BOILING BED OR BOILING-DRIVEN HYBRID HYDROCONVERSION OF A FEED COMPRISING A VEGETABLE OR ANIMAL OIL FRACTION

Abstract

The present invention relates to a process for the hydroconversion of a feedstock comprising a fraction of vegetable and / or animal oil (102), in particular used oil, and a heavy hydrocarbon fraction (101) containing a portion of at least 50% by weight having a boiling point of at least 300°C, and containing sulfur and nitrogen, the sum of the vegetable and / or animal oil fraction (102) and the heavy hydrocarbon fraction (101) forming 100% by weight of said feedstock. The hydroconversion uses one or more ebullated bed or hybrid ebullated-entrained bed reactors (20), and preferably two successive hydroconversion stages, with a view to producing higher quality materials with a lower boiling point, for example for the production of fuels or chemicals, while allowing the recovery of said vegetable and / or animal oil fraction. Figure 1 to be published

Description

Title of the invention: BOILING BED OR BOILING-DRIVEN HYBRID HYDROCONVERSION OF A CHARGE COMPRISING A VEGETABLE OR ANIMAL OIL FRACTION Technical field

[0001] The present invention relates to the field of hydroconversion of feedstocks comprising a fraction of vegetable and / or animal oil, in particular used as a cooking oil, and a heavy hydrocarbon fraction, in particular a heavy hydrocarbon fraction containing a portion of at least 50% by weight, preferably at least 80% by weight, having a boiling point of at least 300°C. The heavy hydrocarbon fraction may be a crude oil or may be derived from the distillation and / or refining of a crude oil, typically a topped crude oil, a residue from the atmospheric and / or vacuum distillation of a crude oil. Preferably, the heavy hydrocarbon fraction is of the vacuum residue type composed of at least 50% by weight, preferably at least 80% by weight of hydrocarbons having a boiling point of at least 450°C.

[0002] In particular, the present invention relates to a process for the hydroconversion of such a mixed feedstock, comprising at least one hydroconversion step using one or more reactors operating in an ebullated bed or in an entrained ebullated hybrid bed, and preferably two successive hydroconversion steps, with a view to producing higher quality materials, with a lower boiling point, for example for the purposes of producing fuels or chemical products, while allowing the recovery of used vegetable or animal oil. Prior art

[0003] For several years, we have seen the emergence, within the fuel and chemical sectors, of processes incorporating products other than traditional petroleum products, for example products of renewable origin such as vegetable and animal oils or waste such as plastics or used oils, in addition to or as a substitute for products of fossil origin.

[0004] The hydrotreatment and / or hydroconversion of vegetable or animal oils leads to the production of fuel bases of excellent quality, particularly in terms of smoke point of kerosene cuts and cetane number of diesel cuts. The hydrocarbons produced during the conversion are obtained mainly by decarboxylation and / or decarbonylation of monoglycerides, diglycerides and triglycerides. contained in used vegetable oils and animal fats which are then converted into paraffins.

[0005] For example, patent US20060186020 is known relating to a fixed-bed hydrotreatment process for a mixed feedstock composed of between 1 and 75% by weight of vegetable oil and the remainder of hydrocarbon of fossil origin. The hydrotreatment of a vegetable oil generates significant heat due to the rapid deoxygenation reactions. This exotherm is particularly difficult to control in a fixed bed and can be the cause of blockage at the inlet of the catalytic bed due to the formation of unwanted compounds such as gums. In addition, the operating conditions of temperature (320°C-400°C) and hourly space velocity WH (0.5-2h ') disclosed in patent US20060186020 do not allow thermal cracking of the fossil hydrocarbon to be envisaged in parallel with the conversion of the vegetable oil.

[0006] Patent WO2008151792 is also known, which describes an ebullated bed hydroconversion process comprising a supported catalyst and a nano-dispersed catalyst capable of treating heavy hydrocarbon feedstocks, in particular vegetable oils. This patent does not mention the possibility of carrying out co-treatment of vegetable oil or animal fat with a fossil-type hydrocarbon feedstock. However, the injection of a pure vegetable oil feedstock or animal fat into such a process is likely to result in a conversion of the feedstock entirely, or largely, into products which will be in gas form under the operating conditions of the process. A small quantity of liquid, or even an absence of liquid, is operationally impossible for the operation of an ebullated bed reactor.Low or no liquid is also a problem in controlling the exothermicity generated by the conversion of vegetable oil. Objectives and Summary of the Invention

[0007] The present invention relates to the field of the recovery of heavy loads that are difficult to recover, such as petroleum residues, which generally contain high levels of impurities such as metals, sulfur, nitrogen, Conradson carbon and asphaltenes, to convert them into lighter products that can be recovered as fuels, for example to produce gasoline or diesel, or raw materials for petrochemicals.

[0008] The inventors have demonstrated that, surprisingly, it is possible to incorporate a fraction of vegetable and / or animal oil, in particular used oil, into a heavy hydrocarbon feedstock, typically a vacuum residue, traditionally treated in a hydroconversion process in an ebullated bed or hybrid entrained ebullated bed, and thus increase the overall conversion of the feedstock, improve the yields of the fuels of interest, while maintaining good operation of the process and good stability of the unconverted fraction.

[0009] The present invention thus proposes a process for the hydroconversion of a heavy hydrocarbon feedstock, in particular of the vacuum residue type, in an entrained bubbling or hybrid bubbling bed, said feedstock including a fraction of vegetable and / or animal oil, in particular used cooking oil, thus enabling the production of basic fuels and other recoverable hydrocarbons, and therefore the recovery of said fraction.

[0010] Thus, to overcome the problems of the prior art set out above, and to achieve at least one of the above-mentioned objectives, among others, the present invention provides, according to a first aspect, a process for hydroconversion of a feedstock comprising a vegetable and / or animal oil fraction and a heavy hydrocarbon fraction containing a portion of at least 50% by weight having a boiling point of at least 300°C, and containing sulfur and nitrogen, the sum of the vegetable and / or animal oil fraction and the heavy hydrocarbon fraction forming 100% by weight of said feedstock, the process comprising the following successive steps: (a) conditioning and introducing the feedstock into a first hydroconversion section comprising at least one first ebullated bed or ebullated-entrained hybrid bed hydroconversion reactor comprising a first porous supported hydroconversion catalyst; (b) a first step of hydroconversion of the feedstock in the presence of hydrogen in said first hydroconversion section to obtain a first hydroconverted effluent; (c) optionally a step of separating part or all of said first effluent resulting from step (b), to form at least one heavy cut boiling mainly at a temperature greater than or equal to 350°C; (d) optionally a second hydroconversion step in a second hydroconversion section comprising at least one second ebullated bed or ebullated-entrained hybrid bed hydroconversion reactor of part or all of said first effluent resulting from step (b) or optionally of said heavy cut from step (c), said second hydroconversion reactor comprising a second porous supported catalyst and operating in the presence of hydrogen, to produce a second hydroconverted effluent; step (b) and optional step (d) being carried out at an absolute pressure of between 2 MPa and 38 MPa, at a temperature of between 405°C and 550°C, at an hourly space velocity relative to the volume of each hydroconversion reactor of between 0.05 h 1 and 10 h 1, and with a quantity of hydrogen of between 50 Nm3 / m3 and 5000 Nm3 / m3, (e) a step of fractionating all or part of said first hydro- effluent converted from step (b) or said second hydroconverted effluent from step (d), in a fractionation section, to produce at least one heavy liquid product which boils predominantly at a temperature greater than or equal to 350°C, said heavy liquid product containing a residual fraction which boils at a temperature greater than or equal to 540°C.

[0011] According to one or more implementations of the invention, in step (a), the vegetable and / or animal oil fraction and the heavy hydrocarbon fraction of the feedstock are premixed before their introduction into said at least one first hydroconversion reactor of the first hydroconversion section.

[0012] According to one or more implementations of the invention, in step (a), the vegetable and / or animal oil fraction and the heavy hydrocarbon fraction of the feedstock are introduced separately into said at least one first hydroconversion reactor of the first hydroconversion section.

[0013] According to one or more implementations of the invention, step (a) comprises a step of preheating the heavy hydrocarbon fraction, preferably at a temperature between 280°C and 450°C, and optionally a step of preheating the vegetable and / or animal oil fraction, preferably at a temperature between room temperature and 350°C, before introducing the feedstock into the first hydroconversion reactor of the first hydroconversion section.

[0014] According to one or more implementations of the invention, the feedstock comprises between 1% and 50% by weight of the vegetable and / or animal oil fraction and between 50% and 99% by weight of the heavy hydrocarbon fraction.

[0015] According to one or more implementations of the invention, the feedstock comprises between 5% and 30% by weight, preferably between 5% and 20% by weight, of the vegetable and / or animal oil fraction, and between 70% and 95% by weight, preferably between 80% and 95% by weight, of the heavy hydrocarbon fraction.

[0016] According to one or more implementations of the invention, the vegetable and / or animal oil fraction of the feedstock is a vegetable oil, preferably chosen from the list consisting of rapeseed oil, soybean oil, sunflower oil, palm oil, palm kernel oil, olive oil, copra oil, castor oil, cottonseed oil, peanut oil, linseed oil, crambe oil, Purghère oil, or a mixture thereof.

[0017] According to one or more implementations of the invention, the heavy hydrocarbon fraction of the feedstock is chosen from the list consisting of a crude oil, a topped crude oil, an atmospheric residue or a vacuum residue from the atmospheric and / or vacuum distillation of a crude oil or an effluent from a thermal conversion, hydrotreatment, hydrocracking or hydroconversion unit, an aromatic cut extracted from a lubricant production unit, a deasphalted oil from a deasphalting unit, an asphalt from a deasphalting unit phalting, a residual fraction from the direct liquefaction of coal, a vacuum distillate from the direct liquefaction of coal, or their mixture.

[0018] According to one or more implementations of the invention, the feedstock consists of a vegetable oil fraction and a heavy hydrocarbon fraction consisting of a vacuum residue, preferably a vacuum residue from the primary fractionation of a crude oil.

[0019] According to one or more implementations of the invention, the vegetable and / or animal oil fraction is a used oil, preferably a used cooking oil.

[0020] According to one or more implementations of the invention, the process comprises the separation step (c) separating a part, or all, of the first hydroconverted effluent from step (b) to produce at least the heavy cut boiling predominantly at a temperature greater than or equal to 350°C, and comprising the second hydroconversion step (d) of said heavy cut.

[0021] According to one or more implementations of the invention, an additional vegetable and / or animal oil fraction is introduced into said at least second ebullated bed or hybrid ebullated-entrained bed hydroconversion reactor.

