulfidation constitutes an additional step that complicates the synthesis or hydroconversion process.

[0014] In general, the performance of hydroconversion processes for hydrocarbon feedstocks is directly dependent on the catalysts used in the hydroconversion reactors. To improve the performance of these processes, catalysts and implementations of these catalysts are continually being researched. ever more efficient, as well as advantageous and simplified methods for synthesizing such catalysts. Objectives and Summary of the Invention

[0015] In the context described above, the present description aims to provide a process for the hydroconversion of heavy hydrocarbon feedstocks in entrained bed reactor(s) which is simple to implement and which makes it possible to do without a step of sulfidation of the entrained catalyst before its use for the hydroconversion of the feedstock.

[0016] The invention also aims to provide a simple to manufacture, highly dispersible, driven hydroconversion catalyst (i.e. unsupported within the meaning of the present invention) exhibiting good performance with regard to conversion and hydrotreating reactions during driven bed hydroconversion of a heavy hydrocarbon feedstock, while limiting sediment formation.

[0017] Thus, to achieve at least one of the aforementioned objectives, among others, the present invention relates to a hydroconversion process for a heavy hydrocarbon feedstock, i.e. comprising a fraction of at least 50% by weight having a boiling point of at least 300°C, said process comprising: (a) a hydroconversion step of said hydrocarbon feedstock in a hydroconversion section comprising at least one entrained-bed hydroconversion reactor in the presence of hydrogen and at least one entrained solid hydroconversion catalyst, to produce a hydroconverted effluent, said entrained solid hydroconversion catalyst being in the form of bimetallic sulfide nanoparticles MMoS, M being a group VIIIB metal, obtained by a preparation process comprising (i) a decomposition step of a first organosoluble precursor comprising at least one molybdenum-sulfur bond and a second organosoluble precursor comprising at least one metal M-sulfur bond, in the presence of an organic stabilizing agent, at a temperature between 100°C and 350°C and for a duration between 1 minute and 24 h, said first and second organosoluble precursors comprising a ligand selected from the following families: dithiocarbamates,dithiophosphates, xanthates, dithioimidophosphinates, and dithioimidophosphates, said organic stabilizing agent being selected from the group consisting of: , - alkylamines selected from primary amines and secondary amines having a hydrocarbon chain from C4 to C34; - alkylthiols containing a hydrocarbon chain in C6 to C18; - carboxylic acids with a hydrocarbon chain from C6 to Cl8; - phosphines (eg organophosphines).

[0018] According to one or more embodiments of the invention, the first organosoluble precursor is from the family of oxymolybdenum dithiocarbamates corresponding to the general formula (I) or from the family of oxymolybdenum dithiophosphates corresponding to the general formula (II),

[0019] [Chem.l] OO R> -^x Z^X R3 Mo' Mo R / X S X Xs" R 4

[0020] [Chem.2] OO AH / Sxll A / OR3 ^.PZ Mo Mo z \P X R2° XSZ or4

[0021] wherein the radicals RI, R2, R3, R4 are independently selected from linear or branched alkyl groups, in C12 to C12, cycloalkyl groups in C6 to C12, and aryl or alkyl-aryl groups in C6 to C12, preferably identical linear alkyl groups in C6 to C12 or identical branched alkyl groups in C12 to C12, and

[0022] -the second organosoluble precursor is from the family of dithiocarbamates of metal M corresponding to the general formula (III) or from the family of dithiophosphates of metal M corresponding to the general formula (IV):

[0023] [Chem.3] Ri Z^XZ^XR 3 / NC< PC-Nj R 2 S Z S r 4

[0024] [Chem.4] RA ZSX A xOR3 m;

[0025] wherein the radicals RI, R2, R3, R4 are independently selected from linear or branched alkyl groups, in C12 to C12, preferably in C1-C6, from cycloalkyl groups in C6 to C12, and from aryl or alkyl-aryl groups in C6 to C12, preferably identical linear alkyl groups in C6

[0026] According to one or more embodiments of the invention, the first organosoluble precursor is chosen from the list consisting of oxymolybdenum dimethyldithiocarbamate, oxymolybdenum diethyldithiocarbamate, the oxymolybdenum dipropyldithiocarbamate, oxymolybdenum dibutyldithiocarbamate, oxymolybdenum dipentyldithiocarbamate, oxymolybdenum dihexyldithiocarbamate, oxymolybdenum dimethylphosphorodithioate, oxymolybdenum diethylphosphorodithioate, oxymolybdenum dipropylphosphorodithioate, oxymolybdenum dibutylphosphorodithioate, oxymolybdenum dipentylphosphorodithioate, oxymolybdenum dihexylphosphorodithioate, and oxymolybdenum di(2-ethylhexyl)phosphoodithioate, and the second organosoluble precursor is chosen from the list consisting of: nickel dimethyldithiocarbamate, nickel diethyldithiocarbamate, oxymolybdenum dipropyldithiocarbamate nickel, nickel dibutyldithiocarbamate, nickel dipentyldithiocarbamate, nickel dihexyldithiocarbamate, nickel dimethyldithiophosphate, nickel dimethyldithiophosphate, nickel dimethyldithiophosphate, nickel dimethyldithiophosphate, nickel dimethyldithiophosphate,and nickel dimethyldithiophosphate.

[0027] According to one or more embodiments of the invention, the metal M is nickel.

[0028] According to one or more embodiments of the invention, the stabilizing agent organic is chosen from the group consisting of: - alkylamines chosen from primary amines and secondary amines having a hydrocarbon chain in C12 to C18, preferably chosen from the list consisting of octylamine, dodecylamine, hexadecylamine, octadecylamine, and oleylamine; - the alkylthiols chosen from the list consisting of 1-hexane thiol, 1-octanethiol, 1-dodecanethiol, and 1-hexadecanethiol; - carboxylic acids chosen from the list consisting of citric acid, octanoic acid, decanoic acid, palmitic acid, and oleic acid; - the phosphines chosen from the list consisting of tributylphosphine, trioocty Iphosphine

[0029] According to one or more embodiments of the invention, the organic stabilizing agent is an alkylamine chosen from the list consisting of octylamine, dodecylamine, hexadecylamine, octadecylamine, and oleylamine, and preferably is hexadecylamine or oleylamine.

[0030] According to one or more embodiments of the invention, in step (i) the molar ratio of metallic elements (M+Mo) to organic stabilizing agent (for example the molar ratio of the sum of the elements Ni and Mo (Ni+Mo) to organic stabilizing agent) is between 0.001 and 0.1, and the molar ratio of metal M to molybdenum M / Mo, preferably Ni / Mo, is between 0.1 and 1.

[0031] According to one or more embodiments of the invention, step (i) of decomposition is carried out in the presence of at least one organic synthesis solvent boiling point above 100°C, preferably chosen from the list consisting of toluene, ethylbenzene, xylene, mesitylene, decane, and dodecane.

[0032] According to one or more embodiments of the invention, the nanoparticles of entrained solid hydroconversion catalyst obtained at the end of the decomposition step (i) are in the form of single sheets and have an average size of between 1 nm and 25 nm, preferably between 1 nm and 10 nm, preferably between 1 nm and 5 nm.

[0033] According to one or more embodiments of the invention, the process for preparing the nanoparticles of the entrained solid hydroconversion catalyst further comprises (ii) a separation step between the nanoparticles of the entrained solid hydroconversion catalyst and the organic stabilizing agent and optionally an organic synthesis solvent from a colloidal solution obtained at the end of the decomposition step (i), and optionally a washing step (iii) and / or a drying step (iv) of said nanoparticles separated at the end of step (ii).

[0034] Advantageously, the preparation process does not implement a sulfuration step to form the MMoS bimetallic sulfide nanoparticles.

[0035] According to one or more embodiments of the invention, the entrained solid hydroconversion catalyst is introduced into said hydroconversion reactor in its form of MMoS bimetallic sulfide nanoparticles without implementing a sulfidation step of the entrained solid hydroconversion catalyst prior to the hydroconversion step a) or during said process of preparing said entrained solid hydroconversion catalyst.

[0036] According to one or more embodiments of the invention, the entrained solid hydroconversion catalyst is introduced into the hydroconversion reactor with the heavy hydrocarbon feed in the same flow, said entrained solid catalyst having been previously mixed with the feed, preferably during an active dispersion step of said entrained solid hydroconversion catalyst in the feed.

[0037] According to one or more embodiments of the invention, the entrained solid hydroconversion catalyst is introduced into said hydroconversion reactor at the hydroconversion stage independently of the heavy hydrocarbon feed.

[0038] According to one or more embodiments of the invention, the entrained solid hydroconversion catalyst is pre-mixed with the feed in the form of a colloidal solution comprising organic stabilizing agent and optionally organic synthesis solvent used during the catalyst preparation process.

[0039] According to one or more embodiments of the invention, the concentration of the entrained solid hydroconversion catalyst is between 10 ppm and 10,000 ppm by weight of molybdenum relative to the heavy hydrocarbon feedstock at the inlet of the hydroconversion reactor, preferably between 50 ppm and 6,000 ppm by weight, of preferred method between 100 ppm and 1000 ppm by weight, particularly preferred method between 100 ppm and 800 ppm by weight.

[0040] According to one or more embodiments of the invention, the hydroconversion step is carried out under an absolute pressure of between 2 MPa and 38 MPa, at a temperature of between 300°C and 550°C, at an hourly volumetric rate WH relative to the volume of each reactor of between 0.05 h 1 and 10 h 1 and under a quantity of hydrogen mixed with the feed entering the reactor of between 50 and 5,000 normal cubic meters per cubic meter of feed.

[0041] According to one or more embodiments of the invention, the heavy hydrocarbon feedstock comprises, or is constituted by, one of the following feedstocks, alone or in mixture: crude oil, synthetic crude oil, coal tar, bitumen from oil sands, heavy oil from oil shale, an atmospheric residue or a vacuum residue from the atmospheric or vacuum distillation of crude oil, an atmospheric residue or a vacuum residue from the atmospheric or vacuum distillation of an effluent from a thermal conversion, hydrotreating, hydrocracking, hydroconversion, or direct coal liquefaction unit, a vacuum distillate obtained directly from crude oil or from a cut from a fluidized bed catalytic cracking unit, a hydrocracking unit, a hydroconversion unit, a coking unit, or a unit of viscoreductiona vacuum distillate from the direct liquefaction of coal, aromatic cuts extracted from a lubricant production unit, deasphalted oil or a resin fraction or an asphalt fraction from a deasphalting unit, a bio-oil, a biocrude, a pyrolysis oil from plastics and / or tires and / or solid recovered fuels, and preferably a vacuum residue from the vacuum distillation of crude oil.

