Ebullated or hybrid ebullated-bed hydroconversion of a feedstock comprising a fraction of plastic pyrolysis oil and / or solid recovery fuels

Abstract

The present invention relates to a process for hydroconversion of a feedstock comprising a fraction of less than 50% by weight of plastic pyrolysis oil and / or CSR (102) and a heavy hydrocarbon fraction (101) containing a part of at least 50% by weight having a boiling point of at least 300 °C, and containing sulfur and nitrogen. The hydroconversion uses one or more ebullated-bed or hybrid ebullated-bed reactors (20), and preferably two successive hydroconversion steps. The process according to the invention makes it possible to produce higher quality materials with a lower boiling point, for example for the production of fuels or chemical compounds for petrochemistry, with an improved yield of certain cuts while allowing for facilitated treatment of the hydroconverted products in downstream steps as fixed bed hydrotreatment and maintaining good stability of the unconverted fraction.

Description

[0001] BOILING BED OR BOILING-DRIVEN HYBRID HYDROCONVERSION OF A FEED COMPRISING A FRACTION OF PYROLYSIS OIL FROM PLASTICS AND / OR RECOVERED SOLID FUELS

[0002] Technical field

[0003] The present invention relates to the field of hydroconversion of feedstocks comprising mainly 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, and a minor fraction of pyrolysis oil from plastics and / or solid recovered fuels (SRF), loaded with impurities. 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.

[0004] 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 production of fuels, or chemical products, while allowing the capture of impurities from the plastics pyrolysis oil and / or CSR.

[0005] Prior art

[0006] For several years now, we have seen the emergence of processes in the fuel and chemical sectors 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.

[0007] In particular, plastics from collection and sorting channels can undergo a pyrolysis step to obtain, among other things, pyrolysis oils. These plastic pyrolysis oils are generally burned to generate electricity and / or used as fuel in industrial boilers or district heating.

[0008] Solid recovered fuels (SRF), also known as refuse derived fuel (RDF), or solid recovered fuels (SRF), are solid non-hazardous waste prepared for energy recovery, whether they come from household and similar waste, waste from economic activities or construction and demolition waste. SRF are generally a mixture of any combustible waste such as used tires, food by-products (fats, animal meal, etc.), viscose and wood waste, light fractions from shredders (e.g. from used vehicles, electrical and electronic equipment (WEEE), household and commercial waste, residues from the recycling of various types of waste, including certain municipal waste, plastic waste, textiles, wood among others. SRF generally contains plastic waste.SRFs are currently mainly used for energy. They can be used directly as substitutes for fossil fuels in co-incineration plants (coal and lignite thermal power plants, cement plants, lime kilns) or in household waste incineration units, or indirectly in pyrolysis units dedicated to energy recovery: SRF pyrolysis oils are thus generally burned to generate electricity, or even used as fuel in industrial boilers or district heating.

[0009] Plastic and CSR pyrolysis oils can also be recovered through refining processes to produce fuels, such as gasoline or diesel, and / or chemicals such as olefins for the production of various polymers in the chemical industry.

[0010] However, this other way of recovering plastic pyrolysis oils and CSR is faced with the problems generated by the specific composition of these oils, in particular by the impurities they contain, the composition of these oils itself being linked to the diversity of the components of plastic waste or CSR.

[0011] Indeed, plastic waste or CSR are generally mixtures of several polymers, for example mixtures of polyethylene, polypropylene, polyethylene terephthalate, polyvinyl chloride, polystyrene. In addition, depending on the uses, plastics may contain, in addition to polymers, other compounds, such as plasticizers, pigments, dyes or even residues of polymerization catalysts, as well as other very varied impurities, organic and mineral, coming from the separation operations of sorting centers, an operation whose selectivity cannot be total.

[0012] Oils from the pyrolysis of plastics or CSR thus generally contain a lot of diolefins and impurities, in particular metals, silicon, or even halogenated compounds, notably chlorine-based compounds, heteroelements such as sulfur, oxygen and nitrogen, insolubles, often at high levels and which may be incompatible with certain refining units, such as fixed-bed hydrotreatment units.

[0013] The processing of these oils can pose operability problems, including corrosion, coking, catalytic deactivation, and incompatibility problems with the target polymers. The presence of diolefins, for example, very often leads to problems of instability of the pyrolysis oil, characterized by the formation of gums. Gums and insolubles that may be present in the pyrolysis oil can cause clogging problems in the equipment.

[0014] Application WO2018 / 055555 proposes, for example, a comprehensive, very general and relatively complex process for recycling plastic waste, ranging from the actual step of pyrolysis of the plastic waste to a steam cracking step which makes it possible to produce highly recoverable products in the petrochemical field such as olefins and aromatic compounds. The process comprises, among other things, a hydrocracking step of the liquid phase resulting directly from the pyrolysis, preferably in a fixed bed.

[0015] Patent applications FR3107530, FR3113060 and FR31113061 describe processes for treating plastic pyrolysis oil, comprising, among other things, a selective hydrogenation step of the plastic pyrolysis oil and a fixed-bed hydrotreatment of the hydrogenated effluent. The naphtha cut resulting from a water-specific separation of the hydrotreated effluent followed by fractionation of the separated hydrocarbon stream can be sent to a steam cracker or used as a fuel base. According to patent applications FR3113060 and FR31113061, the process integrates one or two fixed-bed hydrocracking steps after the hydrotreatment step, to minimize the yield of the heavy cut and maximize the yield of the naphtha cut by transforming the heavy cut at least in part into a naphtha cut by hydrocracking, a cut generally favored for a steam cracking unit.

[0016] Due to the impurity content of plastic pyrolysis oils, especially when they are heavily loaded with impurities, deactivation of the catalysts in the hydrotreatment unit operated in a fixed bed can occur, which reduces the cycle time. Indeed, the main constraint of fixed bed units is the need to shut down the unit to replace the catalysts. In addition, plastic pyrolysis oils, especially those heavily loaded with diolefins and impurities, can create clogging problems, particularly in preheating furnaces, feedstock / effluent exchangers or on the bed heads of fixed bed catalytic reactors.

[0017] Unpublished patent application FR 20 / 09.750 describes a process for treating plastics pyrolysis oil and / or CSR comprising, among other things, ebullated bed, entrained bed and / or moving bed hydroconversion of the feedstock, optionally previously hydrogenated. The feedstock contains at least 50% by weight of plastics pyrolysis oil and / or CSR, and preferably consists of plastics pyrolysis oil and / or CSR. After successive steps of water separation, fractionation of the separated hydrocarbon stream, hydrotreatment of the 385°C cut and fractionation of the hydrotreated stream, a liquid effluent well suited to a steam cracking unit is obtained.The implementation of a hydroconversion step in an ebullated, entrained and / or moving bed allows a long cycle time of the hydroconversion unit, due to the conventional use in this type of unit of a system for adding fresh catalyst and withdrawing used catalyst without stopping the unit. This in fact results in compensation for the deactivation of the catalysts which can be caused by the impurities of the feedstock, unlike what can occur in reactors operated in a fixed bed and in which the clogging of the catalyst beds constitutes a problem. In addition, this hydroconversion step upstream of the hydrotreatment makes it possible to increase the cycle time of the hydrotreatment unit thanks to the hydrotreatment reactions carried out partly beforehand in the hydroconversion unit, and a simpler hydrotreatment due to the transformation of at least part of the heavy compounds into lighter compounds during hydroconversion.

[0018] Unpublished patent application FR 21 / 04.873 describes a process for treating plastics and / or CSR pyrolysis oil similar to application FR 20 / 09.750, in which there is in particular no separation step between the hydroconversion step and the hydrotreatment step.

