Process for hydroconversion in a hybrid bubbling-entrained bed of heavy hydrocarbon feedstocks with molybdenum disulfide nanoparticles

Abstract

The present invention relates to a process for hydroconversion in a hybrid bubbling-entrained bed of a heavy hydrocarbon feedstock in the presence of a hydroconversion catalyst in the form of single-layer nanoparticles of molybdenum disulfide (MoS2) obtained according to an ex-situ preparation process from an organosoluble precursor comprising a molybdenum-sulfur bond.

Description

[0001] BOILING-DRIVED HYBRID BED HYDROCONVERSION PROCESS OF HEAVY HYDROCARBONATE FILLERS WITH MOLYBDENINE DISULFIDE NANOPARTICLES

[0002] technical field

[0003] The present invention relates to a process for hydroconversion of heavy hydrocarbon fillers in a bubbling-entrained hybrid 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 the catalytic activity as well as a surface for the deposition of metals and asphaltenes from the feedstock.

[0008] 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. Hybrid technologies combining the use of different types of catalyst beds are sometimes employed to achieve the hydroconversion of heavy feedstocks.

[0009] Hydroconversion processes for heavy hydrocarbon feedstocks are known to utilize hybrid bubbling-entrained bed reactors operating in the presence of hydrogen. These reactors employ a conventionally supported, millimeter-sized solid catalyst maintained as an expanded bed within the reactor, while a slurry catalyst exits with the hydroconverted effluent. US patent 8431016 and application WO2023 / 280624 illustrate such hybrid processes. This type of hybrid process is known to improve upon the traditional bubbling bed process, particularly since the addition of an entrained catalyst reduces sediment and coke precursor formation in hydroconversion reactors, enhancing hydroconversion performance. This allows for higher feed conversion rates, improved product quality, and greater product stability.Indeed, it is known that during the operation of a boiling bed reactor, the heavy hydrocarbon feedstock is heated to a temperature at which the high-boiling-point fractions of the feedstock, typically possessing a high molecular weight and / or a low hydrogen-to-carbon ratio (an example being a family of complex compounds grouped under the name "asphaltenes"), tend to undergo thermal cracking to form short-chain free radicals. These free radicals can react with other free radicals, or with other molecules, to produce coke precursors and sediments. A driven catalyst passing through the reactor, while the reactor already contains a supported catalyst maintained within the reactor, provides additional catalytic hydrogenation activity, particularly in areas of the reactor that are generally devoid of a supported catalyst.The entrained catalyst therefore reacts with free radicals in these areas, forming stable molecules, and thus helps to control and reduce the formation of sediments and coke precursors. Since coke and sediment formation is the main cause of the deactivation of conventional catalysts and the fouling of hydroconversion plants, such a hybrid process increases the lifespan of the supported catalyst and prevents fouling of downstream equipment, such as separation vessels, distillation columns, heat exchangers, etc.

[0010] 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.

[0011] Entrained (unsupported) hydroconversion catalysts are typically metal sulfides that can be prepared in various ways.

[0012] 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.

[0013] For example, nanoparticulate catalysts (which can also be called colloidal or molecular) formed in-situ from organosoluble metal compounds (i.e., soluble in an organic substance or solvent), precursors of the entrained catalyst, such as molybdenum naphthenate or molybdenum octoate (molybdenum 2-ethylhexanoate, also called Mo-octoate in Anglo-Saxon terminology), are disclosed in patents US4244839, US2005 / 0241991, US2014 / 0027344 and WO2013 / 034642. Patent application US2005 / 0241991, for example, describes a hydroconversion process for heavy hydrocarbon feedstocks using one or more chained bubbling bed reactors, these reactors being able to operate in hybrid mode with the addition of an organosoluble metal precursor dispersed in the feedstock.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 HzS from the hydrodesulfurization of the feedstock.

[0014] Water-soluble metallic compounds, such as phosphomolybdic acid cited in patents US3231488, US4637870, and US4637871, ammonium heptamolybdate cited in patent US6043182, 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.

[0015] 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.

[0016] 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.

[0017] 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.

[0018] 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)6 and nickel (II) acetylacetonate or cobalt(III) acetylacetonate, in the presence of a sulfurizing agent which is elemental sulfur and in the presence of oleylamine.

[0019] 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.

[0020] 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.

[0021] Objectives and Summary of the Invention

[0022] In the context described above, the present description aims to provide a process for the hydroconversion of heavy hydrocarbon feedstocks in hybrid bubbling-entrained bed reactor(s), which is simple to implement and which eliminates the need for a sulfidation step of the entrained catalyst before its use for the hydroconversion of the feedstock.

[0023] The invention also aims to provide a simple to manufacture, highly dispersible driven (i.e. unsupported within the meaning of the present invention) hydroconversion catalyst exhibiting good performance with regard to conversion and hydrotreating reactions during the hydroconversion of a heavy hydrocarbon feedstock, while limiting sediment formation.

[0024] Thus, to achieve at least one of the aforementioned objectives, among others, the present invention proposes, according to a first aspect, 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 as a hybrid bubbling-entrained bed in the presence of hydrogen, at least one supported solid hydroconversion catalyst and at least one entrained solid hydroconversion catalyst, to produce a hydroconverted effluent, said entrained solid hydroconversion catalyst being in the form of molybdenum disulfide MoS2 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 comprising a ligand selected from the list of the following families: dithiocarbamates, dithiophosphates, xanthates, dithioimidophosphinates, and dithioimidophosphates, and said organic stabilizing agent being selected from the group consisting of: - alkylamines selected from primary amines and secondary amines comprising a hydrocarbon chain from C4 to C34;

[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 of the process for preparing the entrained solid hydroconversion catalyst is chosen from the group consisting of: - alkylamines chosen from primary amines and secondary amines having a hydrocarbon chain in C12 to C18, preferably chosen from the list consisting of octylamine, dodecylamine, hexadecylamine, octadecylamine, and oleylamine;

[0032] - the alkylthiols chosen from the list consisting of 1-hexane thiol, 1-octanethiol, 1-dodecanethiol, and 1-hexadecanethiol;

[0033] - carboxylic acids chosen from the list consisting of citric acid, octanoic acid, decanoic acid, palmitic acid, and oleic acid;

[0034] - the phosphines chosen from the list consisting of tributylphosphine, triooctylphosphine.