[0042] According to one or more embodiments of the invention, the heavy hydrocarbon feed comprises at least one of the following characteristics: sulfur in a content greater than 0.5% by weight, a Conradson carbon residue of at least 0.5% by weight, C7 asphaltenes in a content greater than 1% by weight, transition and / or post-transition metals and / or metalloids in a content greater than 2 ppm by weight, and alkali and / or alkaline earth metals in a content greater than 2 ppm by weight.

[0043] According to one or more embodiments of the invention, the hydroconversion process further comprises a subsequent treatment step of the hydroconverted effluent, comprising: b) an additional hydroconversion step in at least one additional entrained bed reactor, of at least part, or all, of the effluent hydroconverted resulting from the hydroconversion step a) or optionally from a heavy liquid fraction which boils predominantly at a temperature greater than or equal to 350°C resulting from an optional separation step separating part, or all, of said hydroconverted effluent, to produce a second hydroconverted effluent with a reduced Conradson carbon residue, and possibly a reduced amount of sulfur, and / or nitrogen, and / or metals; (c) a fractionation step of part, or all, of said second hydroconverted effluent in a fractionation section to produce at least one heavy cut which boils predominantly at a temperature greater than or equal to 350°C, said heavy cut containing a residual fraction which boils at a temperature greater than or equal to 540°C; (d) an optional step of deasphalting, in a deasphalter, some or all of said heavy cut from the fractionation step (c) with at least one hydrocarbon solvent to produce deasphalted oil DAO and residual asphalt; and said hydroconversion step a) and the additional hydroconversion step b) being carried out under an absolute pressure of between 2 MPa and 38 MPa, at a temperature of between 300°C and 550°C, at an hourly volumetric velocity WH relative to the volume of each entrained bed reactor of between 0.05 h 1 and 10 h 1 and under an amount of hydrogen mixed with the feed entering each reactor of between 50 and 5,000 normal cubic meters (Nm3) per cubic meter (m3) of feed.

[0044] Other objects and advantages of the invention will become apparent from the following description of particular embodiments of the invention, given by way of non-limiting examples. Description of the implementation methods

[0045] In the following detailed description, numerous specific details are set forth to provide a more thorough understanding of the processes of the invention. However, it will be apparent to those skilled in the art that the processes can be implemented without necessarily all of these specific details. In other cases, well-known features have not been described in detail to avoid unnecessarily complicating the description.

[0046] In the present description, the different embodiments presented can be implemented separately or in combination with each other, without limitation of combinations when this is technically feasible. Terminology

[0047] It is specified that, throughout this description, the expression "between ... and ..." should be understood as including the limits mentioned, unless otherwise specified.

[0048] In this description, the term "include" is synonymous with "comprise," "include," and "contain," and is inclusive or open-ended and does not exclude other elements not mentioned. It is understood that the term "include" includes the exclusive and closed term "consist."

[0049] Furthermore, when used in this description, and unless otherwise indicated, the terms "essentially" or "significantly" or "approximately" or "mainly" in relation to a reference value correspond to an approximation of ± 10%, preferably ± 5%, most preferably ± 2%, or even more preferably ± 1% of that reference value, which may be a temperature, a pressure, a dimensional quantity such as a length, a quantity, a speed, a flow rate, a content of compound(s), etc.

[0050] In the present description, the different parameter ranges for a given step, such as pressure ranges and temperature ranges, can be used alone or in combination. For example, in the sense of the present invention, a preferred range of pressure values ​​can be combined with a more preferred range of temperature values.

[0051] According to the present invention, the pressures are absolute pressures, also noted as abs., and are given in absolute MPa (or abs. MPa), unless otherwise indicated.

[0052] In this description, the term "hydroconversion," also referred to by the acronyms "HDC" and "HCK," and by the term "hydrocracking" more commonly used when the feed in question is a light feed, refers to a process whose main purpose is to reduce the boiling point range of a heavy hydrocarbon feed, typically comprising at least 50% by weight of a heavy hydrocarbon fraction having a boiling point of at least 300°C, and in which a substantial portion of the feed is converted into products having lower boiling point ranges than those of the original feed. Hydroconversion generally involves the fragmentation of larger hydrocarbon molecules into smaller molecular fragments having a smaller number of carbon atoms and a higher hydrogen-to-carbon ratio.The reactions involved in hydroconversion reduce the size of hydrocarbon molecules, primarily through the cleavage of carbon-carbon bonds, in the presence of hydrogen to saturate the broken bonds and aromatic rings. The mechanism by which hydroconversion occurs typically involves the formation of hydrocarbon free radicals during fragmentation, mainly through thermal cracking, followed by the capping of the free radical terminations or fragments with hydrogen in the presence of active catalyst sites. Of course, During a hydroconversion process, other reactions typically associated with hydrotreating may occur, such as, among others, the removal of sulfur, oxygen, or nitrogen from the feedstock, or the saturation of olefins, and as more broadly defined below.

[0053] The term "hydrotreating," commonly referred to as "HDT," describes a gentler operation than hydroconversion, the main purpose of which is to remove impurities such as sulfur, nitrogen, oxygen, halides, and trace metals from the feed, and to saturate olefins and / or stabilize hydrocarbon free radicals by causing them to react with hydrogen rather than allowing them to react with themselves. The main purpose is not to change the boiling point range of the feed. Thus, hydrotreating includes hydrodesulfurization reactions (commonly called "HDS"), hydrodeazotation reactions (commonly called "HDN") and hydrodemetallation reactions (commonly called "HDM"), accompanied by hydrogenation, hydrodeoxygenation, hydrodearomatization, hydroisomerization, hydrodealkylation, hydrocracking, hydrodeasphalting and Conradson carbon reduction reactions.Hydrotreating is most often implemented using a fixed bed reactor, although other reactors can also be used for hydrotreating, for example an entrained bed, bubbling or hybrid bed hydrotreating reactor.

[0054] The term "hydroconversion reactor" refers to any vessel in which the hydroconversion of a feedstock is the primary objective, e.g., the cracking of the feedstock (i.e., the reduction of the boiling point range), in the presence of hydrogen and a hydroconversion catalyst. Hydroconversion reactors typically include an inlet port through which a heavy hydrocarbon feedstock and hydrogen can be introduced and an outlet port from which valuable material can be withdrawn. Specifically, hydroconversion reactors are also characterized by the fact that they possess sufficient thermal energy to cause the fragmentation of larger hydrocarbon molecules into smaller molecules by thermal decomposition.Examples of hydroconversion reactors include, but are not limited to, driven bed reactors, also known as 'slurry' reactors (three-phase reactors - liquid, gas, solid - in which the solid and liquid phases can behave as a homogeneous phase), bubbling bed reactors (three-phase fluidized reactors), moving bed reactors (three-phase reactors with downward movement of the solid catalyst and upward or downward flow of liquid and gas), and fixed bed reactors (three-phase reactors with downward trickling of liquid charge over a fixed bed of catalyst supported with flowing hydrogen). typically simultaneously with the liquid, but possibly counter-currently in some cases).

[0055] The terms "entrained bed" and "slurry" for a hydroconversion reactor refer to an entrained bed hydroconversion reactor comprising an entrained solid catalyst that is the sole hydroconversion catalyst in the entrained bed reactor (100% of the catalyst in the reactor(s) is an entrained catalyst; no porous supported catalyst is maintained in the reactor during operation as in a bubbling bed or hybrid reactor). The entrained solid catalyst, also commonly called a "slurry catalyst," is entrained out of the reactor with the effluent (recovered feed). Similarly, for a hydroconversion process, these terms thus refer to a process comprising only entrained bed hydroconversion reactors. According to the present invention, the entrained solid catalyst is a catalyst in the form of specific nanoparticles, as defined below.

[0056] The terms "hybrid bed" and "hybrid bubbling bed" and "hybrid bubbling-entrained bed" for a hydroconversion reactor refer to a bubbling bed hydroconversion reactor comprising an entrained catalyst in addition to the porous supported catalyst maintained in the bubbling bed reactor.

[0057] In the present description, the term “entrained solid hydroconversion catalyst”, or more succinctly “entrained solid catalyst”, means a catalyst in the form of very small solid particles, i.e. particles of colloidal size, e.g. less than 1 pm in size (average size), preferably less than 500 nm in size, more preferably less than 250 nm in size, or less than 100 nm in size, or less than 50 nm in size, or less than 25 nm in size, or less than 10 nm in size, or less than 5 nm in size, which can be used in an entrained bed hydroconversion process of a hydrocarbon feedstock (100% of the catalyst in the reactor(s) is an entrained catalyst).Such a driven solid hydroconversion catalyst is not a supported solid hydroconversion catalyst, which typically comprises a catalyst support with a large surface area and many interconnected channels or pores and an active phase in the form of fine particles such as cobalt, nickel, tungsten, molybdenum sulfides, or mixed sulfides of these elements (e.g., NiMo, CoMo, etc.), optionally phosphorus and / or sulfur, dispersed in the pores of said support (supported catalysts commonly produced as cylindrical extrudates (“pellets”) or spherical solids, although other shapes are possible). According to the invention, the catalyst obtained by the specific synthesis process from organosoluble precursors comprising at least one metal-sulfur bond, and used in as a solid catalyst entrained in an entrained bed hydroconversion process according to the invention, is in the form of bimetallic sulfide nanoparticles MMoS (M being a group VIIIB metal) of the single-sheet type, with a sheet length less than or equal to about 25 nm as detailed later in the description.

[0058] Elemental analyses, typically by inductively coupled plasma (ICP) spectrometry, in particular by inductively coupled plasma atomic emission spectroscopy (ICP-AES), or by X-ray fluorescence spectrometry, more commonly called X-ray fluorescence (FX), make it possible to quantify the content of certain elements of the catalyst, including metals such as molybdenum, nickel, etc.

[0059] The size of the catalyst nanoparticles is determined by transmission electron microscopy (TEM). In particular, the TEM measurement of the size of the catalyst nanoparticles can be carried out on a powder formed by the nanoparticles, or on a suspension containing said nanoparticles.

[0060] In this description, the groups of chemical elements may be 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 (or VIIIB) according to the CAS classification corresponds to the metals in columns 8, 9, and 10 according to the new IUP AC classification, and group VIB to the metals in column 6.

[0061] Where standards are cited in this description, they refer to the most recent published versions at the date of filing of this application, unless otherwise specified.

[0062] Process for preparing the solid entrained hydroconversion catalyst

[0063] According to the hydroconversion process according to the invention, the entrained solid hydroconversion catalyst is prepared according to a simple preparation process to be implemented, comprising a single step of formation of bimetallic sulfide nanoparticles MMoS, M being metal of group VIIIB, preferably nickel or cobalt, and more preferably nickel (NiMoS), in the form of monosheets, in particular of very small dimensions (medium size), by decomposition of organosoluble precursors containing at least one metal-sulfur bond as described below.

