Ebullated bed or hybrid ebullated bed hydroconversion of feedstocks containing fractions of plastic pyrolysis oils and / or solid recovered fuels

Abstract

The present invention relates to a process for the hydroconversion of a feedstock comprising at least 50% by weight of a fraction of plastic pyrolysis oil and / or CSR (102) and a fraction of a heavy hydrocarbon fraction (101), the latter containing at least 50% by weight of a portion with 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, preferably two successive hydroconversion steps. The process according to the invention allows to produce materials with a lower boiling point and with improved yields of a given fraction for the production of chemical compounds, for example for fuels or petrochemicals, of higher quality, while facilitating the processing of the hydroconverted products in downstream processes such as fixed bed hydrotreating and maintaining good stability of the unconverted fraction.

Description

[Technical field]

[0001] The present invention relates to the field of hydroconversion of a feedstock full of impurities, mainly comprising a heavy hydrocarbon fraction, in particular a heavy hydrocarbon fraction containing at least 50% by weight, preferably at least 80% by weight, of a portion with a boiling point of at least 300° C., and lower proportions of pyrolysis oils of plastics and / or pyrolysis oils of solid recovery fuels (SRF). The heavy hydrocarbon fraction may be crude oil or may be obtained from distillation and / or refining, typically atmospheric residue, which is the residue from atmospheric and / or vacuum distillation of 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 with a boiling point of at least 450° C.

[0002] In particular, the present invention relates to a process for the hydroconversion of such mixed feedstocks, comprising at least one hydroconversion step, preferably two successive hydroconversion steps, using one or more reactors operating in ebullated beds or in ebullated-entrained hybrid beds, aimed at producing higher quality, lower boiling point materials, e.g. for the production of fuels or for the production of chemicals, while at the same time allowing the removal of impurities from the plastic pyrolysis oil and / or SRF pyrolysis oil. [Background technology]

[0003] Over the past few years, the fuel and chemical industries have seen the emergence of methods to incorporate products other than traditional petroleum products, for example products of renewable origin, such as plant or animal oils or oils from waste materials, such as plastics or used oils, in addition to or as a replacement for products of fossil origin.

[0004] In particular, plastics obtained from the collection and sorting industry can undergo a process of pyrolysis to obtain, among other things, pyrolysis oils, which are generally incinerated to generate electricity and / or used as fuel in industrial or municipal heating boilers.

[0005] Solid recovered fuels (SRFs), also called refuse-derived fuels (RDFs), are solid non-hazardous waste materials prepared for energy recovery, whether they originate from household waste and similar waste materials, waste from economic activity or construction and demolition waste. SRF is generally a mixture of any combustible waste, e.g. used tyres, food by-products (fats, animal meals etc.), viscose and wood waste, light debris obtained from shredders (e.g. used vehicles, electrical and electronic equipment (WEEE), household and commercial waste, residues from recycling of different types of waste, including certain municipal waste, plastic waste, textiles or wood etc. SRF generally contains plastic waste. Currently, SRF are mainly upgraded for energy. They can be used directly as a replacement for fossil fuels in co-combustion plants (coal and lignite power plants, cement plants, lime kilns) or household waste incineration units, or indirectly in pyrolysis units dedicated for energy upgrading: SRF pyrolysis oil is thus generally combusted to generate electricity or further used as fuel in boilers for industrial or urban heating.

[0006] Plastic pyrolysis oils and SRF pyrolysis oils can also be upgraded via refinery processing to produce fuels, e.g., gasoline or diesel, and / or chemicals, e.g., olefins, for the production of various polymers in the chemical industry.

[0007] However, this and other routes for the upgrading of SRF pyrolysis oils are faced with challenges posed by the specific composition of these oils and in particular the impurities they contain, which are themselves related to the diversity of the components of the plastic waste or SRF.

[0008] Specifically, plastic waste or SRF is generally a mixture of several polymers, such as polyethylene, polypropylene, polyethylene terephthalate, polyvinyl chloride and polystyrene. Furthermore, depending on the application, the plastics may contain other compounds in addition to the polymers, such as plasticizers, pigments, dyes or residues of polymerization catalysts, as well as other highly diverse organic or inorganic impurities originating from the separation operations in the sorting centers, the selectivity of which may not be complete.

[0009] The oils obtained from plastic pyrolysis or SRF pyrolysis thus generally contain many diolefins and impurities, in particular metals, silicon or also halogenated compounds, especially chlorine-based compounds, heteroelements such as sulfur, oxygen and nitrogen, insoluble matter, often in high and sometimes incompatible contents with certain refining units, for example fixed bed hydrotreating units.

[0010] The processing of these oils can present operability problems, especially problems of corrosion, coking or catalyst deactivation, or also problems of incompatibility in the application of the target polymer. For example, the presence of diolefins often leads to problems of instability of the pyrolysis oil, characterized by the formation of gums. Gums and insolubles sometimes present in pyrolysis oils can cause clogging problems in equipment.

[0011] In patent application WO 02 / 04336, for example, a very general and relatively complex overall process for the recycling of plastic waste is provided, ranging from the actual step of pyrolysis of the plastic waste to a steam cracking step, which makes it possible to obtain products that are highly upgradeable in the field of petrochemistry, such as olefins and aromatics. This process includes, inter alia, a step of hydrocracking, preferably in a fixed bed, of the liquid phase obtained directly from the pyrolysis.

[0012] Patent applications (Patent Documents 2-4) describe methods for the treatment of plastic pyrolysis oil, which include, inter alia, a step of selective hydrogenation of plastic pyrolysis and a step of fixed-bed hydrotreating of the hydrogenated effluent. The naphtha fraction obtained from the specific separation of the hydrotreated effluent with water and the subsequent fractionation of the separated hydrocarbon stream can be sent to a steam cracker or used as a fuel base. According to patent applications (Patent Documents 3 and 4), the method incorporates one or two steps of hydrocracking in a fixed bed after the hydrotreating step, minimizing the yield of heavy fractions and maximizing the yield of naphtha fractions by hydrocracking at least partially converting the heavy fractions to naphtha fractions, which are the fractions generally supported in steam cracking units.

[0013] Due to the content of impurities in plastic pyrolysis oils, especially when they contain a large amount of impurities, deactivation of the catalyst of hydrotreating units operated in fixed beds may be observed, which shortens the cycle time.In fact, the main limitation of fixed bed units is the fact that the units need to be shut down to replace the catalyst.In addition, plastic pyrolysis oils, especially those containing a large amount of diolefins and impurities, may cause clogging problems, especially in preheating furnaces, feed / effluent exchangers or on the bed head of fixed bed catalytic reactors.

[0014] The unpublished patent application FR 20 / 09750 describes a method for treating plastic pyrolysis oils and / or SRF pyrolysis oils, which comprises, inter alia, ebullated, entrained and / or moving bed hydroconversion of an optionally prehydrogenated feedstock. The feedstock contains a minimum of 50 wt. % plastic pyrolysis oils and / or SRF pyrolysis oils, and preferably consists of plastic pyrolysis oils and / or SRF pyrolysis oils. After successive steps of separation with water, fractionation of the separated hydrocarbon-based stream, hydrotreatment of the 385° C.-fraction and fractionation of the hydrotreated stream, a liquid effluent suitable for a steam cracking unit is obtained. The use of ebullated, entrained and / or moving bed hydroconversion steps allows long hydroconversion unit cycle times as a result of the conventional use in this type of unit of a system for adding fresh catalyst and withdrawing used catalyst without shutting down the unit. This compensates for catalyst deactivation, which may be caused by impurities in the feed, unlike in fixed bed reactors where plugging of the catalyst bed is an issue. Additionally, this hydroconversion step upstream of hydroprocessing allows for longer hydroprocessing unit cycle times on the strength of the hydroprocessing reactions carried out in part in the upstream hydroconversion unit, and allows for easier hydroprocessing due to the conversion of at least a portion of the heavy compounds to lighter compounds during hydroconversion.

[0015] Unpublished patent application FR 21 / 04873 describes a process for treating plastic pyrolysis oils and / or SRF pyrolysis oils which is similar to the process of patent application FR 20 / 09750, in which, inter alia, there is no separation step between the hydroconversion and hydrotreatment steps.

[0016] Unpublished patent application FR 21 / 04874 describes a method for the co-processing of plastic pyrolysis oil with a feedstock from a renewable source, such as vegetable oil, similar to the method of patent application 21 / 04873, in which the plastic pyrolysis oil is optionally pre-hydrogenated and sent to a hydrodemetallization step, and the demetallized effluent is then sent to a hydrotreating step. The hydrodemetallization and hydrotreating steps may be carried out in an ebullated bed. The feedstock from a renewable source is fed to the hydrogenation step, and / or the hydrodemetallization step and / or the hydrotreating step. [Prior art documents] [Patent documents]

[0017] [Patent Document 1] International Publication No. 2018 / 055555 [Patent Document 2] French Patent Application Publication No. 3107530 (Patent Publication No. 2023-514896) [Patent Document 3] French Patent Application Publication No. 3113060 (Patent Publication No. 2023-535638) [Patent Document 4] French Patent Application Publication No. 3113061 (Patent Publication No. 2023-535637) Summary of the Invention [Means for solving the problem]

[0018] (Objectives and Summary of the Invention) The present invention is in the field of upgrading heavy feedstocks, e.g. petroleum residuals, which generally contain high levels of impurities such as metals, sulfur, nitrogen, Conradson carbon and asphaltenes and are difficult to upgrade, and converting them into lighter products that can be upgraded as fuels, e.g. to produce gasoline or gas oil, or raw materials for the petrochemical industry.

[0019] The inventors have demonstrated in a surprising way that it is possible to incorporate smaller proportions of impurity-filled plastic pyrolysis oil and / or SRF pyrolysis oil into fossil-based heavy hydrocarbon feedstocks, typically vacuum residues, which are customarily processed in ebullated bed or ebullated-entrained hybrid bed hydroconversion processes, thus improving the production of fuel-based and / or other upgradeable hydrocarbons, while at the same time removing the impurities, e.g. silicon, originally present in the pyrolysis oil in the supported catalyst of the hydroconversion process, thus allowing easier processing of the products in downstream processes, e.g. fixed bed hydroprocessing, while maintaining good stability of the unconverted portion.

[0020] The invention therefore proposes a method for the hydroconversion in an ebullated or ebullated-entrained hybrid bed of fossil-based heavy hydrocarbon feedstocks, in particular of vacuum residue type, said feedstocks containing smaller fractions of plastic pyrolysis oils and / or SRF pyrolysis oils, thus allowing the production of fuel-based and other upgradeable hydrocarbons and therefore the upgrading of said fractions.

[0021] Therefore, in order to overcome the problems of the prior art presented above and to achieve at least one of the above mentioned objectives, inter alia, the present invention proposes, according to a first aspect, a method for hydroconversion of a feedstock comprising a fraction of plastic pyrolysis oil and / or solid recovered fuel pyrolysis oil and a fossil-based hydrocarbon heavy fraction, containing at least 50% by weight of a portion with 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 method comprising: (a) conditioning and introducing the feedstock into a first hydroconversion section comprising at least a first ebullated bed or ebullated-entrained hybrid bed hydroconversion reactor containing a first porous supported hydroconversion catalyst; (b) a first step of hydroconversion of said feedstock in said first hydroconversion section in the presence of hydrogen; obtaining a first hydroconverted effluent; (c) optionally separating some or all of said first effluent from step (b) to form at least one heavy fraction boiling primarily at a temperature of 350° C. or greater; (d) an optional second hydroconversion step; hydroconverting a part or all of the first effluent from step (b) or the heavy fraction from optional step (c) in a second hydroconversion section comprising at least a second ebullated bed or ebullated-entrained hybrid bed hydroconversion reactor, said second hydroconversion reactor comprising a second porous supported catalyst and operating in the presence of hydrogen; producing a second hydroconverted effluent; Step (b) and optional step (d) are carried out at an absolute pressure of 2 MPa to 38 MPa, at a temperature of 300° C. to 550° C., and at a space velocity of 0.05 h -1 ~10h -1 and the associated amount of hydrogen is 50 Nm 3 / m 3 ~5000Nm 3 / m 3 That is, (e) fractionating all or a portion of the first hydroconverted effluent from step (b) or the second hydroconverted effluent from step (d) in a fractionation section; producing at least one heavy liquid product predominantly boiling at a temperature greater than or equal to 350° C.; the heavy liquid product containing a residual fraction boiling at a temperature greater than or equal to 540° C.

