Ebullated bed or hybrid bed hydroconversion of feedstocks comprising plastic fractions and non-asphaltene heavy hydrocarbon fractions

Abstract

The invention relates to a process for the hydroconversion of a feedstock comprising a plastic fraction (102), in particular derived from plastic waste, containing at least 70% by weight of PE in high-density and / or low-density form, and a heavy fraction (101) of non-asphaltene hydrocarbons containing at least 90% by weight of fractions having a boiling point of at least 300 DEG C, for example of the VGO or DAO type. The hydroconversion uses one or more ebullated bed or hybrid ebullated-entrained bed reactors (20), and preferably two successive hydroconversion steps, to produce higher quality, lower boiling materials, for example for fuel production purposes, while being able to upgrade the plastic waste.

Description

TECHNICAL FIELD

[0001] The present invention relates to the field of hydroconversion of feedstocks comprising a specific plastic fraction of polyethylene (PE) type, in particular originating from plastic waste, and a heavy hydrocarbon fraction, in particular a non-asphaltene heavy hydrocarbon fraction containing at least 90 wt% of a fraction having a boiling point of at least 300°C.

[0002] The heavy hydrocarbon fraction is typically a deasphalted oil (DAO) or a vacuum distillate oil (VGO) known as vacuum gas oil (VGO), for example originating from crude oil or from the effluent of a crude oil refining process.

[0003] According to the invention, such a non-asphaltene hydrocarbon heavy fraction is combined with a plastic fraction containing at least 70 wt% of polyethylene in high density and / or low density form (HDPE and LDPE, i.e. high density polyethylene and low density polyethylene, respectively). This plastic fraction is advantageously originating from production waste and / or waste.

[0004] In particular, the invention relates to a process for the hydroconversion of such a mixed feedstock comprising at least one hydroconversion step, and preferably two successive hydroconversion steps, using one or more reactors operating in ebullated bed or hybrid ebullated-entrained bed, to produce a higher quality, lower boiling point material, for example for fuel production purposes, while being able to upgrade plastic waste. PRIOR ART

[0005] In the last few years, the fuel and chemical industry has seen the emergence of processes incorporating products other than conventional petroleum products, for example products of renewable origin, such as lignocellulosic biomass, or products such as plastic waste, as a complement or replacement to fossil origin products.

[0006] For example, patent US 8 623 102 is known, which relates to a process for the liquefaction of biomass selected from algae, lignocellulosic biomass or one or more lignocellulosic biomass constituents selected from cellulose, hemicellulose and lignin, to produce a fuel base, said process comprising two successive hydroconversion steps at high hydrogen pressure using a supported catalyst of petroleum residue hydroconversion type and a suspension comprising biomass and solvent in an ebullated bed reactor.

[0007] In particular, in the context of the circular economy and the reduction of waste, particular attention is paid to plastics, which are conventionally petroleum-derived products, to upgrade them.

[0008] The upgrading of plastic waste can include the conversion of the plastic by mechanical and / or chemical means in order to be able to produce plastic or plastic-based objects again. This is the recycling of plastic waste.

[0009] This upgrading of plastic waste can also follow the route of energy upgrading, in particular for plastic waste that is not recyclable or difficult to recycle, in some cases as an alternative to landfill.

[0010] Generally, the energy upgrading of plastic waste consists in producing energy in the form of electricity and / or heat. For example, it is known to subject plastic obtained from collection and sorting channels to a pyrolysis step in order to produce, inter alia, plastic pyrolysis oil, which is generally incinerated to produce electricity and / or used as fuel in industrial boilers or for urban heating.

[0011] Plastic waste can also be converted by hydroconversion under high hydrogen pressure to produce hydrocarbon cuts, which can in particular be upgraded into fuels, for example for the production of gasoline or gas oil, or into petrochemical raw materials.

[0012] In the field of hydroconversion, i.e. the conversion of a hydrocarbon feedstock under high hydrogen pressure into products with a boiling point range lower than the original feedstock, the patent application WO 2020 / 129020 describes a hydroconversion process of a polymer mixture based on the use of an entrained catalyst, also called a “slurry” hydroconversion process. Very small catalysts are dispersed in the reaction medium, homogeneously distributed in the reactor and entrained with the products leaving the reactor. According to the process, a plastic mixture is processed using slurry technology and converted into hydrocarbons with a boiling point of 65°C to 175°C, corresponding to a naphtha cut, based on the use of a reactor operating with an entrained catalyst. Finally, this is a method for the chemical recycling of plastic waste, which allows the conversion of waste plastics into a naphtha cut, which is one of the main reagents for the production of plastics. The feedstock in the slurry hydroconversion process according to the patent application WO 2020 / 129020 is a solid polymer mixture, which can be mixed with a residue under vacuum and introduced as a slurry (solid suspension) into a reactor operating as an entrained bed. Although the slurry process is known for treating heavy feedstocks and achieving a higher conversion than other processes, such as hydroconversion processes using a fluidized bed reactor, which uses a supported catalyst that remains in the reactor, the main drawback of the slurry process is the complex and expensive management of the catalyst entrained with the conversion products, in particular its separation from the final product.