[0064] According to the invention, it is possible to dispense with a sulfidation step of the entrained catalyst before it is used for hydroconversion in the entrained bed hydroconversion reactor, that is to say, before any mixing or contact with the The charge to be treated in the hydroconversion process, whether it is in-situ sulfidation during the hydroconversion process or ex-situ sulfidation during the ex-situ preparation of the catalyst, is because the entrained catalyst from the preparation process (ex-situ) is already in an active sulfide form. It is referred to as the entrained solid catalyst.

[0065] The nanoparticles obtained are detailed below, after the description of the process for preparing the entrained solid catalyst.

[0066] The synthesis of the nanoparticles of driven solid catalyst is carried out from organosoluble precursors comprising at least one molybdenum-sulfur bond, for a first organosoluble precursor comprising molybdenum, and at least one metal-sulfur bond for a second organosoluble precursor comprising a metal M, said metal M of the metal-sulfur bond belonging to group VIIIB. These organosoluble precursors include a ligand selected from the following families: dithiocarbamates, dithiophosphates, xanthates, dithioimidophosphinates, and dithioimidophosphates. These organosoluble precursors are coordination complexes comprising at least one metal-sulfur bond (molybdenum-sulfur or metal M-sulfur) and organic ligands whose structure is that of the aforementioned families.

[0067] Dithiocarbamates are a family of compounds comprising a sulfur atom and a thiolate group bonded to a carbon atom, which is itself bonded to an amine group, with a general structure of RR'NC(S)S-.

[0068] Dithiophosphates, also called dithiophosphorodithioates, are a family of compounds possessing bonds between phosphorus, oxygen and sulfur, with a general structure (RO)(R'O)P(S)S-.

[0069] Xanthates are a family of compounds with the general structure ROC(S)S-.

[0070] Dithioimidophosphinates are a family of compounds comprising a phosphorus-sulfur bond and a phosphorus-nitrogen bond, with a general structure of -P(S)NHR.

[0071] Dithioimidophosphates are a family of compounds similar to the dithioimidophosphinate family but with an oxygen atom bonded to the phosphorus, with the general structure -P(S)(OR)NR'R”.

[0072] The process for preparing the entrained solid catalyst comprises (i) a step of decomposing the first organosoluble precursor comprising at least one molybdenum-sulfur (Mo-S) bond and the second organosoluble precursor comprising a metal M-sulfur (MS) bond, M being a Group VIII metal, e.g., nickel, said first and second organosoluble precursors comprising a ligand selected from the list of families consisting of dithiocarbamates, dithiophosphates, xanthates, dithioimidophosphinates, and dithioimidophosphates, in the presence of an organic stabilizing agent, at a temperature between 100°C and 350°C, preferably between 150°C and 230°C, and preferably equal to approximately 200°C, for example at 220°C, and for a period of between 1 minute and 24 h, preferably between 10 minutes and 24 h, preferably between 20 minutes and 5 h, more preferably between 45 minutes and 3 h, for example for 1 h.

[0073] According to one or more embodiments, step (i) includes the implementation of a mechanical action such as the application of a shear force.

[0074] According to one or more embodiments of the invention, the first organosoluble precursor corresponds to the general formulas (I) or (II) described below, and the second organosoluble precursor corresponds to the general formulas (III) or (IV) described below.

[0075] The first organosoluble precursor comprising molybdenum, with at least one molybdenum-sulfur bond, is preferably from the family of molybdenum dithiocarbamates, and preferably from the family of oxymolybdenum dithiocarbamates corresponding to the following general formula (I):

[0076] [Chem.l] in which the radicals RI, R2, R3, R4 are chosen independently from linear or branched alkyl groups, comprising from 1 to 12 carbon atoms (Cl-C12), cycloalkyl groups comprising from 6 to 12 carbon atoms (C6-C12), and aryl or alkyl-aryl groups comprising from 6 to 12 atoms (C6-C12). The radicals RI, R2, R3, R4 can thus be identical or different.

[0077] The first organosoluble precursor comprising molybdenum, with at least one molybdenum-sulfur bond, may also be from the family of molybdenum dithiophosphates, and preferably from the family of oxymolybdenum dithiophosphates corresponding to the following general formula (II):

[0078] [Chem.2] in which the radicals RI, R2, R3, R4 are chosen independently from linear or branched alkyl groups, comprising from 1 to 12 carbon atoms (Cl-C12), cycloalkyl groups comprising from 6 to 12 carbon atoms (C6-C12), and aryl or alkyl-aryl groups comprising 6 to 12 atoms (C6-C12). The radicals RI, R2, R3, R4 can therefore be identical or different.

[0079] The second organosoluble precursor comprising a metal M from group VIII, with at least one metal-sulfur bond MS, e.g. nickel with at least one Ni-S bond, is preferably from the family of dithiocarbamates of metal M corresponding to the general formula (III) or from the family of dithiophosphates of metal M of general formula (IV).

[0080] [Chem.3] R1 Sx ZS r3 NC / M ;x~i< R2 s R4

[0081] [Chem.4] R^O. AA ,or3 x in which the radicals RI, R2, R3, R4 are chosen independently from linear or branched alkyl groups, comprising from 1 to 12 carbon atoms (Cl-C12), cycloalkyl groups comprising from 6 to 12 carbon atoms (C6-C12), and aryl or alkyl-aryl groups comprising from 6 to 12 atoms (C6-C12). The radicals RI, R2, R3, R4 can thus be identical or different.

[0082] In the general formulas (I), (II), (III) and (IV), the bonds shown in dotted lines correspond to a delocalized double bond.

[0083] Preferably, the group VIII metal M of the second organosoluble precursor is nickel or cobalt, and more preferably nickel.

[0084] According to one or more embodiments, the first organosoluble precursor is of the family of oxymolybdenum dithiocarbamates of general formula (I) or oxymolybdenum dithiophosphates of general formula (II) in which the radicals RI, R2, R3, R4 are identical linear or branched alkyl groups comprising from 1 to 12 carbon atoms (C1-C12), and preferably identical linear alkyl groups comprising from 1 to 6 carbon atoms (C1-C6) or identical branched alkyl groups comprising from 1 to 12 carbon atoms (Cl-Cl2). For example, the first organosoluble precursor is chosen from the list consisting of: oxymolybdenum dimethyldithiocarbamate, oxymolybdenum diethyldithiocarbamate, oxymolybdenum dipropyldithiocarbamate, oxymolybdenum dibutyldithiocarbamate, oxymolybdenum dipentyldithiocarbamate, oxymolybdenum dihexyldithiocarbamate.

[0085] According to one or more embodiments, the first organosoluble precursor is from the family of molybdenum dithiophosphates (dithiophosphorodithioates), and preferably from the family of oxymolybdenum dithiophosphates of general formula (II) in which the radicals RI, R2, R3, R4 are identical linear or branched alkyl groups comprising from 1 to 12 carbon atoms (Cl-C12), and preferably identical linear alkyl groups comprising from 1 to 6 carbon atoms (C1-C6) or identical branched alkyl groups comprising from 1 to 12 carbon atoms (C1-C12).For example, the first organosoluble precursor is chosen from the list consisting of: oxymolybdenum dimethylphosphorodithioate (dimethyldithiophosphate), oxymolybdenum diethylphosphorodithioate (diethyldithiophosphate), oxymolybdenum dipropylphosphorodithioate (dipropyldithiophosphate), oxymolybdenum dibutylphosphorodithioate (dibutyldithiophosphate), oxymolybdenum dipentylphosphorodithioate (dipentyldithiophosphate), oxymolybdenum dihexylphosphorodithioate (dihexyldithiophosphate), and oxymolybdenum di(2-ethylhexyl)phosphorodithioate.

[0086] According to one or more embodiments, the first organosoluble precursor is chosen from the list consisting of oxymolybdenum dimethyldithiocarbamate, oxymolybdenum diethyldithiocarbamate, oxymolybdenum dipropyldithiocarbamate, oxymolybdenum dibutyldithiocarbamate, oxymolybdenum dipentyldithiocarbamate, oxymolybdenum dihexyldithiocarbamate, oxymolybdenum dimethylphosphorodithioate, oxymolybdenum diethylphosphorodithioate, oxymolybdenum dipropylphosphorodithioate, oxymolybdenum dibutylphosphorodithioate, oxymolybdenum dipentylphosphorodithioate, oxymolybdenum dihexylphosphorodithioate, and the oxymolybdenum di(2-ethylhexyl) phosphorodithioate.

[0087] Preferably, the first organosoluble precursor is oxymolybdenum dibutyldithiocarbamate, oxymolybdenum dibutyldithiophosphate or oxymolybdenum di(2-ethylhexyl)phosphoodithioate.

[0088] According to one or more embodiments, the second organosoluble precursor comprising the metal M, e.g. nickel, with at least one MS bond, is of the family of dithiophosphates of metal M corresponding to the general formula (IV), and preferably in which the radicals RI, R2, R3, R4 are identical linear or branched alkyl groups comprising from 1 to 12 carbon atoms (Cl-Cl2), and more preferably identical linear alkyl groups comprising from 1 to 6 carbon atoms (C1-C6). For example, if the metal M is nickel, the second organosoluble precursor is chosen from the list consisting of: nickel dimethyldithiophosphate, Nickel diethyldithiophosphate, nickel dipropyldithiophosphate, nickel dibutyldithiophosphate, nickel dipentyldithiophosphate, and nickel dihexyldithiophosphate are examples of dithiophosphate compounds. Similar dithiophosphate compounds (linear C1-C6 alkyl chains) with another Group VIII metal can, for example, be used as a second organosoluble precursor.

[0089] According to one or more embodiments, the second organosoluble precursor comprising the metal M, e.g. nickel, with at least one MS bond, is of the family of dithiocarbamates of metal M corresponding to the general formula (III), and preferably in which the radicals RI, R2, R3, R4 are identical linear or branched alkyl groups comprising from 1 to 12 carbon atoms (Cl-Cl2), and more preferably identical linear alkyl groups comprising from 1 to 6 carbon atoms (C1-C6). For example, if the metal M is nickel, the second organosoluble precursor is chosen from the following list: nickel dimethyldithiocarbamate, nickel diethyldithiocarbamate, nickel dipropyldithiocarbamate, nickel dibutyldithiocarbamate, nickel dipentyldithiocarbamate, and nickel dihexyldithiocarbamate. Similar metal dithiocarbamate compounds (linear C1-C6 alkyl chains) with another Group VIII metal can also be used as the second organosoluble precursor.

[0090] Preferably, the second organosoluble precursor is nickel dibutyldithiocarbamate.