[0022] According to one or more implementations of the present invention, in step (a), the pyrolysis oil fraction and the heavy hydrocarbon fraction of the feedstock are premixed before being introduced into the at least one first hydroconversion reactor of the first hydroconversion section.

[0023] According to one or more implementations of the present invention, in step (a), the pyrolysis oil fraction and the heavy hydrocarbon fraction of the feedstock are introduced separately into the at least one first hydroconversion reactor of the first hydroconversion section.

[0024] According to one or more implementations of the present invention, step (a) comprises preheating the heavy hydrocarbon fraction, preferably to a temperature of from 280° C. to 450° C., and optionally preheating the pyrolysis oil fraction, before the feedstock is introduced into the first hydroconversion reactor of the first hydroconversion section.

[0025] According to one or more implementations of the present 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 preferentially between 2% and 25% by weight of the feedstock, and even more preferentially between 3% and 20% by weight of the feedstock.

[0026] According to one or more implementations of the present invention, the feedstock is comprised of the pyrolysis oil fraction and the heavy hydrocarbon fraction, the pyrolysis oil fraction comprising 1 wt% to 45 wt%, preferably 2 wt% to 30 wt%, of the feedstock, and the heavy hydrocarbon fraction comprising 55 wt% to 99 wt%, preferably 70 wt% to 98 wt% of the feedstock.

[0027] According to one or more implementations of the present invention, the pyrolysis oil fraction is plastic pyrolysis oil.

[0028] According to one or more implementations of the invention, the heavy hydrocarbon fraction is selected from the list consisting of crude oil, atmospheric residue, atmospheric or vacuum residue obtained from atmospheric and / or vacuum distillation of crude oil or effluent originating from a thermal conversion, hydrotreating, hydrocracking or hydroconversion unit, aromatic fraction extracted from a unit for the manufacture of lubricating oils, deasphalted oil obtained from a deasphalting unit, asphalt obtained from a deasphalting unit, residual fraction obtained from direct coal liquefaction, vacuum distillate obtained from direct coal liquefaction, or mixtures thereof.

[0029] According to one or more implementations of the present invention, the heavy hydrocarbon fraction is a vacuum product, preferably derived from a primary fractionation of crude oil.

[0030] According to one or more implementations of the invention, the process includes a separation step (c) in which some or all of the first hydroconverted effluent from step (b) is separated to produce at least a heavy fraction boiling primarily at a temperature above 350° C., and the process includes a second step (d) of hydroconverting the heavy fraction.

[0031] According to one or more implementations of the present invention, the one or more hydroconversion reactors of the first hydroconversion section in step (b) and, optionally, in the hydroconversion step (d) are boiling-entrained hybrid bed reactors, and the method also includes the step of introducing a catalyst precursor into the feedstock, the catalyst precursor preferably comprising molybdenum 2-ethylhexanoate, followed by injection of the feedstock into the at least one first boiling-entrained hybrid bed reactor of the first hydroconversion section, such that a colloidal or molecular catalyst, preferably comprising molybdenum disulfide, is formed upon reaction of the feedstock with sulfur.

[0032] According to one or more implementations of the present invention, the first hydroconversion catalyst, and optionally the second hydroconversion catalyst, contain at least one non-noble Group VIII metal and at least one Group VIB metal and include an amorphous support, the non-noble Group VIII metal is selected from nickel and cobalt, and preferably is nickel, the Group VIB metal is selected from molybdenum and tungsten, and preferably is molybdenum, and the amorphous support is preferably alumina.

[0033] According to one or more embodiments of the present invention, step (b) and optional step (d) are carried out at a temperature between 405°C and 450°C.

[0034] According to one or more implementations of the invention, the optional intermediate separation step (c) is carried out in a separation section, said separation section and / or the fractionation section in step (e) comprising means for washing at least one separated fraction by contact with an aqueous solution.

[0035] According to one or more implementations of the invention, the process also comprises a step (f) of further processing the heavy liquid product from fractionation step (e) and / or one or more other products, said step (f) comprising at least one step selected from the list consisting of hydrotreating, steam cracking, fluid catalytic cracking, hydrocracking, deasphalting, lube oil extraction, preferably a fixed bed hydrotreating step (f2) in a hydrotreating section, said hydrotreating section preferably comprising at least one fixed bed reactor containing n catalyst beds, n being an integer equal to or greater than 1, each containing at least one hydrotreating catalyst, said hydrotreating section being fed with at least a portion of the liquid product from step e) and a gaseous stream comprising hydrogen to obtain a hydrotreated effluent.

[0036] According to a second aspect, the present invention relates to a product obtained via the process according to the invention.

[0037] According to one or more implementations, the product is a hydroconverted effluent obtained at the end of the first hydroconversion step (b) or the second hydroconversion step (d), comprising a liquid portion having a silicon content of less than or equal to 5 ppm by weight and / or an elemental chlorine content of less than or equal to 10 ppm by weight, relative to the total weight of said liquid portion of the effluent.

[0038] Other subjects and advantages of the present invention will become apparent on reading the following description of particular exemplary embodiments of the invention, given by way of non-limiting example, said description being made with reference to the accompanying drawings, in which: DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0039] (List of Drawings) FIG. 1 illustrates one embodiment of a hydroconversion process according to the present invention.

[0040] FIG. 2 illustrates another embodiment of a hydroconversion process according to the present invention.

[0041] In the drawings, the same reference numbers indicate the same or similar elements.

[0042] (Description of the embodiment) An embodiment of the method according to the present invention will now be described in detail. In the following detailed description, many specific details are disclosed to provide a deeper understanding of the method. However, it will be apparent to those skilled in the art that the method can be performed without these specific details. In other cases, well-known features are not described in detail to avoid unnecessarily complicating the description.

[0043] For a better understanding of the invention, a few definitions are given below.

[0044] In this description, the term "to comprise" is synonymous with (meaning the same thing as) "to include" and "to contain" and is inclusive or open-ended and does not exclude other elements not recited. The term "to comprise" is understood to include the exclusive closed term "to consist of."

[0045] In this description, the expression "between A and B" means that both limits of the interval (A, B) are included in the stated range of values, unless otherwise specified.

[0046] In the present invention, different value ranges of a given parameter may be used alone or in combination, for example, a preferred pressure value range may be combined with a more preferred temperature value range, or a preferred value range of one chemical compound or element may be combined with a more preferred value range of another chemical compound or element.

[0047] The term "hydroconversion" refers to a process in which the main objective is to reduce the boiling range of a feedstock containing at least 50% heavy hydrocarbon fractions with a boiling point of at least 300°C, even at least 450°C, in which a substantial portion of the feedstock is converted to products having a boiling range lower than that of the starting feedstock. Hydroconversion generally involves fragmenting larger hydrocarbon molecules to give smaller molecular fragments having a smaller number of carbon atoms and a higher hydrogen to carbon ratio. The reactions carried out during hydroconversion make it possible to reduce the size of the hydrocarbon molecules, which is done by breaking carbon-carbon bonds in the presence of hydrogen, saturating the broken bonds and aromatic rings. The mechanism by which hydroconversion is carried out typically involves the formation of hydrocarbon free radicals, mainly by thermal cracking, during fragmentation, followed by capping of the ends or fragments of the free radicals with hydrogen in the presence of active catalytic sites. Of course, other reactions typically associated with hydroprocessing may take place during the hydroconversion process, such as, inter alia, the removal of sulfur or nitrogen from the feedstock, or the saturation of olefins, as more broadly defined below.

[0048] The term "hydrotreating", commonly referred to as "HDT", refers to a milder operation whose main purpose is to remove impurities, such as sulfur, nitrogen, oxygen, halides and trace metals, from the feedstock and to saturate the olefins and / or stabilize the free radicals of the hydrocarbons by reacting them with hydrogen rather than with themselves. Its main purpose is not to change the boiling range of the feedstock. Hydrotreating therefore includes, among others, hydrodesulfurization (commonly known as "HDS"), hydrodenitrification (commonly known as "HDN") and hydrodemetalization (commonly known as "HDM") reactions, accompanied by hydrogenation, hydrodeoxygenation (commonly known as "HDO"), hydrodearomatization, hydroisomerization, hydrodealkylation, hydrocracking or hydrodealkylation reactions and the reduction of Conradson carbon. Hydrotreating is most often carried out using a fixed bed reactor, although other reactors can be used for hydrotreating, for example, ebullated bed hydrotreating reactors.

[0049] The term "hydroconversion reactor" refers to any vessel whose primary purpose is the hydroconversion of a feedstock, e.g., cracking (i.e., reducing the boiling range) of the feedstock in the presence of hydrogen and a hydroconversion catalyst. Hydroconversion reactors typically include at least one inlet orifice through which the feedstock and hydrogen can be introduced and an outlet orifice through which upgraded materials can be withdrawn. Specifically, hydroconversion reactors are also characterized in that they have sufficient thermal energy to cause fragmentation of larger hydrocarbon molecules to give smaller molecules by pyrolysis. Examples of hydroconversion reactors include, but are not limited to, entrained bed reactors, also called slurry reactors (reactors having three phases (liquid, gas, solid); in such reactors the solid and liquid phases can behave as homogeneous phases), ebullated bed reactors (fluidized reactors having three phases), moving bed reactors (reactors having three phases with downward movement of solid catalyst and upward or downward flow of liquid and gas), and fixed bed reactors (reactors having three phases in which hydrogen typically flows co-currently with the liquid, but occasionally in some cases counter-currently, with the liquid feedstock trickling downward onto a fixed bed of supported catalyst).

[0050] The terms "hybrid bed" and "hybrid ebullated bed" and "ebullated-entrained hybrid bed" for hydroconversion reactors refer to ebullated bed hydroconversion reactors that contain an entrained catalyst in addition to a porous supported catalyst maintained in the ebullated bed reactor. In a similar manner, for hydroconversion processes, these terms therefore refer to processes that include a hybrid operation of ebullated and entrained beds in at least one identical hydroconversion reactor. A hybrid bed is necessarily a mixed bed of two types of catalysts of different particle sizes and / or densities, where one type of catalyst - the "porous supported catalyst" - is maintained in the reactor and the other type of catalyst - the "entrained catalyst", also commonly referred to as "slurry catalyst" - is entrained with the effluent (upgraded feedstock) from the reactor. In the present invention, the entrained catalyst is a colloidal or molecular catalyst, as defined below.

[0051] The terms "colloidal catalyst" and "colloidal dispersion catalyst" refer to catalyst particles that are colloidal, e.g., have a particle size 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 catalysts or molecular dispersion catalyst compounds.

[0052] The terms "molecular catalyst" and "molecularly dispersed catalyst" refer to catalyst compounds that are essentially "dissolved" in the feed, non-volatile liquid fraction, bottoms fraction, residue, or other feedstock or product in which the catalyst may be found, or that are completely dissociated from other catalyst compounds or molecules. They also refer to very small catalyst particles or sheets that contain only a few catalyst molecules bound together (e.g., 15 molecules or less).

[0053] The terms "porous supported catalyst", "solid supported catalyst" and "supported catalyst" refer to catalysts typically used in conventional ebullated bed and fixed bed hydroconversion systems, including catalysts designed primarily for hydrocracking or hydrodemetallization and catalysts designed primarily for hydrotreating. Such catalysts typically contain (I) a catalyst support having a large surface area and numerous interconnected channels or pores, and (ii) fine particles of active catalyst, such as sulfides of cobalt, nickel, tungsten or molybdenum, or mixed sulfides of these elements (e.g., NiMo, CoMo, etc.), dispersed in the pores. Supported catalysts are usually produced in the form of cylindrical extrudates (pellets) or spherical solids, although other forms are possible.

[0054] In the following text, the term "pyrolysis oil" refers to the oil obtained from the pyrolysis of plastics and / or SRF, unless otherwise stated, and for the sake of brevity, the term "heavy hydrocarbon fraction" of the feedstock refers to the fossil-based heavy hydrocarbon fraction, unless otherwise stated.

[0055] The method according to the invention and its functioning are explained in more detail below, with particular reference being made to Figures 1 and 2, which are schematic representations of exemplary embodiments of the method according to the invention, for a better understanding of the invention, without, however, being limited to these examples.