[0013] Applicant filed French patent application No. FR 21 / 14 037, which relates to a process for hydroconversion of a mixed feedstock comprising a heavy hydrocarbon fraction and a plastics fraction, which comprises at least one hydroconversion step using one or more reactors operated in ebullated bed or ebullated-entrained hybrid bed, and which particularly pursues similar overall objectives as the present invention, i.e. to produce higher quality materials with lower boiling points, for example for fuel production purposes, while allowing upgrading of plastic waste. Said patent application describes various methods of conditioning the feedstock and introducing the feedstock into the hydroconversion section. The heavy hydrocarbon fraction comprises a number of possible feedstocks, the plastics fraction likewise comprises a number of types of plastics, and one example shows good performance of the hydroconversion process of a mixed feedstock formed from vacuum residue directly from crude distillation combined with a polyethylene plastics fraction.

[0014] The present invention proposes the same type of process for hydroconversion of a more specific mixed feedstock.

[0015] Object and summary of the invention The present invention relates to the field of upgrading of heavy feedstocks that are difficult to upgrade, such as vacuum distillate oil or deasphalted oil, which are usually derived from crude oil refining, which usually contain high contents of impurities such as sulfur and nitrogen, or even Conradson carbon residue, to convert them into lighter products that can be upgraded into fuels, for example to produce gasoline or gas oil, or into petrochemical raw materials.

[0016] The inventors have surprisingly shown that it is possible to incorporate a plastics fraction derived from waste comprising at least 70% by weight of polyethylene (PE) in high density and / or low density form into a non-asphaltic heavy hydrocarbon feedstock that is traditionally treated in an ebullated bed or hybrid ebullated-entrained bed hydroconversion process, in various ways, without significantly degrading the overall conversion rate of the feedstock. Surprisingly, by combining a non-asphaltic heavy hydrocarbon feedstock fraction with a specific plastics fraction, it is even possible to improve the conversion of the plastics during the course of the process under specific conditions, while ensuring good process operability, in particular limiting the formation of deposits.

[0017] The present invention thus proposes a process for hydroconversion in an ebullated bed or hybrid ebullated-entrained bed of a mixed feedstock comprising a heavy fraction of non-asphaltic hydrocarbons and a plastics fraction derived from waste and comprising at least 70% by weight of polyethylene (PE) in high density and / or low density form, to enable production of fuel base stocks and other upgradable hydrocarbons (light hydrocarbons, distillates intended for steam crackers, in particular for the production of recycled polyolefins, base stocks for the production of bitumen, lubricants, etc.), while ensuring upgrading of plastic waste that would otherwise be intended for landfill or incineration. More generally, the present invention helps to increase the proportion of plastic waste sent to recycling while treating the plastic impurities.

[0018] Accordingly, to achieve at least one of the above-mentioned objects, the present application proposes, among others, a feedstock hydroconversion process comprising the following successive steps: (a) conditioning said feedstock and introducing said feedstock into a first hydroconversion section (20) comprising at least a first ebullated bed or hybrid ebullated-entrained bed hydroconversion reactor, said reactor comprising a first porous supported hydroconversion catalyst; said feedstock comprising a minor fraction of plastic fractions containing at least 70 wt% of polyethylene in high density form (HDPE) and / or low density form (LDPE) and mainly comprising a heavy fraction of non-asphaltene hydrocarbons containing at least 90 wt% of fractions having a boiling point of at least 300°C and containing less than 1 wt% of asphaltenes; (b) a first step of hydroconverting said feedstock in the presence of hydrogen in said first hydroconversion section (20) to obtain a first hydroconversion effluent (105); (c) optionally, a step of separating a part or all of the first effluent obtained from step (b) to form at least one heavy fraction boiling mainly at a temperature greater than or equal to 350°C; (d) optionally, a second hydroconversion step of a part or all of the first effluent obtained from step (b) or optionally of the heavy fraction obtained from step (c) in a second hydroconversion section comprising at least a second ebullated bed or hybrid ebullated-entrained bed hydroconversion reactor, said second hydroconversion reactor comprising a second porous supported catalyst and operating in the presence of hydrogen to produce a second hydroconversion effluent; steps (b) and optionally (d) are carried out at a pressure between 2 MPa and 38 MPa absolute, at a temperature between 350°C and 550°C, at a space time velocity relative to the volume of each hydroconversion reactor between 0.05 h -1 and 10 h -1 and at a hydrogen amount between 50 Nm 3 / m 3 and 5000 Nm 3 / m 3 , (e) a step of fractionating all or a part of the first hydroconversion effluent from step (b) or of the second hydroconversion effluent from step (d) in a fractionation section (30) to produce at least one liquid product (106a) boiling mainly at a temperature lower than 350°C.