[0091] The organic stabilizing agent, whose role is notably to stabilize the nanoparticles during formation, in particular to control their size and shape by limiting their growth or agglomeration, is preferably chosen from the group consisting of: - alkylamines selected from primary and secondary amines having a hydrocarbon chain comprising 4 to 34 carbon atoms (C4-C34), preferably comprising 12 to 18 carbon atoms (C12-C18), and optionally comprising one or more unsaturations, preferably selected from the list consisting of octylamine, dodecylamine, hexadecylamine, octadecylamine, and oleylamine; - alkylthiols having a hydrocarbon chain from C6 to C18 (i.e. having 6 to 18 carbon atoms), preferably chosen from the list consisting of 1-hexane thiol, 1-octanethiol, 1-dodecanethiol, and 1-hexadecanethiol; - carboxylic acids having a hydrocarbon chain comprising 6 to 18 carbon atoms (C6-C18), preferably chosen from the list consisting of citric acid, octanoic acid, decanoic acid, palmitic acid, and oleic acid; - phosphines, preferably chosen from the list consisting of tributylphosphine, triooctylphosphine, trioctylphosphine oxide, and triphenylphosphine.

[0092] Preferably, the organic stabilizing agent is an alkylamine chosen from the list consisting of roctylamine, dodecylamine, hexadecylamine, octadecylamine, and oleylamine, and preferably is hexadecylamine.

[0093] The organic stabilizing agent is preferably in molar excess with respect to the organosoluble precursors (total number of moles of metals M and Mo of the first and second organosoluble precursors).

[0094] Preferably, the molar ratio of metallic elements (M+Mo) to organic stabilizing agent, e.g. the molar ratio of the sum of Ni and Mo elements (Ni+Mo) to organic stabilizing agent, is between 0.001 and 0.1, more preferably is between 0.005 and 0.05.

[0095] The molar ratio M / Mo, e.g. Ni / Mo, is preferably between 0.1 and 1, more preferably between 0.2 and 0.8.

[0096] Preferably, the decomposition step, the thermal decomposition, is carried out at atmospheric pressure.

[0097] The decomposition step can be carried out in an organic synthesis solvent with a boiling point above 100°C (by "organic synthesis solvent" is meant an organic solvent used in the synthesis of nanoparticles), or directly in the organic stabilizing agent. This organic synthesis solvent can be chosen, for example, from: toluene, ethylbenzene, xylene, mesitylene, decane, dodecane, etc.

[0098] Preferably, an active mixing, for example a mixing by magnetic stirring, mechanical stirring or any other means of stirring, is implemented at the decomposition stage, in order to ensure good mixing of the compounds and good formation of the nanoparticles.

[0099] The decomposition step of the process for preparing the entrained solid catalyst allows the obtaining of metal sulfide nanoparticles without requiring a sulfidation step under H2S or by adding another sulfurating agent, during the synthesis itself or post-synthesis, before use of the entrained solid catalyst.

[0100] By controlling the various parameters, such as temperature, synthesis time, nature of the organic stabilizing agent, and possibly the quantity of the organic stabilizing agent, agitation, etc., it is possible to control the size and shape of the nanoparticles obtained, detailed later.

[0101] Following the decomposition step (i), the nanoparticles are preferably in a solution containing an organic stabilizing agent, and optionally a solvent of organic synthesis if such an organic synthesis solvent was used during the decomposition step, forming a colloidal solution.

[0102] The process for preparing the entrained solid catalyst may include a step of separating (ii) the nanoparticles from the colloidal solution, i.e. a separation between the hydroconversion catalyst nanoparticles and the organic stabilizing agent or the organic stabilizing agent / organic synthesis solvent mixture) from a colloidal solution obtained at the end of the decomposition step (i), and optionally a washing step (iii) and / or a drying step (iv) of said separated nanoparticles.

[0103] The separation step (ii) can be any liquid-solid separation method known to the person skilled in the art, and is preferably carried out by centrifugation or filtration.

[0104] The washing step (iii) is preferably carried out with an organic washing solution, for example with toluene, xylene, mesitylene, methanol, or ethanol, and advantageously with an amount of washing solution equal to the amount of filtered solid.

[0105] The drying step (iv) is preferably carried out at a temperature between 15°C and 200°C, and more preferably between 20°C and 150°C, using any technique known to those skilled in the art, advantageously for a duration of between 10 minutes and 24 hours, more preferably between 20 minutes and 24 hours, and more preferably between 30 minutes and 3 hours. Preferably, said drying step (iv) is carried out under an inert gas, and more preferably under vacuum. Preferably, the drying is carried out using a vacuum manifold.

[0106] Preferably, the synthesis process according to the invention does not include a calcination or heating step at a temperature above 200°C.

[0107] Nanoparticles of the entrained solid hydroconversion catalyst obtained from the preparation process

[0108] The catalyst nanoparticles obtained, which are bimetallic sulfide nanoparticles MMoS, e.g. NiMoS, are advantageously in the form of single sheets, i.e. mainly without stacking, and advantageously have an average size, corresponding to the average length of the sheet in the present description, substantially between 1 nm and 25 nm, preferably between 1 nm and 10 nm, and preferably between 1 nm and 6 nm, more preferably between 1 nm and 5 nm.

[0109] By mainly without stacking, it is understood that the nanoparticles can be in the form of isolated sheets formed by monosheets and / or stacks of monosheets comprising a maximum of five monosheets, preferably a maximum of two monosheets, and preferably formed by monosheets without any stacking of monosheets.

[0110] The catalyst nanoparticles exhibit good monodispersity, i.e. a size distribution between 0.1 nm and 5 nm, preferably between 0.2 nm and 3 nm and preferably between 0.2 nm and 2 nm relative to the average size (average length).

[0111] A person skilled in the art is familiar with the appropriate techniques for determining the average particle size and is also aware of the degree of uncertainty in these measurements. For example, the length of the sheets in an assembly, the standard deviation, and the size distribution can be determined by statistical studies using microscopy images, and in particular by transmission electron microscopy (TEM). The number-average length is calculated on at least 250 nanoparticles. The standard deviation is calculated as the square root of the variance.

[0112] The single-sheet crystalline structure of the nanoparticles obtained can be demonstrated by TEM or any other technique known to those skilled in the art.

[0113] Bimetallic sulfide nanoparticles MMoS, e.g. NiMoS, correspond to Mo disulfide (MoS2) crystallites in the form of sheets, in particular single sheets, comprising the metal M, e.g. nickel, as decoration, at the periphery of the sheets, the metal M (e.g. Ni) replacing molybdenum at certain positions.

[0114] The nanoparticles obtained by the synthesis process described advantageously form an active sulfide-entrained solid catalyst which can be used directly in an entrained bed hydroconversion process according to the invention, without necessarily having to implement an additional sulfidation step to have a functional entrained solid catalyst available, which is the active sulfide-entrained catalyst.

[0115] The nanoparticles obtained by the described synthesis process can be used as an entrained catalyst for a hydroconversion process, but also for a hydrotreating process without departing from the scope of the present invention. They are therefore suitable for use as an entrained catalyst in hydrotreating. Hydroconversion process

[0116] The present invention relates to a hydroconversion process for a heavy hydrocarbon feedstock, i.e., a hydrocarbon feedstock comprising a fraction of at least 50% by weight having a boiling point of at least 300°C, comprising: a) a hydroconversion step of said heavy hydrocarbon feedstock in a hydroconversion section comprising at least one hydroconversion reactor operating in a driven bed in the presence of hydrogen, and at least one driven solid hydroconversion catalyst, to produce a hydroconverted effluent, said driven solid hydroconversion catalyst being in the form of bimetallic sulfide nanoparticles MMoS, e.g. NiMoS, obtained by the ex-preparation process situ described in detail above, in particular said preparation process (ex-situ) comprising (i) a decomposition step of a first organosoluble precursor comprising at least one molybdenum-sulfur bond and of a second organosoluble precursor comprising at least one metal M-sulfur bond, in the presence of an organic stabilizing agent, at a temperature between 100°C and 350°C and for a duration between 1 minute and 24 h, said first and second organosoluble precursors comprising a ligand selected from the list of the following families: dithiocarbamates, dithiophosphates, xanthates, dithioimidophosphinates, and dithioimidophosphates, and said organic stabilizing agent being selected from the group consisting of: - alkylamines selected from primary amines and secondary amines comprising a hydrocarbon chain from C4 to C34; - alkylthiols containing a hydrocarbon chain in C6 to C18; - carboxylic acids with a hydrocarbon chain from C6 to Cl8; - phosphines.

[0117] By ex-situ in reference to the catalyst preparation process, it is understood that the solid nanoparticles of the entrained catalyst comprising the metal sulfides are formed before any mixing or contact with the feed to be treated in the hydroconversion process. Charge

[0118] In this description, the term "charge" or "hydrocarbon charge" means the heavy hydrocarbon charge sent to hydroconversion, as defined below, unless otherwise specified.

[0119] The hydrocarbon feed sent to hydroconversion is a feed. It contains a fraction of at least 50% by weight having a boiling point of at least 300°C, preferably of at least 350°C, preferably of at least 375°C, of ​​at least 450°C, preferably of at least 500°C, and even more preferably of at least 540°C.

[0120] The hydrocarbon charge can be a charge of fossil origin.

[0121] Preferably, the hydrocarbon feedstock comprises, and may consist of, one of the following fossil-based feedstocks, alone or in mixture: - crude oil, - synthetic crude oil, - a coal tar, - a bitumen made from tar sands, - a heavy oil derived from oil shale, - an atmospheric residue or a vacuum residue resulting from the atmospheric or vacuum distillation of crude oil, - an atmospheric residue or a vacuum residue from the atmospheric or vacuum distillation of an effluent from a thermal conversion unit or hydrotreating or hydrocracking or hydroconversion unit or a direct coal liquefaction unit (for example operated according to the H-Coal® process), - a vacuum distillate obtained directly from crude oil or a cut from a fluidized bed catalytic cracking unit (also called FCC for Fluid Catalytic Cracking according to Anglo-Saxon terminology) or from a hydrocracking unit or a hydroconversion unit or a coking unit or a visbreaking unit, - a vacuum distillate from the direct liquefaction of coal, aromatic cuts extracted from a lubricant production unit, - a deasphalted oil (also called DAO for Deasphalted oil according to Anglo-Saxon terminology), or a resin fraction or an asphalt fraction from a deasphalting unit.

[0122] The aforementioned fillers of the type vacuum distillates, aromatic cuts, deasphalted oils and resin fractions may enter into the composition of the hydrocarbon filler preferably in a minor quantity with another type of filler mentioned above.

[0123] The aforementioned feedstocks are liquid under the operating conditions of hydroconversion.

[0124] Preferably, the hydrocarbon feedstock comprises, and may consist of, one of the following feedstocks, alone or in mixture: - crude oil, - synthetic crude oil, - coal tar, - bitumen from oil sands, - a heavy oil derived from oil shale, - an atmospheric residue or a vacuum residue resulting from the atmospheric or vacuum distillation of crude oil, - an atmospheric residue or a vacuum residue from the atmospheric or vacuum distillation of an effluent from a thermal conversion unit or hydrotreating or hydrocracking or hydroconversion unit or a direct coal liquefaction unit (for example operated according to the H-Coal® process), a vacuum residue from the vacuum distillation of crude oil.

