Process for hydroconversion in an entrained bed of heavy hydrocarbon feedstocks with molybdenum disulfide nanoparticles

Abstract

The present invention relates to a process for the hydroconversion of a heavy hydrocarbon feedstock implementing at least one entrained bed reactor in the presence of a solid catalyst entrained in the form of single-sheet molybdenum disulfide (MoS2) nanoparticles, obtained according to an ex-situ preparation process from an organosoluble precursor comprising at least one molybdenum-sulfur bond.

Description

[0001] HYDROCONVERSION PROCESS IN A DRIVE BED OF HEAVY HYDROCARBONATE FILLERS WITH MOLYBDENINE DISULFIDE NANOPARTICLES

[0002] technical field

[0003] 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 molybdenum disulfide nanoparticles M0S2 obtained by an ex-situ synthesis process from an organosoluble precursor comprising at least one molybdenum-sulfur bond.

[0004] Previous technique

[0005] The purification and conversion of heavy hydrocarbon feedstocks is well-established in petroleum refining and aims to convert heavy fractions into lighter, more valuable fractions, typically used 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.

[0006] 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. Within 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 on its metal content, its tolerance to impurities and the conversion intended.

[0007] Entrained bed hydroconversion processes utilize 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. This promotes the hydrogenation of radicals formed by thermal cracking reactions and limits coke formation. The dispersed catalyst, also called an "entrained catalyst" or more commonly a "slurry catalyst," provides catalytic activity as well as a surface for the deposition of metals and asphaltenes from the feedstock. The very small catalyst (micrometer or nanometer in size), dispersed within the feedstock, is carried out of the reactor with the effluent, since the catalyst and the heavy hydrocarbon feedstock behave as a homogeneous phase.

[0008] 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 employing hybrid bubbling-entrained 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 patent US8431016 and application WO2023 / 280624.

[0009] Entrained catalysts are typically unsupported catalysts (also sometimes called "bulk" catalysts in Anglo-Saxon terminology), although entrained catalysts produced by grinding supported catalysts are also known. Entrained (unsupported) catalysts offer several advantages compared to conventional millimeter-sized supported catalysts: they have a high specific surface area (which increases with particle size), 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.

[0010] Entrained (unsupported) hydroconversion catalysts are typically metal sulfides that can be prepared in various ways.

[0011] The solid particles of the entrained catalyst containing metal sulfides can be formed after the catalyst precursors are mixed with the feedstock upstream of the hydroconversion reactor or within the hydroconversion reactor itself. This is a type of entrained catalyst formation 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.

[0012] 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 according to 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 feeds employing one or more bubbling-entrained hybrid bed reactors, operating with a supported solid catalyst and an entrained solid catalyst dispersed in the feed formed by the addition of an organosoluble metallic precursor to the feed.The addition of a dispersed organosoluble catalyst precursor, typically molybdenum 2-ethylhexanoate, which is pre-diluted in vacuum gas oil (VGO), is implemented 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) upon heating, through reaction with H₂S from the hydrodesulfurization of the feedstock.

[0013] 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.

[0014] The solid particles of the entrained catalyst, including metal sulfides, can also be formed before any mixing or contact with the feedstock. Such a formation of the entrained solid catalyst can therefore be described as ex-situ.

[0015] Documents W02006 / 031575, W02006 / 031543 and W02006 / 031570 describe, for example, this type of preparation of ex-situ entrained catalysts, and more particularly the dissolving of a group VIB oxide with an aqueous ammonia solution to form a solution which is then sulfided, possibly promoted by the addition of a group VIB metal after said sulfidation, and mixed with the feed in the last step.

[0016] 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 describes 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 carbon disulfide (CS2) in decahydronaphthalene and under hydrogen is performed before injecting the catalyst into the reactor containing the VGO feedstock to test its catalytic activity.

[0017] 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 (HDS and HDN) reactions 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)g 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.

[0018] In ex-situ syntheses of entrained solid catalysts, sulfidation of the catalyst is generally required. This is carried out using a sulfurizing agent (H₂S, elemental sulfur, C₂S, etc.) during catalyst synthesis or the hydroconversion process, before its injection into the hydroconversion reactor, for example, in a dedicated sulfidation step. This sulfidation constitutes an additional step that complicates the synthesis or hydroconversion process.

[0019] 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, continuous research is underway to develop more efficient catalysts and implementation methods, as well as advantageous and simplified methods for synthesizing such catalysts.

[0020] Objectives and Summary of the Invention

[0021] In the context described above, the present description aims to provide a hydroconversion process for heavy hydrocarbon feedstocks in entrained bed reactor(s) that is simple to implement and that eliminates the need for a sulfidation step of the entrained catalyst before its use for the hydroconversion of the feedstock.

[0022] 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.

[0023] 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 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 molybdenum disulfide M0S2 nanoparticles obtained by a preparation process comprising (i) a decomposition step of a first organosoluble precursor comprising at least one molybdenum-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 organosoluble precursor comprises 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:,

[0024] - alkylamines selected from primary amines and secondary amines having a hydrocarbon chain from C4 to C34;

[0025] - alkylthiols containing a hydrocarbon chain in C6 to C18;

[0026] - carboxylic acids with a hydrocarbon chain from C6 to C18;

[0027] - phosphines (eg organophosphines).

[0028] 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),

[0029] Chem 1 in which the radicals RI, R2, R3, R4 are independently selected from linear or branched alkyl groups, in Cl to C12, cycloalkyl groups in C6 to C12, and aryl or alkyl-aryl groups in C6 to C12, preferably identical linear alkyl groups in Cl to C6 or identical branched alkyl groups in Cl to C12.

[0030] According to one or more embodiments of the invention, 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 di(2-ethylhexyl) oxymolybdenum phosphorodithioate.