[0019] According to one or more embodiments of the application, the non-asphaltene heavy hydrocarbon fraction is selected from the following fractions, alone or as a mixture: i) a straight run from crude oil or a vacuum gas oil from other refining processes selected from the group consisting of cracking processes, preferably fluidized bed catalytic cracking processes or hydrocracking processes, thermal conversion processes, preferably coking processes or visbreaking processes, coal liquefaction processes, biomass liquefaction processes, liquefaction processes of plastics and / or tires and / or solid recovered fuel, preferably pyrolysis, and / or ii) a deasphalted oil from a solvent deasphalting process, preferably from solvent deasphalting of a straight run residue of a crude oil or a deasphalted oil of other refining processes, and / or iii) one or more aromatic fractions extracted from a lubricant production unit.

[0020] According to one or more embodiments of the present application, the heavy fraction of non-asphaltene hydrocarbons is a vacuum gas oil containing at least 90 wt% of fractions having a boiling point of at least 300°C and not more than 20 wt% of fractions having a boiling point of at least 540°C.

[0021] According to one or more embodiments of the present application, the heavy fraction of non-asphaltene hydrocarbons is of fossil origin.

[0022] According to one or more embodiments of the present application, the heavy fraction of non-asphaltene hydrocarbons is a vacuum gas oil obtained from vacuum distillation of a crude oil or a deasphalted oil obtained from a solvent deasphalting process of a straight run residue of a crude oil.

[0023] According to one or more embodiments of the present application, wherein the plastic fraction contains at least 80 wt%, preferably at least 90 wt%, preferably at least 95 wt% of polyethylene PE in high density form (HDPE) and / or in low density form (LDPE).

[0024] According to one or more embodiments of the present application, the plastic fraction contains from 50 wt% to 95 wt% of low density polyethylene (LDPE) and from 5 wt% to 50 wt% of high density polyethylene (HDPE), in particular from 55 wt% to 70 wt% of LDPE and from 30 wt% to 45 wt% of HDPE.

[0025] According to one or more embodiments of the present application, the feedstock comprises: - between 0.1 wt% and 49 wt%, preferably between 0.5 wt% and 45 wt%, preferably between 1 wt% and 30 wt%, preferably between 2 wt% and 25 wt% or even between 2.5 wt% and 20 wt% of said plastic fraction, and - between 51 wt% and 99.9 wt%, preferably between 55 wt% and 99.5 wt%, preferably between 70 wt% and 99 wt%, preferably between 75 wt% and 98 wt%, or even between 80 wt% and 97.5 wt% of said heavy fraction of non-asphaltene hydrocarbons.

[0026] According to one or more embodiments of the application, in step (a), the plastic fraction of the feedstock and the heavy fraction of non-asphaltene hydrocarbons are mixed and introduced into the at least one first hydroconversion reactor of the first hydroconversion section.

[0027] According to one or more embodiments of the application, in step (a), the plastic fraction in solid particle form, optionally premixed with a diluent, is mixed with the heavy fraction of non-asphaltene hydrocarbons to form a suspension which is heated to a temperature above the melting point of the plastic fraction to form a feedstock introduced into the first hydroconversion reactor.

[0028] According to one or more embodiments of the application, in step (a), the fractions of the feedstock and the heavy fraction of non-asphaltene hydrocarbons are introduced separately into the at least one first hydroconversion reactor of the first hydroconversion section.

[0029] According to one or more embodiments of the application, in step (a), the plastic fraction in solid particle form is mixed with a diluent in a mixing section (1 1 ) and heated to a temperature above the melting point of the plastic fraction, preferably between 60°C and 295°C, in a heating section, before being introduced into the first hydroconversion reactor, the heating step possibly being carried out before or after mixing with the diluent, preferably after mixing with the diluent.

[0030] According to one or more embodiments of the application, the process comprises a separation step (c) which separates a part or all of the first hydroconversion effluent from step (b) to produce at least a heavy fraction which boils mainly at a temperature greater than or equal to 350°C, and a second step (d) of hydroconversion of the heavy fraction.