[0019] Unpublished patent application FR 21 / 04.874 describes a process for the simultaneous treatment of a plastic pyrolysis oil and a feedstock from renewable sources, such as a vegetable oil, similar to application 21 / 04.873, in which the plastic pyrolysis oil, possibly previously hydrogenated, is sent to a hydrodemetallization step, then the demetallated effluent is sent to a hydrotreatment step. The hydrodemetallization and hydrotreatment steps can be carried out in an ebullated bed. The feedstock from renewable sources is introduced into the hydrogenation step, and / or into the hydrodemetallization step and / or into the hydrotreatment step.

[0020] Objectives and Summary of the Invention

[0021] 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.

[0022] The inventors have demonstrated that, surprisingly, it is possible to incorporate a minor fraction of plastics and / or CSR pyrolysis oil, loaded with impurities, into a heavy hydrocarbon feedstock of fossil origin, typically a vacuum residue, traditionally treated in an ebullated bed or hybrid entrained ebullated bed hydroconversion process, and thus improve the production of basic fuels and / or other recoverable hydrocarbons, while capturing in the supported catalyst of the hydroconversion step the impurities initially present in the pyrolysis oil, such as silicon, which allows easier treatment of the products in downstream steps such as fixed bed hydrotreatment, and while maintaining good stability of the unconverted fraction.

[0023] The present invention thus proposes a process for the hydroconversion of a heavy feedstock of hydrocarbons of fossil origin, in particular of the vacuum residue type, in an entrained bubbling bed or hybrid bubbling bed, said feedstock including a minor fraction of plastic pyrolysis oil and / or CSR, thus enabling the production of basic fuels and other recoverable hydrocarbons, and therefore the recovery of said fraction.

[0024] 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 proposes, according to a first aspect, a process for hydroconversion of a feedstock comprising a fraction of pyrolysis oil from plastics and / or solid recovered fuels and a heavy fraction of hydrocarbons of fossil origin containing a portion of at least 50% by weight having a boiling point of at least 300°C and containing sulfur and nitrogen, said pyrolysis oil fraction constituting less than 50% by weight of said feedstock, said process comprising:

[0025] (a) conditioning and introducing said feed into a first hydroconversion section comprising at least one first ebullated bed or hybrid ebullated-entrained bed hydroconversion reactor comprising a first porous supported hydroconversion catalyst;

[0026] (b) a first step of hydroconversion of said feedstock in the presence of hydrogen in said first hydroconversion section to obtain a first hydroconverted effluent;

[0027] (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;

[0028] (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 300°C and 550°C, at an hourly space velocity of between 0.05 h 1 and 10 a.m. 1 , and with a quantity of hydrogen between 50 Nm 3 / m 3 and 5000 Nm 3 / m 3, (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, 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.

[0029] According to one or more implementations of the invention, in step (a), the pyrolysis 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.

[0030] According to one or more implementations of the invention, in step (a), the pyrolysis oil fraction of the feedstock is introduced separately from the heavy hydrocarbon fraction into said at least first hydroconversion reactor of the first hydroconversion section.

[0031] According to one or more implementations of the invention, step (a) comprises a step of preheating said heavy hydrocarbon fraction, preferably at a temperature between 280°C and 450°C, and optionally a step of preheating the pyrolysis oil fraction, before introducing the feedstock into the first hydroconversion reactor of the first hydroconversion section.

[0032] According to one or more implementations of the invention, the pyrolysis oil fraction constitutes between 1% and 45% by weight of the feedstock, preferably between 2% and 30% by weight of the feedstock, more preferably between 2% and 25% by weight of the feedstock, and even more preferably between 3% and 20% by weight of the feedstock.

[0033] According to one or more implementations of the invention, the feedstock consists of said pyrolysis oil fraction and said heavy hydrocarbon fraction, said pyrolysis oil fraction constituting between 1% and 45% by weight, preferably between 2% and 30% by weight, of said feedstock and the heavy hydrocarbon fraction constituting between 55% and 99% by weight, preferably between 70% and 98% by weight, of the feedstock.

[0034] According to one or more implementations of the invention, the pyrolysis oil fraction is a plastic pyrolysis oil.

[0035] According to one or more implementations of the invention, wherein the heavy hydrocarbon fraction 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.

[0036] According to one or more implementations of the invention, the heavy hydrocarbon fraction is a vacuum residue, preferably from the primary fractionation of a crude oil.

[0037] According to one or more implementations of the invention, the process comprises the separation step (c) separating 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.

[0038] According to one or more implementations of the invention, the hydroconversion reactor(s) of the first hydroconversion section in step (b), and optionally in hydroconversion step (d), are bubbling-entrained hybrid bed reactors, said method further comprising a step of introducing a catalyst precursor into the feedstock, preferably said catalyst precursor comprising 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.

[0039] 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.

[0040] According to one or more implementations of the invention, step (b) and optional step (d) are carried out at a temperature between 405°C and 450°C.

[0041] According to one or more implementations of the invention, the optional intermediate separation step (c) is carried out in a separation section, and wherein said separation section and / or the fractionation section in step (e) comprise means for washing at least one cut separated by contact with an aqueous solution.

[0042] According to one or more implementations of the invention, the method further comprises a step (f) of further treatment of the heavy liquid product and / or the other product(s) resulting from the fractionation step (e), said step (f) comprising at least one step chosen from the list consisting of hydrotreatment, steam cracking, fluidized bed catalytic cracking, hydrocracking, deasphalting, extraction of lubricating oils, and preferably a hydrotreatment step (f 2) in a fixed bed in a hydrotreatment section, said hydrotreatment section preferably comprising at least one fixed bed reactor having n catalytic beds, n being an integer greater than or equal to 1, each comprising at least one hydrotreatment catalyst, said hydrotreatment section being fed with at least a portion of a liquid product resulting from step e) and a gaseous stream comprising hydrogen, to obtain a hydrotreated effluent.

[0043] According to a second aspect, the invention relates to a product obtained by the method according to the invention.

[0044] According to one or more embodiments, the product is the hydroconverted effluent obtained at the end of the first hydroconversion stage (b) or the second hydroconversion stage (d), and comprises a liquid part comprising, relative to the total weight of said liquid part of the effluent, a silicon content of less than or equal to 5 ppm by weight, and / or a chlorine element content of less than or equal to 10 ppm by weight.

[0045] 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 figures described below.

[0046] List of figures

[0047] Figure 1 schematically illustrates an embodiment of the hydroconversion process according to the invention.

[0048] Figure 2 schematically illustrates another embodiment of the hydroconversion process according to the invention.

[0049] In the figures, the same references designate identical or similar elements.

[0050] Description of the embodiments

[0051] 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.

[0052] Some definitions are given below for a better understanding of the invention.

[0053] In this specification, the term "comprise" is synonymous with (means the same as) "include" and "contain", and is inclusive or open and does not exclude other elements not mentioned. It is understood that the term "comprise" includes the exclusive and closed term "consist". In this specification, the expression "between ... and ..." means that the limiting values ​​of the interval are included in the range of values ​​described, unless otherwise specified.

[0054] 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.

[0055] 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 lower 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 occurs typically 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.

[0056] 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.

[0057] 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 can be introduced and an outlet from which an upgraded material can 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 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).

[0058] The terms "hybrid bed" and "hybrid bubbling bed" and "hybrid bubbling-entrained bed" for a hydroconversion reactor refer to an 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 referred to as a "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.

[0059] 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.

[0060] 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 found. They also refer to very small catalyst particles or sheets that contain only a few catalyst molecules joined together (e.g., 15 molecules or fewer).

[0061] 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 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.

[0062] In the following text, "pyrolysis oil" means an oil resulting from the pyrolysis of plastics and / or CSR, unless otherwise stated. Also for the sake of simplification, the "heavy hydrocarbon fraction" of the feedstock means a heavy hydrocarbon fraction of fossil origin, unless otherwise stated.

[0063] 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.