[0125] Preferably, the hydrocarbon feed comprises, and may consist of, a vacuum residue from the vacuum distillation of crude oil.

[0126] The hydrocarbon load can also come from the conversion of biomass, in particular algae or lignocellulosic biomass, and in particular be a “bio-oil” or a “bio-crude”.

[0127] The term biomass refers to material derived from recently living organisms, including plants, animals, and their by-products. The term lignocellulosic biomass refers to biomass derived from plants or their by-products. Lignocellulosic biomass is composed of carbohydrate polymers (cellulose, hemicellulose) and an aromatic polymer (lignin).

[0128] The biomass from which these bio-oils and bio-crudes are derived can be chosen from algae, plants, grasses, trees, wood chips, seeds, fibers, seed coats, aquatic plants, hay and other sources of lignocellulosic materials, such as, for example, those from municipal waste, agri-food waste, forestry waste, logging residues, agricultural and industrial waste (such as, for example, sugar cane bagasse, waste from oil palm cultivation, sawdust or straw), paper pulp and by-products of recycled or non-recycled paper or by-products from the paper industry.

[0129] A bio-oil corresponds to the liquid products obtained by thermochemical liquefaction of biomass, preferably by pyrolysis, and most preferably by rapid or slow pyrolysis with or without a catalyst (in the presence of a catalyst, this is called catalytic pyrolysis). Pyrolysis is a thermal decomposition in the absence of oxygen, with thermal cracking of the feedstock into gas, liquid, and solid. A catalyst can advantageously be added to enhance the conversion during so-called catalytic pyrolysis. Rapid pyrolysis, for example, tends to maximize the liquid yield. During rapid pyrolysis, the temperature of the biomass, possibly finely divided, is rapidly raised to values ​​above approximately 300°C and preferably between 300 and 900°C, and the liquid products are condensed in the form of bio-oil. A bio-oil is a complex mixture of oxygenated compounds, obtained from the breakdown of biopolymers present in the original biomass. In the case of lignocellulosic biomass, the structures derived from its three main components—cellulose, hemicellulose, and lignin—are well represented by the components of the bio-oil. In particular, a bio-oil is a polar, highly oxygenated hydrocarbon product that generally contains at least 10% by weight of oxygen, preferably 10 to 60% by weight, and preferably 20 to 50% by weight of oxygen relative to the total mass of said bio-oil. Generally, the oxygenated compounds are alcohols, aldehydes, esters, ethers, organic acids, and aromatic oxygenated compounds. A portion of the oxygen is present as free water, representing at least 5% by weight, preferably at least 10% by weight, and preferably at least 20% by weight of the bio-oil.

[0130] A biocrude corresponds to the products obtained by hydrothermal liquefaction of biomass (acronym "HTL" according to the Anglo-Saxon terminology "HydroThermal Liquefaction"), and consists mainly of organic molecules, an aqueous phase comprising water-soluble organic compounds (alcohols, acids, ketones, phenols, etc.) and salts, gas, and possibly biochar. Biochar is a solid product rich in carbon; "char" comes from the English word "charcoal." The gas produced consists mainly of CO2 but may also contain hydrogen, methane, and CO. Biocrude is therefore a complex mixture of compounds, consisting mainly of hydrocarbons and oxygenated compounds. Generally, the oxygenated compounds are organic acids, ketones, oxygenated aromatic compounds, alcohols, aldehydes, esters, ethers, and water. Water typically represents less than 15% of the biocrude's weight. In the case of a lignocellulosic biomass feedstock, the biocrude contains compounds derived from cellulose, hemicellulose, and lignin (the structure present in lignocellulosic biomass). Biocrude has an oxygen, sulfur, and nitrogen content that varies greatly depending on the biomass load of the hydrothermal liquefaction (algae, wood, etc.). For example, biocrude resulting from hydrothermal liquefaction of wood generally contains 5 to 20% by weight of oxygen, less than 0.5% by weight of sulfur, and less than 5% by weight of nitrogen in the dry (water-free) biocrude.

[0131] The biocrude may contain up to 4% by weight of inorganic (mineral) compounds, primarily metals such as sodium and potassium, but also calcium, iron, etc. These mineral compounds may originate from the catalysts used for hydrothermal liquefaction, from the biomass feedstock of the hydrothermal liquefaction itself, and from any metals used to grind the hydrothermal liquefaction feedstock. Sodium and potassium may be present in relatively large quantities in the biocrude because the hydrothermal liquefaction process generally uses alkali-based catalysts (NaOH, KOH, K2CO3, Na2CO3, etc.) in significant quantities.

[0132] Bio-oils and bio-crudes feedstocks can be pre-treated, for example stabilized and / or demineralized before hydroconversion.

[0133] The hydrocarbon charge can also be obtained from the conversion by thermochemical liquefaction of plastic waste, tires or solid recovered fuels (SRF), and in particular be a pyrolysis oil of plastics, tires or SRF. The pyrolysis oil from plastics, tires, or RDF can be obtained by a pyrolysis process with or without a catalyst (thermal pyrolysis versus catalytic pyrolysis), or by hydropyrolysis (pyrolysis in the presence of a catalyst). and hydrogen). Plastics are typically production by-products and / or waste (e.g., household, building, electrical and electronic equipment waste), and preferably include alkene, diene, vinyl, styrenic, polyester, and / or polyamide polymers, and more preferably polyolefins, such as polyethylene (PE), polypropylene (PP), or ethylene and propylene copolymers.

[0134] The pyrolysis oil of plastics, and / or tires, and / or RDF is an oil, advantageously in liquid form at room temperature, and comprises hydrocarbon compounds and impurities such as in particular mono- and / or di-olefins, naphthenes and aromatics, metals, in particular silicon and iron, halogenated compounds, in particular chlorinated compounds, heteroelements supplied by sulfur compounds, oxygenated compounds and / or nitrogenous compounds. These impurities (halogenated compounds and contaminants of a metallic nature including alkali metals, alkaline earth metals, transition metals, poor metals and metalloids) are often present at high levels, for example up to 350 ppm by weight or even 700 ppm by weight or even 1000 ppm by weight of halogenated elements brought by halogenated compounds, and up to 100 ppm by weight, or even 200 ppm by weight of contaminants of a metallic nature.

[0135] The hydrocarbon charge typically contains metals (also referred to here as metallic contaminants) and other impurities such as sulfur, nitrogen, Conradson carbon and asphaltenes, in particular C7 asphaltenes which are insoluble in heptane. The metal content in the charge can be greater than or equal to 2 ppm by weight, or greater than or equal to 20 ppm by weight, or greater than or equal to 50 ppm by weight, or even 100 ppm or 200 ppm by weight.

[0136] The sulfur content may be greater than or equal to 0.1% by weight, or even greater than or equal to 0.5% or 1%, and may be greater than or equal to 2% by weight. The nitrogen content can be between 1 ppm and 8000 ppm by weight, more generally between 200 ppm and 8000 ppm by weight, for example between 2000 ppm and 8000 ppm by weight. The content of C7 asphaltenes (heptane-insoluble compounds according to ASTM D 6560, which also corresponds to NF T60-115) can be as low as 1% by weight and is often greater than or equal to 3% by weight (except for feedstock consisting primarily of DAO). C7 asphaltenes are known to inhibit the conversion of residual cuttings, both through their ability to form heavy hydrocarbon residues, commonly called coke, and through their tendency to produce sediments that can severely limit the operability of hydroconversion units. The Conradson carbon content can be greater than or equal to 3% by weight, or even at least 5% by weight. The Conradson carbon content is defined by ASTM D482 and represents, for those skilled in the art, a well-known assessment of the amount of carbon residue produced after pyrolysis under standard temperature and pressure conditions.

[0137] These contents are expressed as a percentage by weight of the total weight of the hydrocarbon feedstock.

[0138] According to one or more embodiments, a co-feedstock can be sent to the hydroconversion stage with the hydrocarbon feedstock as described above, preferably said co-feedstock being in the minority with respect to the hydrocarbon feedstock and, for example, represented less than 30% by mass, preferably less than 20% or 10% by mass with respect to the hydrocarbon feedstock.

[0139] Preferably, the co-charge comprises, and may consist of, one of the following co-charges, alone or in mixture: - A vegetable and / or animal oil or fat, typically containing triglycerides and / or free fatty acids and / or esters, which may be crude or refined. Vegetable oils may be derived, for example, from rapeseed, soybean, sunflower, palm, palm kernel, olive, coconut, castor, cottonseed, peanut, flax, crambe, and jatropha, including all oils obtained through genetic modification or hybridization. Vegetable and animal oils may be used oils, such as frying oils, or any used oil or fat from the food service industry. Animal oils and fats may be, for example, fish oil, tallow, or lard. - biomass such as algae, lignocellulosic biomass, or one or more lignocellulosic biomass constituents chosen from the group formed by cellulose, hemicellulose and lignin. - plastics, and / or tires and / or RDF, the plastics being typically production waste and / or refuse as already described above.

[0140] The co-charge may undergo a pre-treatment step, for example mechanical and / or chemical treatment, such as drying and / or roasting and / or grinding for biomass, or grinding and / or washing and / or drying and / or heating liquefaction and / or dissolution for plastics, before being sent to the hydroconversion step.

[0141] The co-feed and the hydrocarbon feed can be sent independently, or mixed, into the hydroconversion reactor. In the following description, no reference is made to the co-feed itself, it being understood that what is described for the hydroconversion of the feed applies to the co-feed treated with the feed. Implementation Hydroconversion stage

[0142] The heavy hydrocarbon feedstock is introduced into at least one hydroconversion reactor operating in a driven bed configuration of the hydroconversion section, together with hydrogen. Said reactor includes the driven solid catalyst, which can be injected in mixture with the feedstock or independently of the feedstock injection, as detailed later in the description.