[0022] According to one or more implementations of the invention, the hydroconversion reactor(s) of the first hydroconversion section in step (b), and optionally in the hydroconversion step (d), are bubbling-entrained hybrid bed reactors, said method further comprising a step of introducing a catalyst precursor into the feedstock, preferably molybdenum 2-ethylhexanoate, before injecting said feedstock into said at least one first bubbling-entrained hybrid bed reactor of the first hydroconversion section, such that a colloidal or molecular catalyst, preferably comprising molybdenum disulfide, is formed when said feedstock reacts with sulfur.

[0023] According to one or more implementations of the invention, the first hydroconversion catalyst, and optionally the second hydroconversion catalyst, contains at least one non-noble group VIII metal chosen from nickel and cobalt, preferably nickel, and at least one group VIB metal chosen from molybdenum and tungsten, preferably molybdenum, and comprising an amorphous support, preferably alumina.

[0024] Other objects and advantages of the invention will appear on reading the following description of particular examples of embodiments of the invention, given as non-limiting examples, the description being made with reference to the appended figure described below. List of figures

[0025] [Fig.l]

[0026] [Fig.l] schematically illustrates an embodiment of the method hydroconversion according to the invention.

[0027] [Fig.2]

[0028] [Fig.2] schematically illustrates another embodiment of the method hydroconversion according to the invention.

[0029] In the figures, the same references designate identical or similar elements. Description of the embodiments

[0030] Embodiments of the method according to the invention will now be described in detail. In the following detailed description, numerous specific details are set forth in order to provide a more thorough understanding of the method. However, it will be apparent to those skilled in the art that the method can be carried out without these specific details. In other cases, well-known features have not been described in detail to avoid unnecessarily complicating the description.

[0031] Some definitions are given below for a better understanding of the invention.

[0032] In this description, the term "comprise" is synonymous with (means the same as) "include" and "contain", and is inclusive or open and does not exclude other elements that are not mentioned. It is understood that the term "comprise" includes the exclusive and closed term "consist".

[0033] In this description, the expression "between ... and ..." means that the limit values ​​of the interval are included in the range of values ​​described, unless otherwise specified.

[0034] In the present invention, the different ranges of values ​​of given parameters may be used alone or in combination. For example, a preferred range of pressure values ​​may be combined with a more preferred range of temperature values, or a preferred range of values ​​of one chemical compound or element may be combined with a more preferred range of values ​​of another chemical compound or element.

[0035] The term "hydroconversion" refers to a process whose primary purpose is to reduce the boiling point range of a feedstock comprising at least 50% of a heavy hydrocarbon fraction having a boiling point of at least 300°C, or even at least 450°C, and in which a substantial portion of the feedstock is converted to products with lower boiling point ranges than the original feedstock. Hydroconversion generally involves the fragmentation of larger hydrocarbon molecules into smaller molecular fragments having a smaller number of carbon atoms and a higher hydrogen to carbon ratio. The reactions carried out during hydroconversion reduce the size of hydrocarbon molecules, primarily by cleavage of carbon-carbon bonds, in the presence of hydrogen to saturate the cleaved bonds and aromatic rings. The mechanism by which hydroconversion typically occurs involves the formation of hydrocarbon free radicals during fragmentation primarily by thermal cracking, followed by capping of the free radical termini or fragments with hydrogen in the presence of active catalyst sites. Of course, during a hydroconversion process, other reactions typically associated with hydrotreating may occur, such as, among others, the removal of sulfur or nitrogen from the feedstock, or the saturation of olefins, and as more broadly defined below.

[0036] The term "hydrotreating", commonly referred to as "HDT", refers to a milder operation whose 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 reacting them with hydrogen rather than allowing them to react with themselves. The primary purpose is not to change the boiling point range of the feedstock. Thus, hydrotreatment includes in particular hydrodesulfurization reactions (commonly called "HDS"), hydrodenitrogenation reactions (commonly called "HDN") and hydrodemetalation reactions (commonly called "HDM"), accompanied by hydrogenation reactions, hydrodeoxygenation (commonly called "HDO"), hydrodearomatization, hydroisomerization, hydrodealkylation, hydrocracking, hydrodeasphalting and Conradson carbon reduction.Hydroprocessing is most commonly carried out using a fixed bed reactor, although other reactors can also be used for hydroprocessing, for example an ebullated bed hydroprocessing reactor.

[0037] The term "hydroconversion reactor" refers to any vessel in which the hydroconversion of a feedstock is the primary purpose, e.g., cracking the feedstock (i.e., reducing the boiling point range), in the presence of hydrogen and a hydroconversion catalyst. Hydroconversion reactors typically include at least one inlet through which the feedstock and hydrogen may be introduced and an outlet from which an upgraded material may be withdrawn. Specifically, hydroconversion reactors are also characterized by possessing sufficient thermal energy to cause the fragmentation of larger hydrocarbon molecules into smaller molecules by thermal decomposition.Examples of hydroconversion reactors include, but are not limited to, entrained bed reactors, also known as slurry reactors (three-phase reactors - liquid, gas, solid - in which the solid and liquid phases can be mixed). behave as a homogeneous phase), ebullated bed reactors (three-phase fluidized reactors), moving bed reactors (three-phase reactors with downward movement of solid catalyst and upward or downward flow of liquid and gas), and fixed bed reactors (three-phase reactors with downward flow of liquid feedstock over a fixed bed of supported catalyst with hydrogen typically flowing concurrently with the liquid, but possibly countercurrently in some cases).

[0038] The terms "hybrid bed" and "hybrid bubbling bed" and "hybrid bubbling-entrained bed" for a hydroconversion reactor refer to a bubbling bed hydroconversion reactor comprising an entrained catalyst in addition to the porous supported catalyst maintained in the bubbling bed reactor. Similarly, for a hydroconversion process, these terms thus refer to a process comprising a hybrid operation of an bubbling bed and an entrained bed in at least one hydroconversion reactor. The hybrid bed is a mixed bed of two types of catalysts of necessarily different particle size and / or density, one type of catalyst - the "porous supported catalyst" - being maintained in the reactor and the other type of catalyst - the "entrained catalyst", also commonly called "slurry catalyst" - being entrained out of the reactor with the effluents (upgraded feedstock).In the present invention, the entrained catalyst is a colloidal catalyst or a molecular catalyst, as defined below.

[0039] The terms "colloidal catalyst" and "colloidally dispersed catalyst" refer to catalyst particles having a particle size that is colloidal, e.g., less than 1 μm in size (diameter), 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. The term "colloidal catalyst" includes, but is not limited to, molecular or molecularly dispersed catalyst compounds.

[0040] The terms "molecular catalyst" and "molecularly dispersed catalyst" refer to catalyst compounds that are essentially "dissolved" or completely dissociated from other catalyst compounds or molecules in a feedstock, non-volatile liquid fraction, bottoms fraction, residue, or other feedstock or product in which the catalyst may be located. They also refer to very small catalyst particles or sheetlets that contain only a few catalyst molecules joined together (e.g., 15 molecules or less).

[0041] The terms "porous supported catalyst", "solid supported catalyst", and "supported catalyst" refer to catalysts that are typically used in conventional ebullated bed and fixed bed hydroconversion systems, including including catalysts designed primarily for hydrocracking or hydrodemetallization and catalysts designed primarily for hydroprocessing. Such catalysts typically comprise (i) a catalyst support having a large surface area and numerous interconnected channels or pores and (ii) fine particles of an active catalyst such as sulfides of cobalt, nickel, tungsten, molybdenum, or mixed sulfides of these elements (e.g., NiMo, CoMo, etc.), dispersed within the pores. Supported catalysts are commonly produced as cylindrical extrudates (“pellets”) or spherical solids, although other shapes are possible.

[0042] The method according to the invention and its operation are described in more detail below, in particular with reference to Figures 1 and 2 which are schematic representations of examples of embodiment of the method according to the invention, for a better understanding of the invention, without however the invention being limited to these examples.

[0043] The object of the invention is to propose a process for the hydroconversion of a feedstock consisting of a vegetable and / or animal oil fraction 102 and a heavy hydrocarbon fraction 101 containing a portion of at least 50% by weight having a boiling point of at least 300°C, and containing sulfur and nitrogen, the process comprising the following successive steps: (a) conditioning and introducing said feed into a first hydroconversion section 20 comprising at least one first ebullated bed or hybrid ebullated-entrained bed hydroconversion reactor comprising a first porous supported hydroconversion catalyst; (b) a first step of hydroconversion of said feedstock in the presence of hydrogen in said first hydroconversion section 20 to obtain a first hydroconverted effluent 105; (c) optionally a step of separating part or all of said first effluent resulting from step (b), to form at least one heavy cut boiling mainly at a temperature greater than or equal to 350°C; (d) optionally a second hydroconversion step in a second hydroconversion section comprising at least one second ebullated bed or ebullated-entrained hybrid bed hydroconversion reactor of part or all of said first effluent resulting from step (b) or optionally of said heavy cut from step (c), said second hydroconversion reactor comprising a second porous supported catalyst and operating in the presence of hydrogen, to produce a second hydroconverted effluent; step (b) and optional step (d) being carried out at an absolute pressure of between 2 MPa and 38 MPa, at a temperature of between 405°C and 550°C, at an hourly space velocity relative to the volume of each hydroconversion reactor of between 0.05 h 1 and 10 h 1, and with a quantity of hydrogen of between 50 Nm3 / m3 and 5000 Nm3 / m3, (e) a step of fractionating all or part of said first hydroconverted effluent from step (b) or said second hydroconverted effluent from step (d), in a fractionation section 30, to produce at least one heavy liquid product 106b which boils predominantly at a temperature greater than or equal to 350°C, said heavy liquid product containing a residual fraction which boils at a temperature greater than or equal to 540°C. The charge

[0044] According to a primary aspect of the invention, the feedstock comprises a fraction of vegetable and / or animal oil and a heavy fraction of hydrocarbons.

[0045] The sum of the vegetable and / or animal oil fraction and the heavy hydrocarbon fraction is equal to 100% by weight of the feedstock sent to the first hydroconversion stage. In other words, the feedstock consists of a vegetable and / or animal oil fraction and a heavy hydrocarbon fraction. The process according to the invention is thus specific to the hydroconversion of a mixture of a vegetable and / or animal oil and a heavy fraction of hydrocarbons of fossil origin. According to the invention, the feedstock does not comprise other fractions, such as biomass such as algae, lignocellulosic biomass, or one or more constituents of lignocellulosic biomass chosen from the group formed by cellulose, hemicellulose and lignin. Indeed, these other feedstocks generally require the implementation of specific steps for their treatment, which are not the subject of the present invention.

[0046] Preferably, the vegetable and / or animal oil fraction constitutes between 1% and 50% by weight of the filler (total weight of the filler), preferably between 5% and 30% by weight of the filler, and more preferably between 5% and 20% by weight of the filler.