[0064] The object of the invention is to propose a process for hydroconversion of a feedstock comprising a fraction of plastics and / or CSR pyrolysis oil 102 and a heavy fraction of fossil hydrocarbons 101 containing a portion of at least 50% by weight having a boiling point of at least 300°C and containing sulfur and nitrogen, said pyrolysis oil fraction constituting less than 50% by weight of said feedstock, the process comprising the following steps: (a) conditioning and introducing said feedstock into a first hydroconversion section 20 comprising at least one first ebullated bed or ebullated-entrained hybrid bed hydroconversion reactor comprising a first porous supported hydroconversion catalyst;

[0065] (b) a first step of hydroconversion of said feedstock in the presence of hydrogen in said first hydroconversion section to obtain a first hydroconverted effluent;

[0066] (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;

[0067] (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 300°C and 550°C, at an hourly space velocity of between 0.05 h 1 and 10 a.m. 1 , and with a quantity of hydrogen between 50 Nm 3 / m 3 and 5000 Nm 3 / m 3 ,

[0068] (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 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.

[0069] The charge

[0070] According to a key aspect of the invention, the feedstock comprises mainly a heavy fraction of hydrocarbons of fossil origin and a minor fraction of plastic pyrolysis oil and / or CSR.

[0071] According to a preferred embodiment, the feedstock consists of said minor fraction of plastic pyrolysis oil and / or CSR and a heavy fraction of fossil hydrocarbons.

[0072] The process according to the invention is thus specific to the hydroconversion of a mixture of plastic pyrolysis oil and / or low-content CSR and a heavy fraction of fossil-based hydrocarbons.

[0073] The fraction of plastic pyrolysis oil and / or CSR constitutes less than 50% by weight of the feedstock (total weight of the feedstock), preferably between 1% and 45% by weight of the feedstock, more preferably between 2% and 30% by weight of the feedstock, even more preferably between 2% and 25% by weight of the feedstock, even more preferably between 3% and 20% by weight of the feedstock, and even more preferably between 5% and 20% by weight of the feedstock, or even between 5% and 15% by weight of the feedstock.

[0074] The feedstock may consist of only these two fractions: the pyrolysis oil fraction and the heavy hydrocarbon fraction, the sum of the pyrolysis oil fraction and the heavy hydrocarbon fraction forming 100% by weight of the feedstock. The heavy hydrocarbon fraction may constitute, preferably when the feedstock consists of said heavy hydrocarbon fraction and the pyrolysis oil fraction, between 55% and 99% by weight of the feedstock, preferably between 70% and 98% by weight of the feedstock, more preferably between 75% and 98% by weight of the feedstock, even more preferably between 80% and 97% by weight of the feedstock, and even more preferably between 80% and 95% by weight of the feedstock, or even between 85% and 95% by weight of the feedstock.

[0075] According to the invention, a "plastic pyrolysis oil or CSR pyrolysis oil" is an oil, advantageously in liquid form at room temperature, resulting from the pyrolysis of plastics, preferably from plastic waste originating in particular from collection and sorting channels, or resulting from the pyrolysis of CSR. It comprises in particular a mixture of hydrocarbon compounds, in particular paraffins, olefins, naphthenes and aromatics. At least 80% by weight of these hydrocarbon compounds preferably have a boiling point below 700°C, and preferably below 550°C. In particular, depending on the origin of the pyrolysis oil, it may comprise up to 70% by weight of paraffins, up to 90% by weight of olefins and up to 90% by weight of aromatics, it being understood that the sum of the paraffins, olefins and aromatics is equal to 100% by weight of the hydrocarbon compounds.

[0076] The density of pyrolysis oil, measured at 15°C according to the ASTM D4052 method, is generally between 0.75 g / cm 3 and 0.99 g / cm 3 , preferably between 0.75 g / cm 3 and 0.95 g / cm 3 .

[0077] Pyrolysis oil may include, and most often does include, impurities such as metals, including iron, silicon, halogenated compounds, including chlorinated compounds. These impurities may be present in the pyrolysis oil at high levels, for example up to 500 ppm by weight or 1000 ppm by weight or even 5000 ppm by weight of halogenated elements (e.g. chlorine) provided by halogenated compounds (e.g. chlorinated compounds), and up to 2500 ppm by weight or even 10000 ppm by weight of metallic or semi-metallic elements. Alkali metals, alkaline earth metals, transition metals, poor metals and metalloids may be considered contaminants of a metallic nature, called metals or metallic or semi-metallic elements. Pyrolysis oil can contain up to 200 ppm by weight or 1000 ppm by weight of silicon, and up to 15 ppm by weight or 100 ppm by weight of iron.The pyrolysis oil may also include other impurities such as heteroelements provided in particular by sulfur compounds, oxygenated compounds and / or nitrogen compounds, at contents generally less than 20,000 ppm by weight of heteroelements, and preferably less than 10,000 ppm by weight of heteroelements.

[0078] The process according to the invention is particularly well suited to treating a pyrolysis oil loaded with impurities, in combination with a heavy hydrocarbon feedstock as defined in more detail below. By loaded with impurities, it is meant that the pyrolysis oil has the following properties:

[0079] - an aromatic content of between 0 and 90% by weight, often between 20 and 90% by weight, and which may be between 50 and 90% by weight;

[0080] - a halogen content of between 2 ppm by weight and 5000 ppm by weight, often between 200 ppm by weight and 5000 ppm by weight, and possibly between 500 ppm by weight and 5000 ppm by weight;

[0081] - a content of metallic elements between 10 ppm by weight and 10,000 ppm by weight, often between 2,000 ppm by weight and 10,000 ppm by weight, and possibly between 2,250 ppm by weight and 5,000 ppm by weight;

[0082] - with an iron element content of between 0 and 100 ppm by weight, often between 10 ppm by weight and 100 ppm by weight, and possibly between 15 ppm by weight and 100 ppm by weight;

[0083] - a silicon element content of between 0 and 1000 ppm by weight, often between 50 ppm by weight and 1000 ppm by weight, or even between 80 ppm by weight or 100 ppm by weight and 1000 ppm by weight, and which may also be between 200 ppm by weight and 1000 ppm by weight.

[0084] The process according to the invention is particularly well suited to treating pyrolysis oil with a high impurity content, in combination with a heavy hydrocarbon feedstock as defined in more detail below. By high impurity content, it is meant that the pyrolysis oil has the following properties:

[0085] - an aromatic content of between 30 and 70% by weight;

[0086] - a halogen content of between 500 ppm by weight and 5000 ppm by weight;

[0087] - a content of metallic elements between 300 ppm by weight and 5000 ppm by weight;

[0088] - with an iron element content of between 15 ppm by weight and 100 ppm by weight;

[0089] - a silicon element content of between 200 ppm by weight and 1000 ppm by weight.

[0090] The plastics and / or CSR pyrolysis oil may be obtained from a thermal or catalytic pyrolysis treatment or may be prepared by hydropyrolysis (pyrolysis in the presence of a catalyst and hydrogen). The heavy hydrocarbon fraction of fossil origin in the feedstock of the process according to the invention is 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, preferably at least 350°C, and even more preferably at least 375°C.

[0091] This heavy hydrocarbon fraction of the feedstock may be crude oil, or may come from the refining of crude oil or the processing of another fossil hydrocarbon source in a refinery.

[0092] The heavy hydrocarbon fraction of the feedstock may be crude oil, topped crude oil or may include, or consist of, atmospheric residues and / or vacuum residues from atmospheric and / or vacuum distillation of a crude oil.

[0093] 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.

[0094] Preferably, the heavy hydrocarbon fraction of the feedstock is a heavy hydrocarbon fraction containing a portion of at least 50% by weight, or even at least 80% by weight, having a boiling point of at least 450°C, preferably at least 500°C, and even more preferably at least 540°C, such as a vacuum residue.

[0095] 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).

[0096] The heavy hydrocarbon fraction of the feedstock can 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).