[0031] According to one or more embodiments of the application, the hydroconversion reactors of the first hydroconversion section in step (b) and optionally in the hydroconversion step (d) are hybrid boiling-entrained bed reactors, the process further comprising a step of introducing a catalyst precursor, preferably molybdenum 2-ethylhexanoate, before injecting the feedstock into the at least one first hybrid boiling-entrained bed reactor of the first hydroconversion section, in such a way that a colloidal or molecular catalyst is formed when the catalyst precursor reacts with sulfur, which preferably comprises molybdenum disulfide.

[0032] According to one or more embodiments of the application, the first hydroconversion catalyst and optionally the second hydroconversion catalyst contain at least one Group VIII non-noble metal chosen from nickel and cobalt, preferably nickel, and at least one Group VIB metal chosen from molybdenum and tungsten, preferably molybdenum, and comprise an amorphous support, preferably alumina.

[0033] Other subjects and advantages of the application will become apparent upon reading the following description of particular exemplary embodiments of the application given as non-limiting examples, this description being made with reference to the appended drawings.

[0034] List of figures Figures 1A to 1D Figure illustrates a first embodiment of the hydroconversion process according to the application, in which the non-asphaltene heavy fraction and the plastic fraction of the feedstock are injected separately into the hydroconversion reactor, i.e. without mixing them before introducing them into the hydroconversion reactor. This first embodiment is referred to as direct injection.

[0035] Figures 2A to 2E Figure illustrates a second embodiment of the hydroconversion process according to the application, in which the non-asphaltene heavy fraction and the plastic fraction of the feedstock are mixed before introducing them into the hydroconversion reactor. This second embodiment is referred to as indirect injection.

[0036] Figure 1A is a block diagram illustrating a first variant of the first embodiment of the hydroconversion process according to the application, according to which the plastic fraction is heated before it is introduced into the hydroconversion reactor in substantially liquid form.

[0037] Figure 1B is a block diagram illustrating a second variant of the first embodiment of the hydroconversion process according to the application, according to which the plastic fraction is mixed with a diluent and then heated in order to be injected into the hydroconversion reactor in substantially liquid form.

[0038] Figure 1C is a block diagram illustrating a third variant of the first embodiment of the hydroconversion process according to the application, according to which the plastic fraction is injected into the hydroconversion reactor in the form of a suspension.

[0039] Figure 1D is a block diagram illustrating a fourth variant of the first embodiment of the hydroconversion process according to the application, according to which the plastic fraction is injected into the hydroconversion reactor in the form of a suspension via a supported catalyst injection device.

[0040] Figure 2A is a block diagram illustrating a first variant of the second embodiment of the hydroconversion process according to the application, according to which the plastic fraction is mixed in solid form with the non-asphaltene heavy fraction.

[0041] Figure 2B is a block diagram illustrating a second variant of the second embodiment of the hydroconversion process according to the application, according to which the plastic fraction is mixed in solid form with a diluent and then with the non-asphaltene heavy fraction.

[0042] Figure 2Cis a block diagram illustrating a third variant of the second embodiment of the hydroconversion process according to the present application, whereby the plastic fraction is heated to be in substantially liquid form, then mixed with the non-asphaltene heavy fraction.

[0043] Figure 2D is a block diagram illustrating a fourth variant of the second embodiment of the hydroconversion process according to the present application, whereby the plastic fraction is mixed with the diluent in solid form, then heated to be in substantially liquid form, then mixed with the non-asphaltene heavy fraction.

[0044] Figure 2E is a block diagram illustrating a fifth variant of the second embodiment of the hydroconversion process according to the present application, whereby the plastic fraction is heated to be in substantially liquid form, then mixed with the diluent, then mixed with the non-asphaltene heavy fraction.

[0045] In the drawings, like reference numerals refer to like or similar elements throughout. Identical or similar elements can have different reference numerals, however.

[0046] Description of the embodiments Embodiments of the process according to the present application will now be described in detail. In the following detailed description, numerous specific details are disclosed to provide a thorough understanding of the process. However, it will be apparent to one of ordinary skill in the art that the process can be practiced without these specific details. In other instances, well-known features have not been described in detail to avoid unnecessarily complicating the description.

[0047] Some definitions are given below for a better understanding of the present application.

[0048] In the present description, the term "comprising" is synonymous with "including" and "containing" (meaning the same), and is inclusive or open-ended and does not exclude additional, unrecited elements. It is to be understood that the term "comprising" encompasses the exclusive and closed-ended term "consisting of".