[0035] 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.

[0036] 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.

[0037] 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 synthesis solvent with a boiling point above 100°C, preferably chosen from the list consisting of toluene, ethylbenzene, xylene, mesitylene, decane, and dodecane.

[0038] 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.

[0039] Advantageously, the process for preparing the solid hydroconversion catalyst does not involve a sulfidation step to form the M0S2 nanoparticles.

[0040] According to one or more embodiments of the invention, the process for preparing the entrained solid hydroconversion catalyst further comprises (il) 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 (il).

[0041] 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 hydroconversion 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.

[0042] According to one or more embodiments of the invention, the entrained solid hydroconversion catalyst is introduced into said hydroconversion reactor at the hydroconversion stage independently of the heavy hydrocarbon feed.

[0043] According to one or more embodiments of the invention, the entrained solid hydroconversion catalyst is in the form of a colloidal solution comprising an organic stabilizing agent and optionally an organic synthesis solvent used in step (i) of the process of preparing the entrained solid hydroconversion catalyst.

[0044] According to one or more embodiments of the invention, the entrained solid hydroconversion catalyst is introduced into said hydroconversion reactor in its form of M0S2 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.

[0045] According to one or more embodiments of the invention, the concentration of the entrained solid hydroconversion catalyst is between 5 ppm and 500 ppm by weight of molybdenum relative to the heavy hydrocarbon feed at the inlet of the hydroconversion reactor.

[0046] 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 bubbling-entrained hybrid reactor of between 0.05 h 1 and 10 a.m. 1 and under a quantity of hydrogen mixed with the feed entering the bubbling-entrained hybrid bed reactor of between 50 and 5000 normal cubic meters per cubic meter of feed.

[0047] According to one or more embodiments of the invention, the heavy hydrocarbon feed comprises, and may consist of, 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.

[0048] According to one or more embodiments of the invention, the heavy hydrocarbon feed comprises at least the following elements: sulfur in a content greater than 0.5% by weight, a Conradson carbon residue of at least 0.5% by weight, C7 asphaltenes in a content greater than 1% by weight, transition and / or post-transition metals and / or metalloids in a content greater than 2 ppm by weight, and alkali and / or alkaline earth metals in a content greater than 2 ppm by weight.

[0049] According to one or more embodiments of the invention, the supported solid hydroconversion catalyst is in the form of extrudates or beads, preferably with an equivalent diameter between 0.4 mm and 4.4 mm.

[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 bubbling-entrained hybrid bed reactor, of at least a portion, or all, of the hydroconverted effluent resulting from hydroconversion step a) or optionally of a heavy liquid fraction that predominantly boils at a temperature greater than or equal to 350°C resulting from an optional separation step separating a portion, or all, of said hydroconverted effluent, said additional supported solid catalyst being the same as or a different supported solid catalyst from the reactor of step a), 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 the fractionation step (c) with at least one hydrocarbon solvent to produce a deasphalted oil DAO and a 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 bubbling-entrained hybrid bed reactor between 0.05 h; 1 and 10 a.m.1 and 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 ) of charge. Other objects and advantages of the invention will become apparent from the following description of examples of particular embodiments of the invention, given by way of non-limiting examples.

[0051] Description of the implementation methods

[0052] 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.

[0053] In this description, the various embodiments presented can be implemented separately or in combination with each other, without limitation of combinations where technically feasible.

[0054] Terminology

[0055] It is specified that, throughout this description, the expression "between ... and ..." should be understood as including the cited limits, unless otherwise specified.

[0056] 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."

[0057] In addition, when used in this description, and unless otherwise indicated, the terms "essentially" or "substantially" or "approximately" or "mainly" in relation to a reference value correspond to an approximation of ± 10%, preferably ± 5%, most preferably ± 2%, or even more preferably ± 1% of that reference value, which may be a temperature, a pressure, a dimensional quantity such as length, a quantity, a speed, a flow rate, a content of compound(s), etc.

[0058] In this description, the different parameter ranges for a given step, such as pressure ranges and temperature ranges, can be used alone or in combination. For example, in the context of the present invention, a preferred range of pressure values ​​can 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 a bubbling bed 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 "hybrid bed," "hybrid bubbling bed," and "hybrid bubbling-entrained bed" for a hydroconversion reactor refer to a bubbling bed hydroconversion reactor that includes an entrained catalyst in addition to the porous supported catalyst maintained within the bubbling bed reactor. Similarly, for a hydroconversion process, these terms refer to a process comprising a hybrid operation of a bubbling bed and an entrained bed in at least one of the same hydroconversion reactor. The hybrid bed is a mixed bed of two types of catalysts with necessarily different particle sizes and / or densities. One type of catalyst—the "porous supported catalyst"—is maintained within the reactor, and the other type—the "entrained catalyst," also commonly called a "slurry catalyst"—is entrained from the reactor with the effluent (recovered feedstock).According to the present invention, the driven catalyst is a catalyst in the form of specific nanoparticles, as defined below.