[0097] 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 catalytic cracking (FCC) effluent such as a heavy cycle oil (HCO) or a slurry oil (SLO). The heavy hydrocarbon fraction of the feedstock may also be a residual fraction from direct coal liquefaction (an atmospheric residue and / or a vacuum residue from, for example, the H-Coal® process), a vacuum distillate from direct coal liquefaction, such as the H-Coal® process.

[0098] All these fractions of fossil origin can be used to constitute the heavy hydrocarbon fraction of the charge treated according to the invention, alone or in a mixture.

[0099] According to one or more implementations, the heavy hydrocarbon fraction comprises, and may consist of, at least one of the following feedstocks, alone or in 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 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 crude oil).

[0100] 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 asphaltenes which are insoluble in heptane.

[0101] The metal contents may be greater than or equal to 20 ppm by weight, preferably greater than or equal to 100 ppm by weight.

[0102] 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% by weight, and may be greater than or equal to 2% by weight.

[0103] 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.

[0104] The level of C7 asphaltenes (heptane-insoluble compounds according to ASTM D6560, 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 essentially a 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.

[0105] 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 D482 and represents for those skilled in the art a well-known assessment of the amount of carbon residue produced after pyrolysis under standard conditions of temperature and pressure.

[0106] These contents of metals, sulfur, nitrogen, asphaltenes, Conradson carbon of the heavy fraction of hydrocarbons are expressed in % by weight of the total weight of the heavy fraction of hydrocarbons of the charge.

[0107] According to one or more implementations, the feedstock of the process according to the invention may further comprise, at a low content, typically between 1% and 20% by weight of the feedstock, or even between 1% and 10% or 5% by weight, a fraction of vegetable and / or animal oil or fat, and / or a hydrocarbon fraction resulting from thermal and / or catalytic conversion processes of lignocellulosic biomass, such as an oil produced from lignocellulosic biomass, according to various liquefaction methods such as hydrothermal liquefaction or pyrolysis, which is then co-treated with the pyrolysis oil from plastics and / or CSR and the heavy fraction of hydrocarbons of fossil origin.

[0108] Oils / fats of vegetable and / or animal origin contain triglycerides and / or free fatty acids and / or esters. Vegetable oils can advantageously be crude or refined, totally or partially, and can be derived from the following plants: rapeseed, sunflower, soybean, palm, palm kernel, olive, coconut, jatropha (purja), castor oil, cotton, peanuts, flax, crambe, this list not being exhaustive. Algal or fish oils are also relevant. Oils / fats of vegetable and / or animal origin can be used, for example used cooking oils. Animal fats can be chosen from lard or fats composed of residues from the food industry or from the catering industries.

[0109] The term "lignocellulosic biomass" means compounds derived from plants or their by-products, and includes constituents selected from the group consisting of cellulose, hemicellulose (carbohydrate polymers) and / or lignin (aromatic polymer).

[0110] According to one or more implementations, the feedstock of the process according to the invention does not comprise a fraction of vegetable and / or animal oil or fat, or a hydrocarbon fraction resulting from thermal and / or catalytic conversion processes of lignocellulosic biomass such as biomass pyrolysis oil.

[0111] (a) Conditioning and injection stage of the feedstock into the first hydroconversion reactor

[0112] The method according to the invention comprises a step (a) of conditioning and introducing the feedstock into a first hydroconversion section 20 comprising at least one first ebullated bed or hybrid bed reactor comprising a first porous supported hydroconversion catalyst. 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 plastics pyrolysis oil fractions and / or CSR and heavy hydrocarbon fraction before introducing the feedstock into the reactor, a removal of possible solid particles from the plastics pyrolysis oil fraction and / or CSR (by filtration, centrifugation, electrostatic separation, washing using an aqueous solution, adsorption, etc.).

[0113] Indeed, the plastics and / or CSR pyrolysis 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 pyrolysis oil fraction is liquid and pumpable at ambient temperature. This mixing may be carried out in a dedicated capacity 10 as shown in FIG. 1, 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 the installation of 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.

[0114] Another possibility, shown in Figure 2, is the separate injection of the plastics pyrolysis oil fraction and / or CSR102 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 diolefin and olefin contents of the plastics pyrolysis oil and / or CSR may lead to the formation of gum).

[0115] 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 description will refer to the preheating step. It is specified that said target temperature in the hydroconversion reactor, i.e. the temperature during the hydroconversion step, is generally not the preheating temperature, the latter being conventionally lower than the target temperature in the hydroconversion reactor.

[0116] 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.

[0117] This preheating may also comprise heating the pyrolysis 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 pyrolysis oil fraction 102, when it is injected into the first reactor separately from the heavy hydrocarbon fraction 101, 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, even more preferably between 100°C and less than 230°C, or even between 150°C and less than 200°C.

[0118] In the case of a mixture of the two fractions, preheating can be carried out after mixing, before or during.

[0119] According to an embodiment where the preheating is carried out separately for the fractions 101 and 102, and where the fractions 101 and 102 are then mixed, the plastics and / or CSR pyrolysis oil fraction 102 is preheated to a lower temperature than the heavy hydrocarbon fraction 101 so as to limit the formation of gums and / or coking of the preheating equipment (for example furnaces and / or heat exchangers) due to the presence of olefins and diolefins in the pyrolysis oil fraction 102. According to this embodiment, the preheating temperature of the plastics and / or CSR pyrolysis oil fraction 102 is preferably less than 230°C, preferably less than 200°C, more preferably less than or equal to 175°C, and very preferably less than or equal to 100°C.According to this embodiment, the heavy fraction 101 can be preheated, before mixing with the pyrolysis oil fraction 102, to 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.

[0120] According to another embodiment where the heavy fractions of hydrocarbons 101 and pyrolysis oil

[0121] 102 are mixed, the pyrolysis oil fraction 102 is heated indirectly by mixing with the heavy hydrocarbon fraction 101 (i.e. heat exchange between the two fractions by bringing said two fractions which have different temperatures into contact) which has been preheated preferably 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, so that a target hydroconversion temperature can then be reached in the first hydroconversion reactor.

[0122] According to yet another embodiment, it is the mixture of the heavy hydrocarbon fractions 101 and pyrolysis oil 102 which is preheated, advantageously using heating means such as already described below (e.g. furnace, heat exchangers, etc.), preferably 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, so that a target hydroconversion temperature can then be reached in the first hydroconversion reactor.

[0123] According to one embodiment, the preheating may further comprise the exchange of calories between the feedstock and a stream comprising preheated hydrogen (not shown in the figures), typically having a temperature between 350°C and 560°C, for example approximately 500°C or 540°C, so that a target hydroconversion temperature can then be reached in the first hydroconversion reactor.

[0124] Any means known to a person skilled in the art capable of preheating said feedstock 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 feedstock flows, a mixer of the feedstock with H2, any type of suitable heat exchanger, for example tubular or spiral heat exchangers into which the feedstock flows, etc. Before its introduction into the first hydroconversion reactor, the feedstock 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.

[0125] According to one or more embodiments, the fraction of plastic pyrolysis oil and / or CSR 102 may first undergo a filtration step and / or a centrifugation step and / or an electrostatic separation step and / or a washing step using an aqueous solution and / or an adsorption step, to remove impurities which may be naturally present in the plastic pyrolysis oils and / or CSR, in particular to remove solid particles.

[0126] 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, such 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.

[0127] The entrained catalyst precursor 104 may also be mixed with the pyrolysis oil fraction 102 before mixing the latter with the heavy hydrocarbon fraction 101 (not shown in FIG. 1), or else be mixed with the feedstock 114 formed by mixing 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 of the catalyst precursor and the pyrolysis oil fraction 102 is preferably less than 230°C, or even less than 200°C (and in all cases preferably at a temperature below a temperature at which a substantial portion of the catalyst precursor begins to decompose).

[0128] It is specified that within the meaning of the present invention, the catalyst precursor, possibly diluted, is not part of the feedstock as defined above which comprises the fraction of plastic pyrolysis oil and / or CSR and the heavy hydrocarbon fraction.