[0056] The subject of the present invention is to propose a method for the hydroconversion of a feedstock comprising a pyrolysis oil fraction (102) of plastics and / or SRF and a heavy hydrocarbon fraction (101) of fossil origin, containing at least 50% by weight of a portion 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 method comprising the following steps: (a) conditioning the feedstock and introducing it into a first hydroconversion section (20), which section includes at least a first ebullated bed or ebullated-entrained hybrid bed hydroconversion reactor, which reactor contains a first porous supported hydroconversion catalyst; (b) a first step of hydroconversion of said feedstock in said first hydroconversion section in the presence of hydrogen; obtaining a first hydroconverted effluent; (c) optionally separating some or all of said first effluent from step (b) to form at least one heavy fraction boiling primarily at a temperature of 350° C. or greater; (d) an optional second hydroconversion step; in a second hydroconversion section, said first effluent from step (b) or optionally a part or all of said heavy fraction from step (c) are hydroconverted; said section comprises at least a second ebullated bed or ebullated-entrained hybrid bed hydroconversion reactor; said second hydroconversion reactor comprises a second porous supported catalyst and is operated in the presence of hydrogen; producing a second hydroconverted effluent; Step (b) and optional step (d) are carried out at an absolute pressure of 2 MPa to 38 MPa, at a temperature of 300° C. to 550° C., and at a space velocity of 0.05 h -1 ~10h -1 and the amount of hydrogen is 50 Nm 3 / m 3 ~5000Nm 3 / m 3 That is, (e) fractionating all or a portion of the first hydroconverted effluent from step (b) or the second hydroconverted effluent from step (d) in a fractionation section (30); producing at least one heavy liquid product predominantly boiling at a temperature above 350° C., said heavy liquid product containing a residual fraction boiling at a temperature above 540° C.

[0057] (Feed material) According to an essential aspect of the invention, the feedstock comprises mainly a fossil-based heavy hydrocarbon fraction and a lesser fraction of plastic pyrolysis oil and / or SRF pyrolysis oil.

[0058] According to a preferred embodiment of the invention, the feedstock is composed of said lighter fractions of plastic pyrolysis oil and / or SRF pyrolysis oil and a fossil-based heavy hydrocarbon fraction.

[0059] The process according to the invention is therefore specialized for the hydroconversion of mixtures of low content plastic pyrolysis oils and / or SRF pyrolysis oils with heavy fossil-based hydrocarbon fractions.

[0060] The plastic pyrolysis oil and / or SRF pyrolysis oil fraction 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 preferentially between 2% and 30% by weight of the feedstock, even more preferentially between 2% and 25% by weight of the feedstock, even more preferentially between 3% and 20% by weight of the feedstock, even more preferably between 5% and 20% by weight of the feedstock, or even more preferentially between 5% and 15% by weight of the feedstock.

[0061] The feedstock may consist only of these two fractions: the pyrolysis oil fraction and the heavy hydrocarbon fraction, the sum of which forms 100% by weight of the feedstock. The heavy hydrocarbon fraction, preferably when the feedstock consists of said heavy hydrocarbon fraction and the pyrolysis oil fraction, may constitute 55% to 99% by weight of the feedstock, preferably 70% to 98% by weight of the feedstock, more preferentially 75% to 98% by weight of the feedstock, even more preferentially 80% to 97% by weight of the feedstock, even more preferably 80% to 95% by weight of the feedstock, or even 85% to 95% by weight of the feedstock.

[0062] According to the invention, "plastic pyrolysis oil or SRF pyrolysis oil" is an oil, advantageously in liquid form at room temperature, obtained from the pyrolysis of plastics, preferably plastic waste, especially originating from collection and sorting channels or from the pyrolysis of SRF. It comprises in particular a mixture of hydrocarbon compounds, especially paraffins, olefins, naphthenes and aromatics. The boiling point of at least 80% by weight of these hydrocarbon compounds is preferably below 700° C., preferably below 550° C. In particular, depending on the origin of the pyrolysis oil, said oil may comprise up to 70% by weight of paraffins, up to 90% by weight of olefins and up to 90% by weight of aromatics, the sum of paraffins, olefins and aromatics being understood to be equal to 100% by weight of hydrocarbon compounds.

[0063] The density of pyrolysis oil is generally less than 0.75 g / cm3 at 15°C according to the method of ASTM D4052. 3 ~0.99g / cm 3 , preferably 0.75 g / cm 3 ~0.95g / cm 3 It is.

[0064] Pyrolysis oils may contain, and usually contain, impurities such as metals, especially iron, silicon or halogenated compounds, especially chlorinated compounds. These impurities may be present in high concentrations in pyrolysis oils, for example up to 500 ppm by weight, or even up to 1000 ppm by weight, or even up to 5000 ppm by weight of halogen elements (e.g. chlorine) provided by halogenated compounds (e.g. chlorinated compounds), and up to 2500 ppm by weight, or even up to 10,000 ppm by weight of metallic or semimetallic elements. Alkali metals, alkaline earth metals, transition metals, post-transition metals and metalloids may be likened to contaminants of metallic nature and are called metals or metallic or semimetallic elements. Pyrolysis oils may contain up to 200 ppm by weight, or even up to 1000 ppm by weight of silicon, and up to 15 ppm by weight, or even up to 100 ppm by weight of iron. The pyrolysis oil may also contain other impurities, such as those provided by heteroelements, in particular sulfur compounds, oxygen compounds and / or nitrogen compounds, generally in a content of less than 20,000 ppm by weight of heteroelements, preferably less than 10,000 ppm by weight of heteroelements.

[0065] The process according to the invention is particularly suitable for processing pyrolysis oil full of impurities in combination with a heavy hydrocarbon feedstock as defined in more detail below. The term "full of impurities" means that the pyrolysis oil has the following properties: the content of aromatic compounds is between 0 and 90% by weight, often between 20% and 90% by weight, it may be between 50% and 90% by weight; the content of halogenated compounds is between 2 ppm and 5000 ppm by weight, often between 200 ppm and 5000 ppm by weight, it may be between 500 ppm and 5000 ppm by weight; the content of metal elements is between 10 ppm and 10,000 ppm by weight, often between 2000 ppm and 10,000 ppm by weight, it may be between 2250 ppm and 5000 ppm by weight; the metal element comprises iron element, the content being 0 ppm to 100 ppm by weight, often 10 ppm to 100 ppm by weight, which may be 15 ppm to 100 ppm by weight; The content of silicon element is 0 ppm by weight to 1000 ppm by weight, often 50 ppm by weight to 1000 ppm by weight, even 80 ppm by weight or 100 ppm by weight to 1000 ppm by weight, it may be 200 ppm by weight to 1000 ppm by weight.

[0066] The process according to the invention is particularly suitable for processing pyrolysis oils containing a large amount of impurities in combination with heavy hydrocarbon feedstocks as defined in detail below. The term "containing a large amount of impurities" means that the pyrolysis oil has the following characteristics: - the content of aromatic compounds is between 350% and 70% by weight; - the content of halogenated compounds is between 500 ppm and 5000 ppm by weight; - the content of metal elements is 300 ppm by weight to 5000 ppm by weight; - the metal element includes an iron element, and the content is 15 ppm by weight to 100 ppm by weight; The content of silicon element is 200 ppm by weight to 1000 ppm by weight.

[0067] The pyrolysis oils of SRF and / or plastics may be obtained from thermal or catalytic pyrolysis processes or may alternatively be prepared by hydropyrolysis (pyrolysis in the presence of a catalyst and hydrogen).

[0068] The fossil-based heavy hydrocarbon fraction of the feedstock for the process according to the invention is a heavy hydrocarbon fraction containing at least 50% by weight, preferably at least 80% by weight, of moieties having a boiling point of at least 300° C., preferably at least 350° C., even more preferably at least 375° C.

[0069] This heavy hydrocarbon fraction of the feedstock may be crude oil or may originate from the refining of crude oil in a refinery or the processing of another fossil hydrocarbon source.

[0070] The heavy hydrocarbon fraction of the feedstock may be crude oil, atmospheric resid, or may comprise or consist of atmospheric and / or vacuum resid from atmospheric and / or vacuum distillation of crude oil.

[0071] The heavy hydrocarbon fraction of the feedstock may also consist of atmospheric and / or vacuum residues obtained from atmospheric and / or vacuum distillation of effluents originating from thermal conversion, hydrotreating, hydrocracking and / or hydroconversion units.

[0072] Preferably, the heavy hydrocarbon fraction of the feedstock is a heavy hydrocarbon fraction containing at least 50 wt. % or even at least 80 wt. % of moieties having a boiling point of at least 450° C., preferably at least 500° C., even more preferably at least 540° C., e.g., a vacuum residue.

[0073] Advantageously, the heavy hydrocarbon fraction of the feedstock is composed of one or more vacuum residues, which can be directly from crude oil or from other refinery units, such as, inter alia, residual hydrotreating, residual hydrocracking or residual visbreaking. Preferably, the vacuum residue is a vacuum residue from a vacuum distillation column of the first (straight-run (SR)) fraction of crude oil.

[0074] The heavy hydrocarbon fraction of the feedstock may consist of aromatic fractions extracted from lubricant oil producing units, deasphalting oil from a deasphalting unit, also known as DAO (deasphalting unit raffinates), and asphalt from a deasphalting unit (deasphalting unit residue).

[0075] The heavy hydrocarbon fraction of the feedstock may consist of settling oil or recycle oil (typically having a boiling range of 360° C. to 550° C.), for example FCC fluidized bed catalytic cracking effluents such as heavy cycle oil (HCO) or slurry oil (SLO).

[0076] The heavy hydrocarbon fraction of the feedstock may be a residual fraction from direct coal liquefaction (e.g., atmospheric and / or vacuum residue from an H-Coal® process) or a vacuum distillate from direct coal liquefaction, e.g., an H-Coal® process.

[0077] All these fractions of fossil origin can be used, alone or as mixtures, to constitute the heavy hydrocarbon fraction of the feedstock to be treated according to the present invention.

[0078] According to one or more implementations, the heavy hydrocarbon fraction may comprise or consist of at least one of the following feedstocks, either alone or in mixture: crude oil, atmospheric residua, atmospheric or vacuum residue from atmospheric or vacuum distillation of crude oil (preferably the first fraction of crude oil), atmospheric or vacuum residue from atmospheric or vacuum distillation obtained via a direct coal liquefaction process, preferably vacuum residue from vacuum distillation of crude oil (preferably the first fraction of crude oil).

[0079] The heavy hydrocarbon fraction of the feedstock treated according to the present invention contains impurities such as sulfur and nitrogen. It may also contain impurities such as metals, Conradson carbon and asphaltenes, particularly C7 asphaltenes, which are insoluble in heptane.

[0080] The metal content may be 20 ppm by weight or more, preferably 100 ppm by weight or more.

[0081] The sulfur content may be 0.1% by weight or more, further 0.5% by weight or more, or 1% by weight or more, and may be 2% by weight or more.

[0082] The nitrogen content is usually from 1 ppm to 8000 ppm by weight, more usually from 200 ppm to 8000 ppm by weight, for example from 2000 ppm to 8000 ppm by weight.

[0083] The content of C7 asphaltenes (compounds insoluble in heptane according to the standard ASTM D6560 and also corresponding to the standard NF T60-115) can range as low as 1% by weight and is often greater than 3% by weight (excluding the heavy hydrocarbon fractions essentially containing DAO). C7 asphaltenes are compounds known to inhibit the conversion of the residual fractions, both by their ability to form heavy hydrocarbon residues, commonly known as coke, and by their tendency to give rise to sediments that significantly limit the operability of hydrotreating and hydroconversion units.

[0084] The Conradson carbon content may be 3% by weight or more, or even as low as 5% by weight. The Conradson carbon content is defined by standard ASTM D482 and represents a well-known assessment to those skilled in the art of the amount of carbon residue generated after pyrolysis under standard conditions of temperature and pressure.

[0085] These metal, sulfur, nitrogen, asphaltene and Conradson carbon contents of the heavy hydrocarbon fraction are expressed as weight percent of the total weight of the heavy hydrocarbon fraction of the feedstock.

[0086] According to one or more implementations, the feedstock for the process according to the invention may contain low contents, typically between 1% and 20% by weight, or even between 1% and 10% or 5% by weight of the feedstock, of plant and / or animal oil or fat fractions and / or hydrocarbon fractions obtained from processes for the thermal and / or catalytic conversion of lignocellulosic biomass, e.g. oils resulting from various liquefaction processes, e.g. hydrothermal liquefaction or pyrolysis of lignocellulosic biomass, which are then co-processed with plastic pyrolysis oil and / or SRF pyrolysis oil and fossil-based heavy hydrocarbon fractions.