[0064] In this description, a "supported solid hydroconversion catalyst," or more succinctly, a "porous supported catalyst" or simply a "supported catalyst," refers to a porous supported catalyst that can be used in a bubbling bed or hybrid bubbling-entrained bed hydroconversion process of a hydrocarbon feedstock. Such catalysts typically comprise (i) a catalyst support with a large surface area and numerous interconnected channels or pores, and (ii) an active phase in the form of fine particles such as cobalt, nickel, tungsten, or molybdenum sulfides, or mixed sulfides of these elements (e.g., NiMo, CoMo, etc.), optionally phosphorus and / or sulfur, dispersed within the pores. Supported catalysts are commonly produced as cylindrical extrudates ("pellets") or spherical solids, although other shapes are possible.Such a supported catalyst is detailed further in the description.

[0065] In this description, "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 implemented in a hydroconversion process of a hydrocarbon feedstock in a hybrid bubbling-entrained bed or in an entrained bed (100% of the catalyst in the reactor(s) is an entrained catalyst).

[0066] According to the invention, the catalyst obtained by the specific synthesis process from an organosoluble precursor comprising at least one molybdenum-sulfur bond, and used as a solid catalyst driven in a hybrid bed hydroconversion process, is in the form of single-sheet molybdenum sulfide nanoparticles MoS2, 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 at the date of filing of this application, unless otherwise specified.

[0071] Process for preparing the solid entrained hydroconversion catalyst

[0072] According to the hydroconversion process of the invention, the entrained solid hydroconversion catalyst is prepared by a simple preparation process comprising a single step of forming molybdenum disulfide (MoS2) nanoparticles in the form of mono-sheets, particularly of very small dimensions (medium size), by decomposition of an organosoluble precursor containing at least one molybdenum-sulfur bond. This organosoluble precursor comprises at least one Mo-S bond and includes a ligand selected from the following families: dithiocarbamates, dithiophosphates, xanthates, dithioimidophosphinates, and dithioimidophosphates.According to the invention, it is possible to eliminate a sulfidation step of the entrained catalyst before it is used for hydroconversion in the bubbling-entrained hybrid 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.

[0073] The nanoparticles of the entrained catalyst obtained are detailed below, after the description of the process for preparing the solid entrained catalyst.

[0074] 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.

[0075] The organosoluble precursor containing molybdenum is therefore chosen from the following families: molybdenum dithiocarbamates, molybdenum dithiophosphates, molybdenum xanthates, molybdenum dithioimidophosphinates, and molybdenum dithioimidophosphates.

[0076] 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-,

[0077] 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-. Xanthates are a family of compounds with the general structure ROC(S)S-.

[0078] Dithioimidophosphinates are a family of compounds with a phosphorus-sulfur bond and a phosphorus-nitrogen bond, with the general structure -P(S)NHR.

[0079] 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".

[0080] The process for preparing the entrained solid catalyst includes (i) a step of decomposing a first organosoluble precursor having at least one molybdenum-sulfur (Mo-S) bond and composing 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. According to one or more embodiments, step (i) includes the implementation of a mechanical action such as the application of a shear force.

[0081] According to one or more embodiments of the invention, the first organosoluble precursor corresponds to the general formulas (I) or (II) described below.

[0082] 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):

[0083] 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.

[0084] 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):

[0085] 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.

[0086] 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). 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.

[0087] 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 (C1-C6) or identical branched alkyl groups comprising from 1 to 12 carbon atoms (C1-C12).For example, the first organosoluble precursor is chosen from the list consisting of: oxymolybdenum dimethylphosphorodithioate (dimethyldithiophosphate), oxymolybdenum diethylphosphorodithioate (diethyldithiophosphate), oxymolybdenum dipropylphosphorodithioate (dipropyldithiophosphate), oxymolybdenum dibutylphosphorodithioate (dibutyldithiophosphate), oxymolybdenum dipentylphosphorodithioate (dipentyldithiophosphate), oxymolybdenum dihexylphosphorodithioate (dihexyldithiophosphate), and oxymolybdenum di(2-ethylhexyl)phosphoodithioate.

[0088] 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 dimethylhexyl phosphorodithioate. of oxymolybdenum.

[0089] Preferably, the first organosoluble precursor is oxymolybdenum dibutyldithiocarbamate, oxymolybdenum dibutyldithiophosphate or oxymolybdenum di(2-ethylhexyl)phosphoodithioate.

[0090] 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 chosen from the group consisting of:

[0091] - alkylamines selected from primary and secondary amines having a hydrocarbon chain comprising 4 to 34 carbon atoms (C4 to C34), preferably comprising 12 to 18 carbon atoms (C12 to C18), and optionally comprising one or more unsaturations, preferably selected from the list consisting of octylamine, dodecylamine, hexadecylamine, octadecylamine, and oleylamine; - alkylthiols having a hydrocarbon chain comprising 6 to 18 carbon atoms (C6 to C18), preferably selected from the list consisting of 1-hexane thiol, 1-octanethiol, 1-dodecanethiol, and 1-hexadecanethiol;

[0092] - carboxylic acids having a hydrocarbon chain comprising 6 to 18 carbon atoms (C6 to C18), preferably chosen from the list consisting of citric acid, octanoic acid, decanoic acid, palmitic acid, and oleic acid;

[0093] - phosphines, preferably chosen from the list consisting of tributylphosphine, triooctylphosphine, trioctylphosphine oxide, and triphenylphosphine.

[0094] 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.

[0095] 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).

[0096] The metal molar ratio Mo to organic stabilizing agent can be between 0.001 and 0.1, preferably between 0.002 and 0.05.