[0129] The entrained catalyst precursor may be selected from any metal catalyst precursor 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 enabling the hydroconversion of the feedstock after its injection into the first hydroconversion reactor.

[0130] The catalyst precursor is advantageously an oil-soluble catalyst precursor containing at least one transition metal.

[0131] The catalyst precursor preferably comprises an oil-soluble organometallic compound or complex.

[0132] 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.

[0133] 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.

[0134] 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.

[0135] 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.

[0136] One skilled in the art can select a mixing temperature profile that results in mixing of the chosen precursor without substantial thermal decomposition prior to formation of the colloidal or molecular catalyst.

[0137] 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, US10822553 or US10941353 and recalled below.

[0138] 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 advantageously for a period of time of 1 second to 30 minutes.

[0139] Typically, the catalyst precursor diluent may be a hydrocarbon oil composed of hydrocarbons of which at least 50% by weight, relative to 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, vacuum gas oil known as "VGO" (which typically has a boiling range of 360°C to 524°C), decanter oil or recycle oil (which typically has a boiling range of 360°C to 550°C), for example, FCC fluidized catalytic cracking effluent such as heavy cycle oil (HCO) or light cycle oil (LCO), pyrolysis oil from a hydrocracker, 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 524°C or higher), deasphalted oils, and resins. The catalyst precursor diluent is preferably atmospheric residue, vacuum residue, VGO.

[0140] 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.

[0141] 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).

[0142] Without mixing with a diluent, it is best 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 entrained catalyst is formed. However, a long mixing time, for example 24 hours, can be prohibitively expensive for some industrial operations.

[0143] 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 period of time required for large-scale industrial operations to be economically viable.

[0144] 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 the range of 1 second to 10 minutes, and even more preferably in the 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 feedstock 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.

[0145] 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.

[0146] Under the operating conditions of the hydroconversion reactor in the hydroconversion step (b), the catalyst precursor 104 is completely decomposed and the precursor metal has combined with sulfur (e.g. dissolved H2S present in the feedstock, or H2S contained in hydrogen recycled to the hydroconversion reactor, or sulfur originating from sulfur-containing organic molecules present in the feedstock or possibly previously introduced into the feedstock) to give the colloidal or molecular catalyst.

[0147] The metal concentration of the catalyst, preferably Mo, in the feedstock 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.

[0148] Preferably, the colloidal or molecular catalyst comprises, or consists of, molybdenum disulfide.

[0149] It has been described above that the pyrolysis oil fraction 102 is introduced, mixed or not with the heavy hydrocarbon fraction 101, into the first hydroconversion reactor of the first hydroconversion section 20. However, the first hydroconversion stage may comprise several hydroconversion reactors in series, and the pyrolysis oil fraction 102 may be introduced into a hydroconversion reactor downstream of the first hydroconversion reactor of the first hydroconversion section 20 without departing from the scope of the present invention.

[0150] (b) first hydroconversion step

[0151] The feedstock is introduced, whether the fractions that 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 (stream not shown). Said first reactor comprises a first porous supported hydroconversion catalyst.

[0152] 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 (relative to the feed) of hydrocarbons having a boiling point of at least 300°C, or at least 350°C, 375°C, 450°C, 500°C, or even 540°C depending on the nature of the feed. Said first hydroconverted effluent 105 may also have a reduced content, relative to the feed, of sulfur, and / or metals, and / or silicon, and / or halogenated compounds (e.g. chlorine), 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 feed.In particular, said first hydroconverted effluent 105 may advantageously have a reduced content, relative to the feed, of sulfur, metals, silicon, halogenated compounds (eg chlorine), nitrogen, Conradson carbon, and asphaltenes.

[0153] The silicon and / or halogenated compound (e.g. chlorine) content of the first hydroconverted effluent 105 obtained at the end of step b) is advantageously reduced compared to that of the same impurities (e.g. silicon and / or halogenated compounds such as chlorine) included in the feed. Preferably, the first hydroconverted effluent 105 comprises a liquid fraction (PI+ fraction) having:

[0154] - a silicon content of less than or equal to 5 ppm by weight, preferably less than or equal to 2 ppm by weight, or even less than or equal to 1 ppm by weight, relative to the total weight of said liquid part of the first hydroconverted effluent 105, and / or

[0155] - a chlorine element content of less than or equal to 10 ppm by weight, preferably less than or equal to 5 ppm by weight, or even less than or equal to 2 ppm by weight or even 1 ppm by weight, relative to the total weight of said liquid part of the first hydroconverted effluent 105.

[0156] 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 of between 300°C and 550°C, more preferably between 350°C and 500°C, preferably between 370°C and 450°C, and even more preferably between 405°C and 450°C, or even between 410°C and 450°C. The hourly space velocity (WH) is preferably between 0.05 h 1 and 10 a.m. 1(WH relative to the volume of each reactor). The hourly space velocity (WH), also called liquid hourly space velocity (LHSV) or hourly space velocity (HSV) according to English terminology, is defined here as the ratio between the hourly volume flow rate of the liquid feedstock (sent to the hydroconversion stage) and the volume of each hydroconversion reactor. According to a preferred implementation, the WH is between 0.1 h 1 and 10 a.m. 1 , more preferably between 0.1 h 1 and 5 a.m. 1 , even more preferably between 0.15 h 1 and 2 hours 1 , and even more preferably between 0.15 h 1 and 1 hour 1 .

[0157] According to 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 used in step b), is between 0.05 h 1 and 0.09 h 1 .

[0158] The amount of hydrogen mixed with the charge is preferably between 50 and 5000 normal cubic meters (Nm 3 ) per cubic meter (m 3 ) of liquid charge, preferably between 100 Nm 3 / m 3 and 2000 Nm 3 / m 3 and very preferably between 200 Nm 3 / m 3 and 1000 Nm 3 / m 3 .

[0159] The first hydroconversion section 20 comprises one or more ebullated bed or hybrid 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 can 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 called 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.

[0160] The bubbling bed reactor preferably comprises at least one inlet located at or near the lower part of the reactor through which the feedstock is introduced together with the hydrogen, and in particular two inlets in the case where the pyrolysis oil fraction 102 of the feedstock is introduced separately from the heavy hydrocarbon fraction 101, and an outlet 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 bubbling bed reactor further comprises an expanded catalyst zone comprising the porous supported catalyst.The ebullated 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 ebullated 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.

[0161] 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 most preferably alumina, may be used.

[0162] 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.

[0163] In this 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 IUPAC classification.

[0164] 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. 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.

[0165] This first supported catalyst is advantageously used in the form of extrudates or beads. The beads have, for example, a diameter between 0.4 mm and 4.0 mm. The extrudates have, for example, a cylindrical shape with a diameter between 0.5 mm and 4.0 mm and a length between 1 mm and 5 mm. The extrudates can also be objects of a different shape such as trilobes, regular or irregular tetralobes, or other multilobes. Porous supported catalysts of other shapes can also be used. The size of these different shapes of porous supported catalysts can 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 between 0.4 mm and 4.4 mm.These catalysts are well known to those skilled in the art.

[0166] 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 out of 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.

[0167] 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.

[0168] 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.

[0169] 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 the colloidal or molecular catalyst being dispersed throughout the feed in the hybrid bed reactor, including both in the expanded catalyst zone and in zones free of supported catalyst, and thus available to stimulate upgrading reactions in what constitute catalyst-free zones in conventional ebullated bed reactors.

[0170] 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 supported catalyst deactivation. This can allow a reduction in the amount of porous supported catalyst that would otherwise be required to carry out a desired hydroconversion reaction. It 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 be carried out 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).

[0171] 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.

[0172] 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 higher than the used supported catalyst to be replaced, and / or regenerated supported catalyst, and / or rejuvenated supported catalyst (catalyst from a rejuvenation zone in which the majority of the deposited metals are removed, before sending the used 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 used supported catalyst preferably from 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 used supported catalyst is preferably carried out at regular time intervals, and preferably in bursts or almost continuously. This withdrawal and replacement are carried out using a withdrawal and injection device which advantageously allows the continuous operation of this hydroconversion step.