[0087] The fats and oils of vegetable and / or animal origin contain triglycerides and / or free fatty acids and / or esters. The vegetable oils, which may be crude or fully or partially refined, may advantageously be obtained from the following plants, this list being non-limiting: rapeseed, sunflower, soybean, palm, palm kernel, olive, coconut, jatropha (physic nut in French), castor oil plant, cotton, groundnut, flax or seaweed. Algal oils and fish oils are also relevant. The fats and oils of vegetable and / or animal origin may be waste fats, for example waste cooking oils. The animal fats may be chosen from pig fat or fats composed of residues obtained from the food industry or from the catering industry.

[0088] The term "lignocellulosic biomass" refers to compounds derived from plants or their by-products and includes components selected from the group formed by cellulose, hemicellulose (carbohydrate polymers) and / or lignin (aromatic polymer).

[0089] According to one or more implementations, the feedstock for the process according to the invention does not comprise plant and / or animal oil or fat fractions, or hydrocarbon fractions obtained from processes for the thermal and / or catalytic conversion of lignocellulosic biomass, such as biomass pyrolysis oil.

[0090] (a) conditioning and injecting a feedstock into a first hydroconversion reactor The process according to the invention comprises step (a) of conditioning and introducing a feedstock into a first hydroconversion section (20), which comprises at least a first ebullated bed or hybrid bed reactor, which reactor contains a first porous supported hydroconversion catalyst.

[0091] The term "conditioning of the feedstock" means bringing said feedstock into a state suitable for the hydroconversion step b), in particular bringing it under temperature and pressure conditions suitable for hydroconversion in a first hydroconversion reactor, optionally after mixing the plastic pyrolysis oil and / or SRF pyrolysis oil fraction and the heavy hydrocarbon fraction, into which the feedstock is introduced and optionally removing solid particles from the plastic pyrolysis oil and / or SRF pyrolysis oil fraction (by filtration, centrifugation, electrostatic separation, washing with aqueous solutions, adsorption, etc.).

[0092] In particular, the plastic pyrolysis oil and / or SRF pyrolysis oil fraction (102) can be premixed with the heavy hydrocarbon fraction of the feedstock (101) before entering the first hydroconversion reactor in the first hydroconversion step (b). In this case, the two fractions can be preheated to ensure that they are in a liquid state and are then mixed by any heating device known to those skilled in the art. Alternatively, only the heavy hydrocarbon fraction (101) can be heated, especially if the pyrolysis oil fraction is liquid at ambient temperature and pumpable. This mixing can be carried out in a dedicated vessel (10) in which the mixing can optionally be active (for example a pump with an impeller rotor or a propeller), as represented in FIG. 1, or directly by the connection of 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 technique well known to those skilled in the art.

[0093] By mixing the fractions, a more homogeneous feedstock (114) is introduced into the first hydroconversion reactor, which is advantageous for example for a better fluidization of the catalyst and for a better hydrodynamic functioning of the reactor in general, which may allow the use of common equipment, such as ovens, feedstock distributors, mixers for mixing hydrogen with the feedstock, such as T-mixer type, which may contribute to reducing the investment costs.

[0094] Another possibility is shown in Figure 2 and is the individual injection of the plastic pyrolysis oil and / or SRF pyrolysis oil fraction (102) and the heavy hydrocarbon fraction (101) into the first hydroconversion reactor in the first hydroconversion step (b). This mode of injection may be preferred in order to avoid any problems related to chemical incompatibility between the two fractions (e.g. risk of phase separation or asphaltene precipitation) or else to prevent possible accelerated fouling of the preheat oven (the high content of diolefins and olefins in the plastic pyrolysis oil and / or SRF pyrolysis oil can lead to the formation of gums).

[0095] According to these two alternative embodiments, i.e. mixing or not mixing the fractions before their introduction into the first hydroconversion reactor, the feedstock, in particular the heavy hydrocarbon fraction of the feedstock (101), is heated to a temperature suitable for hydroconversion in the first hydroconversion reactor, i.e. such a temperature advantageously reaches the target temperature in the first hydroconversion reactor. This will be referred to as the preheating step in the present description. It is pointed out that said target temperature in the hydroconversion reactor, i.e. the temperature during the hydroconversion step, is generally not the preheating temperature, which is customarily lower than the target temperature in the hydroconversion reactor.

[0096] The temperature at which preheating of the heavy hydrocarbon fraction is carried out is preferably between 280°C and 450°C, even more preferably between 300°C and 400°C, even more preferably between 320°C and 365°C.

[0097] This preheating may also comprise heating the pyrolysis oil fraction (102), especially if said fraction is injected separately from 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 injected separately from the heavy hydrocarbon fraction (101) into the first reactor, may be heated to a temperature between room temperature, for example between 15°C and 350°C, preferably between 100°C and 350°C, more preferentially between 100°C and 250°C, even more preferentially between 100°C and less than 230°C, or even between 150°C and less than 200°C.

[0098] In the case of a mixture of two fractions, preheating can be carried out after, before or during mixing.

[0099] According to one embodiment, in which preheating is carried out for fractions (101) and (102) individually and fractions (101) and (102) are then mixed, fraction (102) of plastic pyrolysis oil and / or SRF pyrolysis oil is preheated to a lower temperature than fraction (101) of heavy hydrocarbons, so as to limit the formation of gums and / or coking of preheating equipment (e.g. 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 fraction (102) of plastic pyrolysis oil and / or SRF pyrolysis oil is preferably below 230°C, preferably below 200°C, more preferentially below 175°C and highly preferably below 100°C. According to this embodiment, the heavy fraction (101) may be preheated to a temperature between 280°C and 450°C, even more preferably between 300°C and 400°C, even more preferably between 320°C and 365°C, before being mixed with the pyrolysis oil fraction (102).

[0100] According to another embodiment, in which the heavy hydrocarbon fraction (101) and the pyrolysis oil fraction (102) are mixed, the pyrolysis oil fraction (102) is indirectly heated by mixing it with the heavy hydrocarbon fraction (101) (i.e. heat exchange between the two fractions having different temperatures by placing them in contact), which can be preheated preferably to 280°C to 450°C, even more preferably to 300°C to 400°C, even more preferably to 320°C to 365°C, such that the target hydroconversion temperature is achieved in the first hydroconversion reactor.

[0101] According to yet another embodiment, it is the mixture of the heavy hydrocarbon fraction (101) and the pyrolysis oil fraction (102) that is preheated, advantageously using heating means as described below (for example furnaces, heat exchangers, etc.), preferably to a temperature between 280° C. and 450° C., even more preferably between 300° C. and 400° C., even more preferably between 320° C. and 365° C., so that the target hydroconversion temperature can be achieved in the first hydroconversion reactor.

[0102] According to one embodiment, preheating may involve heat exchange between the feedstock and a stream (not shown in the figure) containing preheated hydrogen and typically having a temperature between 350° C. and 560° C., e.g., about 500° C. or 540° C., such that the target hydroconversion temperature can be achieved in the first hydroconversion reactor.

[0103] Any means known to those skilled in the art capable of preheating the feedstock may be used. Use may be made of at least one oven, commonly known as a preheat oven, including, for example, at least one heated section and / or tube through which the feedstock flows, a mixer for mixing the feedstock with H2, any suitable type of heat exchanger, for example a tubular or spiral heat exchanger through which the feedstock flows, etc.

[0104] Before its introduction into the first hydroconversion reactor, the feedstock is subjected to a pressurization step to bring it to the pressure prevailing in the first hydroconversion reactor, for example by means of a suitable pump. This pressurization step is preferably carried out before the preheating step.

[0105] According to one or more embodiments, the plastic pyrolysis oil and / or SRF pyrolysis oil fraction (102) may first undergo a filtration step and / or a centrifugation step and / or an electrostatic separation step and / or a washing step and / or an adsorption step using an aqueous solution in order to remove impurities that may be naturally present in the plastic pyrolysis oil and / or the SRF pyrolysis oil, in particular to remove solid particles.

[0106] 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 the entrained catalyst precursor (104) as depicted in FIGS. 1 and 2, such that the entrained catalyst comprises colloidal or molecular catalyst dispersed in the feedstock, particularly when the entrained catalyst is formed by reaction with sulfur.

[0107] The entrained catalyst precursor (104) may be mixed with the pyrolysis oil fraction (102) before it is mixed with the heavy hydrocarbon fraction (101) (not shown in FIG. 1 ) or with the feedstock (114) (not shown in FIG. 2 ) formed by mixing said fractions (101) and (102), in a manner similar to that described below for the mixture between the heavy hydrocarbon fraction (101) and the entrained catalyst precursor (104), except that the temperature for mixing the catalyst precursor with the pyrolysis oil fraction (102) is preferably below 230° C., or even below 200° C. (in any case, it is preferably carried out at a temperature below the temperature at which a substantial part of the catalyst precursor begins to decompose).

[0108] For the purposes of the present invention, it is specified that the catalyst precursor, optionally diluted, does not form part of the feedstock as defined above, the feedstock comprising a fraction of plastic pyrolysis oil and / or SRF pyrolysis oil and a heavy hydrocarbon fraction.

[0109] The entrained catalyst precursor may be selected from any metal catalyst precursor known to one of skill in the art that is capable of forming a colloidal or molecularly dispersed catalyst (i.e., an entrained catalyst) in the presence of hydrogen and / or H2S and / or any other sulfur source and that enables the hydroconversion of the feedstock after injection into the first hydroconversion reactor.

[0110] The catalyst precursor is advantageously an oil-soluble catalyst precursor containing at least one transition metal.

[0111] The catalyst precursor preferably comprises an oil-soluble organometallic compound or complex.

[0112] The catalyst precursor may comprise an oil-soluble organometallic or bimetallic compound or complex containing one or two of the following metals: Mo, Ni, V, Fe, Co or W, or a mixture of such compounds / complexes.

[0113] The decomposition temperature of the oil soluble catalyst precursor (the temperature below which the catalyst precursor is substantially chemically stable) is preferably within the range of 100°C to 350°C, more preferably within the range of 150°C to 300°C, and most preferably within the range of 175°C to 250°C.

[0114] The oil-soluble organometallic compound or complex is preferably selected from the group consisting of molybdenum 2-ethylhexanoate, molybdenum naphthanate, vanadium naphthanate, vanadium octanoate, molybdenum hexacarbonyl, vanadium hexacarbonyl, and iron pentacarbonyl. These compounds are non-limiting examples of oil-soluble catalyst precursors.

[0115] More preferably, the catalyst precursor comprises Mo, for example a compound selected from the group consisting of molybdenum 2-ethylhexanoate, molybdenum naphthanate and molybdenum hexacarbonyl.

[0116] A presently preferred catalyst precursor comprises or consists of molybdenum 2-ethylhexanoate (also commonly known as molybdenum octoate), which typically contains 15% by weight molybdenum and has a sufficiently high decomposition temperature or range to avoid significant thermal decomposition when mixed with heavy hydrocarbon fractions below 250° C.

[0117] One skilled in the art may select a mixing temperature profile that results in mixing of the selected precursors without significant thermal decomposition prior to the formation of the colloidal or molecular catalyst.

[0118] The catalyst precursor (104), preferably an oil soluble catalyst precursor, may be premixed with a diluent hydrocarbon stream to form a diluted precursor mixture, as described in US2005 / 0241991, US10822553 or US10941353 and recalled below.

[0119] The catalyst precursor (104) may be premixed with a diluent to form a diluted precursor mixture, said premixing being preferably carried out at a temperature below the temperature at which a substantial portion of the catalyst precursor begins to decompose, preferably at ambient temperature, for example between 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, even more preferably between 75°C and 100°C, advantageously for a period ranging from 1 second to 30 minutes.

[0120] Typically, the catalyst precursor diluent may be a hydrocarbon-based oil, with at least 50% by weight of the hydrocarbons having a boiling point between 180° C. and 540° C., relative to the total weight of the hydrocarbon-based oil. Examples of hydrocarbon-based diluents suitable for precursor dilution include, but are not limited to, vacuum gas oil, also known as VGO (typically having a boiling range between 360° C. and 524° C.), settling oil or recycled oil (typically having a boiling range between 360° C. and 550° C.), e.g., FCC fluidized bed catalytic cracking effluent, e.g., heavy cycle oil (HCO) or light cycle oil (LCO), pyrolysis oil from hydrocrackers, light gas oil (typically having a boiling range between 200° C. and 360° C.), atmospheric residue, vacuum residue (typically having a boiling range above 524° C.), deasphalted oil, and resin. The catalyst precursor diluent is preferably atmospheric residue, vacuum residue or VGO.