[0049] In the present description, the expression "between... and..." means that the limit values of the interval are included in the numerical range described, unless otherwise stated.

[0050] In the present application, different numerical ranges for a given parameter can be used, alone or in combination. For example, a preferred range of values for a pressure value can be combined with a more preferred range of values for a temperature value, or a preferred range of values for a value of one chemical compound or element can be combined with a more preferred range of values for a value of another chemical compound or element.

[0051] In the present specification, a mixture of substances in the form of a suspension, also called a slurry, generally corresponds to a system formed of solid particles dispersed in a liquid (liquid dispersion). More particularly, the plastic fraction of the raw material in the form of a suspension corresponds to a system comprising solid plastic particles dispersed in a liquid, for example a system comprising between 1 and 50% by weight of solid plastic particles dispersed in a liquid, or even between 1 and 30% by weight, or between 5 and 20% by weight. The liquid continuous phase in which the solid plastic particles are dispersed can be a diluent and / or a non-asphaltic liquid heavy fraction of the raw material. According to the definition given, it does not contain the polymer of the melted plastic fraction.

[0052] The term "hydroconversion" refers to a process whose main purpose is to reduce the boiling point range of a feedstock comprising at least 50% of a heavy hydrocarbon fraction and in which a substantial portion of the feedstock is converted into products having a boiling point range lower than that of the starting feedstock. Hydroconversion generally involves breaking larger hydrocarbon molecules into smaller molecular fragments having fewer carbon atoms and a higher hydrogen-carbon ratio. The reactions carried out during hydroconversion enable the size of the hydrocarbon molecules to be reduced in the presence of hydrogen, mainly by cleavage of carbon-carbon bonds, to saturate the broken bonds and aromatic rings. The mechanism of hydroconversion that occurs generally involves the formation of hydrocarbon radicals during cleavage, mainly by thermal cracking, followed by capping of the ends or fragments of the radicals with hydrogen in the presence of active catalyst sites. Of course, during the course of the hydroconversion process, other reactions that are generally associated with hydrotreating can occur, notably for example the removal of sulfur and nitrogen from the feedstock, or olefin saturation, and as more broadly defined hereinafter.

[0053] The term "hydrotreating", often 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 olefins and / or stabilize hydrocarbon radicals by reacting them with hydrogen rather than with themselves. The main purpose is not to change the boiling point range of the feedstock. Thus, hydrotreating notably comprises hydrodesulfurization (often referred to as "HDS") reactions, hydrodenitrogenation (often referred to as "HDN") reactions and hydrodemetallization (often referred to as "HDM") reactions, accompanied by hydrogenation, hydrodeoxygenation, hydrodearomatization, hydroisomerization, hydrodealkylation, hydrocracking or hydrodeasphalting reactions and by a reduction in Conradson carbon. Hydrotreating is most often carried out using fixed bed reactors, although other reactors can also be used for hydrotreating, for example ebullated bed hydrotreating reactors.

[0054] The term "hydroconversion reactor" refers to any vessel in which the hydroconversion of a feedstock is the primary purpose, e.g., cracking (i.e., reduction in boiling point range) of the feedstock in the presence of hydrogen and a hydroconversion catalyst. Hydroconversion reactors typically include at least one feed inlet through which the feedstock and hydrogen can be introduced and at least one discharge outlet from which upgraded material can be withdrawn. In particular, hydroconversion reactors are further characterized in that they have sufficient thermal energy to break larger hydrocarbon molecules into smaller molecules by thermal decomposition. Examples of hydroconversion reactors include, but are not limited to, an entrained bed reactor, also known as a slurry reactor (a reactor with three phases - liquid, gas, solid - in which the solid and liquid phases can behave like a homogeneous phase), a boiling bed reactor (a fluidized reactor with three phases), a moving bed reactor (a reactor with three phases in which the solid catalyst moves downward and the liquid and gas flow upward or downward), and a fixed bed reactor (a reactor with three phases in which the liquid feed flows downward through a fixed bed of supported catalyst, with hydrogen typically flowing concurrently with the liquid, but in some cases can be countercurrent).

[0055] The terms "hybrid bed" and "hybrid boiling bed" and "hybrid boiling-entrained bed" for a hydroconversion reactor refer to a boiling bed hydroconversion reactor that contains an entrained catalyst in addition to the porous supported catalyst that is maintained in the boiling bed reactor. In a similar manner, for a hydroconversion process, these terms thus refer to a process that contains a hybrid operation of a boiling bed and an entrained bed in at least one same hydroconversion reactor. A hybrid bed is a mixed bed of two types of catalysts with necessarily different particle sizes and / or densities, one type of catalyst, i.e., "porous supported catalyst," is maintained in the reactor, and the other type of catalyst, i.e., "entrained catalyst," also commonly referred to as "slurry catalyst," is entrained out of the reactor with the effluent (upgraded feedstock). In the present invention, the entrained catalyst is a colloidal catalyst or a molecular catalyst as defined below.