[0047] The heavy hydrocarbon fraction containing a portion of at least 50% by weight having a boiling point of at least 300°C, preferably at least 450°C, and containing sulfur, Conradson carbon, metals, nitrogen, and asphaltenes, constitutes between 50% and 99% by weight of the feedstock, preferably between 70% and 95% by weight of the feedstock, and more preferably between 80% and 95% by weight of the feedstock.

[0048] The vegetable and / or animal oil fraction of the feedstock of the process according to the invention comprises one or more vegetable oils, or one or more animal fats, or mixtures of such feedstocks in all proportions. Examples that may be mentioned are rapeseed, soybean, sunflower, palm, palm kernel, olive, copra, castor, cotton, peanut, linseed, crambe, Purghères (jatropha) oils. This list non-limiting also includes all oils obtained by genetic modification or hybridization. Used oils, such as frying oils, as well as all used oils and fats from the catering industry, can also be used. With regard to animal fats, mention may be made, without being limited, of fish oils, tallow, lard. The expressions "animal fat" and "animal oil" are used interchangeably in this description, the only difference between a fat and an oil being the state of the fatty substance at room temperature: liquid for an oil and solid for a grease. These vegetable and / or animal oils can be crude or refined, in whole or in part. Typically, the distinction between a crude or refined vegetable oil refers to its extraction method, mainly under pressure for a crude oil (typically a single cold pressing without additives) and generally using a solvent for a refined oil. The vegetable and / or animal oil fraction thus defined contains monoglyceride, diglyceride, triglyceride and / or fatty acid structures, the fatty chains of which have a carbon number generally between 8 and 25 (i.e. number of carbon atoms of the fatty acid). The vegetable and / or animal oil fraction is thus mainly composed of these monoglyceride, diglyceride, triglyceride, and / or fatty acid compounds. By essentially composed is meant that it comprises at least 80% by weight of said compounds, or even at least 85% by weight, 90% by weight, or even 95% by weight of said compounds.

[0049] These vegetable and / or animal oils may contain phospholipids up to 5% by weight, free fatty acids up to 5% by weight (fatty acids not linked to a glycerol), unsaponifiables up to 5% by weight such as sterols, tri-terpene alcohols, vitamins up to 1% by weight such as tocopherols, colored compounds up to 100 ppm such as carotenoids, various metals and minerals up to 200 ppm, sulfur compounds up to contents of the order of 2000 ppm, and nitrogen compounds up to contents of 2% by weight. Due to their use at high temperatures in cooking, used vegetable or animal (food) oils may also contain triglyceride polymers, for example at contents of a few % by weight, e.g. 5% by weight, which are precursors to the formation of gums. These vegetable and / or animal oils have low aromatic contents, generally less than 5% by weight.

[0050] The density at 15°C of these vegetable and / or animal oils is generally between 850 kg / m3 and 970 kg / m3, and their kinematic viscosity at 40°C is typically between 20 mm2 / s and 400 mm2 / s, more generally between 30 mm2 / s and 50 mm2 / s.

[0051] The heavy hydrocarbon fraction of the feedstock of the process according to the invention is a heavy hydrocarbon fraction containing a portion of at least 50% by weight having a boiling point of at least 300°C, preferably at least 350°C, and even more preferably at least 375°C.

[0052] This heavy hydrocarbon fraction of the feedstock may be crude oil, or come from the refining of crude oil or the processing of another fossil hydrocarbon source in a refinery.

[0053] Preferably, the heavy hydrocarbon fraction of the feedstock is a crude oil, a topped crude oil or consists of atmospheric residues and / or vacuum residues from the atmospheric and / or vacuum distillation of a crude oil.

[0054] The heavy hydrocarbon fraction of the feedstock may also consist of atmospheric and / or vacuum residues from atmospheric and / or vacuum distillation of effluents from thermal conversion, hydrotreatment, hydrocracking and / or hydroconversion units.

[0055] Preferably, the heavy hydrocarbon fraction of the feedstock is a heavy hydrocarbon fraction containing a portion of at least 50% by weight having a boiling point of at least 450°C, preferably at least 500°C, and even more preferably at least 540°C.

[0056] Advantageously, the heavy hydrocarbon fraction of the feedstock consists of one or more vacuum residues. The vacuum residues may come directly from the crude oil, or from other refining units, such as, among others, residue hydrotreatment, residue hydrocracking, and residue visbreaking. Preferably, the vacuum residues are vacuum residues from the vacuum distillation column of the primary fractionation of crude oil (called "straight run", or "SR" for short, according to English terminology).

[0057] The heavy hydrocarbon fraction of the feedstock may also consist of aromatic cuts extracted from a lubricant production unit, deasphalted oils from a deasphalting unit also called DAO (raffinates from the deasphalting unit), asphalts from a deasphalting unit (residues from the deasphalting unit).

[0058] The heavy hydrocarbon fraction of the feedstock may also consist of a decantation oil or a recycle oil (which typically has a boiling range of 360°C to 550°C), for example a fluidized bed catalytic cracking effluent FCC such as a heavy cycle oil (HCO) or a slurry oil (SLO).

[0059] The heavy hydrocarbon fraction of the feedstock may also be a re-fraction sidual from the direct liquefaction of coal (an atmospheric residue and / or a vacuum residue from, for example, the H-Coal® process), a vacuum distillate from the direct liquefaction of coal, such as the H-Coal® process.

[0060] All these fractions can be used to constitute the heavy hydrocarbon fraction of the charge treated according to the invention, alone or in a mixture.

[0061] According to one or more implementations, the heavy hydrocarbon fraction comprises, and may consist of, at least one of the following feedstocks, alone or as a mixture: a crude oil, a topped crude oil, an atmospheric residue or a vacuum residue from the atmospheric or vacuum distillation of a crude oil (preferably from the primary fractionation of the crude oil), an atmospheric residue or a vacuum residue from the atmospheric or vacuum distillation obtained during a direct coal liquefaction process, and preferably is a vacuum residue from the vacuum distillation of a crude oil (preferably from the primary fractionation of the crude oil).

[0062] The heavy hydrocarbon fraction of the feedstock treated according to the invention contains impurities, such as sulfur and nitrogen. It may also contain impurities such as metals, Conradson carbon and asphaltenes, in particular C7 as-phaltenes which are insoluble in heptane. The metal contents may be greater than or equal to 20 ppm by weight, preferably greater than or equal to 100 ppm by weight. The sulfur content may be greater than or equal to 0.1% by weight, or even greater than or equal to 0.5% or 1%, and may be greater than or equal to 2% by weight. The nitrogen content is usually between 1 ppm and 8000 ppm by weight, more generally between 200 ppm and 8000 ppm by weight, for example between 2000 ppm and 8000 ppm by weight. The level of C7 asphaltenes (heptane-insoluble compounds according to ASTM D 6560, also corresponding to NF T60-115) can be at least 1% by weight and is often greater than or equal to 3% by weight (with the exception of a heavy hydrocarbon fraction comprising mainly DAO). C7 asphaltenes are compounds known to inhibit the conversion of residual cuts, both by their ability to form heavy hydrocarbon residues, commonly called coke, and by their tendency to produce sediments which severely limit the operability of hydrotreatment and hydroconversion units. The Conradson carbon content may be greater than or equal to 3% by weight, or at least 5% by weight. The Conradson carbon content is defined by ASTM D 482 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.

[0063] These contents are expressed as % by weight of the total weight of the heavy hydrocarbon fraction of the charge.

[0064] (a) Step of conditioning and injection of the charge into the first hydroconversion reactor

[0065] The method according to the invention comprises a step (a) of conditioning and introducing the feed into a first hydroconversion section 20 comprising at least one first ebullated bed or hybrid bed reactor comprising a first porous supported hydroconversion catalyst.

[0066] By conditioning the feedstock is meant its placing in a state suitable for the hydroconversion step b), in particular its placing at temperature and pressure conditions suitable for hydroconversion in the first hydroconversion reactor, a possible mixing of the vegetable / animal oil fractions and heavy hydrocarbon fraction before the introduction of the feedstock into the reactor, a possible filtration of the vegetable and / or animal oil fraction. Step a) does not include any transformation of the feedstock, in particular of the vegetable and / or animal oil fraction, aimed at significantly changing its composition, in particular the molecular weight distribution of said fraction, for example by hydroforming in the presence of hydrogen and a catalyst, under pressure.

[0067] Indeed, the vegetable and / or animal oil fraction 102 may be premixed with the heavy hydrocarbon fraction 101 of the feedstock before entering the first hydroconversion reactor in the first hydroconversion step (b). In this case, the two fractions may be preheated to ensure that they are in the liquid state before being mixed, by means of any heating device known to those skilled in the art. Alternatively, only the heavy hydrocarbon fraction 101 may be heated, in particular if the vegetable and / or animal oil fraction is liquid and pumpable at ambient temperature. This mixing may be carried out in a dedicated capacity 10 as shown in [Fig.l], the mixing being able to be active (e.g. a pump with a propeller or a turbine rotor) or not, or directly by the connection of the two conduits transporting the products.In the latter case, the homogeneity of the mixture can be ensured by installing an in-line static mixer, a technology well known to those skilled in the art. By mixing fractions, a more homogeneous feed 114 is introduced into the first hydroconversion reactor, which is for example favorable to good fluidization of the catalyst, and to the good hydrodynamic operation of the reactor in general. It can also allow the use of common equipment, such as furnaces, feed distributors, hydrogen mixers with the feed, for example of the T-shaped type ("T-mixer" in English), which can contribute to reducing investment costs.

[0068] Another possibility, shown in [Fig.2], is the separate injection of the vegetable and / or animal oil fraction 102 and the heavy hydrocarbon fraction 101 into the first hydroconversion reactor at the first hydroconversion stage (b). This injection method may be preferred to avoid any problem that would be linked to a chemical incompatibility between the two fractions (risk of demixing or precipitation of asphaltenes for example), or to avoid possible accelerated fouling of the preheating furnace (the high triglyceride polymer contents of the used vegetable or animal oil risk leading to the formation of gum).

[0069] According to these two alternative embodiments, whether or not the fractions are mixed before their introduction into the first hydroconversion reactor, the feedstock, and in particular the heavy hydrocarbon fraction 101 of the feedstock, is heated to a temperature suitable for hydroconversion in the first hydroconversion reactor, i.e. in such a way as to advantageously reach a target temperature in the first hydroconversion reactor. This will be referred to as a preheating step in the present description. The preheating of the heavy hydrocarbon fraction is preferably carried out at a temperature between 280°C and 450°C, even more preferably between 300°C and 400°C, and even more preferably between 320°C and 365°C. This preheating may also comprise heating the vegetable and / or animal oil fraction 102, in particular if said fraction is injected separately from the fraction 101 into the first hydroconversion reactor, however preferably at a lower temperature than for the heavy hydrocarbon fraction 101. Advantageously, the vegetable and / or animal oil fraction 102 may be heated to a temperature between ambient temperature, e.g. 15°C, and 350°C, preferably between 100°C and 350°C, more preferably between 100°C and 250°C, and even more preferably between 150°C and 250°C.In the case where the vegetable and / or animal oil fraction is mixed with the heavy hydrocarbon fraction, preheating of said vegetable and / or animal oil fraction can be carried out by simple contact with the heavy hydrocarbon fraction 101, or alternatively the vegetable and / or animal oil fraction can be heated before its mixing with the fraction 101 by any suitable heating means known to those skilled in the art.