[0143] The hydroconversion step a) is carried out under conditions that produce a hydroconverted effluent containing the conversion products. The hydroconverted effluent has, in particular, a reduced content (compared to the feed) of hydrocarbons having a boiling point of at least 300°C, or at least 350°C, 375°C, 450°C, 500°C, or even 540°C, depending on the nature of the feed. This hydroconverted effluent also has a reduced content, compared to the feed, of metals, and / or sulfur, and / or nitrogen, and / or Conradson carbon, and / or asphaltenes, and / or other impurities initially present in the feed, depending on the reactions carried out in the hydroconversion reactor and the composition of the feed. In particular, the said hydroconverted effluent may advantageously have a reduced content, relative to the load, of metals, sulfur, nitrogen, Conradson carbon, and asphaltenes. The hydroconversion step a) is preferably carried out under an absolute pressure between 2 MPa and 38 MPa, more preferably between 5 MPa and 25 MPa, and even more preferably between 6 MPa and 20 MPa, at a temperature between 300°C and 550°C, more preferably between 350°C and 500°C, preferably between 370°C and 450°C, and even more preferably between 400°C and 450°C. The hourly space velocity (WH) is preferably between 0.05 h₁ and 10 h₁ (WH relative to the volume of each reactor). The hourly space velocity (WH), also called the hourly volumetric velocity (liquid hourly space velocity "LHSV" or hourly space velocity "HSV" according to Anglo-Saxon terminology), is defined here as the ratio between the hourly volumetric flow rate of the liquid feed (sent to the hydroconversion stage) and the volume of each hydroconversion reactor. In a preferred implementation, the WH is between 0.1 h₁ and 10 h₁, more preferably between 0.1 h₁ and 5 h₁, and even more preferably between 0.15 h₁ and 2 h₁. According to another implementation, the overall WH, i.e. the flow rate of liquid feed sent to stage a) relative to the volume of all reactors if several hydroconversion reactors are implemented in stage a), is between 0.05 h 1 and 0.09 h'. The quantity of hydrogen mixed with the feed is preferably between 50 and 5000 normal cubic meters (Nm3) per cubic meter (m3) of liquid feed, preferably between 100 Nm / m and 2000 Nm / m and most preferably between 500 Nm / m3 and 1500 Nm3 / m3.

[0144] The hydroconversion section comprises one or more reactors operating in a driven bed.

[0145] When several entrained bed hydroconversion reactors are implemented, they can be in series and / or in parallel.

[0146] The entrained bed reactor is a three-phase reactor comprising a liquid hydrocarbon phase including the heavy hydrocarbon feed, a solid phase including the entrained solid catalyst which is dispersed in the heavy hydrocarbon feed, and a gaseous phase including hydrogen.

[0147] This type of reactor is well known to those skilled in the art. The entrained bed hydroconversion reactor preferably includes an upward flow of liquid and gas.

[0148] During operation with an upward flow of liquid and gas, the entrained bed reactor preferably includes an inlet port located at or near the lower part of the entrained bed reactor through which the feed is introduced together with the hydrogen (or two inlet ports in the case where the feed is introduced separately from the entrained solid catalyst by means of two separate flows), and an outlet port at or near the upper part of the reactor through which the hydroconverted effluent (recovered feed) is withdrawn.

[0149] The entrained solid catalyst exits the entrained bed reactor with the hydroconverted effluent.

[0150] The entrained bed reactor may include at its lower part a device for dispersing hydrogen and charge more uniformly.

[0151] The entrained bed reactor may include a former bubbling bed reactor converted into an entrained bed reactor by removing the porous supported catalyst from the former bubbling bed reactor.

[0152] Many processes operating in a driven bed are known, which differ essentially in their catalysts and operating conditions. Entrained bed processes are described, for example, in US patents 4,299,685, 6,660,158, 7,001,502, 7,223,713, 7,585,406, 7,651,604, 7,691,256, 7,892,416, 8,017,000, 8,105,482, and 8,110,090, or in the article by Castaneda et al., "Current situation of emerging technologies for upgrading of heavy oils," published in 2014 in Catalysis Today, vol. 15, pp. 220-222, pages 248-273, or in Chapter 18, "Catalytic Hydrotreatment and Hydroconversion: Fixed Bed, Moving Bed, Ebullated Bed and Entrained Bed" from the book "Heavy Crude Oils: From Geology to Upgrading, An OverView", published by Editions Technip in 2011. The theoretical advantages of entrained bed processes lie in significantly improved hydrogenation, particularly of heavier products, thanks to better accessibility of active sites, resulting in higher conversion rates, improved product quality, and greater product stability. The use of such entrained bed reactors, as with bubbling bed reactors, also allows operation under more severe conditions (e.g., temperature, hydrogen partial pressure, residence time) than, for example, those encountered in a fixed-bed catalyst reactor, enabling better overall feed conversion. Furthermore, the use of entrained bed reactors eliminates the need for unit shutdowns to replace a supported solid catalyst, as is the case with fixed-bed technologies.Furthermore, compared to bubbling bed technologies employing a supported solid catalyst, catalyst deactivation is greatly reduced due to the shorter catalyst residence time in the reactor.

[0153] The entrained solid catalyst has a particle size and density adapted for its entrainment in the entrained bed hydroconversion reactor. Entrainment of the entrained solid catalyst means its circulation in the hydroconversion reactor(s) by the liquid streams, said entrained solid catalyst circulating with the feed in said reactor(s), and being withdrawn from said reactor(s) with the produced liquid effluent.Thanks to its nanometric size, more particularly because the entrained solid catalyst is in the form of monosheets typically between 1 nm and 25 nm in length, preferably between 1 nm and 10 nm, more preferably between 1 nm and 6 nm, and even more preferably between 1 nm and 5 nm, the entrained catalyst is very well dispersed in the feed to be converted, thus greatly improving the hydrogenation and hydroconversion reactions throughout the reactor(s), considerably limiting the formation of coke and sediments and allowing in particular a very good conversion of the heavy fraction of the feed.

[0154] According to one or more embodiments, the concentration of the entrained solid catalyst is between 10 ppm and 10000 ppm by weight of molybdenum relative to the heavy hydrocarbon feed at the reactor inlet (does not take into account possible recycles of the entrained solid catalyst), preferably between 50 ppm and 6000 ppm by weight, preferably between 100 ppm and 1000 ppm by weight, particularly preferably between 100 ppm and 800 ppm by weight.

[0155] According to one or more embodiments, a portion of the used entrained solid catalyst from the hydroconversion step is recycled in one or more hydroconversion reactors in order to limit the consumption of fresh entrained catalyst. The used entrained solid catalyst can be recovered from the heavy cuts of the hydroconverted effluent, for example, from a fractionation section, and can be reinjected into one or more entrained-bed hydroconversion reactors. Generally, instead of directly recycling the catalyst in an entrained-bed reactor, it undergoes one or more separations and possibly one or more treatments, such as combustion, solvent washing, gasification, or any other separation technique, or a combination of these steps. The heavy cuts of the hydroconverted effluent can also be obtained, for example, by a deasphalting process, and in this case, the entrained solid catalyst can be recycled to the hydroconversion stage along with the asphalt fraction. Injection of the driven solid catalyst

[0156] The entrained solid catalyst can be introduced into the hydroconversion reactor according to different implementations.

[0157] According to one or more embodiments, the entrained solid catalyst is injected into the hydroconversion reactor with the heavy hydrocarbon feed in the same flow, said entrained solid catalyst having been previously mixed with the feed. The nanoparticles of the entrained solid catalyst can be mixed with the feed in the different ways (A), (B) or (C) below:

[0158] (A) at the end of the process for preparing the solid hydroconversion catalyst Entrained solid catalyst nanoparticles can be in the form of a colloidal solution containing an organic stabilizing agent, and possibly an organic synthesis solvent (used during the nanoparticle preparation process). The colloidal solution can then be mixed with the heavy hydrocarbon filler.

[0159] (B) at the end of the process for preparing the solid hydroconversion catalyst The nanoparticles may have been separated from excess organic stabilizing agent, and possibly from the organic synthesis solvent, by any separation method known to those skilled in the art, preferably by centrifugation or filtration, and may then optionally have been dried. The nanoparticles thus separated, and optionally dried, obtained at the end of the preparation process, can then be mixed with the heavy hydrocarbon filler.

[0160] (C) at the end of the process for preparing the solid hydroconversion catalyst The nanoparticles, once prepared, may have been separated from the excess organic stabilizing agent, and possibly the organic synthesis solvent, by any separation method known to those skilled in the art, preferably by centrifugation or filtration. The nanoparticles thus separated, obtained at the end of the preparation process, may then be redispersed in a liquid, forming a mixture. colloidal, before being mixed with the heavy hydrocarbon filler, said liquid may comprise, or consist of, one or more of the following liquids: -an organic solvent such as toluene, xylene, mesitylene; - any other liquid hydrocarbon such as naphtha, gasoline, diesel, pyrolysis oil for example from a steam cracker, fluidized bed catalytic cracking effluent FCC such as light cycle oil (LCO) or heavy cycle oil (HCO), aromatic extract for example from a lubricant production unit, VGO, vacuum residue (RSV), or effluent from a deasphalting process such as DAO, and preferably VGO; - any other recycled liquid effluent from the hydroconversion process. Preferably, the separated nanoparticles obtained at the end of the preparation process are redispersed in a VGO.

[0161] During the mixing of the entrained solid feed / catalyst, it is possible to carry out an active dispersion step, i.e. implementing a mixing system, preferably a high shear mixer such as a mixer comprising a pump with a propeller or a turbine rotor, to help disperse the nanoparticles in the heavy hydrocarbon feed. In general, mixing can be carried out, without limitation, by means of a mixing system comprising one or more of the following devices taken alone or in combination: a static inline mixer, a high shear inline mixer, a high shear mixer comprising a pump with a propeller or turbine rotor, a recirculation pump with a buffer tank, a multi-stage centrifugal pump. According to one or more embodiments, continuous mixing rather than discontinuous mixing by successive batches can be implemented using high-energy pumps having several compartments in which the entrained solid catalyst and the heavy hydrocarbon feedstock are stirred and mixed. The mixing system described above can also be used for step (C) of redispersing the separated entrained solid catalyst nanoparticles from the preparation process in a liquid to form a colloidal mixture, before mixing said solution with the heavy hydrocarbon feed.

[0162] According to one or more embodiments, the entrained solid catalyst can be injected into the hydroconversion reactor independently of the heavy hydrocarbon feedstock, i.e., as a separate stream from the feedstock stream injected into the reactor. In this case, the catalyst can be introduced into the reactor in the form of the colloidal solution obtained at the end of the solid catalyst preparation process. entrained, comprising organic stabilizing agent and possibly organic synthesis solvent, or in the form of a colloidal solution obtained by redispersing the separated (and possibly washed and / or dried) nanoparticles obtained at the end of the entrained solid catalyst preparation process, in a hydrocarbon liquid as previously described for the injection method (C) above. Further treatment of the hydroconverted effluent

[0163] The hydroconverted effluent from step a) can be further treated.

[0164] Examples of such further treatment include, without limitation, at least one of the following: intermediate separation of hydrocarbon fractions of the hydroconverted effluent, for example gas / liquid separation; deeper hydroconversion in one or more additional entrained bed reactors to produce a second, further treated / converted hydroconverted effluent; fractionation into hydrocarbon fractions of the hydroconverted effluent; deasphalting of at least a portion of the hydroconverted effluent or of a heavy liquid fraction resulting from fractionation of the hydroconverted effluent or of a second hydroconverted effluent; purification in a guard bed of the hydroconverted effluent or of the second hydroconverted effluent to remove at least a portion of the entrained solid catalyst and metallic impurities.