[0031] According to one or more embodiments of the invention, the organic stabilizing agent for the process of preparing the entrained solid hydroconversion catalyst is chosen from the group consisting of:

[0032] - 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;

[0033] - the alkylthiols chosen from the list consisting of 1-hexane thiol, 1-octanethiol, 1-dodecanethiol, and 1-hexadecanethiol;

[0034] - carboxylic acids chosen from the list consisting of citric acid, octanoic acid, decanoic acid, palmitic acid, and oleic acid;

[0035] - the phosphines chosen from the list consisting of tributylphosphine, triooctylphosphine.

[0036] 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.

[0037] According to one or more embodiments of the invention, in step (i) of the process of preparing the entrained solid hydroconversion catalyst, the molar ratio Mo to organic stabilizing agent is between 0.001 and 0.1.

[0038] According to one or more embodiments of the invention, step (i) of the process for preparing the entrained solid hydroconversion catalyst is carried out in the presence of at least one organic solvent with a boiling point above 100°C, preferably chosen from the list consisting of toluene, ethylbenzene, xylene, mesitylene, decane, and dodecane.

[0039] According to one or more embodiments of the invention, the nanoparticles of the entrained solid hydroconversion catalyst obtained at the end of the preparation process 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.

[0040] Advantageously, the process for preparing the solid hydroconversion catalyst does not involve a sulfidation step to form the MoS2 nanoparticles.

[0041] According to one or more embodiments of the invention, the process for preparing the entrained solid hydroconversion catalyst further comprises (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).

[0042] According to one or more embodiments of the invention, the entrained solid hydroconversion catalyst is introduced into said hydroconversion reactor in its form of MoS2 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.

[0043] 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 said heavy hydrocarbon feed, preferably during an active dispersion step of said entrained solid hydroconversion catalyst in the feed.

[0044] According to one or more modes of the invention, the driven solid hydroconversion catalyst is introduced into said hydroconversion reactor at the hydroconversion stage independently of the heavy hydrocarbon feed.

[0045] According to one or more embodiments of the invention, the entrained solid hydroconversion catalyst is pre-mixed with the heavy hydrocarbon feed in the form of a colloidal solution comprising organic stabilizing agent and optionally organic solvent used during the catalyst preparation process.

[0046] According to one or more embodiments of the invention, the concentration of the entrained solid hydroconversion catalyst is between 10 ppm and 10000 ppm by weight of molybdenum relative to the heavy hydrocarbon feed at the inlet of the hydroconversion reactor, 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.

[0047] According to one or more embodiments of the invention, the hydroconversion step is carried out under an absolute pressure between 2 MPa and 38 MPa, at a temperature between 300°C and 550°C, at an hourly volumetric velocity WH relative to the volume of each reactor of between 0.05 h 1 and 10 a.m. 1 and under a quantity of hydrogen mixed with the feed entering the reactor of between 50 and 5000 normal cubic meters per cubic meter of feed.

[0048] According to one or more embodiments of the invention, the heavy hydrocarbon feed comprises, or is constituted by, one of the following feeds, 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 unit or hydrotreating unit or hydrocracking unit or hydroconversion unit or a direct coal liquefaction unit, a vacuum distillate obtained directly from crude oil or from a cut from a fluidized bed catalytic cracking unit or 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, 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.

[0049] 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, 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.

[0050] 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 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 separation step separating part, or all, of said hydroconverted effluent, to produce a second hydroconverted effluent having 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 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 deasphalting step, in a deasphalter, of part, or all, of said heavy cut from 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 between 2 MPa and 38 MPa, at a temperature between 300°C and 550°C, at an hourly volumetric rate WH relative to the volume of each entrained bed reactor of between 0.05 h; 1 and 10 a.m. 1and under a quantity of hydrogen mixed with the feed entering each reactor of between 50 and 5,000 normal cubic meters (Nm³) 3 ) per cubic meter (m 3 ) dump.

[0051] 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.

[0052] Description of the implementation methods

[0053] In the following detailed description, numerous specific details are presented 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 including all of these specific details. In other cases, well-known features have not been described in detail to avoid unnecessarily complicating the description.

[0054] In this description, the various embodiments presented can be implemented separately or in combination with each other, without limitation of combinations where technically feasible.

[0055] Terminology

[0056] It is specified that, throughout this description, the expression "between ... and ..." should be understood as including the cited limits, unless otherwise specified.

[0057] In this description, the term "include" is synonymous with "comprise," "include," and "contain," and is inclusive or open-ended, not excluding other elements not mentioned. It is understood that the term "include" includes the exclusive and closed term "consist."

[0058] Furthermore, when used in this description, and unless otherwise specified, the terms "essentially," "approximately," "about," 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, pressure, a dimensional quantity such as length, a quantity, a velocity, a flow rate, a compound content, etc. In this description, the various parameter ranges for a given step, such as pressure ranges and temperature ranges, may be used alone or in combination. For example, in the context of the present invention, a preferred range of pressure values ​​may be combined with a more preferred range of temperature values.

[0059] According to the present invention, pressures are absolute pressures, also noted as abs., and are given in absolute MPa (or abs. MPa), unless otherwise indicated.

[0060] In this description, the term "hydroconversion," also referred to by the acronyms "HDC" and "HCK," and more commonly as "hydrocracking" when the feedstock is light, refers to a process whose primary purpose is to reduce the boiling point range of a heavy hydrocarbon feedstock, typically comprising at least 50% by weight of a heavy hydrocarbon fraction with a boiling point of at least 300°C, and in which a substantial portion of the feedstock is converted into products with lower boiling point ranges than the original feedstock. Hydroconversion generally involves the fragmentation of larger hydrocarbon molecules into smaller molecular fragments with a lower number of carbon atoms and a higher hydrogen-to-carbon ratio.The reactions involved in hydroconversion reduce the size of hydrocarbon molecules, primarily by breaking 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 can occur, such as, among others, the removal of sulfur, oxygen, or nitrogen from the feedstock, or the saturation of olefins, as more broadly defined below.