[0070] Any means known to a person skilled in the art capable of preheating said charge may be used. At least one furnace, commonly called a preheating furnace, may be used, comprising for example at least one heating compartment, and / or tubes into which the charge flows, a mixer of the charge with H2, any type of suitable heat exchangers, for example tubular or spiral heat exchangers into which the charge flows, etc.

[0071] Before its introduction into the first hydroconversion reactor, the feed undergoes a pressurization step to be adapted to the pressure operated in the first hydroconversion reactor, for example using a suitable pump. This pressurization step is preferably carried out before the preheating step.

[0072] According to one or more embodiments, the vegetable oil and / or animal fat fraction may undergo a filtration step, before its mixing with the heavy hydrocarbon fraction 101 or its separate introduction from the heavy hydrocarbon fraction 101 into the first hydroconversion reactor, to remove impurities which may be naturally present in the vegetable oils and animal fats, in particular to remove solid particles.

[0073] Prior to its introduction into the first hydroconversion reactor, the feedstock may be mixed with an entrained catalyst precursor 104, for example the heavy hydrocarbon fraction 101 may be mixed with an entrained catalyst precursor 104, as shown in Figures 1 and 2, so that, upon formation of an entrained catalyst, in particular by reaction with sulfur, the entrained catalyst will comprise a colloidal or molecular catalyst dispersed in the feedstock.

[0074] The entrained catalyst precursor 104 may also be mixed with the vegetable and / or animal oil fraction 102 before mixing the latter with the heavy hydrocarbon fraction 101 (not shown in [Fig.l]), or else be mixed with the feedstock 114 formed by the mixture of said fractions 101 and 102 (not shown in [Fig.2]), in the same manner as described below for a mixture between the heavy hydrocarbon fraction 101 and the entrained catalyst precursor 104, except that the mixing temperature with the vegetable and / or animal oil fraction 102 is preferably less than or equal to 250°C (and in all cases preferably at a temperature lower than a temperature at which a substantial portion of the catalyst precursor begins to decompose).

[0075] It is specified that within the meaning of the present invention, the catalyst precursor, optionally diluted, is not part of the charge as defined above which exclusively comprises the vegetable and / or animal oil fraction and the heavy hydrocarbon fraction.

[0076] The entrained catalyst precursor may be chosen from all the metal catalyst precursors known to a person skilled in the art, capable of forming a colloidally or molecularly dispersed catalyst (i.e. the entrained catalyst) in the presence of hydrogen and / or H2S and / or any other sulfur source, and allowing the hydroconversion of the feedstock after its injection into the first hydroconversion reactor. The catalyst precursor is advantageously an oil-soluble catalyst precursor containing at least one transition metal. The catalyst precursor preferably comprises an or- oil-soluble ganometallic. The catalyst precursor may comprise an oil-soluble organometallic or bimetallic compound or complex comprising one or two of the following metals: Mo, Ni, V, Fe, Co or W, or mixtures of such compounds / complexes. The oil-soluble catalyst precursor preferably has a decomposition temperature (temperature below which the catalyst precursor is substantially chemically stable) in a range of 100°C to 350°C, more preferably in a range of 150°C to 300°C, and most preferably in a range of 175°C to 250°C. The oil-soluble organometallic compound or complex is preferably selected from the group consisting of molybdenum 2-ethylhexanoate, molybdenum naphthanate, vanadium naphthanate, vanadium octoate, molybdenum hexacarbonyl, vanadium hexacarbonyl, and iron pentacarbonyl. These compounds are non-limiting examples of oil-soluble catalyst precursors. More preferably, the catalyst precursor comprises Mo and, for example, comprises a compound selected from the group consisting of molybdenum 2-ethylhexanoate, molybdenum naphthanate, and molybdenum hexacarbonyl. A currently preferred catalyst precursor comprises, or consists of, molybdenum 2-ethylhexanoate (also commonly referred to as molybdenum octoate). Typically, molybdenum 2-ethylhexanoate contains 15% by weight of molybdenum and has a decomposition temperature or decomposition temperature range sufficiently high to avoid substantial thermal decomposition when mixed with a heavy hydrocarbon fraction at a temperature below 250°C.

[0077] One skilled in the art can select a mixing temperature profile that results in mixing of the selected precursor without substantial thermal decomposition prior to formation of the colloidal or molecular catalyst.

[0078] The catalyst precursor 104, preferably an oil-soluble catalyst precursor, may be pre-mixed with a diluent hydrocarbon stream to form a dilute precursor mixture, as described in US2005 / 0241991, US 10822553 or US 10941353 and recalled below.

[0079] The catalyst precursor 104 may be premixed with a diluent to form a dilute precursor mixture, said premixing preferably being carried out at a temperature below a temperature at which a substantial portion of the catalyst precursor begins to decompose, preferably between room temperature, e.g. 15°C, and 300°C, more preferably between 15°C and 200°C, even more preferably between 50°C and 200°C, even more preferably between 75°C and 150°C, and even more preferably between 75°C and 100°C, and preferably ously for a period of time from 1 second to 30 minutes. Typically, the catalyst precursor diluent may be a hydrocarbon oil composed of hydrocarbons of which at least 50% by weight, based on the total weight of the hydrocarbon oil, have a boiling temperature between 180°C and 540°C.Examples of suitable hydrocarbon diluents for diluting the precursor include, but are not limited to, a vacuum gas oil known as “VGO” (for Vacuum Gas Oil according to English terminology, and which typically has a boiling range of 360°C to 524°C), a decanter oil or a recycle oil (which typically has a boiling range of 360°C to 550°C), for example, a fluidized catalytic cracking (FCC) effluent such as a heavy cycle oil (HCO) or a light cycle oil (LCO), a pyrolysis oil from a hydrocracker, a light gas oil (which typically has a boiling range of 200°C to 360°C), atmospheric residues, vacuum residues (which typically have a boiling range of greater than or equal to 524°C), deasphalted oils and resins.The catalyst precursor diluent is preferably atmospheric residue, vacuum residue, VGO. Then, the diluted precursor may be mixed with the heavy hydrocarbon fraction 101, preferably at a temperature between room temperature, e.g. 15°C, and 300°C, and advantageously for a period of time of 1 second to 30 minutes, preferably 1 second to 10 minutes, and even more preferably in a range of 2 seconds to 3 minutes. In the present description, a mixing time (or residence time for the mixture) of 1 second comprises instantaneous mixing. The mass ratio of catalyst precursor 104 to hydrocarbon oil diluent is preferably in a range of about 1:500 to about 1:1, more preferably in a range of about 1:150 to about 1:2, and even more preferably in a range of about 1:100 to about 1:5 (eg 1:100, 1:50, 1:30, or 1:10). Without mixing with a diluent, it is preferable to ensure that the components are mixed for a sufficient time to completely / intimately mix the catalyst precursor into the heavy hydrocarbon fraction before the formation of the entrained catalyst. However, a long mixing time, for example 24 hours mixing, may be prohibitively expensive for some industrial operations.

[0080] Premixing the catalyst precursor 104 with a hydrocarbon diluent greatly facilitates the complete and intimate mixing of the precursor into the heavy hydrocarbon fraction, particularly in the relatively short time period required for large-scale industrial operations to be economically viable.

[0081] The dilute precursor is preferably combined with the heavy hydrocarbon fraction and mixed for a sufficient time and in a manner to disperse the catalyst precursor throughout the heavy fraction so that the catalyst precursor is completely / intimately mixed with the heavy hydrocarbon fraction. In order to achieve sufficient mixing prior to formation of the colloidal or molecular catalyst, the dilute precursor and the heavy fraction are more preferably mixed for a period of time in a range of 1 second to 10 minutes, and even more preferably in a range of 2 seconds to 3 minutes. Increasing the vigor and / or shear energy of the mixing process generally reduces the time required to achieve complete / intimate mixing.Examples of mixing apparatuses that may be used to effect complete / intimate mixing of the catalyst precursor 104 and the heavy hydrocarbon 101 include, but are not limited to, high shear mixing such as mixing created in a pump with a propeller or turbine rotor, multiple static in-line mixers, multiple static in-line mixers in combination with high shear in-line mixers, multiple static in-line mixers in combination with high shear in-line mixers, multiple static in-line mixers in combination with high shear in-line mixers followed by recirculation pumping into the surge tank, combinations of the above apparatuses followed by one or more multi-stage centrifugal pumps.

[0082] The heavy hydrocarbon fraction 101 and the diluted precursor are preferably mixed and conditioned at a temperature in a range of 50°C to 200°C, more preferably in a range of 75°C to 175°C. Preferably, the gauge pressure is between 0 MPa and 25 MPa, more preferably between 0.01 MPa and 5 MPa.

[0083] The step of preheating the heavy hydrocarbon fraction, prior to introducing the feedstock into the first hydroconversion reactor, as detailed above, advantageously causes a release of the sulfur contained in the heavy hydrocarbon fraction which can combine with the metal of the catalyst precursor. The colloidal or molecular catalyst can form, or at least begin to form, in situ in the heavy hydrocarbon fraction during this preheating step. In order to form the colloidal or molecular catalyst, sulfur must be available (e.g. as H2S) to combine with the metal of the dispersed catalyst precursor composition. The entrained catalyst can also form in hydroconversion step (b).

[0084] In the case where the heavy hydrocarbon fraction comprises sulfur in sufficient quantity or in excess, the final activated catalyst can be formed in situ by heating of said heavy fraction at a temperature sufficient to release the sulfur therefrom. A source of sulfur may thus be H2S dissolved in the heavy hydrocarbon fraction, or H2S contained in hydrogen recycled to the hydroconversion reactor, or H2S originating from sulfur-containing organic molecules present in the heavy hydrocarbon fraction or possibly introduced beforehand into said heavy fraction (e.g. injection of dimethyl disulfide, thioacetamide, any hydrocarbon feedstock containing sulfur of the mercaptan type, sulfides, petroleum containing sulfur, diesel containing sulfur, vacuum distillate containing sulfur, residue containing sulfur). Thus, a source of sulfur may be sulfur compounds in the heavy fraction of hydrocarbons or a sulfur compound added to said heavy fraction. The temperature during preheating of the heavy hydrocarbon fraction and / or the temperature in step (b) allows the formation of the metal sulfide catalyst.