[0173] With this supported catalyst withdrawal / injection operation, 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 deactivation. In addition, working under constant operating conditions makes it possible to obtain constant yields and product qualities throughout the cycle. Also, because the supported catalyst is kept agitated by significant liquid recycling, the pressure drop on the reactor remains low and constant, and the reaction exotherms are quickly averaged over the catalytic bed, which is therefore almost isothermal and does not require, for example, 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 ebullated bed or hybrid ebullated-entrained bed to continue the conversion of pyrolysis oil into lighter products thanks to the combination of a high temperature and the presence of a catalyst which allows the hydrogenation of unsaturated molecules (olefins or aromatics). The co-treatment of pyrolysis oil thus makes it possible to improve the yield of certain cuts obtained in the hydroconverted effluent, in particular the gasoline cut.

[0174] Another advantage of the invention, linked to the use of a hydroconversion reactor operating in an ebullated or hybrid ebullated-entrained bed for the co-treatment of pyrolysis oil, is to capture impurities such as silicon or metals thanks to the supported catalyst. This makes it possible to obtain products low in impurities and which can thus be more easily treated in downstream processes such as fixed-bed hydrotreatment processes for example. The advantage of the ebullated or hybrid ebullated-entrained bed is that the supported catalyst is replaced continuously and it is easy to compensate for more severe deactivation by increasing the catalytic replacement if necessary, particularly in the case of pyrolysis oil heavily loaded with impurities.

[0175] 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 pre-mixed 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. According to one embodiment, it comprises 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 (egMo) is between 0.1:1 and 20:1, more preferably between 0.75:1 and 7:1, and even more preferably between 1:1 and 5:1.

[0176] (c) optional intermediate separation step

[0177] 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.

[0178] The other cut(s) are one or more light and intermediate cut(s). The light cut thus separated mainly contains gases (H2, HCl, H2S, NH3, and Ci-C4), naphtha (or gasoline, cut which boils at a temperature below 150°C), kerosene (or diesel, cut which boils between 150°C and 250°C), and at least part of the diesel (fraction which boils between 250°C and 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. This fractionation unit can be that of the fractionation step (e), in particular in the case where a second hydroconversion step (d) is implemented.The hydrogen gas thus recovered, which may have been sent to a purification and compression facility, 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.

[0179] The optional separation step (c) is carried out in a separation section (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 referred to as a "hot separator". The separation section may also comprise means for washing the light cut containing mainly gases by contact with an aqueous solution.

[0180] According to a preferred embodiment, the optional separation step (c) comprises a hot separator operated at a temperature greater than or equal to 300°C, or even 350°C, so as to avoid the formation of ammonium chloride salts in the liquid phase; the gas phase of the hot separator or at least one of the phases resulting from the subsequent separation of the gas phase of the hot separator, is advantageously brought into contact with water or a basic aqueous solution (soda solution, amine(s) for example) in order to eliminate at least in part the hydrogen chloride (HCl) and / or to dissolve at least in part the ammonium chloride salts. The separation equipment or tanks may comprise at the bottom a zone allowing the separate decantation of a hydrocarbon fraction and an aqueous fraction comprising chloride salts, or even comprise a column for washing the gases by bringing them into contact with water or a basic solution.

[0181] (d) optional second hydroconversion step

[0182] According to one or more preferred embodiments (not shown in the figures), the method 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 resulting 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 105, 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 be provided with a further reduced Conradson carbon residue compared to the first hydroconverted effluent 105, and optionally with a further reduced quantity of sulfur, and / or nitrogen, and / or metals, and / or silicon, and / or halogenated compounds (e.g. chlorine) and / or asphaltenes. In particular, said second hydroconverted effluent may advantageously have a reduced content, compared to the first hydroconverted effluent 105 and / or compared to the feedstock, of sulfur, metals, silicon, halogenated compounds (e.g. chlorine), nitrogen, Conradson carbon, and asphaltenes. The content of silicon and / or halogenated compounds (e.g. chlorine) in the second hydroconverted effluent obtained at the end of step d) is advantageously reduced compared to that of the same impurities (e.g. silicon and / or halogenated compounds such as chlorine) included in the first hydroconverted effluent 105 and / or in the feedstock.

[0183] Preferably, the second hydroconverted effluent comprises a liquid fraction (PI+ fraction) having:

[0184] - a silicon content of less than or equal to 5 ppm by weight, preferably less than or equal to 2 ppm by weight, or even less than or equal to 1 ppm by weight, relative to the total weight of said liquid part of the second hydroconverted effluent, and / or

[0185] - a chlorine element content of less than or equal to 10 ppm by weight, preferably less than or equal to 5 ppm by weight, or even less than or equal to 2 ppm by weight or even 1 ppm by weight, relative to the total weight of said liquid part of the second hydroconverted effluent.

[0186] 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.

[0187] 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.

[0188] 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, and the amount of hydrogen introduced into the reactor remaining in the range between 50 Nm 3 / m 3 and 5,000 Nm 3 / m 3 liquid charge, preferably between 100 Nm 3 / m 3 and 3,000 Nm 3 / m 3 , and even more preferably between 200 Nm 3 / m 3 and 2,000 Nm 3 / m 3 . The other pressure and WH parameters are in the same ranges as those described for the hydroconversion step (d).

[0189] 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 unconverted feedstock. Hydroconversion of liquid products from the first hydroconversion stage and feedstock conversion are enhanced, as are hydrotreating reactions such as hydrodesulfurization and hydrodenitrogenation, among others. Operating conditions are chosen to minimize the formation of solids (e.g., coke).

[0190] 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).

[0191] It has been described in step (a) that the pyrolysis oil fraction 102 of the feedstock is introduced, mixed or not with the heavy hydrocarbon fraction 101, into the first hydroconversion reactor of the first hydroconversion section 20. However, the pyrolysis oil fraction 102 may be introduced into a hydroconversion reactor of the second hydroconversion section 20 without departing from the scope of the present invention.

[0192] (e) fractionation step

[0193] 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.

[0194] 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).

[0195] 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).

[0196] The fractionation section 30 comprises any separation means known to those skilled in the art.

[0197] The fractionation section 30 may 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. According to one or more embodiments, this fractionation step (e) is carried out by a chain of at least two successive flash drums.

[0198] According to one or more other embodiments, this fractionation step (e) is carried out by one or more steam and / or hydrogen stripping columns.

[0199] 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.

[0200] 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 configuration makes it possible to reduce the size of any downstream deasphalter, thus minimizing investment costs and operating costs.

[0201] 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 feedstocks external to the process (e.g. atmospheric and / or vacuum distillates, atmospheric and / or vacuum residues), a portion of the heavy cut from the separation step (c) if it is implemented, a portion of one or more of the intermediate cuts from the fractionation step (e), a portion of a DAO or a light or heavy fraction of a DAO if a deasphalting step (fl) is carried out. The fractionation section 30 may also comprise means for washing one or more separated products by contact with an aqueous solution.

[0202] According to a preferred embodiment, the fractionation step (e) comprises a hot separator operated at a temperature greater than or equal to 300°C, or even 350°C, so as to avoid the formation of ammonium chloride salts in the liquid phase; the gas phase of the hot separator or at least one of the phases resulting from the subsequent separation of the gas phase of the hot separator, as well as at least a portion of the liquid phase of the hot separator or at least one of the phases resulting from the subsequent separation of the liquid phase of the hot separator, are advantageously brought into contact with water or a basic aqueous solution (soda solution, amine(s) solution for example) in order to eliminate at least part of the hydrogen chloride (HCl) and / or to dissolve at least part of the ammonium chloride salts.The separation equipment or tanks may comprise at the bottom a zone allowing the separate decantation of a hydrocarbon fraction and an aqueous fraction comprising chloride salts, or else comprise a column for washing the gases by bringing them into contact with water or a basic aqueous solution. According to a very preferred embodiment, when separation step c) is carried out, at least part of the separation equipment is common between steps c) and e).