[0061] The term "hydrotreating," commonly referred to as "HDT," describes a gentler process than hydroconversion. Its primary purpose is to remove impurities such as sulfur, nitrogen, oxygen, halides, and trace metals from the feedstock, 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 objective is not to alter the feedstock's boiling point range. 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 energized bed, bubbling or hybrid bed hydrotreating reactor.

[0062] The term "hydroconversion reactor" refers to any vessel in which the primary objective is the hydroconversion of a feedstock, e.g., the cracking of the feedstock (i.e., the reduction of its 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 having sufficient thermal energy to cause the fragmentation of larger hydrocarbon molecules into smaller molecules through 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 supported catalyst with hydrogen typically flowing simultaneously with the liquid, but possibly counter-currently in some cases).

[0063] 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 from 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.

[0064] The terms "hybrid bed" and "hybrid bubbling bed" and "hybrid bubbling-driven bed" for a hydroconversion reactor refer to a bubbling bed hydroconversion reactor comprising a driven catalyst in addition to the porous supported catalyst maintained in the bubbling bed reactor.

[0065] In this 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. colloidal-sized particles, 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 having 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).

[0066] According to the invention, the catalyst obtained by the specific synthesis process from the organosoluble precursor comprising at least one molybdenum-sulfur bond, and used as a solid catalyst driven in a driven bed hydroconversion process according to the invention, is in the form of single-sheet molybdenum sulfide M0S2 nanoparticles, with a sheet length less than or equal to about 25 nm as detailed later in the description.

[0067] 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), allow the content of certain elements of the catalyst to be quantified, including metals such as molybdenum, nickel, etc.

[0068] The size of the catalyst nanoparticles is determined by transmission electron microscopy (TEM). Specifically, the TEM measurement of the catalyst nanoparticle size can be performed on a powder composed of the nanoparticles, or on a suspension containing said nanoparticles.

[0069] 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, 81 ème edition, 2000-2001). For example, group VIII (or VI II B) according to the CAS classification corresponds to the metals of columns 8, 9 and 10 according to the new IUPAC classification, and group VIB to the metals of column 6.

[0070] When standards are cited in this description, they refer to the most recent published versions as of the filing date of this application, unless otherwise specified. Process for preparing the entrained solid hydroconversion catalyst

[0071] According to the hydroconversion process according to the invention, the entrained solid hydroconversion catalyst is prepared by a simple preparation process to be implemented, comprising a single step of formation of molybdenum disulfide MoS2 nanoparticles, in the form of mono-sheets, in particular of very small dimensions (medium size), by decomposition of an organosoluble precursor containing at least one molybdenum-sulfur bond as described below.

[0072] This organosoluble precursor includes at least one Mo-S bond, and comprises a ligand selected from the list of the following families: dithiocarbamates, dithiophosphates, xanthates, dithioimidophosphinates, and dithioimidophosphates.

[0073] According to the invention, it is possible to eliminate a sulfidation step of the entrained catalyst before it is used for hydroconversion in the entrained bed hydroconversion reactor, i.e., before any mixing or contact with the feedstock to be treated in the hydroconversion process. This eliminates the need for in-situ sulfidation during the hydroconversion process or ex-situ sulfidation during the ex-situ preparation of the catalyst, because the entrained catalyst from the preparation process (ex-situ) is already in an active sulfided form. It is referred to as the entrained solid catalyst.

[0074] The nanoparticles of the entrained solid catalyst obtained are detailed below, after the description of the process for preparing the entrained solid catalyst.

[0075] The organosoluble precursor is a coordination complex comprising at least one molybdenum-sulfur bond and organic ligands whose structure is that of the aforementioned families.

[0076] The organosoluble precursor containing molybdenum is therefore chosen from the following families: molybdenum dithiocarbamates, molybdenum dithiophosphates, molybdenum xanthates, molybdenum dithioimidophosphinates, and molybdenum dithioimidophosphates.

[0077] Dithiocarbamates are a family of compounds containing a sulfur atom and a thiolate group bonded to a carbon atom, which is itself bonded to an amine group, with the general structure RR'NC(S)S-.

[0078] Dithiophosphates, also called dithiophosphorodithioates, are a family of compounds possessing bonds between phosphorus, oxygen and sulfur, with the general structure (RO)(R'O)P(S)S-,

[0079] Xanthates are a family of compounds with the general structure ROC(S)S-,

[0080] Dithioimidophosphinates are a family of compounds with a phosphorus-sulfur bond and a phosphorus-nitrogen bond, with the general structure -P(S)NHR.

[0081] 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".The process for preparing the entrained solid catalyst includes (i) a step of decomposing a first organosoluble precursor comprising at least one molybdenum-sulfur (Mo-S) bond, and 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 about 200°C, for example 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 1 h.

[0082] According to one or more embodiments, step (i) includes the implementation of a mechanical action such as the application of a shear force.

[0083] According to one or more embodiments of the invention, the first organosoluble precursor corresponds to the general formulas (I) or (II) described below.

[0084] The first organosoluble precursor containing 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):

[0085] Chem 1 in which the radicals RI, R2, R3, R4 are chosen independently from linear or branched alkyl groups, comprising from 1 to 12 carbon atoms (C1-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.

[0086] The first organosoluble precursor containing molybdenum, with at least one molybdenum-sulfur bond, can also be from the family of molybdenum dithiophosphates, and preferably from the family of oxymolybdenum dithiophosphates corresponding to the following general formula (II):

[0087] 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 (C1-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.

[0088] 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 (C1-C12).

[0089] 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.

[0090] 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 (C1-C12), and preferably identical linear alkyl groups comprising from 1 to 6 carbon atoms (Cl-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)phosphoodithioate.