[0056] The terms "colloidal catalyst" and "colloidal dispersed catalyst" refer to catalyst particles having a colloidal type particle size, e.g., a size (diameter) of less than 1 pm, preferably a size of less than 500 nm, more preferably a size of less than 250 nm, or a size of less than 100 nm, or a size of less than 50 nm, or a size of less than 25 nm, or a size of less than 10 nm, or a size of less than 5 nm. The term "colloidal catalyst" includes, but is not limited to, a molecular or molecular dispersed catalyst compound.

[0057] The terms "molecular catalyst" and "molecularly dispersed catalyst" refer to a catalyst compound that is essentially "dissolved" or completely dissociated into catalyst compound or molecules within the feedstock, non-volatile liquid fraction, bottoms fraction, residue, or other catalyst compounds or molecules in the feedstock or product in which it can be present. They also refer to very small catalyst particles or sheets containing only a small number of catalyst molecules (e.g., 15 molecules or less) that are bound together.

[0058] The terms "porous supported catalyst", "solid supported catalyst", and "supported catalyst" refer to catalysts that are typically used in conventional ebullated bed and fixed bed hydroconversion systems, including catalysts that are primarily designed for hydrocracking or hydrodemetallization and catalysts that are primarily designed for hydrotreating. Such catalysts typically comprise (i) a catalyst support having a large surface area and many interconnected channels or pores and (ii) fine particles of an active catalyst, such as sulfides of cobalt, nickel, tungsten, and molybdenum or mixed sulfides of these elements (e.g., NiMo, CoMo, etc.), dispersed within the pores. Supported catalysts are typically produced in the form of cylindrical extrudates (pellets) or spherical solids, although other forms are possible.

[0059] Reference is made below to the following figures which represent different variants of the process according to the application Figures 1A to 2E The process according to the application and its functioning are described in more detail.

[0060] In all the variants illustrated, certain steps of the hydroconversion process are similar. The sections of the hydroconversion facility implementing these similar steps are represented by the same reference numerals in the figures, for example the sections described below for hydroconversion 20, fractionation 30 and further processing 40.

[0061] It is an object of the present application to propose a process for hydroconversion of a feedstock comprising a minor proportion of a plastic fraction containing at least 70 wt% of PE in high density and / or low density form and mainly comprising a heavy fraction of non-asphaltene hydrocarbons containing at least 90 wt% of a fraction having a boiling point of at least 300°C and containing less than 1 wt% of asphaltenes, the process comprising the following successive steps: (a) conditioning the feedstock and introducing the feedstock into a first hydroconversion section 20 comprising at least a first ebullated bed or hybrid bed reactor containing a first porous supported hydroconversion catalyst; (b) a first step of hydroconversion of the feedstock in the presence of hydrogen in the first hydroconversion section 20 to obtain a first hydroconversion effluent 105; (c) optionally, a step of separating a part or all of the first effluent obtained from step (b) to recover at least one heavy fraction boiling mainly at a temperature greater than or equal to 350°C; (d) optionally, a second hydroconversion step of a part or all of the first effluent obtained from step (b) or optionally of the heavy fraction obtained from step (c) in a second hydroconversion section (not shown in the attached figures) comprising at least a second ebullated bed or hybrid bed reactor, said second reactor comprising a second porous supported catalyst and operating in the presence of hydrogen, to produce a second hydroconversion effluent; steps (b) and optionally (d) being carried out at a pressure comprised between 2 MPa and 38 MPa absolute, at a temperature comprised between 350°C and 550°C, at a space time velocity relative to the volume of each reactor comprised between 0.05 h -1 and 10 h -1 and at a hydrogen amount comprised between 50 Nm 3 / m 3 and 5000 Nm 3 / m 3 , (e) a step of fractionating in a fractionation section (30) all or a part of the first hydroconversion effluent 105 from step (b) or of the second hydroconversion effluent from step (d) to produce at least one heavy product boiling mainly at a temperature greater than or equal to 350°C.

[0062] Feedstock According to one essential aspect of the present application, the feedstock comprises a minor amount (i.e. less than 50 wt%) of a plastic fraction and mainly (i.e. at least 50 wt%) of a heavy fraction of non-asphaltene hydrocarbons.