[0165] The various hydrocarbon fractions that can be produced from the hydroconverted effluent can be sent to different processes within the refinery, and details of these post-treatments are not described here since they are generally known to those skilled in the art and would unnecessarily complicate the description. For example, gaseous fractions, naphtha, middle distillates, VGO, and DAO can be sent to hydrotreating, steam cracking, fluidized bed catalytic cracking (FCC), hydrocracking, lubricating oil extraction, etc. Residues (atmospheric or vacuum residues) can also be post-treated or used for other applications such as gasification, bitumen production, etc. Heavy fractions, including residues, can also be recycled back into the hydroconversion process, for example, in the entrained bed reactor.

[0166] According to one or more embodiments, the hydroconversion process further comprises: b) optionally an additional hydroconversion step in at least one additional driven bed reactor of at least part, or all, of the hydroconverted effluent resulting from hydroconversion step a) or optionally of a heavy liquid fraction which boils predominantly at a temperature greater than or equal to 350°C resulting from an optional intermediate separation step b') separating part, or all, of said hydroconverted effluent, resulting from hydroconversion step a), said additional entrained bed reactor operating under hydroconversion conditions to produce a second hydroconverted effluent having a reduced heavy residue fraction, a reduced Conradson carbon residue, and optionally a reduced amount of sulfur and / or nitrogen, and / or metals; c) a fractionation step of part, or all, of the hydroconverted effluent from hydroconversion step a) or of said second hydroconverted effluent, in a fractionation section to produce at least one heavy cut which boils predominantly at a temperature greater than or equal to 350°C, said heavy cut containing a residual fraction which boils at a temperature greater than or equal to 540°C; d) an optional step of deasphalting part of, or all of, said heavy cut in a deasphalter with at least one hydrocarbon solvent to produce a deasphalted oil DAO and residual asphalt.

[0167] The said additional hydroconversion step b) is carried out in a manner similar to that described for hydroconversion step a), and its description is therefore not repeated here. This applies in particular to the operating conditions and the equipment used, with the exception of the specifications mentioned below.

[0168] As with the hydroconversion step a), the additional hydroconversion step b) is carried out in at least one additional entrained bed reactor similar to the entrained bed reactor(s) of the hydroconversion step a).

[0169] In this additional hydroconversion step b), the operating conditions may be similar to or different from those in hydroconversion step a), the temperature remaining in the range between 300°C and 550°C, preferably between 350°C and 500°C, more preferably between 370°C and 450°C, more preferably between 400°C and 440°C, and even more preferably between 410°C and 435°C, and the quantity of hydrogen introduced into the reactor remains in the range between 50 and 5,000 Nm³ / m³ of liquid feed, preferably between 100 and 3,000 Nm³ / m³, and even more preferably between 200 and 2,000 Nm³ / m³. The other pressure and WH parameters are in the same ranges as those described for hydroconversion step a). The operating temperature at the additional hydroconversion stage b) may be higher than the operating temperature at the hydroconversion stage a).This can allow for a more complete conversion of the unconverted feedstock. The hydroconversion of liquid products from the hydroconversion step a) and of the feedstock is enhanced, as are hydrotreating reactions such as . Hydrodesulfurization and hydrodeazotation, among others. The operating conditions are chosen to minimize the formation of solids (e.g., coke).

[0170] The optional intermediate separation step b'), separating part, or all, of the hydroconverted effluent from step a), to produce at least two fractions comprising the heavy liquid fraction which boils predominantly at a temperature greater than or equal to 350°C, is implemented in a separation section.

[0171] The other fraction(s) resulting from this step b') are one or more light and / or intermediate fraction(s). The light fraction thus separated contains mainly gases (H2, H2S, NH3, and C1-C4), naphtha (fraction that boils at a temperature below 150°C), kerosene (fraction that boils between 150°C and 250°C), and at least some diesel (fraction that boils between 250°C and 375°C). The light fraction can then be sent, at least partially, to a fractionation unit where the light gases are extracted from said light fraction, for example, by passing through an expansion vessel. The recovered gaseous hydrogen, which may have been sent to a purification and compression plant, can advantageously be recycled in the hydroconversion step a). The recovered gaseous hydrogen can also be used in other refinery facilities.

[0172] The separation section includes any means of separation known to a person skilled in the art. It may include one or more expansion flasks arranged in series, and / or one or more steam and / or hydrogen stripping columns, and / or an atmospheric distillation column, and / or a vacuum distillation column, and is preferably made up of a single expansion flask, commonly called a "hot separator".

[0173] The fractionation step c) separating part, or all, of the hydroconverted effluent from hydroconversion step a) or of the second hydroconverted effluent from the additional hydroconversion step b), to produce at least two fractions comprising at least one heavy liquid fraction that boils predominantly at a temperature above 350°C, preferably above 500°C and preferably above 540°C, is carried out in the fractionation section comprising any separation means known to a person skilled in the art. The other fraction(s) from fractionation step c) are one or more light and / or intermediate fraction(s).

[0174] The heavy liquid cut contains a fraction that boils at a temperature above 540°C, called the vacuum residue (which is the unconverted fraction). It may contain part of the diesel fraction that boils between 250°C and 375°C and a fraction that boils between 375°C and 540°C, called the vacuum distillate.

[0175] This fractionation step therefore produces at least two fractions, including the heavy liquid fraction, the other fraction(s) being light and intermediate fraction(s). The fractionation step may include a gas / liquid separation producing at least one gas stream containing hydrogen and H2S, which can be sent to a hydrogen treatment and recycling step.

[0176] The fractionation section may include one or more expansion flasks arranged in series, and / or one or more steam and / or hydrogen stripping columns, and / or an atmospheric distillation column, and / or a vacuum distillation column, and is preferably made up of a set of several expansion flasks in series and atmospheric and vacuum distillation columns.

[0177] It is possible to recycle, in the hydroconversion step a) (e.g., in the entrained bed reactor in step a) or upstream), a portion of the heavy liquid fraction from fractionation c), and / or a portion or all of another effluent from subsequent treatment (e.g., deasphalting), the heavy liquid fraction from fractionation c). It may then be advantageous to leave the potentially entrained solid catalyst present in the recycle stream. A purge of the recycled stream may be implemented, generally to prevent certain compounds from accumulating at excessive levels.

[0178] Although the present invention relates to a hydroconversion process, the entrained catalyst obtained by the described synthesis process can also be used in a hydrotreating process, and the latter therefore does not fall outside the scope of the invention. Examples

[0179] The following examples illustrate the invention without however limiting its scope.

[0180] Example 1: Synthesis of NiMoS nanoparticles (according to the invention)

[0181] In a flask, 2 g of molybdenum dibutyldithiophosphate and 0.2 g of nickel dibutyldithiocarbamate are added to 50 mL of hexadecylamine. The mixture is heated to 220°C for 2.5 hours with magnetic stirring. After synthesis, the colloidal solution of Ni-promoted MoS2 nanoparticles (also called NiMoS nanoparticles) can be used directly in a catalytic test.

[0182] No sulfuration step is required before using the nanoparticles for the catalytic test.

[0183] To characterize these nanoparticles, centrifugation is performed to recover the nanoparticles, which are then washed three times with ethanol to remove excess hexadecylamine. The nanoparticles are then dried under vacuum to obtain a black powder. The nanoparticles were characterized by transmission electron microscopy. Ni-promoted MoS2 monosheets with a length of 4 nm ± 1.6 nm were observed.

[0184] Example 2: Catalytic test of reference MoS2 nanoparticles (non-compliant)

[0185] The performance of reference MoS2 nanoparticles, in terms of hydroconversion of a heavy hydrocarbon feedstock of residue type (RSV), was evaluated in a 300 mL autoclave-type batch reactor in so-called slurry (or driven) mode.

[0186] The reference MoS2 nanoparticles are prepared according to the method described in patent ENIWO2013 / 034642: the MoS2 nanoparticles are obtained from an organosoluble precursor which is molybdenum octoate (“Mo-octoate”) premixed with the feed which contains sulfur, and heated to the reaction temperature of the catalytic test, in the presence of hydrogen.

[0187] The sulfidation step occurs under these conditions upon contact with the charge.

[0188] The test conditions are as follows: - Temperature: 400°C; - Total absolute pressure: 14.5 MPa; - Duration: 2h30; - Volume of heavy hydrocarbon charge: 0.12 L (120 cc); - Concentration in MB in the load: 750 ppm; - Reactor agitation speed: 900 rpm.

[0189] The main characteristics of the heavy hydrocarbon charge are given in Table 1 below.

[0190] [Tables] Standard Method Edition Unit Charge Density NF EN ISO 121 85 2024 1.024 IBP-350°C ASTM DI 160 2024 % by weight 0 350-540°C ASTM DI 160 2024 % by weight 18 540°C+ ASTM DI 160 2024 % by weight 82.0 N ASTM D5291 2021 % by weight 0.4495 S NF ISO 8754 2003 % by weight 4.89 Ni ASTM D7260 2020 ppm by weight 51.6 V ASTM D7260 2020 ppm by weight 165.9 Asphaltenes C7 NF T60-115 2000 % by weight 12.6 Conradson Carbon NF EN ISO 103 70 2017 % by weight 21.6

[0191] Hydrogen is replenished throughout the test via an H2 ballast to compensate for hydrogen consumption and to maintain the total pressure constant during the test.

[0192] At the end of the test, a mass balance is performed by weighing all the solid, liquid and gaseous phases formed. The solid phase is separated from the liquid phase by hot filtration and allows the quantity of sediment formed during the test to be evaluated (in mass % relative to the effluent liquid). Metal and asphaltene analyses are performed on the filtrate to determine the performance (in mass %) in hydrodesulfurization (HDS), hydrodemetallation (HDV), asphaltene reduction (HDAsC7), Conradson carbon reduction (HDCCR) and hydroconversion of the heavy fraction 540°C+ (HDC540+).

[0193] The HDX rate is defined as follows:

[0194] [Math.l] TW ff. fluent . “ Fyî X WÜ me.hmgAA\c}lm-ge

[0195] Where X refers to the type of performance evaluated (S for hydrodesulfurization, etc.), [X] corresponds to the concentrations of S, V, AsC7, CCR or 540°C+ in the liquid effluents and m corresponds to the mass of charge (mcharge) or the mass of liquid effluent recovered at the end of the test (meffiuent). The sediment content is measured in the liquid effluent according to standard IP375.

[0196] The test is performed three times to ensure good repeatability.

[0197] The results obtained are reported in Table 2 below.

[0198] Example 3: Catalytic test of NiMoS nanoparticles obtained according to example 1 (compliant)

[0199] The NiMoS nanoparticles obtained according to Example 1 are tested under the same conditions as the MoS2 nanoparticles according to Example 2.