[0085] The metal concentration of the catalyst, preferably Mo, in the feedstock (i.e. the combination of heavy hydrocarbon fraction and vegetable and / or animal oil fraction) is preferably between 5 ppm and 500 ppm by weight of the feedstock, more preferably between 10 ppm and 300 ppm by weight, more preferably between 10 ppm and 175 ppm by weight, even more preferably between 10 ppm and 75 ppm by weight, and even more preferably between 10 ppm and 50 ppm by weight.

[0086] Preferably, the colloidal or molecular catalyst comprises molybdenum disulfide. (b) first hydroconversion step

[0087] The feedstock is introduced, whether the fractions which compose it are separated (101 and 102) or mixed (114) according to step (a), into the first hydroconversion reactor of the first hydroconversion section 20, together with hydrogen (flow not shown). Said first reactor comprises a first porous supported hydroconversion catalyst.

[0088] The first hydroconversion step (b) is carried out under conditions making it possible to obtain a first hydroconverted effluent 105. Said first hydroconverted effluent 105 contains the conversion products, in particular said first effluent has a reduced content of hydrocarbons having a boiling point of at least 300°C, or at least 350°C, 375°C, 450°C, 500°C, or even 540°C depending on the nature of the feedstock. Said first hydroconverted effluent 105 may also have a reduced content of sulfur, and / or metals, and / or nitrogen, and / or Conradson carbon, and / or asphaltenes, depending on the reactions carried out in the first hydroconversion reactor and the composition of the feedstock.

[0089] Step (b) is preferably carried out under an absolute pressure of 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 405°C and 550°C, more preferably between 405°C and 500°C, preferably between 405°C and 450°C, and even more preferably between 410°C and 435°C. The hourly space velocity (WH) relative to the volume of each reactor is preferably between 0.05 h 1 and 10 h *. According to a preferred implementation, the WH is between 0.1 h 1 and 10 h1, more preferably between 0.1 h 1 and 5 h1, even more preferably between 0.15 h 1 and 2 h *, and even more preferably between 0.15 h 1 and 1 h1. According to one implementation, the WH is between 0.05 h 1 and 0.49 h1, preferably between 0.1 h 1 and 0.49 h1. According to yet another implementation, the overall WH, i.e. the flow rate of liquid feed sent to step b) relative to the volume of all the reactors if several hydroconversion reactors are implemented in step b), is between 0.05 h 1 and 0.09 h 1. The amount of hydrogen mixed with the feedstock is preferably between 50 and 5000 normal cubic meters (Nm3) per cubic meter (m3) of liquid feedstock, preferably between 100 Nm3 / m3 and 2000 Nm3 / m3 and very preferably between 200 Nm3 / m3 and 1000 Nm3 / m3.

[0090] The first hydroconversion section 20 comprises one or more ebullated or hybrid bed reactors, containing at least one first supported hydroconversion catalyst, the reactors being able to be arranged in series and / or in parallel. At this stage, at least one first supported hydroconversion catalyst is therefore maintained in the reactor(s). According to one or more embodiments of the invention, the first hydroconversion section 20 comprises one or more hydroconversion reactors, which may be in series and / or in parallel, operating in an ebullated bed, as used for the H-Oil® process, as described, for example, in patents US4521295 or US4495060 or US4457831 or US4354852, in the article Aiche, March 19-23, 1995, Houston, Texas, article number 46d, "Second generation ebullated bed technology", or in chapter 3.5 "Hydroprocessing and Hydroconversion of Residue Fractions" from the book "Catalysis by Transition Metal Sulphides", Technip Editions, 2013. According to this or these implementations, each reactor is operated in a fluidized bed known as an ebullated bed. Each reactor advantageously includes a recirculation pump which makes it possible to maintain the porous supported solid catalyst in a ebullated bed by continuous recycling of at least a portion of a liquid fraction withdrawn from the upper part of the reactor and reinjected into the lower part of the reactor.

[0091] The bubbling bed reactor preferably comprises at least one inlet port located at or near the lower part of the reactor through which the feedstock is introduced together with the hydrogen, and in particular two inlet ports in the case where the vegetable and / or animal oil fraction of the feedstock is introduced separately from the heavy hydrocarbon fraction, and an outlet port at or near the upper part of the reactor through which the first hydroconverted effluent 105 is withdrawn. The reactor preferably further comprises an inlet and an outlet for the supported catalyst as already described above in connection with the means for injecting and withdrawing the supported catalyst. The ebullated bed reactor further comprises an expanded catalyst zone comprising the porous supported catalyst.The bubbling bed reactor also includes a lower supported catalyst-free zone located below the expanded catalyst zone, and an upper supported catalyst-free zone located above the expanded catalyst zone. The feed in the bubbling bed reactor continuously recirculates from the upper supported catalyst-free zone to the lower supported catalyst-free zone by means of a recycle conduit in communication with a boiling pump. At the top of the recycle conduit is preferably a funnel-shaped recycle cup through which the feed is drawn from the upper supported catalyst-free zone. The internal recycled feed is mixed with "fresh" feed and additional hydrogen gas.

[0092] The first supported hydroconversion catalyst used in the first hydroconversion step (b) may contain one or more elements from groups 4 to 12 of the periodic table of elements, which may or may not be supported. Advantageously, a catalyst comprising an amorphous support, such as silica, alumina, silica-alumina, titanium dioxide or combinations of these structures, and very preferably alumina, may be used.

[0093] The first supported catalyst may contain at least one non-noble group VIII metal selected from nickel and cobalt, and preferably nickel, said group VIII element preferably being used in association with at least one group VIB metal selected from molybdenum and tungsten, and preferably the group VIB metal is molybdenum.

[0094] In the present description, the groups of chemical elements are given according to the CAS classification (CRC Handbook of Chemistry and Physics, publisher CRC press, editor-in-chief DR Lide, 81st edition, 2000-2001). For example, group VIII according to the CAS classification corresponds to the metals of columns 8, 9 and 10 according to the new IUP AC classification.

[0095] Advantageously, the first supported hydroconversion catalyst used in the first hydroconversion step (b) 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 first supported hydroconversion catalyst comprises nickel as a Group VIII element and molybdenum as a Group VIB element.

[0096] The content of non-noble group VIII metal, in particular nickel, is advantageously between 0.5% and 10% expressed by weight of metal oxide (in particular NiO), and preferably between 1% and 6% by weight, and the content of group VIB metal, in particular molybdenum, is advantageously between 1% and 30% expressed by weight of metal oxide (in particular 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 catalyst.

[0097] This first supported catalyst is advantageously used in the form of extrudates or beads. The beads have, for example, a diameter of between 0.4 mm and 4.0 mm. The extrudates have, for example, a cylindrical shape with a diameter of between 0.5 mm and 4.0 mm and a length of between 1 mm and 5 mm. The extrudates may also be objects of a different shape such as trilobes, regular or irregular tetralobes, or other multilobes. Porous supported catalysts of other shapes may also be used. The size of these different shapes of porous supported catalysts may be characterized by means of the equivalent diameter. The equivalent diameter is defined as six times the ratio between the volume of the particle and the external surface area of ​​the particle. The porous supported catalyst, used in the form of extrudates, beads or other shapes, thus has an equivalent diameter of between 0.4 mm and 4.4 mm.These catalysts are well known to those skilled in the art.

[0098] According to one or more embodiments of the invention, the first hydroconversion section 20 comprises one or more hybrid bed reactors (i.e. bubbling-entrained hybrid beds), simultaneously comprising at least one first supported hydroconversion catalyst which is maintained in the reactor and at least one entrained catalyst which enters the reactor with the feedstock and which is entrained outside the reactor with the effluents. In this case, as already described above in relation to step (a), an entrained catalyst precursor was introduced before the injection of the feedstock into the first hydroconversion reactor, and a colloidal or molecular catalyst, also called dispersed, entrained or slurry catalyst, could have formed upstream or formed in situ in the hybrid bed hydroconversion reactor. These entrained catalysts are well known to those skilled in the art.

[0099] The hybrid bed reactor comprises a solid phase which comprises a porous supported catalyst in the form of an expanded bed, a liquid hydrocarbon phase comprising the feedstock containing the colloidal or molecular catalyst dispersed therein, and a gaseous phase comprising hydrogen.

[0100] The hybrid bed reactor is an ebullated bed hydroconversion reactor as described above, but comprising, in addition to the porous supported catalyst in the form of an expanded bed maintained in the reactor, the molecular or colloidal catalyst entrained from the reactor with the hydroconverted liquid effluent 105.

[0101] According to one or more embodiments, the operation of the hybrid bed hydroconversion reactor is based on that of the ebullated bed reactor already described, and further involves that the colloidal or molecular catalyst is dispersed throughout the feed in the hybrid bed reactor, including both in the expanded catalyst zone and in the supported catalyst-free zones, and thus available to stimulate upgrading reactions in what constitute catalyst-free zones in conventional ebullated bed reactors.

[0102] The presence of colloidal or molecular catalyst in the hybrid bed reactor provides additional catalytic hydrogenation activity, both in the expanded catalyst zone, in the recycle conduit, and in the lower and upper supported catalyst-free zones. Capping free radicals outside the porous supported catalyst minimizes the formation of sediment and coke precursors, which are often responsible for deactivation of the supported catalyst. This can allow a reduction in the amount of porous supported catalyst that would otherwise be required to carry out a desired hydroconversion reaction. This can also reduce the rate at which the porous supported catalyst must be withdrawn and replenished.The use of a colloidal or molecular catalyst in a hybrid bed reactor can also allow hydroconversion to operate at higher temperatures than in the case of an ebullated bed reactor (supported catalyst(s) alone, without entrained catalyst), while remaining within the temperature ranges given above for step (b).

[0103] In one of the implementations of the process according to the invention, a different first supported hydroconversion catalyst may be used in each reactor of the first hydroconversion section, the supported catalyst specific to each reactor being adapted to the feedstock sent to this reactor. In one of the implementations of the process according to the invention, several types of first supported catalyst are used in each reactor.

[0104] As is known, and for example described in patent FR3033797, the first supported hydroconversion catalyst, when used, can be partly replaced by fresh supported catalyst, and / or used supported catalyst but with a catalytic activity greater than the used supported catalyst to be replaced, and / or regenerated supported catalyst, and / or rejuvenated supported catalyst (catalyst from a zone of rejuvenation in which the majority of the deposited metals are removed, before sending the spent and rejuvenated catalyst to a regeneration zone in which the carbon and sulfur it contains are removed, thus increasing the activity of the catalyst), by withdrawing the spent supported catalyst preferably at the bottom of the reactor, and by introducing the replacement supported catalyst either at the top or at the bottom of the reactor. This replacement of the spent supported catalyst is preferably carried out at regular time intervals, and preferably in a burst or almost continuously. This withdrawal and replacement are carried out using a withdrawal and injection device advantageously allowing the continuous operation of this hydroconversion step.