[0097] The decomposition step (i) may include the addition of a second organosoluble precursor having a metal M-sulfur (MS) bond, M being a group VIII metal, e.g. nickel, said second organosoluble precursor having a ligand selected from the list of families consisting of dithiocarbamates, dithiophosphates, xanthates, dithioimidophosphinates, and dithioimidophosphates, so that the nanoparticles formed are M0S2 promoted nanoparticles with the metal M, e.g. Ni-promoted M0S2 nanoparticles, also called MMoS bimetallic sulfide nanoparticles, e.g. NiMoS.

[0098] The second organosoluble precursor is a coordination complex comprising at least one metal M-sulfur bond and organic ligands whose structure is that of the aforementioned families.

[0099] 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).

[0100] Chem 3 Chem 4 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.

[0101] In general formulas (I), (II), (III) and (IV), the bonds shown in dotted lines correspond to a delocalized double bond.

[0102] Preferably, the group VIII metal M of the second organosoluble precursor is nickel or cobalt, and more preferably nickel.

[0103] 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 (Cl-C6).

[0104] For example, if the metal M is nickel, the second organosoluble precursor is chosen from the following list: 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 can also be used as the second organosoluble precursor.

[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 dithiocarbamates of metal M corresponding to the general formula (III), and preferably in which the radicals RI, R2, R3, R4 are identical linear or branched alkyl groups comprising from 1 to 12 carbon atoms (C1-C12), and more preferably identical linear alkyl groups comprising from 1 to 6 carbon atoms (Cl-C6).

[0106] 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.

[0107] Preferably, the second organosoluble precursor is nickel dibutyldithiocarbamate.

[0108] In the case of using a second metallic precursor based on a group VIII metal M, e.g. nickel:

[0109] - the molar ratio of metallic elements (M+Mo) to organic stabilizing agent, e.g. the molar ratio of the sum of Ni and Mo elements (Ni+Mo) to organic stabilizing agent, can be between 0.001 and 0.1, preferably between 0.005 and 0.05;

[0110] - the molar ratio M / Mo, e.g. Ni / Mo, can be between 0.1 and 1, preferably between 0.2 and 0.8.

[0111] Preferably, the decomposition stage, thermal decomposition, is carried out at atmospheric pressure.

[0112] 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.

[0113] 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.

[0114] The decomposition step of the entrained solid catalyst preparation process allows the obtaining of metal sulfide nanoparticles without requiring a sulfidation step under H2S or by adding another sulfurating agent, during the synthesis itself or post-synthesis, before use of the entrained solid catalyst.

[0115] By controlling the various parameters such as temperature, synthesis time, nature of the organic stabilizing agent, and possibly the quantity of organic stabilizing agent, agitation, etc., it is possible to control the size and shape of the nanoparticles obtained, 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 catalyst nanoparticles obtained, which are molybdenum disulfide nanoparticles MoS2, possibly promoted by a group VIII metal M, e.g. nickel, are advantageously in the form of single sheets, i.e. mainly without stacking, and advantageously have a size, corresponding to the average length of the sheet in the present description, substantially between 1 nm and 25 nm, preferably between 1 nm and 10 nm, and preferably between 1 nm and 6 nm, more preferably between 1 nm and 5 nm.

[0124] By mainly without stacking, we mean that the nanoparticles can be in the form of isolated sheets formed by monosheets and / or stacks of monosheets comprising a maximum of five monosheets, preferably a maximum of two monosheets, and preferably formed by monosheets without any stacking of monosheets.

[0125] 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).

[0126] 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 average 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 using at least 250 nanoparticles.

[0127] The standard deviation is calculated as the square root of the variance.

[0128] 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.

[0129] 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.

[0130] The nanoparticles obtained by the synthesis process described advantageously form an active sulfide-energized solid-acting catalyst which can be used directly in the hydroconversion process according to the invention as described below, 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.

[0131] The nanoparticles obtained by the described synthesis process can be used as an entrained catalyst for the 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.

[0132] hydroconversion process

[0133] 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 as a hybrid bubbling-entrained bed in the presence of hydrogen, at least one supported solid hydroconversion catalyst and at least one entrained solid hydroconversion catalyst, to produce a hydroconverted effluent, said entrained solid hydroconversion catalyst being in the form of molybdenum disulfide (MoS2) nanoparticles 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 chosen from the list of the following families: dithiocarbamates, dithiophosphates, xanthates, dithioimidophosphinates, and dithioimidophosphates, and the organic stabilizing agent being chosen from the group consisting of:,

[0134] - alkylamines selected from primary amines and secondary amines having a hydrocarbon chain from C4 to C34;

[0135] - alkylthiols containing a hydrocarbon chain in C6 to C18;

[0136] - carboxylic acids with a hydrocarbon chain from C6 to C18;

[0137] - phosphines.

[0138] 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.

[0139] Charge

[0140] In this description, the term "charge" or "hydrocarbon charge" refers to the heavy hydrocarbon charge sent to hydroconversion, as defined below, unless otherwise specified.

[0141] 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.

[0142] The hydrocarbon load can be a load of fossil origin.

[0143] Preferably, the hydrocarbon feedstock comprises, and may consist of, one of the following feedstocks of fossil origin, alone or in mixture:

[0144] - crude oil,

[0145] - synthetic crude oil,

[0146] - a coal tar,

[0147] - a bitumen made from tar sands,

[0148] - a heavy oil derived from oil shale,

[0149] - an atmospheric residue or a vacuum residue resulting from the atmospheric or vacuum distillation of crude oil,

[0150] - 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),

[0151] - 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, - a vacuum distillate from the direct liquefaction of coal,

[0152] - aromatic cuts extracted from a lubricant production unit,

[0153] - 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.

[0154] 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.

[0155] The charges mentioned are liquid under the operating conditions of hydroconversion.