[0121] The diluted precursor may then be mixed with the heavy hydrocarbon fraction (101), preferably at ambient temperature, for example at a temperature between 15° C. and 300° C., advantageously for a period ranging from 1 second to 30 minutes, preferably from 1 second to 10 minutes, even more preferably from 2 seconds to 3 minutes. In this description, a mixing time (or residence time for mixing) of 1 second means instantaneous mixing.

[0122] The mass ratio of catalyst precursor (104) to hydrocarbon oil diluent is preferably within the range of about 1:500 to about 1:1, more preferably within the range of about 1:150 to about 1:2, and even more preferably within the range of about 1:100 to about 1:5 (e.g., 1:100, 1:50, 1:30, or 1:10).

[0123] It is preferable to ensure that the components are mixed, without mixing with a diluent, for a time sufficient to thoroughly / intimately mix the catalyst precursor with the heavy hydrocarbon fraction before the entrained catalyst is formed, however, long mixing times, e.g., 24 hours, can be prohibitively expensive for certain industrial operations.

[0124] Premixing the catalyst precursor (104) with a hydrocarbon-based diluent greatly facilitates complete and intimate mixing of the precursor with the heavy hydrocarbon fraction, especially in the relatively short time periods required to make large-scale industrial operations economically viable.

[0125] The diluted precursor is preferably combined with the heavy hydrocarbon fraction and mixed in a manner that disperses the catalyst precursor throughout the heavy fraction for a sufficient time such that the catalyst precursor is thoroughly / intimately mixed with the heavy hydrocarbon fraction. To obtain sufficient mixing prior to the formation of colloidal or molecular catalyst, the diluted precursor and the heavy fraction are more preferably mixed for a period within the range of 1 second to 10 minutes, even more preferably within the range of 2 seconds to 3 minutes. Increasing the vigor and / or shear energy of the mixing method generally reduces the time required to achieve a thorough / intimate mixture. Examples of mixing devices that may be used to effect thorough / intimate mixing of the catalyst precursor (104) and the heavy hydrocarbon feedstock (101) include, but are not limited to, high shear mixing, such as a pump equipped with an impeller rotor or propeller, multiple static in-line mixers, a combination of multiple static in-line mixers and high shear in-line mixers, a combination of multiple static in-line mixers and high shear in-line mixers, a combination of multiple static in-line mixers and high shear in-line mixers followed by recirculation pumping in a holding tank, a combination of the above devices followed by one or more multi-stage centrifugal pumping.

[0126] The heavy hydrocarbon fraction (101) and the diluted precursor are preferably mixed and conditioned at a temperature in the range of from 50° C. to 200° C., more preferably in the range of from 75° C. to 175° C. Preferably, the gauge pressure is from 0 MPa to 25 MPa, more preferably from 0.01 MPa to 5 MPa.

[0127] Under the operating conditions of the hydroconversion reactor in the hydroconversion step (b), the catalyst precursor (104) is completely decomposed and the precursor metal is combined with sulfur (e.g., dissolved H2S present in the feedstock, or H2S contained in the hydrogen recycled to the hydroconversion reactor, or sulfur from organic sulfur molecules present in the feedstock or possibly previously introduced into the feedstock) to provide the colloidal or molecular catalyst.

[0128] The concentration of the catalyst metal, preferably Mo, in the feedstock is preferably 5 ppm by weight to 500 ppm by weight, more preferably 10 ppm by weight to 300 ppm by weight, more preferably 10 ppm by weight to 175 ppm by weight, even more preferably 10 ppm by weight to 75 ppm by weight, and even more preferably 10 ppm by weight to 50 ppm by weight, based on the weight of the feedstock.

[0129] Preferably, the colloidal or molecular catalyst comprises or consists of molybdenum disulfide.

[0130] As mentioned above, the pyrolysis oil fraction (102) is introduced into the first hydroconversion reactor of the first hydroconversion section (20) and is mixed or not mixed with the heavy hydrocarbon fraction (101). However, the first hydroconversion step may comprise several hydroconversion reactors in series, and the pyrolysis oil fraction (102) may be placed in a hydroconversion reactor downstream of the first hydroconversion reactor of the first hydroconversion section (20) without departing from the context of the present invention.

[0131] ((b) First Hydroconversion Step) The feedstock, whether the fractions it is composed of are separated ((101) and (102)) or mixed ((114)) according to step (a), is introduced together with hydrogen (stream not represented) into a first hydroconversion reactor in a first hydroconversion section (20). Said first reactor contains a first porous supported hydroconversion catalyst.

[0132] The first hydroconversion step (b) is carried out under conditions that give a first hydroconverted effluent (105). The first hydroconverted effluent (105) contains the conversion products; in particular, the first effluent has a reduced content (relative to the feedstock) of hydrocarbons with 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 first hydroconverted effluent (105) may have a reduced content, relative to the feedstock, 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 feedstock. In particular, the first hydroconverted effluent (105) may advantageously have reduced contents of sulfur, metals, silicon, halogenated compounds (e.g., chlorine), nitrogen, Conradson carbon, and asphaltenes relative to the feedstock.

[0133] The content of silicon and / or halogenated compounds (e.g. chlorine) in the first hydroconverted effluent (105) obtained on conclusion of step b) is advantageously reduced relative to the content of the same impurities (i.e. silicon and / or halogenated compounds, e.g. chlorine) in the feedstock. Preferably, the first hydroconverted effluent (105) comprises a liquid fraction (PI+ fraction), which has: silicon: a 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 portion of the first hydroconverted effluent (105); and / or elemental chlorine; the content is 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 less than or equal to 1 ppm by weight, relative to the total weight of said liquid portion of the first hydroconverted effluent (105).

[0134] The absolute pressure when step (b) is preferably carried out is 2 MPa to 38 MPa, more preferentially 5 MPa to 25 MPa, and even more preferentially 6 MPa to 20 MPa, and the temperature at that time is 300°C to 550°C, more preferentially 350°C to 500°C, preferably 370°C to 450°C, and even more preferentially 405°C to 450°C, and further 410°C to 450°C.

[0135] The hourly space velocity (HSV) (relative to the volume of each reactor) is preferably 0.05 h -1 ~10h -1 The hourly space velocity (HSV), also referred to as the liquid hourly space velocity (LHSV), is defined herein as the ratio between the hourly volumetric flow rate of the liquid feedstock (sent to the hydroconversion process) and the volume of each hydroconversion reactor. According to a preferred implementation, the HSV is less than 0.1 h -1 ~10h -1 , and more preferentially 0.1h -1 ~5h -1 , and even more preferably 0.15h -1 ~2h -1 , and even more preferably 0.15h -1 ~1h -1 It is.

[0136] According to another implementation, the overall HSV, i.e. the flow rate of the liquid feedstock sent to step b), is 0.05 h 2 or less, relative to the volume of all reactors if several hydroconversion reactors are used in step b). -1 ~0.09h -1 It is.

[0137] The amount of hydrogen mixed with the feedstock is preferably 100% by volume (cubic metres (m 3 50 to 5000 standard cubic meters (Nm 3 ), preferably 100 Nm 3 / m 3 ~2000 Nm 3 / m 3 , highly preferably 200Nm 3 / m 3 ~1000Nm 3 / m 3 It is.

[0138] The first hydroconversion section (20) includes one or more ebullated or hybrid bed reactors containing at least one first supported hydroconversion catalyst, the reactors optionally being arranged in series and / or parallel, such that the at least one first supported hydroconversion catalyst is maintained within the reactor or reactors in this process. According to one or more embodiments of the invention, the first hydroconversion section (20) comprises one or more hydroconversion reactors, which may be in series and / or parallel, operated as ebullated beds as used for the H-Oil® process, for example as described in patents US 4 521 295 or US 4 495 060 or US 4 457 831 or US 4 354 852, 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” of the book “Catalysis by Transition Metal Sulphides” published by Technip in 2013. According to this or these embodiments, each reactor is operated as a fluidized bed, also known as an ebullated bed. Each reactor advantageously includes a recirculation pump, which makes it possible to maintain the porous supported solid catalyst as a boiling bed by continuous recycling of at least a portion of the liquid fraction withdrawn at the upper part of the reactor and reinjected at the lower part of the reactor.

[0139] The ebullated bed reactor preferably comprises at least one inlet orifice, in particular two inlet orifices in the case where the pyrolysis oil fraction (102) of the feedstock is introduced separately from the heavy hydrocarbon fraction (101), and an outlet orifice, the inlet orifice being located in or near the lower part of the reactor, through which the feedstock is introduced together with hydrogen, and the outlet orifice being located in or near the upper part of the reactor, through which the first hydroconverted effluent (105) is withdrawn. The reactor preferably also comprises an inlet and an outlet for a supported catalyst, as already described before, connected to the means for injecting and withdrawing the supported catalyst. The ebullated bed reactor also comprises an expanded catalyst zone, which comprises a porous supported catalyst. The ebullated bed reactor also comprises a lower zone free of supported catalyst and an upper zone free of supported catalyst, the lower zone being located below the expanded catalyst zone and the upper zone being located above the expanded catalyst zone. The feedstock in the ebullated bed reactor is continuously circulated from an upper zone free of supported catalyst to a lower zone free of supported catalyst by a recycle pipe in communication with the ebullated pump. A funnel-shaped recycle pan is preferably located in the upper part of the recycle pipe, through which the feedstock is sucked from the upper zone free of supported catalyst. Inside, the recycled feedstock is mixed with "fresh" feedstock and additional hydrogen gas.

[0140] 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 the Elements, which elements may or may not be deposited on a support. Use may be advantageously made of catalysts comprising an amorphous support, such as silica, alumina, silica-alumina, titanium dioxide or a combination of these structuring agents, highly preferably alumina.

[0141] The first supported catalyst may contain at least one non-noble Group VIII metal selected from nickel and cobalt, preferably nickel, and the Group VIII element is preferably used in combination with at least one Group VIB metal selected from molybdenum and tungsten; preferably the Group VIB metal is molybdenum.

[0142] In this description, the groups of chemical elements are given according to the CAS classification (CRC Handbook of Chemistry and Physics, published by CRC Press, edited by DR Lide, 81st edition, 2000-2001). For example, group VIII according to the CAS classification corresponds to the metals in columns 8, 9 and 10 according to the new IUPAC classification.

[0143] Advantageously, the first supported hydroconversion catalyst used in the first hydroconversion step (b) comprises an alumina support, at least one group VIII metal and at least one group VIB metal, the group VIII metal being selected from nickel and cobalt, preferably nickel, and the group VIB metal being selected from molybdenum and tungsten, preferably molybdenum. Preferably, the first supported hydroconversion catalyst comprises nickel as group VIII element and molybdenum as group VIB element.

[0144] The content of non-noble Group VIII metals, in particular nickel, advantageously ranges from 0.5% to 10% by weight, preferably from 1% to 6% by weight, expressed as the weight of metal oxide (in particular NiO), and the content of Group VIB metals, in particular molybdenum, advantageously ranges from 1% to 30% by weight, preferably from 4% to 20% by weight, expressed as the weight of metal oxide (in particular molybdenum trioxide MoO3). The metal contents are expressed as the percentage by weight of metal oxide relative to the weight of the catalyst.

[0145] This first supported catalyst is advantageously used in the form of extrudates or beads. The diameter of the beads is, for example, between 0.4 mm and 4.0 mm. The extrudates have, for example, a cylindrical diameter between 0.5 mm and 4.0 mm and a length between 1 mm and 5 mm. The extrudates may be bodies with different shapes, for example trilobal, tetralobal, which are regular or irregular, or other multilobal. Other forms of supported porous catalysts may be used. The size of these various forms of supported porous catalysts may be characterized by an equivalent diameter. The equivalent diameter is defined as six times the ratio of the volume of the particle to the external surface area of ​​the particle. The equivalent diameter of the supported porous catalysts used in the form of extrudates, beads or other forms is therefore between 0.4 mm and 4.4 mm. These catalysts are well known to those skilled in the art.