[0203] (f) further processing step(s)

[0204] One or more further processing steps (f) of the heavy liquid product 106b and / or of the other product(s) from the fractionation step (e) may be carried out.

[0205] Such step (f) may comprise at least one step selected from the list consisting of hydrotreatment, steam cracking, fluidized bed catalytic cracking, hydrocracking, deasphalting, extraction of lubricating oils. These examples of further treatment are not exhaustive.

[0206] The various hydrocarbon products that may result from the fractionation step (e) in the fractionation means 30 may in fact be sent to different processes in the refinery, illustrated in the figures under the general reference 40, and the details of all these post-treatments are not described here 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).

[0207] 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. We can thus refer to the article by Billon and others 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, Edition Technip, pages 17 - 32 or to 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 of between 60°C and 250°C with at least one hydrocarbon solvent with a low boiling point, 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 / feedstock 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 practically free of C7 asphaltenes, said C7 asphaltene content being preferably 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 load sent to the deasphalter and in particular the quality of the heavy liquid product 106b.

[0208] According to one or more embodiments, the hydroconversion process comprises at least one hydrotreatment step (f2), preferably in a fixed bed, carried out in a hydrotreatment section, of one or more liquid products resulting from the fractionation step (e). The hydrotreatment section may comprise at least one fixed bed reactor having n catalytic beds, n being an integer greater than or equal to 1, each comprising at least one hydrotreatment catalyst, said hydrotreatment reaction section being fed with at least a portion of a liquid product resulting from step e) and a gaseous stream comprising hydrogen, to obtain a hydrotreated effluent.

[0209] Such a step uses hydrotreatment reactions well known to those skilled in the art, and more particularly hydrotreatment reactions such as the hydrogenation of aromatics, olefins, hydrodesulfurization and hydrodenitrogenation.

[0210] Said hydrotreatment reaction section can be carried out at an average temperature (Weight Average Bed Temperature (WABT) according to English terminology) of between 250°C and 430°C, preferably between 300°C and 400°C, at a partial hydrogen pressure of between 1.0 MPa abs. and 20.0 MPa abs., preferably between 3.0 MPa abs. and 15.0 MPa abs, and at an hourly volumetric flow rate (WH) per volume of catalyst(s) of between 0.1 and 1.0 MPa abs. -1 and 10.0 h 1 , preferably between 0.1 h 1 and 5.0 h 1 , preferably between 0.2 h -1 and 2.0 h 1 , preferably between 0.2 h 1 and 1.0 h 1. The hydrogen coverage in step f2) is advantageously between 50 Nm 3 and 2000 Nm 3 , preferably between 100 Nm 3 and 1000 Nm 3 , more preferably between 120 Nm 3 and 800 Nm 3 , of hydrogen per m 3 load which supplies step f2).

[0211] The hydrotreatment section may comprise several, preferably two, reactors, which can operate in series and / or in parallel and / or in permutable mode (or PRS or "lead and lag" in English) and / or in "swing" mode well known to those skilled in the art. Alternatively, the hydrotreatment section may comprise a single fixed-bed reactor with n catalytic beds, n preferably being between 1 and 10, or even between 2 and 5.

[0212] Means for recovering catalyst fines and / or catalysts from hydroconversion may be implemented upstream or at the inlet of the hydrotreatment section, such as one or more filters or reactor internals, for example of the filter tray type, an example of which is described in patent FR3051375. The fixed-bed hydrotreatment catalyst used in step f2) may be chosen from known hydrotreatment and hydrodemetallation catalysts used in particular for the treatment of petroleum cuts. Known hydrotreatment catalysts are, for example, those described in patents EP0113297, EP0113284, US6589908, US4818743 or US6332976. Known hydrodemetallization catalysts are for example those described in patents EP0113297, EP0113284, US5221656, US5827421, US7119045, US5622616 and US5089463.

[0213] In particular, the hydrotreatment catalyst comprises a support, preferably mineral, and at least one metallic element having a hydro-dehydrogenating function.

[0214] Said metallic element with hydro-dehydrogenating function advantageously comprises at least one element from group VIII, preferably chosen from the group consisting of nickel and cobalt, and / or at least one element from group VIB, preferably chosen from the group consisting of molybdenum and tungsten. The total content of oxides of the metallic elements from groups VIB and VIII is preferably between 0.1% and 40% by weight, more preferably between 5% and 35% by weight, relative to the total weight of the hydrotreatment catalyst. The weight ratio between the metal (or metals) from group VIB relative to the metal (or metals) from group VIII, expressed as metal oxide, is preferably between 1 and 20, more preferably between 2 and 10.For example, the hydrotreatment section of step f2) comprises a hydrotreatment catalyst comprising between 0.5% and 10% by weight of nickel, preferably between 1% and 8% by weight of nickel (expressed as nickel oxide NiO relative to the total weight of the hydrotreatment catalyst), and between 1.0% and 30% by total weight of molybdenum and / or tungsten, preferably between 3% and 29% by weight, (expressed as molybdenum oxide MoO3 or tungsten oxide WO3 relative to the total weight of the hydrotreatment catalyst), on a mineral support. The support of the hydrotreatment catalyst is advantageously chosen from alumina, silica, silica-aluminas, magnesia, clays and mixtures thereof. The support may also contain doping compounds (e.g. oxides chosen from boron oxide, in particular boron trioxide, zirconia, ceria, titanium oxide, phosphoric anhydride and a mixture of these oxides).Preferably, the hydrotreatment catalyst comprises an alumina support, preferably an alumina support doped with phosphorus and optionally boron. The alumina used may be, for example, a γ (gamma) or γ (eta) alumina.

[0215] The hydrotreatment catalyst is advantageously used in the form of extrudates or beads, generally of millimetric size, for example having an equivalent diameter of between 0.4 mm and 4.4 mm.

[0216] Advantageously, the hydrotreatment catalyst used in step f2) has a specific surface area (measured by the BET method of determination by nitrogen adsorption according to standard ASTM D3663) greater than or equal to 250 m 2 / g, or even at 300 m 2 / g, and advantageously less than or equal to 800 m 2 / g, or even at 600 m 2 / g, or even at 400 m 2 / g.

[0217] 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. It is specified that, within the meaning of the present invention, such a recycle stream is not part of the feedstock as defined above, which comprises the pyrolysis oil fraction 102 and the heavy hydrocarbon fraction 101.

[0218] Analysis methods used

[0219] The analysis methods and / or standards used to determine the characteristics of the various flows, in particular the load to be treated and the effluents produced, are known to those skilled in the art. They are listed below for information purposes. Other methods deemed equivalent may also be used, in particular equivalent IP, EN or ISO methods. Table 1

[0220] (1) MAV method described in the article: C. Lopez-Garcia et al., Near Infrared Monitoring of Low Conjugated Diolefins Content in Hydrotreated FCC Gasoline Streams, Oil & Gas Science and Technology - Rev. IFP, Vol. 62 (2007), No. 1, pp. 57-68 Examples

[0221] The examples below are intended to demonstrate some of the performance characteristics of the process according to the invention. These examples illustrate the possibility of co-processing plastic pyrolysis oil in an H-Oil® type ebullated bed hydroconversion process which converts it into lighter hydrocarbons, which can be used as bases for manufacturing fuels, lubricants or any other product derived from petroleum refining. The ability of the supported catalyst present in the H-Oil® process to capture impurities present in the pyrolysis oil and thus facilitate the post-treatment of these products is also demonstrated.

[0222] These examples were carried out in a closed reactor (known as a “batch”) representative of the operating conditions of the H-Oil® process.

[0223] Example 1 is a comparative example illustrating the performance of the hydroconversion process for a reference feedstock (vacuum residue) without plastic pyrolysis oil.