[0156] Preferably, the hydrocarbon feedstock comprises, and may consist of, one of the following feedstocks, alone or in mixture:

[0157] - crude oil,

[0158] - synthetic crude oil,

[0159] - a coal tar,

[0160] - a bitumen made from tar sands,

[0161] - a heavy oil derived from oil shale,

[0162] - an atmospheric residue or a vacuum residue resulting from the atmospheric or vacuum distillation of crude oil,

[0163] - 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.

[0164] Preferably, the hydrocarbon feed includes, and can consist of, a vacuum residue from the vacuum distillation of crude oil.

[0165] The hydrocarbon load can also come from the conversion of biomass, in particular algae or lignocellulosic biomass, and in particular be a "bio-oil" or a "biocrude".

[0166] 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).

[0167] 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.

[0168] 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.

[0169] 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.

[0170] 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.

[0171] A biocrude is a product obtained by hydrothermal liquefaction of biomass (HTL), and consists primarily of organic molecules, an aqueous phase containing water-soluble organic compounds (alcohols, acids, ketones, phenols, etc.) and salts, gas, and possibly biochar. Biochar is a carbon-rich solid product; the term "char" comes from the English word "charcoal." The gas produced is mainly CO2 but may also contain hydrogen, methane, and CO.

[0172] 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). The oxygen, sulfur, and nitrogen content of biocrude varies considerably depending on the biomass load of the hydrothermal liquefaction (algae, wood, etc.). For example, biocrude from hydrothermal liquefaction of wood typically includes 5 to 20% by weight of oxygen, less than 0.5% by weight of sulfur and less than 5% by weight of nitrogen in dry biocrude (without water).

[0173] 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, NazCOs, etc.).

[0174] Bio-oils and bio-raw materials can be pre-treated, for example stabilized and / or demineralized before hydroconversion.

[0175] 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.

[0176] 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.

[0177] The pyrolysis oil from 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.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.

[0178] Metal content 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.

[0179] 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.

[0180] The nitrogen content can range from 1 ppm to 8000 ppm by weight, more commonly from 200 ppm to 8000 ppm by weight, for example, from 2000 ppm to 8000 ppm by weight. The C7 asphaltene content (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 cuts, both through their ability to form heavy hydrocarbon residues, commonly called coke, and through their tendency to produce sediments that can severely limit the operability of hydroconversion units. The Conradson carbon content can be greater than or equal to 3% by weight, or even at least 5% by weight.The Conradson carbon content is defined by ASTM D482 and represents for those skilled in the art a well-known assessment of the amount of carbon residue produced after pyrolysis under standard temperature and pressure conditions.

[0181] These contents are expressed as a percentage by weight of the total weight of the hydrocarbon load.

[0182] According to one or more embodiments, a co-load can be sent to the hydroconversion stage with the hydrocarbon load as described above, preferably said co-load being in the minority with respect to the hydrocarbon load and for example represented less than 30% by mass, preferably less than 20% or 10% by mass with respect to the hydrocarbon load.

[0183] Preferably, the co-load comprises, and may consist of, one of the following co-loads, 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. - Plastics, and / or tires and / or RDF, the plastics being typically production by-products and / or waste as already described above.

[0186] 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.

[0187] The co-feed and the hydrocarbon feed can be sent independently, or mixed, to 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.

[0188] Implementation

[0189] Hydroconversion stage

[0190] According to the invention, the heavy hydrocarbon feedstock is introduced into at least one hydroconversion reactor operating in a hybrid bubbling-entrained bed configuration of the hydroconversion section, along with hydrogen. This reactor comprises a supported solid hydroconversion catalyst and an entrained solid catalyst, which can be injected either mixed with the feedstock or independently of the feedstock injection, as detailed later in the description.

[0191] 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.

[0192] 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.

[0193] 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. In 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 , and even more preferably between 0.15 h 1 and 1 hour 1 .

[0194] 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 .

[0195] 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 200 Nm 3 / m 3 and 1000 Nm 3 / m 3 .

[0196] The hydroconversion section comprises one or more reactors operating in a hybrid bubbling-entrained bed.

[0197] When several hybrid bubbling-entrained bed hydroconversion reactors are implemented, they can be in series and / or in parallel.

[0198] The bubbling-entrained hybrid bed reactor comprises a solid phase which includes a solid catalyst supported in the form of an expanded bed, a liquid hydrocarbon phase comprising the heavy hydrocarbon feedstock and the entrained solid catalyst which is dispersed therein, and a gaseous phase comprising hydrogen.

[0199] The hybrid bubbling-entrained bed reactor is a bubbling bed hydroconversion reactor comprising the entrained solid catalyst which exits the reactor with the effluents (recovered feed), in addition to the supported solid catalyst, which is in the form of an expanded bed, and is maintained in the bubbling bed reactor.