[0063] The plastic fraction constitutes less than 50 wt% of the feedstock (total weight of the feedstock), preferably between 0.1 wt% and 49 wt% of the feedstock, more preferably between 0.5 wt% and 45 wt% of the feedstock, again more preferably between 1 wt% and 30 wt% of the feedstock, again more preferably between 2 wt% and 25 wt% of the feedstock, or even between 2.5 wt% and 20 wt% of the feedstock.

[0064] The heavy fraction of non-asphaltene hydrocarbons containing at least 90 wt% of the fraction having a boiling point of at least 300°C constitutes at least 50 wt% of the feedstock, preferably between 51 wt% and 99.9 wt% of the feedstock, preferably between 55 wt% and 99.5 wt% of the feedstock, preferably between 70 wt% and 99 wt% of the feedstock, and more preferably between 75 wt% and 98 wt% of the feedstock, or even between 80 wt% and 97.5 wt% of the feedstock.

[0065] The sum of the plastic fraction and of the heavy fraction of non-asphaltene hydrocarbons equals 100 wt% of the feedstock to be converted in the first hydroconversion step. In other words, the feedstock to be converted consists of said plastic fraction and of said heavy hydrocarbon fraction.

[0066] Plastic fraction The plastic fraction of the feedstock of the process according to the application comprises plastics, which in turn more particularly comprise polymers. The term "plastic fraction" thus refers to the solid fraction of plastics comprising one or more polymers as defined hereinafter, and which can contain other compounds, such as additives of organic or inorganic origin and / or conventional impurities, in particular from the life cycle of the plastic materials and articles and / or from the waste collection and sorting circuit. For example, the conventional impurities can be metallic, organic or mineral; they can be packaging residues, food residues or compostable residues (biomass). The conventional impurities can also comprise glass, wood, cardboard, paper, aluminium, iron, metals, tyres, rubber, silicones, rigid polymers, thermoset polymers, household products, chemical or cosmetic products, used oil or water.

[0067] The plastics comprised in the plastic fraction of the feedstock of the process according to the application are generally production waste and / or waste, in particular household waste, construction waste or electrical and electronic equipment waste. Preferably, the plastic waste originates from the collection and sorting channel. The plastics or plastic materials are generally polymers, which are generally mixed with additives in order to constitute various materials and objects (injection-moulded parts, tubes, films, fibres, fabrics, mastics, paints, etc.) after shaping. The additives for plastics can be organic compounds or inorganic compounds. They are, for example, fillers, colouring agents, pigments, plasticizers, property modifiers, flame retardants, etc.

[0068] The plastic fraction of the feedstock of the process according to the application thus comprises polymers, and in particular thermoplastic plastics.

[0069] According to the application, the plastic fraction of the feedstock contains at least 70% by weight, preferably at least 80% by weight, in a preferred manner at least 90% by weight, and very preferably at least 95% by weight of polyethylene (PE) in high density and / or low density form, or even consists (100%) of polyethylene (PE) in high density and / or low density form. The term "polyethylene" refers to ethylene polymers and belongs to the family of polyolefins, HDPE and LDPE being homopolymers. In particular, the plastic fraction can comprise at least 70% by weight of PE in high density and low density form, for example it can comprise from 50% to 95% by weight of LDPE and from 5% to 50% by weight of HDPE, in particular from 55% to 70% by weight of LDPE and from 30% to 45% by weight of HDPE.

[0070] The plastic fraction of the feedstock can comprise up to 30% by weight, preferably up to 20% by weight, or even up to 10% or even 5% by weight of other conventional polymers and / or additives and impurities.

[0071] According to one or more embodiments, the plastic fraction of the feedstock comprises PE as defined above mixed with other polymers, and in particular with thermoplastics and / or mixtures of thermoplastics and other polymers, and compounds other than these thermoplastics and polymers, especially additives advantageously used for formulating plastic materials and conventional impurities originating from the life cycle of plastic materials and objects and / or from the waste collection and sorting channels.

[0072] In particular, the plastic fraction of the feedstock can comprise up to 30% by weight of polymers other than PE in high density and / or low density form, selected from other olefin polymers such as polypropylene (PP), copolymers of ethylene and propylene, styrene polymers such as polystyrene (PS) and mixtures thereof.

[0073] The plastic fraction of the feedstock can also comprise up to 5% by weight of other polymers selected from poly(vinyl chloride) (PVC), polyamide (PA), poly(methyl methacrylate) (PMMA) and poly(ethylene terephthalate) (PET) and mixtures thereof.