[0091] 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 di(2-ethylhexyl)phosphoodithioate of oxymolybdenum. Preferably, the first organosoluble precursor is oxymolybdenum dibutyldithiocarbamate, oxymolybdenum dibutyldithiophosphate or oxymolybdenum di(2-ethylhexyl)phosphodithioate.

[0092] The organic stabilizing agent, whose role is notably to stabilize the forming nanoparticles, in particular to control their size and shape by limiting their growth or agglomeration, is preferably chosen from the group consisting of:

[0093] - alkylamines selected from primary amines 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;

[0094] - 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;

[0095] - 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;

[0096] - phosphines, preferably chosen from the list consisting of tributylphosphine, triooctylphosphine, trioctylphosphine oxide, and triphenylphosphine.

[0097] Preferably, the organic stabilizing agent is an alkylamine selected from the list consisting of octylamine, dodecylamine, hexadecylamine, octadecylamine, and oleylamine, and preferably is hexadecylamine or oleylamine, and more preferably is oleylamine.

[0098] The organic stabilizing agent is preferably in molar excess relative to the organosoluble precursor (total number of moles of Mo of the first organosoluble precursor).

[0099] The metal molar ratio Mo to organic stabilizing agent can be between 0.001 and 0.1, preferably between 0.002 and 0.05.

[0100] The decomposition step (i) may include the addition of a second organosoluble precursor comprising a metal-sulfur (MS) bond, where M is a group VIII metal, e.g., nickel. This second organosoluble precursor may contain a ligand selected from the list of families consisting of dithiocarbamates, dithiophosphates, xanthates, dithioimidophosphinates, and dithioimidophosphates, so that the nanoparticles formed are MoS2 nanoparticles promoted with the metal M, for example, Ni-promoted MoS2 nanoparticles, also called MMoS bimetallic sulfide nanoparticles, e.g., NiMoS. The second organosoluble precursor is a coordination complex comprising at least one metal-sulfur bond and organic ligands whose structure corresponds to that of the aforementioned families.

[0101] 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).

[0102] Chem 3 in which the radicals RI, R2, R3, R4 are chosen independently from linear or branched alkyl groups, comprising from 1 to 12 carbon atoms (C1-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.

[0103] In general formulas (I), (II), (III) and (IV), the bonds shown in dotted lines correspond to a delocalized double bond.

[0104] Preferably, the group VIII metal M of the second organosoluble precursor is nickel or cobalt, and more preferably nickel.

[0105] 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 (C1-C12), and more preferably identical linear alkyl groups comprising from 1 to 6 carbon atoms (C1-C6).

[0106] For example, if 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. Similar metal dithiophosphate compounds (linear C1-C6 alkyl chains) with another Group VIII metal may, for example, be used as the second organosoluble precursor. According to one or more embodiments, the second organosoluble precursor comprising metal M, e.g.nickel, with at least one MS bond, is of the family of metal M dithiocarbamates 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 (C1-C12), and more preferably identical linear alkyl groups comprising from 1 to 6 carbon atoms (C1-C6).

[0107] 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.

[0108] Preferably, the second organosoluble precursor is nickel dibutyldithiocarbamate.

[0109] In the case of using a second metallic precursor based on a group VIII metal M, e.g. nickel:

[0110] - the molar ratio of metallic elements (M+Mo) to organic stabilizing agent, e.g. the molar ratio of the sum of metallic elements Ni and Mo (Ni+Mo) to organic stabilizing agent, can be between 0.001 and 0.1, preferably between 0.005 and 0.05;

[0111] - the molar ratio M / Mo, e.g. Ni / Mo, can be between 0.1 and 1, preferably between 0.2 and 0.8.

[0112] Preferably, the decomposition stage, thermal decomposition, is carried out at atmospheric pressure.

[0113] The decomposition step can be carried out in an organic synthesis solvent with a boiling point above 100°C (by "organic synthesis solvent" we mean an organic solvent used in the synthesis of nanoparticles), or directly in the organic stabilizing agent. This organic synthesis solvent can, for example, be chosen from at least: toluene, ethylbenzene, xylene, mesitylene, decane, dodecane, etc.

[0114] Preferably, active mixing, for example 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.

[0115] The decomposition step in the preparation process of the entrained solid catalyst allows the production of metal sulfide nanoparticles without requiring a sulfidation step under H2S or by adding another sulfurizing agent, either during the synthesis itself or post-synthesis, before use of the entrained solid catalyst. By controlling various parameters, such as temperature, synthesis time, the nature of the organic stabilizing agent, and possibly its quantity, agitation, etc., it is possible to control the size and shape of the resulting nanoparticles, which are detailed later.

[0116] At the end of the decomposition step (i), the nanoparticles are preferably in a solution containing organic stabilizing agent, and possibly organic synthesis solvent if such an organic synthesis solvent was used during the decomposition step, forming a colloidal solution.

[0117] 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 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.

[0118] The separation step (ii) can be any liquid-solid separation method known to a person skilled in the art, and is preferably carried out by centrifugation or filtration.

[0119] 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.

[0120] 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, preferably between 20 minutes and 24 hours, and more preferably between 30 minutes and 3 hours. Preferably, this 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.

[0121] Preferably, the described synthesis process does not involve a calcination step or heating to a temperature above 200°C.

[0122] Nanoparticles of the solid entrained hydroconversion catalyst obtained from the preparation process

[0123] The resulting catalyst nanoparticles, which are molybdenum disulfide (MOS2) nanoparticles, optionally promoted by a group VIII metal (e.g., nickel), are advantageously in the form of single sheets, i.e., predominantly without stacking, and advantageously have an average size, corresponding to the average sheet length in this 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. By predominantly without stacking, it is understood that the nanoparticles can be in the form of isolated sheets formed by single sheets and / or stacks of single sheets comprising a maximum of five single sheets, preferably a maximum of two single sheets, and preferably formed by single sheets without any stacking of single sheets.