[0146] According to one or more embodiments of the present invention, the first hydroconversion section (20) comprises one or more hybrid bed reactors (i.e. boiling-entrained hybrid beds) containing at least one first supported hydroconversion catalyst maintained in the reactor and at least one entrained catalyst, which enters the reactor with the feedstock and leaves the reactor entrained with the effluent. In this case, the feedstock is injected into the first hydroconversion reactor after the introduction of the entrained catalyst precursor, as already described above in connection with step (a), and the colloidal or molecular catalyst, also known as dispersed, entrained or slurry catalyst, may be formed upstream of the hybrid bed hydroconversion reactor or in situ. These entrained catalysts are well known to those skilled in the art.

[0147] The hybrid bed reactor comprises a solid phase, a liquid hydrocarbon-based phase and a gaseous phase, the solid phase containing a porous supported catalyst in the form of an expanded bed, the liquid hydrocarbon-based phase containing a colloidal or molecular catalyst-containing feedstock dispersed therein, and the gaseous phase containing hydrogen.

[0148] The hybrid bed reactor is an ebullated bed hydroconversion reactor as described above, but in addition to the porous supported catalyst in the form of an expanded bed maintained within the reactor, it contains a molecular or colloidal catalyst entrained with the hydroconverted liquid effluent (105) and removed from the reactor.

[0149] According to one or more embodiments, the functioning of a hybrid bed hydroconversion reactor is based on the functioning of an ebullated bed reactor already described, with the further inclusion of a colloidal or molecular catalyst being dispersed throughout the feedstock in the hybrid bed reactor, which includes both an expanded catalyst zone and a supported catalyst-free zone, and is therefore available to stimulate upgrading reactions in what would otherwise constitute a catalyst-free zone in a conventional ebullated bed reactor.

[0150] The presence of colloidal or molecular catalyst in the hybrid bed reactor provides additional catalytic hydrogenation activity to both the expanded catalyst zone, the recycle pipe, and the lower and upper supported catalyst free zones. Capping of free radicals on the outside of the porous supported catalyst minimizes the formation of sediment and coke precursors that are often responsible for the deactivation of supported catalysts. This may allow a reduction in the amount of porous supported catalyst that would otherwise be required to carry out the desired hydroconversion reaction. This may also reduce the rate at which the porous supported catalyst needs to be withdrawn and replaced. The use of colloidal or molecular catalyst in the hybrid bed reactor may allow the hydroconversion to be carried out at a higher temperature than in the case of an ebullated bed reactor (only one or more supported catalysts, no entrained catalyst), while remaining within the temperature range given for step (b) above.

[0151] In one embodiment of the process according to the invention, a different first hydroconversion supported catalyst may be used in each reactor of the first hydroconversion section, with each reactor's specific supported catalyst being suited to the feedstock fed to that reactor. In one embodiment of the process according to the invention, several types of first supported catalysts are used in each reactor.

[0152] As is known, for example as described in patent FR3033797, the first hydroconversion supported catalyst, when worn out, may be partially replaced with a fresh supported catalyst, and / or a used supported catalyst but with a higher catalytic activity than the used supported catalyst to be replaced, and / or a regenerated supported catalyst, and / or an activity-recovered supported catalyst (a catalyst coming from an activity-recovery zone, in which most of the deposited metals are removed and then the used and activity-recovered catalyst is sent to a regeneration zone, in which the carbon and sulfur it contains are removed, thus increasing the activity of the catalyst), by removing the used supported catalyst, preferably at the bottom of the reactor, and introducing a replacement used catalyst either at the top or at the bottom of the reactor. This replacement of the used supported catalyst is preferably carried out at regular time intervals, preferably explosively or substantially continuously. This withdrawal and exchange is carried out by means of withdrawal and injection devices which advantageously allow the continuous functioning of this hydroconversion step.

[0153] This supported catalyst withdrawal / injection operating mode thus eliminates the need to shut down the unit to change spent catalyst, nor to increase the reaction temperature along the cycle to compensate for deactivation. Moreover, working under constant operating conditions allows for constant product yields and qualities along the cycle.

[0154] Also, due to the fact that the supported catalyst is kept stirred with significant liquid recycle, the pressure drop across the reactor remains low and constant, and the exothermicity of the reaction is quickly averaged across the catalyst bed, which is therefore substantially isothermal and does not require, for example, injection of cooling streams (quenching).

[0155] One of the essential aspects of the invention is the capacity of the ebullated bed or hybrid ebullated-entrained bed reactor to continue the conversion of the pyrolysis oil to lighter products, due to the combination of high temperature and the presence of a catalyst allowing the hydrogenation of unsaturated molecules (olefins or aromatics). The co-processing of the pyrolysis oil thus makes it possible to improve the yield of certain fractions, in particular the gasoline fraction, obtained in the hydroconverted effluent.

[0156] Another advantage of the present invention is the removal of impurities, such as silicon or metals, by supported catalysts in conjunction with the use of hydroconversion reactors operating in ebullated beds or ebullated-entrained hybrid beds for the co-processing of pyrolysis oil.This allows for the production of low-purity products, which can therefore be more easily processed in downstream processing methods, such as fixed-bed hydroprocessing methods.The advantage of ebullated beds or ebullated-entrained hybrid beds is that the supported catalysts can be continuously exchanged, and it is easy to compensate for more severe deactivation, especially in the case of pyrolysis oils with higher impurity content, by increasing the catalyst exchange as necessary.

[0157] According to one or more embodiments, when step (b) is carried out in one or more hybrid bed reactors, the feedstock or the entrained catalyst precursor may be premixed with an organic additive before the feedstock is introduced into the first hydroconversion reactor of the first hydroconversion section (20), in particular to minimize fouling of the equipment before hydroconversion in the one or more hybrid bed reactors. Without being bound by any theory, the organic additive, as a mixture with the feedstock, allows improved solubility of the entrained catalyst precursor in the feedstock, avoiding or reducing fouling, in particular fouling due to metal deposition in equipment upstream of the hydroconversion reactor, for example, in heating devices, and thus improving the dispersion of the entrained catalyst, thereby resulting in improved availability of metal active sites, promoting the hydrogenation of free radicals, which are precursors of coke and sediment, and resulting in a considerable reduction in fouling of the equipment. The organic additive is not a catalyst or a catalyst precursor (e.g., it does not contain a metal) and has at least one carboxylic acid group and / or at least one ester group and / or at least one acid anhydride group. It preferably contains at least 6, even at least 8 carbon atoms, more preferably at least 8 carbon atoms. According to one embodiment, it contains 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, and the molar ratio of the organic additive to the one or more active metals (e.g., Mo) of the catalyst precursor composition is from 0.1:1 to 20:1, preferably from 0.75:1 to 7:1, and even more preferably from 1:1 to 5:1.

[0158] (c) Optional Intermediate Separation Steps According to one or more preferred embodiments, the process according to the invention also comprises a separation step (c), which separates part or all of the first hydroconverted effluent (105) to give at least two fractions, one of which is a heavy fraction mainly boiling at a temperature above 350° C.

[0159] The one or more other fractions are one or more light middle fractions. The light fraction thus separated contains mainly gas (H2, HCl, H2S, NH3 and C1-C4), naphtha (or gasoline, fraction boiling at temperatures below 150°C), kerosene (or gas oil, fraction boiling at 150°C-250°C) and at least part of diesel (fraction boiling at 250°C-375°C). The light fraction may then be sent, at least in part, to a fractionation unit (not shown in the figure) where light gases are extracted from said light fraction, for example by passing through an expansion vessel. This fractionation unit may be that of the fractionation step (e), especially in the case where a second hydrogenation step (d) is carried out. The hydrogen gas thus recovered may be sent to purification and compression facilities, but may advantageously be recycled to the first hydroconversion step (b) and / or to the second hydroconversion step (d), if performed. The recovered hydrogen gas may also be used in other facilities of the refinery.

[0160] The optional separation step (c) is carried out in a separation section (not shown in the figures), which comprises any separation means known to those skilled in the art. Said separation section may comprise one or more expansion vessels arranged in series, and / or one or more steam stripping and / or hydrogen stripping columns, and / or atmospheric distillation columns, and / or vacuum distillation columns, and is preferably composed of a single expansion vessel, commonly known as a "hot separator". The separation section may also comprise means for scrubbing the light ends, mainly containing gas, by contact with an aqueous solution.

[0161] According to a preferred embodiment, the optional separation step (c) comprises a hot separator operated at a temperature of 300° C. or higher, even 350° C. or higher, 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 a subsequent separation of the gas phase from the hot separator, is advantageously placed in contact with water or an aqueous basic solution (for example a sodium hydroxide solution, one or more amine solutions) to at least partially remove the hydrogen chloride (HCl) and / or at least partially dissolve the ammonium chloride salts. The separation equipment or vessel may comprise, at the bottom, a zone for separate precipitation of the hydrocarbon fraction and the aqueous fraction containing the chloride salts, or else a column for scrubbing the gas by contacting it with water or an aqueous basic solution.

[0162] (d) Optional Second Hydroconversion Step According to one or more preferred embodiments (not shown in the figures), the process also comprises a second hydroconversion step of part or all of the first effluent (105) obtained from step (b) or of the heavy fraction optionally from step (c), the second hydroconversion step being carried out in the presence of hydrogen in at least one second ebullated or hybrid bed reactor containing a second porous supported catalyst. This second hydroconversion step is carried out so as to obtain a second hydroconverted effluent. Said second hydroconverted effluent advantageously contains a higher amount of conversion products than the first hydroconverted effluent (105), in particular with a lower content of hydrocarbons with a boiling point of at least 300° C., or at least 350° C., 375° C., 450° C., 500° C. or 540° C., depending on the nature of the feedstock. The second hydroconverted effluent may have a further reduced Conradson carbon residue relative to the first hydroconverted effluent (105), and in some cases further reduced amounts of sulfur, and / or nitrogen, and / or metals, and / or silicon, and / or halogenated compounds (e.g., chlorine) and / or asphaltenes.

[0163] In particular, the second hydroconverted effluent may advantageously have reduced contents of sulfur, metals, silicon, halogenated compounds (e.g., chlorine), nitrogen, Conradson carbon, and asphaltenes relative to the first hydroconverted effluent (105) and / or relative to the feedstock.

[0164] The content of silicon and / or halogenated compounds (e.g. chlorine) of the second hydroconverted effluent obtained on conclusion of step d) is advantageously reduced relative to the content of the same impurities (i.e. silicon and / or halogenated compounds, e.g. chlorine) contained in the first hydroconverted effluent (105) and / or in the feedstock.

[0165] Preferably, the second hydroconverted effluent comprises a liquid fraction (PI+ fraction) having: silicon; a 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 elemental chlorine; the content is 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 less than or equal to 1 ppm by weight, relative to the total weight of said liquid part of the second hydroconverted effluent.

[0166] The second hydroconversion step is carried out in a similar manner as described for the first hydroconversion step (b) and will not be repeated here, this applies in particular to the operating conditions, the equipment used and the porous supported hydroconversion catalyst used, except for the details mentioned below.

[0167] As with the first hydroconversion step (b), the second hydroconversion step is carried out in at least a second ebullated bed or hybrid bed reactor, preferably in one or more ebullated bed reactors if the first hydroconversion step is also carried out in one or more ebullated bed reactors, and preferably in one or more hybrid bed reactors if the first hydroconversion step is carried out in one or more hybrid bed reactors.

[0168] In this second hydroconversion step, the operating conditions may be similar or different to those in hydroconversion step (b), but the temperature still remains in the range of 405°C to 550°C, preferably 405°C to 500°C, more preferably 405°C to 450°C, and the amount of hydrogen introduced into the reactor still varies with the volume (m) of the liquid feedstock. 3 ) 50Nm 3 / m 3 ~5000Nm 3 / m 3 , preferably 100 Nm 3 / m 3 ~3000Nm 3 / m 3 , and even more preferably 200 Nm 3 / m 3 ~2000Nm 3 / m 3 The other pressure and HSV parameters are in the same ranges as described for the hydroconversion step (b).

[0169] The operating temperature in the second hydroconversion step (d) may be higher than the operating temperature in the first hydroconversion step (b). This allows for more complete conversion of the feedstock that has not yet been converted. Hydroconversion of the liquid product from the first hydroconversion step and conversion of the feedstock are enhanced, as are hydrotreating reactions such as hydrodesulfurization and hydrodenitrification, among others. Operating conditions are selected to minimize the formation of solids (e.g., coke).

[0170] 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 the hydroconversion of the feedstock to be treated, as defined for the first supported catalyst used in the first hydroconversion step (b).