[0105] By this operation of withdrawal / injection of the supported catalyst, it is therefore not necessary to stop the unit to change the used catalyst, nor to increase the reaction temperatures along the cycle to compensate for the deactivation. In addition, working at constant operating conditions makes it possible to obtain constant yields and product qualities along the cycle. Also, because the supported catalyst is kept stirring by significant liquid recycling, the pressure drop across the reactor remains low and constant, and the reaction exotherms are quickly averaged across the catalytic bed, which is therefore almost isothermal and does not require the injection of cooling flows ("quenches" in English). One of the key aspects of the invention lies in the ability of the hydroconversion reactor operating in an ebullating bed or hybrid ebullating-entrained bed to manage the specific exotherms linked to the treatment of a feedstock comprising a vegetable and / or animal oil fraction, in particular due to the liquid mixing and therefore a uniform temperature in the reactor as explained above. In addition, the use of a heavy hydrocarbon fraction in combination with the vegetable and / or animal oil fraction makes it possible to guarantee the presence of a sufficient liquid phase in the reactor for its proper operation, and to ensure good operability of the ebullating or hybrid bed hydroconversion process.

[0106] The use of a hydroconversion reactor operating in an ebullating bed or hybrid ebullating-entrained bed also makes it possible to operate under more severe conditions than those operated, for example, in a fixed catalyst bed reactor, making it possible in particular to increase the overall conversion of the feedstock composed of the vegetable and / or animal oil fraction and the heavy hydrocarbon fraction, and to improve the yield of certain cuts obtained in the hydroconverted effluent, in particular the gasoline, kerosene and diesel cuts, and more particularly the diesel cut.

[0107] Another advantage of the invention, linked to the use of a hydroconversion reactor operating in a bubbling or hybrid bubbling-entrained bed, is to allow that the hydroconversion unit has a long cycle time (without stopping the unit to replace the catalyst(s)), in particular thanks to the system for adding fresh catalyst and withdrawing used catalyst without stopping the hydroconversion unit made possible by the operation of such a type of reactor.

[0108] According to one or more embodiments, when step (b) is carried out in one or more hybrid bed reactors, the feedstock or the entrained catalyst precursor may be premixed with an organic additive, before the feedstock is introduced into the first hydroconversion reactor of the first hydroconversion section 20, in particular in order to minimize fouling of the installations before hydroconversion in the hybrid bed reactor(s).Without being bound by any theory, the organic additive, in admixture with the feedstock, allows for better solubility of the catalyst precursor entrained in the feedstock, avoiding or reducing fouling in particular due to metal deposits in the installations upstream of the hydroconversion reactor, such as in the heating devices, and thus improving the dispersion of the entrained catalyst, thus generating increased availability of the metal active sites, promoting the hydrogenation of free radicals which are precursors of coke and sediments, and generating a substantial reduction in fouling of the installations. Said organic additive, which is neither a catalyst nor a catalyst precursor (e.g. it does not contain metal), has at least one carboxylic acid function and / or at least one ester function and / or at least one acid anhydride function.It preferably comprises at least 6, or even at least 8 carbon atoms, and more preferably at least 8 carbon atoms. For example, the organic additive may be 2-ethylhexanoic acid, naphthenic acid, caprylic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, ethyl octanoate, ethyl 2-ethylhexanoate, 2-ethylhexyl 2-ethylhexanoate, benzyl 2-ethylhexanoate, diethyl adipate, dimethyl adipate, bis(2-ethylhexyl) adipate, dimethyl pimelate, dimethyl suberate, monomethyl suberate, hexanoic anhydride, caprylic anhydride, and mixtures thereof. The organic additive is preferably added during the mixing step so that the molar ratio of organic additive to the active metal(s) of the catalyst precursor composition (eg(c) optional intermediate separation step.

[0109] According to one or more preferred embodiments, the method according to the invention further comprises a separation step (c), which separates part, or all, of the first hydroconverted effluent 105, to produce at least two cuts, including a heavy cut boiling mainly at a temperature greater than or equal to 350°C.

[0110] The other cut(s) are one or more light and intermediate cut(s). The light cut thus separated mainly contains gases (H2, H2S, NH3, and C1-C4), naphtha (or gasoline, cut which boils at a temperature below 150°C), kerosene (cut which boils between 150°C and 250°C), and at least part of the diesel (or gas oil, fraction which boils between 250°C and 350°C, or even 375°C). The light cut can then be sent at least partially to a fractionation unit (not shown in the figures) where the light gases are extracted from said light cut, for example by passing through an expansion drum. The gaseous hydrogen thus recovered, which may have been sent to a purification and compression installation, can advantageously be recycled to the first hydroconversion stage (b), and / or to the second hydroconversion stage (d) if it is implemented.The recovered hydrogen gas can also be used in other refinery facilities.

[0111] The optional separation step (c) is implemented in a se separation (not shown in the figures), which comprises any separation means known to a person skilled in the art. Said separation section may comprise one or more flash drums 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 preferably consists of a single flash drum, commonly called a "hot separator". (d) optional second hydroconversion step

[0112] According to one or more preferred embodiments (not shown in the figures), the process further comprises a second hydroconversion step, in at least one second ebullated bed or hybrid bed reactor comprising a second porous supported catalyst, in the presence of hydrogen, of part or all of the first effluent 105 resulting from step (b), or optionally of the heavy cut from step (c). This second hydroconversion step is carried out so as to produce a second hydroconverted effluent. Said second hydroconverted effluent advantageously contains a larger quantity of conversion products than the first hydroconverted effluent, and in particular an even lower content of hydrocarbons having a boiling point of at least 300°C, or at least 350°C, 375°C, 450°C, 500°C, or even 540°C depending on the nature of the feedstock.The second hydroconverted effluent may have a reduced Conradson carbon residue, and optionally a reduced amount of sulfur, and / or nitrogen, and / or metals, and / or asphaltenes.

[0113] According to one or more embodiments, an additional vegetable and / or animal oil fraction may be introduced into said at least second reactor, in addition to said part or all of the first effluent 105 resulting from step (b), or optionally the heavy cut from step (c). Said vegetable oil fraction and / or animal oil fraction may be introduced into the second reactor mixed or separated from the first effluent 105, or optionally from the heavy cut from step (c). Said additional vegetable and / or animal oil fraction may be preheated and / or pressurized before said mixing or said introduction separately into the second reactor, in a manner similar to that described in step (a). Said additional vegetable and / or animal oil fraction may be identical to or different from the vegetable and / or animal oil fraction 102 making up the feed of the first hydroconversion reactor of the first hydroconversion section 20 in step (b).

[0114] The second hydroconversion step is carried out in a manner similar to that described for the first hydroconversion step (b), and is not repeated here. This applies in particular to the operating conditions, the equipment used, the porous supported hydroconversion catalysts used, with the exception of the details mentioned below.

[0115] As for the first hydroconversion step (b), the second hydroconversion step is carried out in at least one second ebullated bed or hybrid reactor. It is preferably carried out in one or more ebullated bed reactors if the first hydroconversion step is also carried out in one or more ebullated bed reactors, and it is preferably carried out in one or more hybrid bed reactors if the first hydroconversion step is carried out in one or more hybrid bed reactors.

[0116] In this second hydroconversion step, the operating conditions may be similar or different from those in hydroconversion step (d), the temperature remaining in the range between 405°C and 550°C, preferably between 405°C and 500°C, more preferably between 405°C and 450°C, even more preferably between 410°C and 435°C, and the amount of hydrogen introduced into the reactor remains in the range between 50 Nm3 / m3 and 5,000 Nm3 / m3 of liquid feed, preferably between 100 Nm3 / m3 and 3,000 Nm3 / m3, and even more preferably between 200 Nm3 / m3 and 2,000 Nm3 / m3. The other pressure and WH parameters are in the same ranges as those described for hydroconversion step (d).

[0117] The operating temperature in the second hydroconversion stage (d) may be higher than the operating temperature in the first hydroconversion stage (b). This may allow for more complete conversion of the feedstock not yet converted. Hydroconversion of liquid products from the first hydroconversion stage and feedstock conversion are enhanced, as are hydrotreatment reactions such as hydrodesulfurization and hydrodenitrogenation, among others. The operating conditions are chosen to minimize the formation of solids (e.g., coke).

[0118] The second porous supported hydroconversion catalyst used in the second hydroconversion reactor may be the same as that used in the first hydroconversion reactor(s) of the first hydroconversion section 20, or may be another porous supported catalyst also suitable for hydroconversion of the treated feedstock, as defined for the first supported catalyst used in the first hydroconversion step (b). (e) fractionation step

[0119] The first hydroconverted effluent 105 from the hydroconversion step (b), or from the second hydroconversion step (d) if such a step is implemented, then undergoes at least in part a fractionation step (e) in a fractionation section 30.

[0120] This fractionation step (e) separates part or all of said hydroconverted effluent into several fractions including at least one heavy liquid product 106b boiling predominantly at a temperature above 350°C, preferably above 500°C and more preferably above 540°C. The heavy liquid product 106b contains a part boiling at a temperature above 540°C, called the residual fraction (or vacuum residue), which is the unconverted part. The heavy liquid product 106b may contain a part of the diesel fraction boiling between 250°C and 375°C and a part boiling between 375°C and 540°C (also called the vacuum distillate).

[0121] This fractionation step therefore produces at least two products including the heavy liquid product 106b as described above, the other product(s) 106a being light and intermediate cut(s). The fractionation section 30 comprises any separation means known to those skilled in the art.

[0122] The fractionation section 30 can thus comprise one or more of the following separation equipment: one or more flash drums arranged in series, and preferably a chain of at least two successive flash drums, one or more steam and / or hydrogen stripping columns, an atmospheric distillation column, a vacuum distillation column.

[0123] According to one or more embodiments, this fractionation step (e) is carried out by a sequence of at least two successive flash balloons.

[0124] According to one or more other embodiments, this fractionation step (e) is carried out by one or more steam and / or hydrogen stripping columns.

[0125] According to one or more preferred embodiments, this fractionation step (e) is carried out by an atmospheric distillation column, and more preferably by an atmospheric distillation column and a vacuum column receiving the atmospheric residue.

[0126] According to the most preferred embodiment(s), this fractionation step (e) is carried out by one or more flash drums, an atmospheric distillation column and a vacuum column receiving the atmospheric residue. This confi guration allows to reduce the size of a possible downstream deasphalter, thus minimizing investment costs and operating costs.

[0127] The fractionation section 30 may also receive, in addition to part or all of the hydroconverted liquid effluent, one or more additional effluents such as one or more hydrocarbon feeds external to the process (e.g. atmospheric and / or vacuum distillates, atmospheric and / or vacuum residues), a part of the heavy cut from the separation step (c) if it is implemented, a part of one or more of the intermediate cuts from the fractionation step (e), a part of a DAO or a light or heavy fraction of a DAO if a deasphalting step (fl) is carried out.