[0124] 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 compared to the average size (average length).

[0125] 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 array, the standard deviation, and the size distribution can be determined by statistical studies of microscopy images, particularly 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.

[0126] The single-sheet crystalline structure of the nanoparticles obtained can be revealed by TEM or any other technique known to those skilled in the art.

[0127] MoS2 nanoparticles correspond to Mo disulfide (MoS2) crystallites in the form of sheets, particularly single sheets. In the case of bimetallic sulfide nanoparticles MMoS, e.g. NiMoS, the structure of the nanoparticles is that of Mo disulfide (MoS2) crystallites in the form of sheets, particularly single sheets, containing 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.

[0128] The nanoparticles obtained by the synthesis process described advantageously form an active sulfide-energized solid-acting catalyst which can be used directly in an energized bed hydroconversion process according to the invention, without necessarily having to implement an additional sulfidation step to have a functional energized solid-acting catalyst available, which is the active sulfide-energized catalyst.

[0129] 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.

[0130] hydroconversion process

[0131] 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, 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 molybdenum disulfide MoS2 obtained by the (ex-situ) preparation process described in detail above, in particular said (ex-situ) preparation process comprising (i) a decomposition step of a first organosoluble precursor comprising at least one molybdenum-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, the first organosoluble precursor 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:,

[0132] - alkylamines selected from primary amines and secondary amines having a hydrocarbon chain from C4 to C34;

[0133] - alkylthiols containing a hydrocarbon chain in C6 to C18;

[0134] - carboxylic acids with a hydrocarbon chain from C6 to C18,

[0135] - phosphines.

[0136] By ex-situ in reference to the catalyst preparation process, we mean that the solid nanoparticles of the entrained catalyst containing the metal sulfides are formed before any mixing or contact with the feed to be treated in the hydroconversion process.

[0137] Charge

[0138] In this description, the term "charge" or "hydrocarbon charge" refers to the heavy hydrocarbon charge sent to hydroconversion, as defined below, unless otherwise specified.

[0139] The hydrocarbon feed sent to hydroconversion is a heavy feed. It contains a fraction of at least 50% by weight having a boiling point of at least 300°C, preferably at least 350°C, preferably at least 375°C, at least 450°C, preferably at least 500°C, and even more preferably at least 540°C.

[0140] The hydrocarbon load can be a load of fossil origin.

[0141] Preferably, the hydrocarbon feedstock comprises, and may consist of, one of the following feedstocks of fossil origin, alone or in mixture:

[0142] - crude oil,

[0143] - synthetic crude oil,

[0144] - a coal tar,

[0145] - bitumen from oil sands, - heavy oil from oil shale,

[0146] - an atmospheric residue or a vacuum residue resulting from the atmospheric or vacuum distillation of crude oil,

[0147] - an atmospheric residue or a vacuum residue resulting 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),

[0148] - a vacuum distillate obtained directly from crude oil or from 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,

[0149] - a vacuum distillate obtained from the direct liquefaction of coal,

[0150] - aromatic cuts extracted from a lubricant production unit,

[0151] - 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.

[0152] The aforementioned fillers such as 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.

[0153] The charges mentioned are liquid under the operating conditions of hydroconversion.

[0154] Preferably, the hydrocarbon feedstock comprises, and may consist of, one of the following feedstocks, alone or in mixture:

[0155] - crude oil,

[0156] - synthetic crude oil,

[0157] - a coal tar,

[0158] - a bitumen made from tar sands,

[0159] - a heavy oil derived from oil shale,

[0160] - an atmospheric residue or a vacuum residue resulting from the atmospheric or vacuum distillation of crude oil,

[0161] - 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.

[0162] Preferably, the hydrocarbon feedstock comprises, and may consist of, a vacuum residue from the vacuum distillation of crude oil. The hydrocarbon feedstock may also originate from the conversion of biomass, particularly algae or lignocellulosic biomass, and in particular be a "bio-oil" or a "biocrude".

[0163] The term biomass refers to material derived from recently living organisms, including plants, animals, and their byproducts. The term lignocellulosic biomass refers to biomass derived from plants or their byproducts. Lignocellulosic biomass is composed of carbohydrate polymers (cellulose, hemicellulose) and an aromatic polymer (lignin).

[0164] 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.

[0165] A bio-oil is a liquid product obtained by the thermochemical liquefaction of biomass, preferably by pyrolysis, and most commonly by rapid or slow pyrolysis with or without a catalyst (in the presence of a catalyst, it 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 catalytic pyrolysis. Rapid pyrolysis, for example, tends to maximize the liquid yield. During rapid pyrolysis, the temperature of the biomass, possibly finely divided, is quickly raised to values ​​above approximately 300°C and preferably between 300 and 900°C, and the liquid products are condensed into bio-oil.

[0166] 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.

[0167] 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.

[0168] A biocrude corresponds to products obtained by hydrothermal liquefaction of biomass (acronym

[0169] "HTL" (Hydrothermal Liquefaction), according to the Anglo-Saxon terminology, is composed primarily of organic molecules, an aqueous phase including 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.

[0170] 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).

[0171] 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.

[0172] Biocrude can contain up to 4% by weight of inorganic compounds (minerals), primarily metals such as sodium and potassium, but also calcium, iron, etc. These minerals can originate from the catalysts used for hydrothermal liquefaction, the biomass feedstock of the hydrothermal liquefaction process itself, and any metals used to grind the feedstock. Sodium and potassium can be present in relatively large quantities in biocrude because the hydrothermal liquefaction process typically uses significant amounts of alkali-based catalysts (NaOH, KOH, K₂CO₃, Na₂CO₃, etc.).