[0171] As described in step (a), the pyrolysis oil fraction (102) of the feedstock is introduced into the first hydroconversion reactor of the first hydroconversion section (20) and is mixed or not with the heavy hydrocarbon fraction (101). However, the pyrolysis oil fraction (102) may be placed in the hydroconversion reactor of the second hydroconversion section (20) without departing from the context of the present invention.

[0172] ((e) Fractionation step) The first hydroconverted effluent (105) from the hydroconversion step (b), or from a second hydroconversion step (d), if such step is carried out, then undergoes, at least in part, a fractionation step (e) in fractionation section (30).

[0173] This fractionation step (e) separates some or all of the hydroconverted effluent into several fractions, including at least one heavy liquid product (106b) boiling mainly at a temperature above 350° C., preferably above 500° C., more preferably above 540° C. The heavy liquid product (106b) contains a portion boiling at a temperature above 540° C., which is called the residual fraction (vacuum residue), which is the unconverted portion. The heavy liquid product (106b) may contain a portion of the gas oil fraction boiling between 250° C. and 375° C. and a portion boiling between 375° C. and 540° C. (also known as vacuum distillate).

[0174] This fractionation process therefore produces at least two products including a heavy liquid product (106b) as described above, and the other product or products (106a) being one or more light middle distillates.

[0175] The fractionation section (30) may comprise any separation means known to those of skill in the art.

[0176] The fractionation section (30) may therefore include one or more of the following separation equipment: one or more flash vessels arranged in series, preferably an arrangement of at least two successive flash vessels, one or more steam and / or hydrogen stripping columns, an atmospheric distillation column, a vacuum distillation column.

[0177] According to one or more embodiments, this fractionation step (e) is carried out by an arrangement of at least two consecutive flash vessels.

[0178] According to one or more other embodiments, this fractionation step (e) is carried out by one or more steam and / or hydrogen stripping columns.

[0179] According to one or more preferred embodiments, this fractionation step (e) is carried out by an atmospheric distillation column, more preferentially by an atmospheric distillation column and a vacuum column receiving the atmospheric residue.

[0180] According to one or more most preferred embodiments, this fractionation step (e) is carried out by one or more flash vessels, an atmospheric distillation column and a vacuum column receiving the atmospheric residue. This configuration allows the size of any downstream deasphalters to be reduced, thus minimizing investment and operating costs.

[0181] Fractionation section (30) may receive, in addition to some or all of the hydroconverted liquid effluent, one or more additional effluents external to the process, such as one or more hydrocarbon feedstocks (e.g., atmospheric and / or vacuum distillate, atmospheric and / or vacuum residue), a portion of the heavy fraction from separation step (c) if performed, one or more portions of the middle distillate from fractionation step (e), a portion of the light or heavy fraction of the DAO or deasphalting step (f1) if performed. Fractionation section (30) may include means for scrubbing one or more separated products by contact with an aqueous solution.

[0182] According to a preferred embodiment, the fractionation step (e) comprises a hot separator operated at a temperature of at least 300° C., even at least 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 a subsequent separation of the gas phase of the hot separator, and also at least a portion of the liquid phase of the hot separator or at least one of the phases resulting from a subsequent separation of the liquid phase of the hot separator, are advantageously placed in contact with water or an aqueous basic solution (for example sodium hydroxide, amine solution) so as to at least partially remove hydrogen chloride (HCl) and / or at least partially dissolve the ammonium chloride salts. The separation equipment or vessel may comprise, at the bottom, a zone for separate precipitation of the hydrocarbon fraction and the aqueous fraction containing chloride salts, or alternatively, a column for scrubbing the gas by contact with water or an aqueous basic solution.

[0183] According to a highly preferred embodiment, when a separation step c) is performed, at least part of the separation equipment is shared between steps c) and e).

[0184] (f) One or more subsequent processing steps One or more subsequent steps (f) of treatment of the heavy liquid product (106b) and / or one or more other products resulting from fractionation step (e) may be carried out.

[0185] Such step (f) may comprise at least one step selected from the list consisting of hydrotreating, steam cracking, fluidized bed catalytic cracking, hydrocracking, deasphalting and extraction of lubricating oils. These examples of further processing are not exhaustive.

[0186] In particular, the various hydrocarbon products that may result from fractionation step (e) in fractionation means (30), as shown in the drawing under general reference sign (40), may be sent to various processes in the refinery, the details of all these post-processing processes being generally known to those skilled in the art and therefore not described here. For example, the gas fraction, naphtha (gasoline), middle distillate, VGO, DAO may be sent to processes such as hydrotreating, steam cracking, fluidized bed catalytic cracking (FCC), hydrocracking, lube oil extraction, etc. The residue (atmospheric or vacuum residue) may be post-processed or used for other applications, for example gasification, production of bitumen, heavy fuel oil, etc. The heavy fraction, including the residue, may also be recycled to hydroconversion processes, for example to the hydroconversion reactor in step (b) or (d).

[0187] According to one or more embodiments, the hydroconversion process includes a step (f1) in which part or all of the heavy liquid product (106b) obtained in the fractionation step (e) is deasphalted in a deasphalting step with at least one hydrocarbon-based solvent to produce a deasphalted oil DAO and residual asphalt ("SDA": Solvent DeAsphalting step).

[0188] Such a deasphalting step (f1) is carried out under conditions well known to those skilled in the art. Reference may thus be made to the article by Billon et al., Revue de l'Institut Francais du Petrole, Vol. 49, No. 5, pp. 495-507, published in 1994, to the book "Raffinage et conversion des produits lourds du petrole" by JF Le Page, SG Chatila and M. Davidson, Edition Technip, pp. 17-32, or to the patents US4239616, US4354922, US4354928, US4440633, US4536283 and US4715946. The deasphalting may be carried out in one or more mixer-settlers or in one or more extraction columns. A deasphalter. thus comprises at least one mixer-settler or at least one extraction column. Deasphalting is a liquid-liquid extraction, generally carried out at an average temperature between 60°C and 250°C with at least one low-boiling hydrocarbon-based solvent, preferably a paraffinic solvent, preferably heavier than propane, preferentially containing 3 to 7 carbon atoms. Suitable solvents include propane, butane, isobutane, pentane, isopentane, neopentane, hexane, isohexane, C6-hydrocarbons, heptane, C7-hydrocarbons, more or less non-polar light gasolines, and also mixtures obtained from the above solvents. Preferably, the solvent is butane, pentane or hexane, and also mixtures thereof. The solvent / feedstock (volume / volume) ratio entering the deasphalter is generally between 3 / 1 and 16 / 1, preferably between 4 / 1 and 8 / 1. Preferably the deasphalter comprises at least one extraction column, preferably only one (e.g. as used in the Solvahl® process), in which the solvent / feed (volume / volume) ratio entering the deasphalter is preferably low, typically between 4 / 1 and 8 / 1, or even between 4 / 1 and 6 / 1.The deasphaltenes produces DAO that is substantially free of C7 asphaltene, the C7 asphaltene content being preferably less than 2 wt%, more preferentially less than 0.5 wt%, even more preferentially less than 0.05 wt%, and the residual asphalt, concentrating most of the impurities in the residue, is drawn off. The DAO yield is generally between 40 wt% and 95 wt%, depending on the operating conditions and the solvent used, and the quality of the feed sent to the deasphaltenes, especially the heavy liquid product (106b).

[0189] According to one or more embodiments, the hydroconversion process includes at least one step (f2) of hydrotreating one or more liquid products from the fractionation step (e), which step is preferably carried out in a fixed bed in a hydrotreating section, which may include at least one fixed bed reactor containing n catalyst beds, n being an integer equal to or greater than 1, each containing at least one hydrotreating catalyst, said hydrotreating reaction section being fed with at least a portion of the liquid products obtained from step e) and with a gas stream containing hydrogen to obtain a hydrotreated effluent.

[0190] Such processes include hydrotreating reactions well known to those skilled in the art, more specifically hydrotreating reactions such as the hydrogenation of aromatics or olefins, hydrodesulfurization and hydrodenitrification.

[0191] The hydrotreating reaction section is advantageously operated at a weight average bed temperature (WABT) of 250° C. to 430° C., preferably 300° C. to 400° C., at which the hydrogen partial pressure is 1.0 MPa (abs) to 20.0 MPa (abs), preferably 3.0 MPa (abs) to 15.0 MPa (abs), and at which the hourly space velocity (HSV) of one or more catalysts is 0.1 h -1 ~10.0h -1 , preferably 0.1h -1 ~5.0h -1 , preferentially 0.2h -1 ~2.0h-1 , preferably 0.2h -1 ~1.0h -1 The hydrogen coverage in step f2) is determined by the volume (m 3 ) Hydrogen is advantageous at 50Nm 3 ~2000Nm 3 , preferably 100 Nm 3 ~1000Nm 3 , more preferentially 120Nm 3 ~800Nm 3 It is.

[0192] The hydrotreating section may comprise several, preferably two, reactors, which may be operated in series and / or parallel and / or PRS (lead-lag) and / or swing mode as known to the skilled person, or alternatively, the hydrotreating section may comprise a single fixed bed reactor containing n catalyst beds, n being preferably between 1 and 10, or even between 2 and 5.

[0193] Means for recovering catalyst fines and / or catalyst from hydroconversion upstream of or at the inlet to the hydrotreatment section may be used, for example one or more filters or even reactor internals, for example of the filter tray type, one example of which is described in patent FR3051375. The fixed bed hydrotreatment catalyst used in step f2) may be selected from known hydrotreatment and hydrodemetallization catalysts, notably used for processing petroleum fractions. 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 EP 0113297, EP 0113284, US 5,221,656, US 5,827,421, US 7,119,045, US 5,622,616 and US 5,089,463.

[0194] In particular, said hydrotreating catalyst comprises a support, preferably a mineral support, and at least one metallic element carrying hydrodehydrogenation functional groups.

[0195] The metal elements carrying hydrodehydrogenation functional groups advantageously comprise at least one group VIII element and / or at least one group VIB element, the group VIII element being preferably selected from the group consisting of nickel and cobalt, and the group VIB element being preferably selected from the group consisting of molybdenum and tungsten. The total content of oxides of metal elements from groups VIB and VIII is preferably between 0.1% and 40% by weight, more preferentially between 5% and 35% by weight, relative to the total weight of the hydrotreating catalyst. The weight ratio, expressed as metal oxide, between one or more group VIB metals relative to one or more group VIII metals is preferably between 1 and 20, more preferentially between 2 and 10. For example, the hydrotreating section of step f2) comprises a hydrotreating catalyst comprising 0.5% to 10% by weight of nickel (expressed as nickel oxide NiO relative to the total weight of the hydrotreating catalyst), preferably 1% to 8% by weight of nickel, and 1.0% to 30% by weight, preferably 3% to 29% by weight, in total weight, of molybdenum and / or tungsten (expressed as molybdenum oxide MoO3 or tungsten oxide WO3 relative to the total weight of the hydrotreating catalyst), on a mineral support.

[0196] The support for the hydrotreating catalyst is advantageously chosen from alumina, silica, silica-alumina, magnesia, clays and mixtures thereof. The support may contain dopant compounds (for example oxides chosen from boron oxides, in particular boron trioxide, zirconia, ceria, titanium oxide, phosphorus pentoxide and mixtures of these oxides).

[0197] Preferably, the hydrotreating catalyst comprises an alumina support, preferably an alumina support doped with phosphorus and optionally with boron. The alumina used may be, for example, γ (gamma) or η (eta) alumina.

[0198] The hydrotreating catalyst is advantageously used in the form of extrudates or beads, generally of millimetre size, for example with an equivalent diameter between 0.4 mm and 4.4 mm.

[0199] Advantageously, the hydrotreating catalyst used in step f2) has a specific surface area of ​​at least 250 m2 (measured by the BET determination by nitrogen adsorption according to standard ASTM D3663). 2 / g or more, even 300m 2 / g or more, and advantageously 800m 2 / g or less, and even 600m 2 / g or less, and even 400m 2 / g or less.

[0200] If it is desired to recycle a portion of the heavy residual fraction (e.g., a portion of the heavy liquid products (106b) and / or a portion of the residual asphalt, or a portion of the DAO) to the hydroconversion system (e.g., to the first hydroconversion reactor or upstream), it may be advantageous to leave the entrained catalyst in the residual and / or residual asphalt fraction in the case where a hybrid bed reactor is functioning. A purge on the recycled stream may generally be carried out to prevent certain compounds from accumulating to excessive levels. For the purposes of the present invention, it is specified that such recycled streams do not form part of the feedstock comprising the pyrolysis oil fraction (102) and the heavy hydrocarbon fraction (101) as defined above.