[0200] The colloidal solution of NiMoS nanoparticles is injected directly into the load.

[0201] The test is performed three times to ensure good repeatability.

[0202] The results obtained are reported in Table 2 below.

[0203] Example 4: Synthesis of NiMoS nanoparticles from molybdenum trioxide (non-compliant)

[0204] NiMoS nanoparticles are prepared ex-situ according to the method described in patent US20060058174 (WO2006 / 031570).

[0205] In a reactor, 540 g of MoO3 are mixed with 79 g of NH3 and 2381 g of water to form a total solution volume of 3000 g. Under vigorous stirring, the solution is then exposed to a 20% H2S gas mixture in H2. The reactor is heated to 65°C at a pressure of 2.7 MPa for 4 h. After the reaction, 460 g of a NiSO4 solution containing 36 g of Ni are added to the reactor. NiMoS nanoparticles of 50 ± 5.2 nm and a 5-layer stack are obtained.

[0206] This synthesis therefore includes a sulfuration step in the presence of H2S.

[0207] Example 5: Catalytic test of NiMoS nanoparticles obtained according to example 4 (non-compliant)

[0208] The NiMoS nanoparticles obtained according to Example 4 are tested under the same conditions as the MoS2 nanoparticles according to Example 2.

[0209] The NiMoS nanoparticle solution from the synthesis according to example 4 is injected directly into the load.

[0210] The test is performed three times to ensure good repeatability.

[0211] The results obtained are reported in Table 2.

[0212] [Tables2] HDS HDV HDAs C7 HDCC R HDC 54 0+ Sediments (% mass) MoS2 test according to example 2 (non-compliant) 26.9 67.8 35.2 25.1 34.1 >0.5 NiMoS test according to example 3 (compliant) 39.1 75.2 45.4 32.2 39.2 0.35 NiMoS test according to example 5 (non-compliant) 36.8 68.6 36.8 27.1 36.5 >0.5

[0213] The test carried out according to example 3 with NiMoS nanoparticles prepared according to example 1 increases performance in terms of HDS, HDV, HDAsC7, HDCCR, and HDC540+, and allows for a significant reduction in sediment compared to the test carried out according to example 2 with unpromoted MoS2 nanoparticles, as well as compared to the test carried out according to example 5 with promoted but larger nanoparticles.

Claims

Demands

1. A hydroconversion process for a heavy hydrocarbon feedstock comprising a fraction of at least 50% by weight having a boiling point of at least 300°C, said process comprising: a) a hydroconversion step of said hydrocarbon feedstock in a hydroconversion section comprising at least one hydroconversion reactor operating in a driven bed in the presence of hydrogen and at least one driven solid hydroconversion catalyst, to produce a hydroconverted effluent, said driven solid hydroconversion catalyst being in the form of bimetallic sulfide nanoparticles MMoS, M being a group VIIIB metal, obtained by a preparation process comprising (i) a decomposition step of a first organosoluble precursor comprising at least one molybdenum-sulfur bond and a second organosoluble precursor comprising at least one metal M-sulfur bond, in the presence of an organic stabilizing agent,at a temperature between 100°C and 350°C and for a duration between 1 minute and 24 h, said first and second organosoluble precursors comprising a ligand selected from the list of the following families: dithiocarbamates, dithiophosphates, xanthates, dithioimidophosphinates, and dithioimidophosphates, and said organic stabilizing agent being selected from the group consisting of: - alkylamines selected from primary amines and secondary amines having a hydrocarbon chain from C4 to C34; - alkylthiols having a hydrocarbon chain from C6 to C18; - carboxylic acids having a hydrocarbon chain from C6 to C18; - phosphines.

2. Hydroconversion process according to claim 1, wherein: -the first organosoluble precursor is from the family of oxymolybdenum dithiocarbamates corresponding to the general formula (I) or from the family of oxymolybdenum dithiophosphates corresponding to the general formula (II), [Chem.l] [Chem.2] in which the radicals RI, R2, R3, R4 are independently selected from linear or branched alkyl groups, in C12 to C12, cycloalkyl groups in C6 to C12, and aryl or alkyl-aryl groups in C6 to C12, preferably identical linear alkyl groups in C6 to C6 or identical branched alkyl groups in C12 to C12, and -the second organosoluble precursor is from the family of dithiocarbamates of metal M corresponding to the general formula (III) or from the family of dithiophosphates of metal M corresponding to the general formula (IV): [Chem. 3] [Chem.4] in which the radicals RI, R2, R3, R4 are independently selected from linear or branched alkyl groups, in Cl to C12, preferably in C1-C6, from cycloalkyl groups in C6 to C12, and from aryl or alkyl-aryl groups in C6 to C12, preferably identical linear alkyl groups in Cl to C6.

3. A hydroconversion process according to claim 1, wherein the first organosoluble precursor is selected from the list consisting of oxymolybdenum dimethyldithiocarbamate, oxymolybdenum diethyldithiocarbamate, oxymolybdenum dipropyldithiocarbamate, oxymolybdenum dibutyldithiocarbamate, oxymolybdenum dipentyldithiocarbamate, oxymolybdenum dihexyldithiocarbamate, oxymolybdenum dimethylphosphorodithioate, oxymolybdenum diethylphosphorodithioate, oxymolybdenum dipropylphosphorodithioate, oxymolybdenum dibutylphosphorodithioate, oxymolybdenum dipentylphosphorodithioate, oxymolybdenum dihexylphosphorodithioate, and oxymolybdenum di(2-ethylhexyl) phosphorodithioate, and the second organosoluble precursor is chosen from the list consisting of: nickel dimethyldithiocarbamate, nickel diethyldithiocarbamate, nickel dipropyldithiocarbamate, nickel dibutyldithiocarbamate,nickel dipentyldithiocarbamate, nickel dihexyldithiocarbamate, nickel dimethyldithiophosphate, nickel dimethyldithiophosphate, nickel dimethyldithiophosphate, nickel dimethyldithiophosphate, nickel dimethyldithiophosphate, and nickel dimethyldithiophosphate.

4. Hydroconversion process according to any one of the preceding claims, wherein the metal M is nickel.

5. A hydroconversion process according to any one of the preceding claims, wherein said organic stabilizing agent is selected from the group consisting of: - alkylamines selected from primary amines and secondary amines having a hydrocarbon chain in C12 to C18, preferably selected from the list consisting of roctylamine, dodecylamine, hexadecylamine, octadecylamine, and oleylamine; - alkylthiols selected from the list consisting of 1-hexane thiol, 1-octanethiol, 1-dodecanethiol, and 1-hexadecanethiol; - carboxylic acids selected from the list consisting of citric acid, octanoic acid, decanoic acid, palmitic acid, and oleic acid; - the phosphines chosen from the list consisting of tributylphosphine, triooctylphosphine.

6. Hydroconversion process according to claim 5, wherein said organic stabilizing agent is an alkylamine selected from the list consisting of octylamine, dodecylamine, hexadecylamine, octadecylamine, and oleylamine, and preferably is hexadecylamine or oleylamine.

7. Hydroconversion process according to any one of the preceding claims, wherein in step (i) the molar ratio of metallic elements (M+Mo) to organic stabilizing agent, preferably the molar ratio of the sum of elements Ni and Mo (Ni+Mo) to organic stabilizing agent, is between 0.001 and 0.1, and the molar ratio of metal M to molybdenum M / Mo, preferably Ni / Mo, is between 0.1 and 1.

8. Hydroconversion process according to any one of the preceding claims, wherein the decomposition step (i) is carried out in the presence of at least one organic synthesis solvent with a boiling point above 100°C, preferably selected from the list consisting of toluene, ethylbenzene, xylene, mesitylene, decane, and dodecane.

9. A hydroconversion process according to any one of the preceding claims, wherein the entrained solid hydroconversion catalyst nanoparticles obtained at the end of the decomposition step (i) are in the form of monolayers and have an average size of between 1 nm and 25 nm, preferably between 1 nm and 10 nm, preferably between 1 nm and 5 nm

10. llili. Hydroconversion process according to any one of the preceding claims, further comprising (ii) a separation step between the hydroconversion catalyst nanoparticles and the organic stabilizing agent and optionally an organic synthesis solvent from a colloidal solution obtained at the end of the decomposition step (i), and optionally a washing step (iii) and / or a drying step (iv) of said nanoparticles separated at the end of step (ii).

11. A hydroconversion process according to any one of the preceding claims, wherein the entrained solid hydroconversion catalyst is introduced into said hydroconversion reactor in its form of MMoS bimetallic sulfide nanoparticles without the implementation of a sulfidation step. of the solid hydroconversion catalyst entrained prior to the hydroconversion step a) or during said process of preparation of said solid entrained hydroconversion catalyst.

12. Hydroconversion process according to any one of the preceding claims, wherein the entrained solid hydroconversion catalyst is introduced into the hydroconversion reactor with the heavy hydrocarbon feed in the same flow, said entrained solid catalyst having been previously mixed with the feed, preferably during an active dispersion step of said entrained solid hydroconversion catalyst in the feed.

13. Hydroconversion process according to any one of the preceding claims, wherein the concentration of the entrained solid hydroconversion catalyst is between 10 ppm and 10,000 ppm by weight of molybdenum relative to the heavy hydrocarbon feed at the inlet of the hydroconversion reactor.

14. A process according to any one of the preceding claims, wherein the hydroconversion step is carried out under an absolute pressure of between 2 MPa and 38 MPa, at a temperature of between 300°C and 550°C, at an hourly volumetric rate WH relative to the volume of each reactor of between 0.05 h 1 and 10 h 1 and under an amount of hydrogen mixed with the feed entering the reactor of between 50 and 5,000 normal cubic meters per cubic meter of feed.

15. A hydroconversion process according to any one of the preceding claims, wherein the heavy hydrocarbon feedstock comprises, or is constituted by, one of the following feedstocks, alone or in mixture: crude oil, synthetic crude oil, coal tar, oil sands bitumen, heavy oil from oil shale, atmospheric residue or vacuum residue from the atmospheric or vacuum distillation of crude oil, atmospheric residue or vacuum residue from the atmospheric or vacuum distillation of effluent from a thermal conversion, hydrotreating, hydrocracking, hydroconversion, or direct coal liquefaction unit, or a vacuum distillate obtained directly from crude oil or a cut from a fluidized bed catalytic cracking unit or unit hydrocracking or hydroconversion unit or coking unit or visbreaking unit, a vacuum distillate from the direct liquefaction of coal, aromatic cuts extracted from a lubricant production unit, deasphalted oil or resin fraction or asphalt fraction from a deasphalting unit, bio-oil, biocrude, pyrolysis oil from plastics and / or tires and / or solid recovered fuels, and preferably a vacuum residue from the vacuum distillation of crude oil.