[0200] In one or more implementations, the operation of the hybrid bubbling-entrained bed hydroconversion reactor is based on that of a bubbling bed reactor as used for the H-Oil® process, for example, in patents US4521295, US4495060, US4457831, or US4354852, in the article Aiche, March 19-23, 1995, Houston, Texas, article number 46d, "Second generation bubbling bed technology," or in Chapter 3.5, "Hydroprocessing and Hydroconversion of Residue Fractions," of the book "Catalysis by Transition Metal Sulphides," Technip Editions, 2013. According to these implementations, the hydroconversion reactor advantageously includes a recirculation pump that makes it possible to maintain the supported solid catalyst in a bubbling bed by continuously recycling at least a portion of a liquid fraction withdrawn from the level of the upper part of the reactor and reinjected at the lower part of the reactor.The bubbling-entrained hybrid bed hydroconversion reactor preferably includes at least one inlet port located at or near the bottom of the reactor through which the feed, preferably including the entrained solid catalyst, is introduced along with hydrogen, and in particular two inlet ports in the case where 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 is removed from the reactor. The bubbling-entrained hybrid bed hydroconversion reactor further includes an expanded catalyst zone comprising the supported solid catalyst.The bubbling-entrained hybrid bed hydroconversion reactor also includes a lower supported solid catalyst-free zone located below the expanded catalyst zone, and an upper supported solid catalyst-free zone located above the expanded catalyst zone. The entrained solid catalyst is dispersed throughout the feed in the bubbling-entrained hybrid bed reactor, including in both the expanded catalyst zone and the supported solid catalyst-free zones, and is therefore available to stimulate upgrade reactions in what constitute catalyst-free zones in conventional bubbling-bed reactors.The feed in the hybrid bubbling-driven bed hydroconversion reactor is continuously recirculated from the upper supported solid catalyst-free zone to the lower supported solid catalyst-free zone via a recycle line connected to a boiling pump. At the top of the recycle line is typically a funnel-shaped recycle cup through which the feed is drawn from the upper supported solid catalyst-free zone. The internal recycled feed is then mixed with fresh feed and additional hydrogen gas.

[0201] As is known, and described for example in patent FR3033797, when worn out, the supported solid hydroconversion catalyst can be partially replaced by fresh catalyst and / or used catalyst with a higher catalytic activity than the worn catalyst being replaced, and / or regenerated catalyst, and / or rejuvenated catalyst (a catalyst from a rejuvenation zone in which most of the deposited metals are removed, before the rejuvenated catalyst is sent to a regeneration zone where the carbon and sulfur it contains are removed, thus increasing the catalyst's activity). Therefore, the worn supported solid hydroconversion catalyst can be withdrawn from the reactor, and a supply of fresh and / or used supported solid catalyst with a higher catalytic activity than the worn catalyst being replaced, and / or regenerated, and / or rejuvenated, can be introduced into the expanded catalyst zone of the reactor.This replacement of the spent catalyst is preferably carried out at regular time intervals, and preferably in bursts or virtually continuously. These withdrawals / replacements are performed using devices that advantageously enable the continuous operation of this hydroconversion step (a). For example, inlet and outlet tube openings in the expanded catalyst zone can be used to introduce / withdraw the fresh and spent supported solid catalyst, respectively. With this withdrawal / injection operation of the supported solid catalyst, it is therefore not necessary to stop the hydroconversion unit to change the spent catalyst, nor to increase the reaction temperatures along the cycle to compensate for the deactivation of the supported solid catalyst.Furthermore, working under constant operating conditions allows for consistent yields and product quality throughout the cycle.

[0202] Because the supported solid catalyst is kept agitated by a large amount of liquid recycling, the pressure drop (delta P) on the reactor remains low and constant, and the reaction exotherms are rapidly averaged over the catalytic bed, which is therefore almost isothermal and does not require, for example, the injection of cooling fluxes ("quenches").

[0203] The use of such hybrid bubbling-entrained bed reactors, as well as bubbling bed reactors, also allows operation under more severe conditions than, for example, those encountered in a fixed-bed catalyst reactor, resulting in better overall feed conversion. Another advantage of using hybrid bubbling-entrained bed reactors, like bubbling bed reactors, is the long cycle time of the hydroconversion unit (without unit shutdown to replace the supported solid catalyst). This is largely due to the supported solid catalyst withdrawal and injection system, which allows for the continuous replacement of spent supported solid catalyst without stopping the hydroconversion unit, a possibility made possible by the operation of this type of reactor.

[0204] The presence of entrained solid catalyst in the bubbling-entrained hybrid bed reactor provides additional catalytic hydrogenation activity, both in the expanded catalyst zone, in the recycle channel, and in the lower and upper supported solid catalyst-free zones. Stabilizing free radicals outside the supported solid catalyst minimizes the formation of sediments and coke precursors, which are often responsible for supporting catalyst deactivation. This can allow a reduction in the amount of supported solid catalyst that would otherwise be required to implement a desired hydroconversion reaction. This can also reduce the rate at which the supported solid catalyst needs to be withdrawn and replenished.

[0205] The supported solid hydroconversion catalyst used in hydroconversion step a) may contain one or more elements from groups 4 to 12 of the Periodic Table of Elements, which are deposited on a porous support. The porous support may advantageously be an amorphous support, such as silica, alumina, silica / alumina, titanium dioxide, or combinations of these structures, and most preferably alumina.

[0206] The supported solid catalyst may contain at least one Group VIII metal selected from nickel and cobalt, preferably nickel, said Group VIII element preferably being used in combination with at least one Group VIB metal selected from molybdenum and tungsten; preferably, the Group VIB metal is molybdenum. Advantageously, the supported solid hydroconversion catalyst comprises an alumina support and at least one Group VIII metal selected from nickel and cobalt, preferably nickel, and at least one Group VIB metal selected from molybdenum and tungsten, preferably molybdenum. Preferably, the supported solid hydroconversion catalyst comprises nickel as a Group VIII element and molybdenum as a Group VIB element.

[0207] The supported solid hydroconversion catalyst can therefore include:

[0208] - at least one metal from Group VIII, preferably chosen from nickel and cobalt, and preferably nickel, preferably in combination with at least one metal from Group VIB, preferably chosen from molybdenum and tungsten, and preferably molybdenum;

[0209] - a porous support, serving as a support for the said metal(s), preferably the porous support comprising, and being able to be made up of, silica, alumina, silica-alumina, titanium dioxide, and even more preferably alumina.