[0128] The fractionation section can also separate the water that may result from hydrodeoxygenation reactions. This separation can be carried out by any means known to those skilled in the art, such as for example by decantation after condensation with the liquid naphtha, kerosene and / or diesel cuts. (0 subsequent treatment step(s)

[0129] One or more further treatment steps (f) of the heavy liquid product 106b and / or of the other product(s) resulting from the fractionation step (e) may be carried out.

[0130] The various hydrocarbon products that may result from the fractionation step (e) in the fractionation means 30 may be sent to various processes in the refinery, illustrated in the figures under the general reference 40, and the details of these post-treatments are not described herein being generally known to those skilled in the art. For example, gaseous fractions, naphtha (gasoline), middle distillates, VGO, DAO may be sent to hydrotreatment, steam cracking, fluidized catalytic cracking (FCC), hydrocracking, lube oil extraction processes, etc. Residues (atmospheric or vacuum residues) may also be post-treated, or used for other applications such as gasification, bitumen production, heavy fuel oils, etc.Heavy fractions, including residues, may also be recycled into the hydroconversion process, for example in a hydroconversion reactor in step (b) or (d).

[0131] According to one or more embodiments, the hydroconversion process comprises a deasphalting step (fl), in a deasphalter, of part or all of said heavy liquid product 106b obtained in the fractionation step (e), with at least one hydrocarbon solvent, to produce a deasphalted oil DAO and a residual asphalt (step "SDA" for Solvent DeAsphalting in English). Such a deasphalting step (fl) is carried out under conditions well known to those skilled in the art. Reference may thus be made to the article by Billon et al. published in 1994 in volume 49, No. 5 of the Revue de l'Institut Français du Pétrole, pages 495 to 507, to the book "Refining and conversion of heavy petroleum products" by JF Le Page, SG Chatila and M Davidson, Technip Edition, page 17 - 32 or patents US4239616, US4354922, US4354928, US4440633, US4536283, and US4715946. Deasphalting can be carried out in one or more mixer-settlers or in one or more extraction columns. The deasphalter thus comprises at least one mixer-settler or at least one extraction column. Deasphalting is a liquid-liquid extraction generally carried out at an average temperature between 60°C and 250°C with at least one low-boiling hydrocarbon solvent, preferably a paraffinic solvent, and preferably heavier than propane, preferably having 3 to 7 carbon atoms.Preferred solvents include propane, butane, isobutane, pentane, isopentane, neopentane, hexane, isohexanes, C6 hydrocarbons, heptane, C7 hydrocarbons, more or less apolar light gasolines, as well as mixtures obtained from the aforementioned solvents. Preferably, the solvent is butane, pentane or hexane, as well as mixtures thereof. The solvent / feed ratios (volume / volume) entering the deasphalter are generally between 3 / 1 and 16 / 1, and preferably between 4 / 1 and 8 / 1. Preferably, the deasphalter comprises at least one extraction column, and preferably only one (e.g. as implemented in the Solvahl™ process) in which the solvent / feedstock ratios (volume / volume) entering the deasphalter are preferably low, typically between 4 / 1 and 8 / 1, or even between 4 / 1 and 6 / 1.The deasphalter produces a DAO which is practically free of C7 asphaltenes, said C7 asphaltene content preferably being less than 2% by weight, more preferably less than 0.5% by weight, even more preferably less than 0.05% by weight, and a residual asphalt concentrating the majority of the impurities in the residue, said residual asphalt being withdrawn. The DAO yield is generally between 40% by weight and 95% by weight depending on the operating conditions and the solvent used, and depending on the feedstock sent to the deasphalter and in particular the quality of the heavy liquid product 106b.

[0132] When it is desired to recycle a portion of the heavy residue fraction (e.g. a portion of the heavy liquid product 106b and / or a portion of the residual asphalt, or a portion of the DAO) in the hydroconversion system (e.g. in the first hydroconversion reactor or upstream), it may be advantageous, in the case of operation in hybrid bed reactors, to leave the catalyst entrained in the residues, and / or the residual asphalt fraction. A purge on the recycled stream may be implemented, generally to prevent certain compounds from accumulating at excessive levels. Examples

[0133] The examples below are intended to show certain performances of the method according to the invention.

[0134] In these examples, the possibility of co-processing used cooking oil in an H-Oil® type ebullated bed hydroconversion process is illustrated, which converts them into lighter hydrocarbons, which can be used as bases for manufacturing (bio-)fuels, (bio-)lubricants or any other (bio-)product from oil refining and bio-sourced products.

[0135] These examples were carried out in a closed reactor (called “batch”) representative of the operating conditions of the H-Oil® process.

[0136] Example 1 is a comparative example illustrating the performance of the hydroconversion process for a reference feedstock (vacuum residue) without used cooking oil.

[0137] Examples 2 and 3 illustrate the performance of an H-Oil® process with a feedstock comprising a fraction of used cooking oil and a heavy fraction, as defined below, with the implementation of a pre-step of homogenization of the medium (optional step), making it possible to convert said oil into lighter hydrocarbons of the light or middle distillate type which can be recovered in the refinery.

[0138] Example 4 illustrates the performance of this same process when the feedstock is used cooking oil, without the addition of a heavy petroleum fraction. Examples 1 and 4 are therefore references to which Examples 2 and 3 can be compared.

[0139] Charge:

[0140] The heavy fraction (I) of the feedstock is a so-called straight-run vacuum residue (RSV-SR) coming directly from the distillation of a crude oil. The used cooking oil fraction (II) of the feedstock is a used cooking oil of vegetable origin.

[0141] The main characteristics of these two fractions of the charge are presented in Table 1 below. Hydroconversion Feed Fraction I Fraction II Feed - RSV-SR Used Cooking Oil Density - 1.004 0.9219 Viscosity cSt 922 (100 °C) 40 (40 °C) Conradson Carbon % wt 18.1 0.4 C7 Asphaltenes % wt 6.1 - C5 Asphaltenes % wt 13 - Nickel + Vanadium ppm 257 < LD* Nitrogen ppm 4895 96 Sulphur - 3.25 % wt 21.2 ppm Oxygen % wt 0.46 11.93 Hydrogen % wt 10.8 11.85 540°C- Content % wt 13.9 21.5 540°C+ Content % wt 86.1 78.5 Free Fatty Acids % wt - 6.7 Monoglycerides % wt - 0.5 Diglycerides % weight - 8.6 Triglycerides % weight - 84.1 Palmitic acid % weight - 25.5 Stearic acid % weight - 5.0 Oleic acid % weight - 42.6 Linoleic acid % weight - 19.0

[0143] (*) LD: Detection Limit

[0144] The operating conditions of these examples are summarized in Table 2 below. Example 1 Reference 100% wt. Fraction I 2 10% wt. used cooking oil 3 50% wt. used cooking oil 4 100% wt. wt. Used cooking oil Charge Fraction I (100% wt.) Fraction I (90% wt.) + Fraction II (10% wt.) Fraction I (50% wt.) + Fraction II (50% wt.) Fraction II (100% wt.) Homogenization stage time h NC** 1 1 NC** Homogenization stage temperature °C NC** 200 200 NC** Reaction temperature °C 420 420 420 420 Reaction time min 150 150 150 150 Reaction pressure MPa 16 16 16 16

[0146] (**) NC: Not Concerned

[0147] Procedure of Example 1:

[0148] The batch reactor is loaded with a predefined mass of catalyst and with 100% by weight of RSV-SR (fraction I of the charge), previously heated to 100-150°C to make it less viscous. The reactor is closed, purged with nitrogen, purged with hydrogen, then pressurized with hydrogen to a pressure of approximately 3 MPa. The reactor is then heated to 100°C. At this temperature, stirring is started at 500 rpm. Gradually, the temperature is increased from 100°C to the reaction temperature and, in parallel, stirring is gradually increased from 500 to 1000 rpm. When the reaction temperature is reached, the pressure in the reactor is instantly adjusted to the target value by adding H2. At this time, the reaction time is counted down. At the end of the experiment duration, the reactor is cooled rapidly to stop the reaction, stirring is stopped when the reactor is at the room temperature, and the liquid effluent and gases are collected for analysis.

[0149] Procedure of Example 2:

[0150] The batch reactor is first charged with the same mass of catalyst as for Example 1 and with the 90% by weight of RSV-SR (fraction I of the charge), previously heated to 100°C (approximately) to make it less viscous, then the 10% by weight of used cooking oil (fraction II of the charge) is added. The reactor is closed, purged with nitrogen, purged with hydrogen, then pressurized with hydrogen to a pressure of approximately 3 MPa. The reactor is then heated to 100°C. At this temperature, stirring is started at 500 rpm *. Gradually, the temperature is increased from 100°C to 200°C and, in parallel, stirring is gradually increased from 500 to 1000 rpm *. At 200°C, the pressure in the reactor is then 4 MPa. A one-hour hold at this temperature is observed, although this step is optional, in order to ensure good dispersion of the used cooking oil (fraction II of the load) in the RSV-SR (load I).Following this stage, the batch reactor is heated to the reaction temperature, at which point the pressure in the reactor is instantly adjusted to the target value by adding H2. At this point, the reaction time is counted. At the end of the experiment duration, the reactor is rapidly cooled to stop the reaction, stirring is stopped when the reactor is at room temperature, and the liquid effluent and gases are sampled for analysis.

[0151] Procedure of Example 3:

[0152] The procedure of Example 3 is in all respects similar to that of Example 2, except that the proportions of RSV-SR and used cooking oil are now 50% weight / 50% weight respectively.

[0153] Procedure of Example 4:

[0154] The batch reactor is loaded with a predefined mass of catalyst and with 100% by weight of used cooking oil (fraction II). The reactor is closed, purged with nitrogen, purged with hydrogen, and then pressurized with hydrogen to a pressure of approximately 3 MPa. The reactor is then heated to 100°C. At this temperature, stirring is started at 500 rpm*. Gradually, the temperature is increased from 100°C to the reaction temperature and, in parallel, stirring is gradually increased from 500 to 1000 rpm*. When the reaction temperature is reached, the pressure in the reactor is instantly adjusted to the target value by adding H2. At this time, the reaction time is counted down. At the end of the experiment duration, the reactor is rapidly cooled to stop the reaction, stirring is stopped when the reactor is at room temperature, and the liquid effluent and gases are collected for analysis.