[0201] (Analysis methods used) The analytical methods and / or standards used to determine the characteristics of the various streams, in particular the feedstock to be treated and the resulting effluents, are known to the person skilled in the art. They are listed below, in particular for information purposes. Other methods that are equivalent can also be used, in particular equivalent IP, EN or ISO methods.

[0202] [Table 1] (1) The MAV method is described in the paper 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.

[0203] (Example) The following examples are directed to illustrating certain performance qualities of the method according to the present invention.

[0204] 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 that can be used as a base for producing fuels, lubricants or any other products obtained from the refining of petroleum. The ability of the supported catalysts present in the H-Oil® process to remove impurities present in the pyrolysis oil and thus facilitate the post-processing of these products is also demonstrated.

[0205] These examples were carried out in a closed reactor (known as a batch reactor) representative of the operating conditions of the H-Oil® process.

[0206] Example 1 is a comparative example illustrating the performance quality of the hydroconversion process for a reference feedstock (vacuum residue) that does not contain plastic pyrolysis oil.

[0207] Example 2 illustrates the performance qualities of the H-Oil® process with a feedstock containing a plastic pyrolysis oil fraction and a fraction of the reference feedstock (vacuum residue) used in Example 1. The mixture was used during the preliminary step of media homogenization (optional step).

[0208] (Feed material) The heavy fraction of the feedstock (I) is a "straight run" vacuum residue (SR-VR) derived directly from the distillation of petroleum crude oil. The plastic pyrolysis oil fraction of the feedstock (II) is a pyrolysis oil obtained from a mixture of plastics and containing high levels of impurities.

[0209] The main characteristics of these two fractions of the feedstock are shown in Table 2 below.

[0210] [Table 2]

[0211] The operating conditions for these examples are summarized in Table 3 below.

[0212] [Table 3]

[0213] (Procedure of Example 1) A batch reactor is loaded with a pre-determined amount of NiMo catalyst on alumina and 100% SR-VR (fraction I of the feedstock). The SR-VR is pre-heated to 100°C to make it low viscosity. The reactor is sealed, purged with nitrogen, purged with hydrogen, and then pressurized with hydrogen to a pressure of about 3 MPa. The reactor is then heated to 100°C. At this temperature, the stirring is started at 500 rpm. The temperature is gradually increased from 100°C to the reaction temperature, and in parallel, the stirring is gradually increased from 500 rpm to 1000 rpm. When the reaction temperature is reached, the pressure in the reactor is instantly adjusted to the target value by adding H2. At this point, the reaction time is counted down. At the end of the experimental time, the reactor is rapidly cooled to stop the reaction, and when the reactor is at room temperature, the stirring is stopped and the liquid effluent and gas are collected for analysis.

[0214] (Procedure of Example 2) The batch reactor is first filled with the same amount of NiMo catalyst on alumina as for Example 1 and 90% by weight of SR-VR (Fraction I of the feedstock) preheated to 100°C to reduce viscosity, then 10% of plastic pyrolysis oil (Fraction II of the feedstock) is added. The reactor is sealed, purged with nitrogen, purged with hydrogen, and then pressurized with hydrogen to a pressure of about 3 MPa. The reactor is then heated to 100°C. At this temperature, the stirring is started at 500 rpm. The temperature is gradually increased from 100°C to 200°C, and in parallel, the stirring is gradually increased from 500 rpm to 1000 rpm. At 200°C, the pressure in the reactor is 4 MPa. A stabilization phase of 1 hour at this temperature is applied to ensure good dispersion of the pyrolysis oil (Fraction II of the feedstock) in the SR-VR (Fraction I of the feedstock), but this step is optional. Following this stabilization phase, the batch reactor is heated to the reaction temperature, at which point the pressure in the reactor is instantaneously adjusted to the target value by adding H2. At this point, the reaction time is counted down. At the end of the experimental time, the reactor is rapidly cooled to stop the reaction, the stirring is stopped when the reactor is at room temperature, and the liquid effluent and gases are collected for analysis.

[0215] (Overall Results and Performance Quality) The results for the total liquid effluent quality and hydroconversion performance quality of these examples are detailed in Tables 4, 5 and 6 below.

[0216] [Table 4]

[0217] [Table 5]

[0218] [Table 6]

[0219] The conversion of the 540° C.+ fraction is calculated by the mass difference between the feed and the total liquid effluent, as follows:

[0220]

number

[0221] It is observed that the presence of plastic pyrolysis oil does not affect the 540°C+ conversion rate, thus allowing a significant increase in the yield of the PI-180°C fraction while at the same time decreasing the yield of the heavy fraction.

[0222] It was also shown that despite the presence of silicon in the plastic pyrolysis oil, the hydroconversion product no longer contained any, indicating that silicon was removed by the supported catalyst. Similarly, chlorine was totally converted. The product obtained from this step is therefore low in impurities and can be fed to, among others, fixed bed hydrotreating processes.

[0223] Furthermore, co-processing of plastic pyrolysis oil does not appear to significantly destabilize the unconverted products, since the sediment content is only 0.04 wt.%, which is a very low and completely tolerable value at the end of the hydroconversion process. Hydroprocessing performance (especially hydrodenitrification and hydrodesulfurization) is also maintained or even improved. [Brief description of the drawings]

[0224] [Figure 1] 1 illustrates one embodiment of a hydroconversion process according to the present invention. [Diagram 2] 1 illustrates another embodiment of a hydroconversion process according to the present invention.

Claims

1. A method for the hydrogenation of a feedstock comprising a pyrolysis oil fraction (102) of plastics and / or solid recovered fuels and a fossil-based heavy hydrocarbon fraction (101), wherein the heavy hydrocarbon fraction (101) contains at least 50% by weight of a portion having a boiling point of at least 300°C and contains sulfur and nitrogen, and the pyrolysis oil fraction (102) constitutes less than 50% by weight of the feedstock, and the method comprises the following steps: (a) A step of conditioning the supply material and introducing it into a first hydrogenation section (20); the hydrogenation section (20) includes at least a first boiling bed or boiling-jet hybrid bed hydrogenation reactor, the reactor containing a first porous supported hydrogenation catalyst; (b) A first step of hydrogenating the feed material in the first hydrogenation section (20) in the presence of hydrogen; obtaining a first hydrogenated effluent (105); (c) Depending on the circumstances, a step of separating some or all of the first effluent obtained from step (b); forming at least one heavy fraction that boils mainly at a temperature of 350°C or higher; (d) A second hydrogenation-conversion step, if applicable; a second hydrogenation-conversion section comprising at least a second boiling bed or boiling-jet hybrid bed hydrogenation-conversion reactor, in which part or all of the first effluent obtained from step (b) or, optionally, the heavy fraction obtained from step (c), the second hydrogenation-conversion reactor comprising a second porous supported catalyst and operating in the presence of hydrogen; producing a second hydrogenation-converted effluent; The absolute pressure during process (b) and / or process (d) is 2 MPa to 38 MPa, the temperature is 300°C to 550°C, and the spatiotemporal velocity is 0.05 h. －１ ~10h －１ The amount of hydrogen associated with this is 50 Nm³ ３ / m ３ ~5000Nm ３ / m ３ That is, (e) Fractionating all or part of the first hydrogenated effluent from step (b) or the second hydrogenated effluent from step (d) in a fractionation section (30); producing at least one heavy liquid product (106b) that boils mainly at a temperature of 350°C or higher; the heavy liquid product containing a residual fraction that boils at a temperature of 540°C or higher.

2. The method according to claim 1, wherein in step (a), the pyrolysis oil fraction (102) and heavy hydrocarbon fraction (101) of the raw material are pre-mixed and then introduced into the at least one first hydrogenation reactor of the first hydrogenation section (20).

3. The method according to claim 1, wherein in step (a), the pyrolysis oil fraction (102) of the raw material is introduced separately from the heavy hydrocarbon fraction (101) into the at least one first hydrogenation reactor of the first hydrogenation section (20).

4. The method according to claim 1, wherein step (a) includes preheating the heavy hydrocarbon fraction (101) to a temperature preferably of 280°C to 450°C, and optionally preheating the pyrolysis oil fraction (102), and thereafter introducing the feedstock into the first hydrogenation reactor of the first hydrogenation section (20).

5. The method according to claim 1, wherein the pyrolysis oil fraction (102) constitutes 1% to 45% by weight of the supply raw material, preferably 2% to 30% by weight of the supply raw material, preferably 2% to 25% by weight of the supply raw material, and more preferably 3% to 20% by weight of the supply raw material.

6. The method according to claim 1, wherein the supply material consists of the pyrolysis oil fraction (102) and the heavy hydrocarbon fraction (101), the pyrolysis oil fraction (102) constitutes 1% to 45% by weight, preferably 2% to 30% by weight, of the supply material, and the heavy hydrocarbon fraction (101) constitutes 55% to 99% by weight, preferably 70% to 98% by weight, of the supply material.

7. The method according to claim 1, wherein the pyrolysis oil fraction (102) is a plastic pyrolysis oil.

8. The method according to claim 1, wherein the heavy hydrocarbon fraction (101) is selected from the list consisting of crude oil, atmospheric residue, atmospheric residue or vacuum residue obtained from atmospheric and / or vacuum distillation of crude oil or effluent originating from units of thermal conversion, hydrotreatment, hydrocracking or hydroconversion, aromatic fractions extracted from units for the production of lubricating oil, desynthesized oil obtained from desynthesized units, asphalt obtained from desynthesized units, residual fraction obtained from direct coal liquefaction, vacuum distillates obtained from direct coal liquefaction, or mixtures thereof.

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

10. The method according to claim 1, comprising a separation step (c), the step comprising a second step (d) of separating part or all of the first hydrogenated effluent (105) obtained from step (b) to produce at least a heavy fraction that mainly boils at a temperature of 350°C or higher, and hydrogenating the heavy fraction.

11. The method according to claim 1, wherein one or more hydrogenation reactors in the first hydrogenation section (20) in step (b) and optionally in the hydrogenation-conversion step (d) are boiling-jet hybrid bed reactors, the method also includes the step of introducing a catalyst precursor (104) into the feedstock, the catalyst precursor (104) preferably comprising molybdenum 2-ethylhexanoate, and thereafter injecting the feedstock into at least one of the first boiling-jet hybrid bed reactors in the first hydrogenation section (20) such that a colloidal or molecular catalyst, preferably comprising molybdenum disulfide, is formed when the feedstock reacts with sulfur.

12. The method according to claim 1, wherein a first hydrogenation-conversion catalyst and optionally a second hydrogenation-conversion catalyst contain at least one non-precious metal of group VIII and at least one metal of group VIB, and an amorphous support, the non-precious metal of group VIII being selected from nickel and cobalt, preferably nickel, the metal of group VIB being selected from molybdenum and tungsten, preferably molybdenum, and the amorphous support being preferably alumina.

13. The method according to claim 1, wherein the temperature when performing step (b) and optionally step (d) is 405°C to 450°C.

14. The method according to claim 1, wherein an optional intermediate separation step (c) is performed in a separation section, and the separation section and / or the fractionation section (30) in step (e) includes means for washing at least one separated fraction by contact with an aqueous solution.

15. The method according to claim 1, further comprising a step (f) of further processing the heavy liquid product (106b) and / or one or more other products from a fractionation step (e), wherein the step (f) comprises at least one step selected from the list of hydrogenation, steam cracking, fluidized bed catalytic cracking, hydrocracking, desying, and lubricating oil extraction, preferably a fixed-bed hydrogenation step (f2) in a hydrogenation section, wherein the hydrogenation section preferably comprises at least one fixed-bed reactor containing n catalyst beds, where n is an integer of 1 or more, each containing at least one hydrogenation catalyst, and the hydrogenation section is supplied with at least a portion of the liquid product from step e) and a gaseous flow containing hydrogen to obtain a hydrogenated effluent.

16. A product obtained by the method according to any one of claims 1 to 15.

17. Hydrogenated effluent according to claim 16, wherein the hydrogenated effluent comprises a liquid portion obtained at the end of the first hydrogenation step (b) or the second hydrogenation step (d), and containing silicon at a content of 5 ppm by weight or less and / or chlorine at a content of 10 ppm by weight or less relative to the total weight of the liquid portion of the effluent.

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