[0210] The content of non-noble group VIII metals, particularly nickel, is advantageously between 0.5% and 10% by weight, expressed as a percentage of metal oxide (particularly NiO), and preferably between 1% and 6% by weight. The content of group VIB metals, particularly molybdenum, is advantageously between 1% and 30% by weight, expressed as a percentage of metal oxide (particularly molybdenum trioxide, MoO3), and preferably between 4% and 20% by weight. The metal contents are expressed as a percentage by weight of metal oxide relative to the weight of the supported solid catalyst.

[0211] The supported solid hydroconversion catalyst may also include at least one dopant element selected from phosphorus, boron, silicon, preferably phosphorus.

[0212] The supported solid hydroconversion catalyst is advantageously used in the form of extrudates or beads. The beads have, for example, a diameter between 0.4 mm and 4.0 mm. The extrudates have, for example, a cylindrical shape with a diameter between 0.5 mm and 4.0 mm and a length between 1 mm and 5 mm. The extrudates can also be objects of different shapes such as trilobes, regular or irregular tetralobes, or other multilobes. Other shapes can also be used.

[0213] The size of these different forms of supported solid catalysts can be characterized by their equivalent diameter. The equivalent diameter is defined as six times the ratio of the particle volume to its external surface area. Porous supported catalysts, used in the form of extrudates, beads, or other shapes, thus have an equivalent diameter ranging from 0.4 mm to 4.4 mm.

[0214] These supported solid hydroconversion catalysts are well known to those skilled in the art.

[0215] Injection of the entrained solid catalyst The entrained solid catalyst can be introduced into the hydroconversion reactor according to different implementations.

[0216] 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.

[0217] The nanoparticles of the driven solid catalyst can be mixed with the feed in the different ways (A), (B) or (C) below:

[0218] (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.

[0219] (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.

[0220] (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:

[0221] -an organic solvent such as toluene, xylene, mesitylene;

[0222] - 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;

[0223] - any other recycled liquid effluent from the hydroconversion process.

[0224] Preferably, the separated nanoparticles obtained at the end of the preparation process are redispersed in a VGO. 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 comprising a pump with a propeller or a turbine rotor, to help disperse the nanoparticles in the heavy hydrocarbon feed.

[0225] 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.

[0226] According to one or more embodiments, continuous rather than batch-by-batch mixing can be implemented using high-energy pumps with multiple compartments in which the entrained solid catalyst and the heavy hydrocarbon feedstock are stirred and mixed. The mixing system described above can also be used for step (C) of redispersing the separated entrained solid catalyst nanoparticles from the preparation process in a liquid to form a colloidal mixture, prior to mixing said solution with the heavy hydrocarbon feedstock.

[0227] 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.

[0228] Depending on one or more implementations, the entrained solid catalyst can be injected into the hydroconversion reactor along with the supported solid catalyst via the injection system for said supported solid catalyst described above. However, this implementation (or these implementations) is / are less preferred than the two other injection types described above.

[0229] Further treatment of the hydroconverted effluent

[0230] The hydroconverted effluent from step a) can be further treated.

[0231] 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 hybrid bubbling-entrained bed reactors or additional bubbling 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; and 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.

[0232] 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 bubbling-entrained hybrid bed reactor.

[0233] According to one or more embodiments, the hydroconversion process further comprises: b) optionally, an additional hydroconversion step in at least one additional bubbling-entrained hybrid bed reactor of at least part, or all, of the hydroconverted effluent resulting from hydroconversion step a) or optionally of a liquid heavy fraction that predominantly boils 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 bubbling-entrained hybrid bed reactor comprising an additional supported solid catalyst and operating under hydroconversion conditions to produce a second hydroconverted effluent having a reduced heavy residue fraction, a reduced Conradson carbon residue,and possibly a reduced amount of sulfur and / or nitrogen, and / or metals; (c) a fractionation step of part, or all, of the hydroconverted effluent from hydroconversion step (a) or of said second hydroconverted effluent, in a fractionation section to produce at least one heavy cut that boils predominantly at a temperature of 350°C or higher, said heavy cut containing a residual fraction that boils at a temperature of 540°C or higher; (d) an optional deasphalting step of part, or all, of said heavy cut in a deasphalter with at least one hydrocarbon solvent to produce deasphalted oil DAO and residual asphalt.

[0234] 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, the equipment used, and the porous supported hydroconversion catalysts used, with the exception of the specifications mentioned below.

[0235] As with hydroconversion step a), the additional hydroconversion step b) is carried out in at least one additional bubbling-energized hybrid bed reactor similar to the bubbling-energized hybrid bed reactor(s) of hydroconversion step a).

[0236] 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 5000 Nm³ 3 / m 3 of liquid charge, preferably between 100 and 3,000 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).

[0237] 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).

[0238] The additional supported catalyst used in the additional bubbling-driven hybrid bed reactor may be the same as that used in the bubbling-driven hybrid bed reactor(s) in step a), or may also be another supported solid catalyst also suitable for the hydroconversion of heavy hydrocarbon feedstocks, as defined for the supported catalyst used in hydroconversion step a).

[0239] 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.

[0240] 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 C1-C4), naphtha (fraction that boils at a temperature below 150°C), kerosene (fraction that boils between 150°C and 250°C), and at least some diesel (fraction that boils between 250°C and 375°C). The light fraction can then be sent, at least partially, to a fractionation unit where the light gases are extracted from said light fraction, for example, by passing through an expansion vessel. The recovered gaseous hydrogen, which may have been sent to a purification and compression plant, can advantageously be recycled in the hydroconversion step a). The recovered gaseous hydrogen can also be used in other refinery facilities.

[0241] 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".

[0242] 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).

[0243] The heavy liquid cut contains a fraction that boils at a temperature above 540°C, called the vacuum residue (which is the unconverted fraction). It may contain part of the diesel fraction that boils between 250°C and 375°C and a fraction that boils between 375°C and 540°C, called the vacuum distillate.