[0173] Bio-oils and bio-raw materials can be pre-treated, for example stabilized and / or demineralized before hydroconversion.

[0174] The hydrocarbon feedstock can also come 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.

[0175] The pyrolysis oil from plastics, and / or tires, and / 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). The plastics are typically production by-products and / or waste (e.g., household, building, electrical and electronic equipment waste), and preferably comprise alkene, diene, vinyl, styrenic, polyester, and / or polyamide polymers, and more preferably polyolefins, such as polyethylene (PE), polypropylene (PP), or ethylene-propylene copolymers.The pyrolysis oil of plastics, tires, 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 diolefins, naphthenes and aromatics, metals, notably silicon and iron, halogenated compounds, notably chlorinated compounds, heteroelements contributed by sulfur compounds, oxygenated compounds, and / or nitrogenous compounds. These impurities (halogenated compounds and metallic contaminants including alkali metals, alkaline earth metals, transition metals, post-transition metals, and metalloids) are often present at high concentrations, for example, up to 350 ppm by weight, or even 700 ppm by weight or 1000 ppm by weight of halogenated elements contributed by halogenated compounds, and up to 100 ppm by weight, or even 200 ppm by weight of metallic contaminants.

[0176] The hydrocarbon load typically contains metals (also referred to here as metallic contaminants) and other impurities such as sulfur, nitrogen, Conradson carbon and asphaltenes, especially C7 asphaltenes which are insoluble in heptane.

[0177] 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.

[0178] 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.

[0179] 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.

[0180] 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.

[0181] 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.

[0182] These contents are expressed as a percentage by weight of the total weight of the hydrocarbon load.

[0183] According to one or more embodiments, a co-feedstock may be sent to the hydroconversion stage with the hydrocarbon feedstock as described above, preferably said co-feedstock being in the minority relative to the hydrocarbon feedstock and, for example, representing less than 30% by mass, preferably less than 20% or 10% by mass relative to the hydrocarbon feedstock. Preferably, the co-feedstock comprises, and may consist of, one of the following co-feedstocks, alone or in mixture:

[0184] - 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.

[0185] - biomass such as algae, lignocellulosic biomass, or one or more lignocellulosic biomass constituents chosen from the group formed by cellulose, hemicellulose and lignin.

[0186] - plastics, and / or tires and / or RDF, the plastics being typically production waste and / or refuse as already described above.

[0187] 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 stage.

[0188] The co-feed and the hydrocarbon feed can be sent independently or mixed together in the hydroconversion reactor. The following description does not refer 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.

[0189] Implementation

[0190] Hydroconversion stage

[0191] According to the invention, 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 comprises the driven solid catalyst, which can be injected mixed with the feedstock or independently of the feedstock injection, as detailed later in the description.

[0192] The hydroconversion step (a) is carried out under conditions that produce a hydroconverted effluent containing the conversion products. This hydroconverted effluent has, in particular, a reduced content (compared to the feed) of hydrocarbons with a boiling point of at least 300°C, or at least 350°C, 375°C, 450°C, 500°C, or 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.

[0193] 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.

[0194] The hourly spatial velocity (WH) is preferably between 0.05 h 1 and 10 a.m. 1(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. According to a preferred implementation, the WH is between 0.1 h 1 and 10 a.m. 1 , more preferably between 0.1 h 1 and 5 a.m. 1 , in an even more preferred manner between 0.15 h 1 and 2 hours 1 .

[0195] According to another implementation, the overall WH, i.e. the liquid feed rate 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 1 .

[0196] The amount of hydrogen mixed with the charge is preferably between 50 and 5000 normal cubic meters (Nm³). 3 ) per cubic meter (m 3 ) of liquid charge, preferably between 100 Nm 3 / m 3 and 2000 Nm 3 / m 3 and in a highly preferred manner between 500 Nm 3 / m 3 and 1500 Nm 3 / m 3 .

[0197] The hydroconversion section comprises one or more reactors operating in an entrained bed.

[0198] When several entrained bed hydroconversion reactors are implemented, they can be in series and / or in parallel.

[0199] 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.

[0200] This type of reactor is well known to those skilled in the art.

[0201] The entrained bed hydroconversion reactor preferably includes an upward flow of liquid and gas.

[0202] The entrained bed hydroconversion reactor, like most entrained bed reactors, can be an empty plug-flow type vessel, since the heavy hydrocarbon feed containing the dispersed entrained solid catalyst behaves as a homogeneous phase. When operating with an upward flow of liquid and gas, the entrained bed reactor preferably includes an inlet port located at or near the bottom of the reactor through which the feed is introduced together with the hydrogen (or two inlet ports if the feed is introduced separately from the entrained solid catalyst by means of two separate streams), and an outlet port at or near the top of the reactor through which the hydroconverted effluent (recovered feed) is withdrawn.

[0203] The entrained solid catalyst exits the entrained bed reactor with the hydroconverted effluent.

[0204] The entrained bed reactor may include at its lower part a device for dispersing hydrogen more uniformly in the feed.

[0205] The entrained bed reactor may include an old bubbling bed reactor converted into an entrained bed reactor by removing the porous supported catalyst from the old bubbling bed reactor.

[0206] 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, pp. 248-273, or 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 Éditions Technip in 2011.

[0207] 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.

[0208] 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 refers to its circulation in the hydroconversion reactor(s) by the liquid streams, with the entrained solid catalyst circulating with the feed in the reactor(s), and being withdrawn from the 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 in the whole of 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.

[0209] 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.

[0210] In one or more embodiments, a portion of the spent entrained solid catalyst from the hydroconversion step is recycled into one or more hydroconversion reactors to limit the consumption of fresh entrained catalyst. The spent entrained solid catalyst can be recovered from 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 into 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.Heavy cuts of the hydroconverted effluent can, for example, also be obtained by a deasphalting process, and in this case the entrained solid catalyst can be recycled to the hydroconversion stage with the asphalt fraction.