[0155] Overall results and performance:

[0156] Results regarding total liquid effluent quality and performance hydroconversion of these examples are detailed in Tables 3 and 4 below. Experiment Example 1 Example 2 (with 10 wt % used cooking oil) Example 3 (with 50 wt % used cooking oil) Example 4 (100 wt % used cooking oil) (reference 100 wt % RSV-SR load) Density - 0.8989 0.8888 0.8451 0.7895 Conradson Carbon % wt 4.1 2.9 3.02 < LD C7 Asphaltenes % wt 0.45 0.55 <0.05 NC** Sediments (IP-375) % wt <LD* 0,06 0,90 < LD* V ppm <2 3,5 <2 < LD* Azote ppm 2915 2850 1905 < LD* Soufre % poids 0,5 0,42 0,34 < LD* Oxygène % poids 0,22 0,39 0,19 < LD* Hydrogène % poids 12,25 12,1 13,12 13,5 Yields % weight / charge H2S 2.9 2.6 1.4 0.0 h2o 0.3 1.4 6.8 13.4 nh3 0.3 0.2 0.1 0.0 Ci 0.9 1.1 0.7 0.3 c2 0.5 0.7 0.5 0.3 c3 0.4 0.7 0.5 0.3 c4 0.2 0.3 0.1 0.0 Ci-C4 1.9 2.7 1.9 0.9 PI-180°C 8.2 8.5 12.5 16.2 180 - 250°C 9.5 9.9 11.2 13.0 250 - 350 °C 16.1 21.1 32.7 47.7 350 - 540°C 40.1 36.9 24.3 10.4 540°C+ 22.2 18.4 10.8 0.0 Conversion cut 540°C+ % weight / 540°C+ load 74.1 78.2 85.9 100

[0158] (*) LD: Limit of detection

[0159] (**) NC: Not Concerned Delta examples: 1-2 1-3 1-4 Yields % weight / charge h2s -0.3 -1.6 -2.9 h2o 1.1 6.5 13.2 nh3 -0.1 -0.2 -0.3 Ci 0.2 -0.2 -0.6 c2 0.2 0.0 -0.2 c3 0.3 0.1 -0.1 c4 0.1 0.0 -0.2 Ci-C4 0.8 -0.1 -1.0 PI -180 °C 0.3 4.2 8.0 180 - 250 °C 0.4 1.8 3.6 250 - 350 °C 5.0 16.6 31.6 350 - 540°C -3.3 -15.8 -29.8 540°C+ -3.8 -11.4 -22.2

[0161] The conversion of the 540°C+ cut is calculated by mass difference between the load and total liquid effluent, such as:

[0162] [Math.l] Conversion 540+ mass 540+ ° C ef fluent i mass 540+ ° C charge /

[0163] An improved conversion of the 540°C+ cut of + 4.1 points is observed between the reference example 1 with RSV-SR alone and example 2 with 10% by weight of used vegetable oil, and of + 11.8 points between example 1 and example 3 with 50% by weight of used cooking oil. These results show a good conversion of the vegetable oil in the process, results which are confirmed by example 4 fed with 100% by weight of used cooking oil.

[0164] A significant increase in the yield of the PL 180, 180-250 and 250-350°C cuts is also noted in Example 2 and in Example 3, which show that the cooking oil is mainly transformed into these hydrocarbon cuts of interest. The increase in the yields of cuts of interest is accompanied by a decrease in the 350-540 and 540°C + cuts of lesser interest. These results are also confirmed by Example 4.

[0165] It is also shown that in both examples 2 and 3, the hydro performances treatment (hydrodesulfurization and hydrodeoxygenation in particular) are excellent: almost all of the oxygen atoms provided by the vegetable oil are removed from the products.

[0166] Furthermore, the co-treatment of cooking oil at a low incorporation rate (10% by weight - example 2) does not appear to significantly destabilize the unconverted product since the sediment content is only 0.06% by weight, which is a very low and perfectly tolerable value at the outlet of the hydroconversion process. On the other hand, a high incorporation rate of used vegetable oils (50% by weight - example 3) leads to greater destabilization of the effluent at the outlet of the process, with 0.9% by weight of sediments measured. With such a sediment content, the operability of the hydroconversion process risks being degraded. No sediment was noted for example 4 with 100% by weight of used cooking oil, which was expected.

[0167] Finally, experiment 3 demonstrates that with 50% by weight of used vegetable oil, the gaseous flow of reaction products increases by more than 10% by weight in the hydroconversion process compared to that of the reference experiment 1 100% by weight VR-SR. Experiment 4 with 100% by weight of used cooking oil sees its flow of gaseous products increase by more than 20% by weight. This can lead to a risk on the hydrodynamics in the reactor and on the quantity of liquid fraction available to be recycled and to keep the catalyst in suspension. It is therefore preferable to keep the incorporation rate of vegetable oils below a certain threshold during co-treatment in a hydroconversion reactor with residue and, similarly, to prefer co-treatment with a 100% vegetable oil weight feed (possibly used).

[0168] We can clearly see here the limits associated with a high rate of incorporation of vegetable oils (possibly used) in the ebullated bed hydroconversion process, and that co-treatment at moderate contents is preferable to guarantee good operability of the process.

Claims

Claims

1. A process for the hydroconversion of a feedstock comprising a vegetable and / or animal oil fraction (102) and a heavy hydrocarbon fraction (101) containing a portion of at least 50% by weight having a boiling point of at least 300°C, and containing sulfur and nitrogen, the sum of the vegetable and / or animal oil fraction (102) and the heavy hydrocarbon fraction (101) forming 100% by weight of said feedstock, said process comprising the following successive steps: (a) conditioning and introducing said feed into a first hydroconversion section (20) comprising at least one first ebullated bed or hybrid ebullated-entrained bed hydroconversion reactor comprising a first porous supported hydroconversion catalyst; (b) a first step of hydroconversion of said feedstock in the presence of hydrogen in said first hydroconversion section (20) to obtain a first hydroconverted effluent (105); (c) optionally a step of separating part or all of said first effluent resulting from step (b), to form at least one heavy cut boiling mainly at a temperature greater than or equal to 350°C; (d) optionally a second hydroconversion step in a second hydroconversion section comprising at least one second ebullated bed or ebullated-entrained hybrid bed hydroconversion reactor of part or all of said first effluent resulting from step (b) or optionally of said heavy cut from step (c), said second hydroconversion reactor comprising a second porous supported catalyst and operating in the presence of hydrogen, to produce a second hydroconverted effluent; step (b) and optional step (d) being carried out at an absolute pressure of between 2 MPa and 38 MPa, at a temperature of between 405°C and 550°C, at an hourly space velocity relative to the volume of each hydroconversion reactor of between 0.05 h 1 and 10 h *, and with a quantity of hydrogen of between 50 Nm3 / m3 and 5000 Nm3 / m3, (e) a step of fractionating all or part of said first effluent hydroconverted from step (b) or said second hydroconverted effluent from step (d), in a fractionation section (30), to produce at least one heavy liquid product (106b) which boils mainly at a temperature greater than or equal to 350°C, said heavy liquid product containing a residual fraction which boils at a temperature greater than or equal to 540°C.

2. A method according to claim 1, wherein, in step (a), the vegetable and / or animal oil fraction (102) and the heavy hydrocarbon fraction (101) of the feedstock are premixed before being introduced into said at least one first hydroconversion reactor of the first hydroconversion section (20).

3. A method according to claim 1, wherein, in step (a), the vegetable and / or animal oil fraction (102) and the heavy hydrocarbon fraction (101) of the feedstock are introduced separately into said at least one first hydroconversion reactor of the first hydroconversion section (20).

4. A method according to any one of the preceding claims, wherein step (a) comprises a step of preheating said heavy hydrocarbon fraction (101), preferably to a temperature between 280°C and 450°C, and optionally a step of preheating the vegetable and / or animal oil fraction (102), preferably to a temperature between room temperature and 350°C, before introducing the feedstock into the first hydroconversion reactor of the first hydroconversion section (20).

5. A method according to any one of the preceding claims, wherein the feedstock comprises between 1% and 50% by weight of the vegetable and / or animal oil fraction (102) and between 50% and 99% by weight of the heavy hydrocarbon fraction (101).

6. A method according to claim 5, wherein the feed comprises between 5% and 30% by weight, preferably between 5% and 20% by weight, of said vegetable and / or animal oil fraction (102), and between 70% and 95% by weight, preferably between 80% and 95% by weight, of said heavy hydrocarbon fraction (101).

7. A method according to any one of the preceding claims, wherein the vegetable and / or animal oil fraction of the feedstock (102) is a vegetable oil, preferably chosen from the list consisting of rapeseed oil, soybean oil, sunflower oil, palm oil, palm kernel oil, olive oil, copra oil, castor oil, cottonseed oil, peanut oil, linseed oil, crambe oil, Purghère oil, or their mixture.

8. A method according to any one of the preceding claims, wherein the heavy hydrocarbon fraction (101) of the feedstock is selected from the list consisting of a crude oil, a topped crude oil, an atmospheric residue or a vacuum residue from the atmospheric and / or vacuum distillation of a crude oil or an effluent from a thermal conversion, hydrotreatment, hydrocracking or hydroconversion unit, an aromatic cut extracted from a lubricant production unit, a deasphalted oil from a deasphalting unit, an asphalt from a deasphalting unit, a residual fraction from the direct liquefaction of coal, a vacuum distillate from the direct liquefaction of coal, or a mixture thereof.

9. A process according to any preceding claim, wherein the feedstock consists of a vegetable oil fraction and a heavy hydrocarbon fraction consisting of a vacuum residue, preferably a vacuum residue from the primary fractionation of a crude oil.

10. A method according to any one of the preceding claims, wherein the vegetable and / or animal oil fraction is a waste oil, preferably a used cooking oil.

11. Method according to any one of the preceding claims, comprising the separation step (c) separating part, or all, of the first hydroconverted effluent (105) from step (b) to produce at least the heavy cut boiling predominantly at a temperature greater than or equal to 350°C, and comprising the second hydroconversion step (d) of said heavy cut.

12. A process according to claim 11, wherein an additional vegetable and / or animal oil fraction is introduced into said at least second ebullated bed or hybrid ebullated-entrained bed hydroconversion reactor.

13. A method according to any one of the preceding claims, wherein the first hydroconversion section hydroconversion reactor(s) (20) in step (b), and optionally in hydroconversion step (d), are ebullated-entrained hybrid bed reactors, said method further comprising a step of introducing a catalyst precursor (104) into the feedstock, preferably molybdenum 2-ethylhexanoate, before injecting said feedstock into the feedstock. said at least one first bubbling-entrained hybrid bed reactor of the first hydroconversion section (20), such that a colloidal or molecular catalyst, preferably comprising molybdenum disulfide, is formed when said feedstock reacts with sulfur.

14. A method according to any one of the preceding claims, wherein the first hydroconversion catalyst, and optionally the second hydroconversion catalyst, contains at least one non-noble Group VIII metal selected from nickel and cobalt, preferably nickel, and at least one Group VIB metal selected from molybdenum and tungsten, preferably molybdenum, and comprising an amorphous support, preferably alumina.

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