[0244] This fractionation step therefore produces at least two fractions, including the heavy liquid fraction, with the other fraction(s) being light and intermediate fraction(s). The fractionation step may include a gas / liquid separation producing at least one gas stream containing hydrogen and H₂S, which can be sent to a hydrogen processing and recycling step.

[0245] 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.

[0246] It is possible to recycle, in the hydroconversion step a) (e.g., in the bubbling-entrained hybrid bed reactor from 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.

[0247] 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.

[0248] Examples

[0249] The following examples illustrate the invention without, however, limiting its scope.

[0250] Example 1: Synthesis of M0S2 nanoparticles (according to the invention)

[0251] 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.

[0252] No sulfuration step is required before using the nanoparticles for the catalytic test.

[0253] To characterize these nanoparticles, they were centrifuged and then washed three times with ethanol to remove excess hexadecylamine. The nanoparticles were then vacuum-dried to obtain a black powder. They were characterized by transmission electron microscopy. Monosheets of M0S2 with a length of 4 nm ± 1.3 nm were observed.

[0254] Example 2: Catalytic test of MoS2 nanoparticles obtained according to example 1 (compliant)

[0255] The performance of MoS2 nanoparticles obtained according to example 1, in hydroconversion of a heavy hydrocarbon feedstock of residue type (RSV), was evaluated in a 300 mL batch reactor of autoclave type in so-called hybrid bubbling-driven mode, i.e. in the presence of a supported solid hydroconversion catalyst of the NiMo on alumina type (NiMo / ALOa).

[0256] The colloidal solution of M0S2 nanoparticles is injected directly into the load.

[0257] The test conditions are as follows:

[0258] - Temperature: 415°C;

[0259] - Total absolute pressure: 14.5 MPa;

[0260] - Duration: 2h30;

[0261] - Volume of heavy hydrocarbon charge: 0.12 L (120 cc);

[0262] - Concentration in MB in the load: 150 ppm;

[0263] - Supported catalyst volume NiMo / ALOa: 0.02 L (20 cc);

[0264] - Reactor agitation speed: 900 rpm. The main characteristics of the heavy hydrocarbon feed are given in Table 1 below.

[0265] Table 1

[0266] The results obtained are reported in Table 2; the tests were carried out 3 times to ensure good repeatability.

[0267] Hydrogen is replenished throughout the test via an H2 ballast to compensate for hydrogen consumption and maintain a constant total pressure during the test.

[0268] 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 the quantity of sediment formed during the test to be evaluated (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+).

[0269] The rate d(HDX) is defined as follows: Math 1

[0270] 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 the feed

[0271] (mcharge) 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.

[0272] The test is performed three times to ensure good repeatability.

[0273] The results obtained are shown in Table 2 below.

[0274] Example 3: Catalytic test of commercial M0S2 nanoparticles (non-compliant)

[0275] Commercial 90 nm M0S2 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 nanoparticles of

[0276] M0S2 conforms to the invention (example 2). The test is performed three times to ensure good repeatability.

[0277] The results obtained are shown in Table 2 below.

[0278] Table 2

[0279] Similar performance was observed for HDS, HDV, HDAsC7, HDCCR, and HDC540+ across all tests. This performance appears to be primarily linked to the supported solid catalyst.

[0280] The test carried out according to example 2 with the nanoparticles prepared according to example 1 allows a considerable reduction of sediments compared to the tests carried out according to example 3, which can in particular be explained by obtaining small size mono-sheets for the entrained solid catalyst prepared according to example 1.

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 hydroconversion step of said hydrocarbon feedstock in a hydroconversion section comprising at least one hydroconversion reactor operating as a hybrid bubbling-entrained bed in the presence of hydrogen, at least one supported solid hydroconversion catalyst and at least one entrained solid hydroconversion catalyst, to produce a hydroconverted effluent, said entrained 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 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 (H), 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.

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

5. 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.

6. A hydroconversion process according to any one of the preceding claims, wherein step (i) of the process for 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 chosen from the list consisting of toluene, ethylbenzene, xylene, mesitylene, decane, and dodecane.

7. Hydroconversion process according to any one of the preceding claims, wherein 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.

8. Hydroconversion process according to any one of the preceding claims, wherein the process for preparing the entrained solid hydroconversion catalyst further comprises (il) 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 (il).

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

10. Hydroconversion process according to any one of claims 1 to 8, wherein the entrained solid hydroconversion catalyst is introduced into said hydroconversion reactor at the hydroconversion stage independently of the heavy hydrocarbon feed.

11. Hydroconversion process according to claim 9 or claim 10, wherein the entrained solid catalyst is in the form of a colloidal solution comprising an organic stabilizing agent and optionally an organic synthesis solvent used in step (i) of the process of preparing the entrained solid hydroconversion catalyst.

12. 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 M0S2 nanoparticles 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.

13. A process according to any one of the preceding claims, wherein the concentration of the entrained solid hydroconversion catalyst is between 5 ppm and 500 ppm by weight of molybdenum relative to the heavy hydrocarbon feed at the inlet of the hydroconversion reactor.

14. A method 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 bubbling-entrained hybrid reactor of between 0.05 h 1 and 10 a.m. 1 and under a quantity of hydrogen mixed with the feed entering the bubbling-entrained hybrid bed reactor of between 50 and 5,000 normal cubic meters per cubic meter of feed.

15. 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 vacuum residue from atmospheric or vacuum distillation of crude oil, atmospheric residue or vacuum residue from atmospheric or vacuum distillation of effluent from a thermal conversion unit or hydrotreating or hydrocracking or hydroconversion unit or a direct coal liquefaction unit,a vacuum distillate obtained directly from crude oil or from a fraction 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 fractions 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.

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