[0211] Injection of the driven solid catalyst

[0212] The entrained solid catalyst can be introduced into the hydroconversion reactor according to different implementations.

[0213] According to one or more implementations, 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.

[0214] The nanoparticles of the driven solid catalyst can be mixed with the feed in the different ways (A), (B) or (C) below:

[0215] (A) Following the preparation process of the entrained solid hydroconversion catalyst, the entrained solid catalyst nanoparticles may be in the form of a colloidal solution comprising an organic stabilizing agent, and optionally the organic synthesis solvent (used during the nanoparticle preparation process). The colloidal solution may then be mixed with the heavy hydrocarbon feedstock.

[0216] (B) Following the preparation process of the entrained solid hydroconversion catalyst, the nanoparticles may have been separated from the excess organic stabilizing agent, and optionally 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, may then be mixed with the heavy hydrocarbon feedstock.

[0217] (C) Following the preparation process of the entrained solid hydroconversion catalyst, the nanoparticles may have been separated from the excess organic stabilizing agent, and optionally from 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 colloidal mixture, before being mixed with the heavy hydrocarbon feedstock, said liquid comprising, or consisting of, one or more of the following liquids:

[0218] -an organic solvent such as toluene, xylene, mesitylene;

[0219] - 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;

[0220] - any other recycled liquid effluent from the hydroconversion process.

[0221] Preferably, the separated nanoparticles obtained at the end of the preparation process are redispersed in a VGO.

[0222] During the mixing of feed / entrained solid 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 with a pump with a propeller or turbine rotor, to help disperse the nanoparticles in the heavy hydrocarbon feed.

[0223] 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.

[0224] Depending on one or more modes, 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.

[0225] 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.

[0226] Depending on one or more implementations, 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 as the colloidal solution obtained at the end of the preparation process for the entrained solid hydroconversion catalyst, comprising an organic stabilizing agent and possibly an organic synthesis solvent, or as a colloidal solution obtained by redispersing the separated (and possibly washed and / or dried) nanoparticles obtained at the end of the preparation process for the entrained solid hydroconversion catalyst, in a hydrocarbon liquid as previously described for injection method (C) above.

[0227] Further treatment of the hydroconverted effluent

[0228] The hydroconverted effluent from step a) can be further treated.

[0229] 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 of the hydroconverted effluent into hydrocarbon fractions; 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.

[0230] 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, and other processes. 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.

[0231] According to one or more embodiments, the hydroconversion process further comprises: b) optionally an additional hydroconversion step in at least one additional entrained 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, or all, of said heavy cut in a deasphalter with at least one hydrocarbon solvent to produce a deasphalted oil DAO and a residual asphalt.

[0232] The additional hydroconversion step b) is carried out in a similar manner 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.

[0233] As with hydroconversion step a), the additional hydroconversion step b) is carried out in at least one additional energized bed reactor similar to the energized bed reactor(s) of hydroconversion step a).

[0234] In this additional hydroconversion step b), the operating conditions may be similar to or different from those in hydroconversion step a), the temperature remaining within the range of 300°C to 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 amount of hydrogen introduced into the reactor remaining within the range of 50 to 5,000 Nm³ 3 / m 3 of liquid charge, preferably between 100 and 3000 Nm 3 / m 3 , and even more preferably between 200 and 2000 Nm 3 / m 3 The other pressure and WH parameters are in the same ranges as those described for hydroconversion step a).

[0235] The operating temperature in the additional hydroconversion step b) can be higher than the operating temperature in the hydroconversion step a). This can allow for more complete conversion of the unconverted feedstock. The hydroconversion of liquid products from the hydroconversion step a) and 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).

[0236] 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.

[0237] The other fraction(s) resulting from this step b') are one or more light and intermediate fraction(s). The light fraction thus separated contains mainly gases (H2, H2S, NH3, and Cl-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.

[0238] 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".

[0239] The fractionation step (c), which separates part or all of the hydroconverted effluent from hydroconversion step (a) or the second hydroconverted effluent from the additional hydroconversion step (b), to produce at least two fractions, each 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).

[0240] The heavy liquid fraction contains a fraction that boils at a temperature above 540°C, called the vacuum residue (which is the unconverted fraction). It may contain a portion 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. This fractionation step therefore produces at least two fractions, including the heavy liquid fraction, with the other fraction(s) being light and intermediate fractions. 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 processing and recycling step.

[0241] 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.

[0242] 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) of the heavy liquid fraction from fractionation c). It may then be advantageous to leave the potentially entrained solid catalyst present in the recycled stream. A purge of the recycled stream can be implemented, generally to prevent certain compounds from accumulating at excessive levels.

[0243] 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.

[0244] Examples

[0245] The following examples illustrate the invention without, however, limiting its scope.

[0246] Example 1: Synthesis of M0S2 nanoparticles (according to the invention)

[0247] In a flask, 2 g of molybdenum dibutyldithiophosphate 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 M0S2 nanoparticles can be used directly in catalytic testing.

[0248] No sulfuration step is required before using the nanoparticles for the catalytic test.

[0249] To characterize these nanoparticles, centrifugation is performed to recover them. They 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. Mono-sheets with a length of 4 nm ± 1.3 nm were observed. Example 2: Catalytic test of M0S2 nanoparticles obtained according to Example 1 (compliant)

[0250] The performance of MoS2 nanoparticles obtained according to Example 1, with regard to the hydroconversion of a heavy hydrocarbon feedstock of the residue type (RSV), was evaluated in a 300 mL autoclave-type batch reactor in slurry (or driven) mode. The colloidal solution of the MoS2 nanoparticles is injected directly into the feedstock.