[0224] Example 2 illustrates the performance of an H-Oil® process with a feedstock comprising a fraction of plastic pyrolysis oil and a fraction of the reference feedstock (vacuum residue) used in Example 1. The mixture was implemented during a pre-stage of homogenization of the medium (optional stage).

[0225] Charge :

[0226] The heavy fraction (I) of the feedstock is a straight-run vacuum residue (SRV) derived directly from the distillation of crude oil. The plastic pyrolysis oil fraction (II) of the feedstock is a pyrolysis oil derived from a plastics mixture and containing a high level of impurities.

[0227] The main characteristics of these two fractions of the load are presented in Table 2 below.

[0228] Table 2

[0229] (*) LD: Detection Limit

[0230] The operating conditions of these examples are summarized in Table 3 below.

[0231] Table 3

[0232] (**) NC: Not Concerned

[0233] Procedure for example 1:

[0234] The batch reactor is loaded with a predefined mass of NiMo-on-alumina catalyst and with 100% RSV-SR (fraction I of the feed), previously heated to 100°C to make it less viscous. 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. 1 . Gradually, the temperature is increased from 100°C to the reaction temperature and, in parallel, the stirring is gradually increased from 500 to 1000 rpm. 1. When the reaction temperature is reached, the pressure in the reactor is instantly adjusted to the target value by adding F . 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.

[0235] Procedure for example 2:

[0236] The batch reactor is first loaded with the same mass of NiMo-on-alumina catalyst as in Example 1 and with 90% RSV-SR (fraction I of the feed), previously heated to 100°C to make it less viscous, then 10% plastic pyrolysis oil (fraction II of the feed) is added. 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. 1 . Gradually, the temperature is increased from 100°C to 200°C and, at the same time, the stirring is gradually increased from 500 to 1000 rpm. 1At 200°C, the pressure in the reactor is then 4 MPa. A one-hour hold at this temperature is respected, although this step is optional, in order to ensure the good dispersion of the pyrolysis oil (fraction II of the feed) in the RSV-SR (feed I). Following this hold, the batch reactor is heated to the reaction temperature, at which temperature 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.

[0237] Results and overall performance:

[0238] The results regarding the quality of the total liquid effluent and the hydroconversion performances of these examples are detailed in Tables 4, 5 and 6 below.

[0239] Table 4

[0240] (*) LD: Limit of Detection

[0241] (**) NC: Not Concerned Table 5

[0242] Table 6

[0243] The conversion of the 540°C+ cut is calculated by mass difference between the feed and the total liquid effluent, such as: Math 1 mass 540 + °C effluent - - — - - - - mass 540 + C charge

[0244] It is observed that the presence of plastic pyrolysis oil does not affect the conversion at 540°C+ and allows a significant increase in the yield of the PI-180°C cut while reducing the yields of the heavy cuts. It is also shown that despite the presence of silicon in the plastic pyrolysis oil, the products resulting from the hydroconversion no longer contain it, which indicates that the silicon has been captured by the supported catalyst. Similarly, the chlorine has been completely converted. The products resulting from this step are therefore low in impurities and can be sent to fixed-bed hydrotreatment processes.

[0245] Furthermore, the co-treatment of plastic pyrolysis oil does not appear to significantly destabilize the unconverted product since the sediment content is only 0.04% by weight, which is a very low and perfectly tolerable value at the outlet of the hydroconversion process. The hydrotreatment performances (hydrodenitrogenation and hydrodesulfurization in particular) are also maintained, or even improved.

Claims

Demands 1. A process for the hydroconversion of a feedstock comprising a pyrolysis oil fraction of plastics and / or solid recovered fuels (102) and a heavy fraction of fossil hydrocarbons (101) containing a portion of at least 50% by weight having a boiling point of at least 300°C and containing sulfur and nitrogen, said pyrolysis oil fraction (102) constituting less than 50% by weight of said feedstock, said process comprising: (a) conditioning and introduction of said feed into a first hydroconversion section (20) comprising at least one first bubbling bed or hybrid bubbling-entrained bed hydroconversion reactor comprising a first porous supported hydroconversion catalyst; (b) a first hydroconversion step of said feed in the presence of hydrogen in said first hydroconversion section (20) to obtain a first hydroconverted effluent (105); (c) optionally a step of separating some or all of said first effluent resulting from step (b), to form at least a heavy cut boiling predominantly 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 bubbling-bed or hybrid bubbling-entrained-bed hydroconversion reactor of some 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 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 300°C and 550°C, at a spatial rate of between 0.05 h 1 and 10 a.m. 1 , and with a quantity of hydrogen between 50 Nm 3 / m 3 and 5000 Nm 3 / m 3 , (e) a fractionation step of all or part of said first hydroconverted effluent from step (b) or of 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.

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

3. Method according to claim 1, wherein, in step (a), the pyrolysis oil fraction (102) of the feed is introduced separately from the heavy hydrocarbon fraction (101) into said at least 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 preheating step of said heavy hydrocarbon fraction (101), preferably at a temperature between 280°C and 450°C, and optionally a preheating step of the pyrolysis oil fraction (102), before the introduction of the feed into the first hydroconversion reactor of the first hydroconversion section (20).

5. A process according to any one of the preceding claims, wherein the pyrolysis oil fraction (102) constitutes between 1% and 45% by weight of said charge, preferably between 2% and 30% by weight of said charge, preferably between 2% and 25% by weight of said charge, more preferably between 3% and 20% by weight of said charge.

6. A method according to any one of the preceding claims, wherein the feed consists of said pyrolysis oil fraction (102) and said heavy hydrocarbon fraction (101), said pyrolysis oil fraction (102) constituting between 1% and 45% by weight, preferably between 2% and 30% by weight, of said feed and the heavy hydrocarbon fraction (101) constituting between 55% and 99% by weight, preferably between 70% and 98% by weight, of the feed.

7. A method according to any one of the preceding claims, wherein the pyrolysis oil fraction (102) is a plastics pyrolysis oil.

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

9. A process according to claim 8, wherein the heavy hydrocarbon fraction (101) is a vacuum residue, preferably from the primary fractionation of crude oil.

10. A 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.

11. A method according to any one of the preceding claims, wherein the first hydroconversion section (20) hydroconversion reactor(s) 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 (104) into the feed, preferably said catalyst precursor (104) comprising molybdenum 2-ethylhexanoate, before injecting said feed into 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 feed reacts with sulfur.

12. A process 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.

13. A method according to any one of the preceding claims, wherein step (b) and step (d) optional are implemented at a temperature between 405°C and 450°C.

14. A method according to any one of the preceding claims, wherein the optional intermediate separation step (c) is carried out in a separation section, and wherein said separation section and / or the fractionation section (30) in step (e) comprise means for washing at least one separated cut by contact with an aqueous solution.

15. A process according to any one of the preceding claims, further comprising a step (f) of further treatment of the heavy liquid product (106b) and / or the other product(s) from the fractionation step (e), said step (f) comprising at least one step selected from the list consisting of hydrotreating, steam cracking, fluidized bed catalytic cracking, hydrocracking, deasphalting, lubricating oil extraction, and preferably a fixed-bed hydrotreating step (f2) in a hydrotreating section, said hydrotreating section preferably comprising at least one fixed-bed reactor having n catalytic beds, n being an integer greater than or equal to 1, each comprising at least one hydrotreating catalyst, said hydrotreating section being fed by at least part of a liquid product from step e) and a gaseous stream including hydrogen, to obtain a hydrotreated effluent.

16. Product obtained by the process according to any one of claims 1 to 15.

17. Hydroconverted effluent according to claim 16, obtained at the end of the first hydroconversion step (b) or the second hydroconversion step (d), and comprising a liquid part comprising, in relation to the total weight of said liquid part of said effluent, a silicon content less than or equal to 5 ppm by weight, and / or a chlorine content less than or equal to 10 ppm by weight.

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