[0251] The test conditions are as follows:

[0252] - Temperature: 400°C;

[0253] - Total absolute pressure: 14.5 MPa;

[0254] - Duration: 2h30; - Volume of heavy hydrocarbon charge: 0.12 L (120 cc);

[0255] - Concentration in MB in the load: 1000 ppm;

[0256] - Reactor agitation speed: 900 rpm.

[0257] The main characteristics of the heavy hydrocarbon feedstock are given in Table 1 below. Table 1

[0258] Hydrogen is replenished throughout the test via an H2a ballast to compensate for hydrogen consumption and maintain a constant total pressure. 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, allowing for the evaluation of the amount of sediment formed during the test (as a mass percentage relative to the effluent liquid). Metal and asphaltene analyses are performed on the filtrate to determine the performance (as a mass percentage) in hydrodesulfurization (HDS), hydrodemetallation (HDV), asphaltene reduction (HDAsC7), Conradson carbon reduction (HDCCR), and hydroconversion of the heavy fraction at 540°C+ (HDC540+).

[0259] The HDX rate is defined as follows:

[0260] Math 1

[0261] Where X refers to the type of performance evaluated (S for hydrodesulfurization, etc.), [X] corresponds to the levels of S, V, AsC7, CCR or 540°C+ in the liquid effluents and m corresponds to the mass of feed (m C charge) or the mass of liquid effluent recovered at the end of the test (m e effluent). The sediment content is measured in the liquid effluent according to the IP375 standard.

[0262] The test is performed three times to ensure good repeatability.

[0263] The results obtained are shown in Table 2 below.

[0264] Example 3: Catalytic test of commercial M0S2 nanoparticles (non-compliant)

[0265] Commercial 90 nm MoS2 nanoparticles are dispersed in an aromatic organic solvent. The resulting colloidal solution is injected directly into the RSV feed. The nanoparticles are tested under the same conditions as those used for the MoS2 nanoparticles according to the invention (Example 2). The test is performed three times to ensure good repeatability.

[0266] The results obtained are shown in Table 2 below.

[0267] Table 2 The test performed according to Example 2 with MoS2 nanoparticles prepared according to Example 1 increases performance in terms of HDS, HDV, HDAsC7, HDCCR, and HDC540+, and results in a significant reduction in sediment compared to the test performed according to Example 3 with MoS2 nanoparticles. This difference in activity is directly related to the small size of the MoS2 nanoparticles obtained according to Example 1, which increases the active surface area of ​​the catalyst.

Claims

Demands 1. A process for the hydroconversion of 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 step of hydroconversion 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 molybdenum disulfide M0S2 nanoparticles obtained by a preparation process comprising (i) a step of decomposition of a first organosoluble precursor comprising at least one molybdenum-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 organosoluble precursor 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 containing a hydrocarbon chain in C6 to C18; - carboxylic acids with 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 1 in which the radicals RI, R2, R3, R4 are chosen independently from linear or branched alkyl groups, in C1 to C12, cycloalkyl groups in C6 to C12, and aryl or alkyl- groups aryls in C6 to C12, preferably linear alkyl groups identical in Cl to C6 or branched alkyl groups identical in Cl to C12.

3. A hydroconversion process according to claim 2, 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 the oxymolybdenum di(2-ethylhexyl) phosphorodithioate.

4. A hydroconversion process according to any one of the preceding claims, wherein said organic stabilizing agent is selected 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, triooctylphosphine.

5. Hydroconversion process according to claim 4, wherein said organic stabilizing agent is an alkylamine selected from the list consisting of octylamine, dodecylamine, hexadecylamine, octadecylamine, and oleylamine, and preferably is hexadecylamine.

6. Hydroconversion process according to any one of the preceding claims, wherein in step (i) of the process of preparing the entrained solid hydroconversion catalyst, the molar ratio Mo to organic stabilizing agent is between 0.001 and 0.

1.

7. Hydroconversion process according to any one of the preceding claims, wherein step (i) of the process of preparing the entrained solid hydroconversion catalyst 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.

8. A hydroconversion process according to any one of the preceding claims, wherein the nanoparticles of the solid hydroconversion catalyst obtained at the end of the process of preparations are in the form of single sheets and have an average size between 1 nm and 25 nm, preferably between 1 nm and 10 nm, preferably between 1 nm and 5 nm.

9. Hydroconversion process according to any one of the preceding claims, further comprising (ii) a separation step between the entrained solid 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).

10. 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 molybdenum disulfide nanoparticles M0S2 without implementation of a sulfidation step of the entrained solid hydroconversion catalyst prior to the hydroconversion step a) or during said process of preparation of said entrained solid hydroconversion catalyst.

11. Hydroconversion process according to any one of the preceding claims, wherein the entrained solid hydroconversion catalyst is introduced into said 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.

12. Hydroconversion process according to any one of claims 1 to 10, wherein the entrained solid hydroconversion catalyst is introduced into said hydroconversion reactor at the hydroconversion stage independently of the heavy hydrocarbon 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 10000 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 a.m. 1and 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.

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, bitumen from oil sands, heavy oil from oil shale, atmospheric residue, or residue vacuum distillate from atmospheric or vacuum distillation of crude oil, atmospheric residue or vacuum residue from atmospheric or vacuum distillation of effluent from a thermal conversion, hydrotreating, hydrocracking, hydroconversion, or direct coal liquefaction unit, vacuum distillate obtained directly from crude oil or a cut from a fluidized bed catalytic cracking, hydrocracking, hydroconversion, coking, or visbreaking unit, vacuum distillate from direct coal liquefaction, aromatic cuts extracted from a lubricant production unit, deasphalted oil or resin fraction or asphalt fraction from a deasphalting unit, bio-oil, biocrude, plastics pyrolysis oil and / or tires and / or solid recovered fuels,and preferably a vacuum residue obtained from the vacuum distillation of crude oil.

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