[0074] The plastic fraction of the feedstock generally comprises less than 30% by weight of these conventional additives and impurities, preferably less than 20% by weight, more preferably less than 10% by weight, and very preferably less than 6% by weight of additives and impurities, relative to the total weight of the plastic fraction of the feedstock.

[0075] It is understood that the sum of the components mentioned (polymers and various impurities) constitutes 100% by weight of the plastic fraction.

[0076] Said plastic fraction of the feedstock can advantageously be pre-treated upstream of the process, in order to remove at least all or part of the "coarse" conventional impurities, i.e. conventional impurities in the form of particles having a size greater than or equal to 10 mm, preferably greater than or equal to 5 mm, or even greater than or equal to 1 mm, of the type of wood, paper, biomass, iron, aluminium, glass, etc., and to shape them, generally in the form of particles (dispersed solids), in order to facilitate their handling in the process. This pre-treatment can comprise a grinding step, a step of washing at atmospheric pressure and / or a drying step. This pre-treatment can be carried out at a different site, for example at a waste collection and sorting centre, or at the same site where the treatment process according to the application is carried out. Preferably, this pre-treatment makes it possible to reduce the content of conventional impurities to less than 6% by weight. At the end of the pre-treatment, the feedstock is generally stored in the form of particles, for example in the form of ground material or powder, in order to facilitate handling and transport until the process.

[0077] In the present description, the term "plastic impurities" means all the compounds in the plastic fraction that are not polymers and that cannot be converted during the course of the hydroconversion step of the process. For example, some organic additives can be at least partially converted during the hydroconversion process in the same way as the polymers. These are thus not considered as plastic impurities. On the other hand, some inorganic additives can be removed during the hydroconversion process, for example those containing metals and / or sulphur and / or nitrogen and / or oxygen and / or other heteroatoms (CI, Br, etc.). They are considered as plastic impurities per se.

[0078] Heavy fraction of non-asphaltene hydrocarbons The heavy fraction of non-asphaltene hydrocarbons of the feedstock of the process according to the application is a heavy hydrocarbon fraction containing at least 90% by weight of a fraction having a boiling temperature (initial boiling point) of at least 300°C, preferably at least 350°C, and again more preferentially at least 375°C.

[0079] The term "non-asphaltene" means that the heavy hydrocarbon fraction comprises less than or equal to 1% by weight, preferably less than or equal to 0.5% by weight, or even less than or equal to 0.1% by weight, or even less than or equal to 0.05% by weight of an asphaltene content, in particular a C7 asphaltene content (compounds insoluble in heptane according to standard ASTM D 6560, also corresponding to standard NFT 60-115).

[0080] This heavy fraction of non-asphaltene hydrocarbons of the feedstock can be derived from the refining of a crude oil, or from the processing of another hydrocarbon source at a refinery, in particular from the atmospheric and / or vacuum distillation of a crude oil and / or of the effluent from thermal conversion, hydrotreatment, hydrocracking and / or hydroconversion units.

[0081] According to one or more embodiments, the heavy fraction of non-asphaltene hydrocarbons is of fossil origin.

[0082] Preferably, the heavy fraction of non-asphaltene hydrocarbons of the feedstock is a vacuum distillate oil (VD or VGO) and / or a deasphalted oil (DAO), advantageously derived from the atmospheric and / or vacuum distillation of a crude oil and / or of the effluent from thermal conversion, hydrotreatment, hydrocracking and / or hydroconversion units.

[0083] The heavy fraction of non-asphaltene hydrocarbons as defined is advantageously used in liquid form. As an indication, such a fraction, in particular a VGO or a DAO, is generally liquid at a temperature higher than 60°C.

[0084] According to one or more embodiments, the heavy fraction of non-asphaltene hydrocarbons of the feedstock of the process contains at least 90% by weight of a fraction having a boiling point of at least 300°C, preferably at least 350°C, again more preferentially at least 375°C, and contains no more than 20% by weight of a fraction having a boiling temperature of at least 540°C, generally corresponding to the definition of a vacuum distillate oil.

[0085] In a preferred manner, the heavy fraction of non-asphaltene hydrocarbons of the feedstock consists of one or more vacuum distillates directly derived from crude oil (also called "straight-run vacuum gas oil" for VGO derived from crude oil) or from distillates from other refining units, especially for example cracking units, such as fluid catalytic cracking (FCC) and hydrocracking, and thermal conversion units, such as coking units or visbreaking units.

[0086] According to one or more embodiments, the heavy fraction of non-asphaltene hydrocarbons of the feedstock consists of one or more deasphalted oils (DAO) from solvent deasphalting units (deasphalting unit raffinates), for example from solvent deasphalting of residues (from straight-run or from conversion processes).

[0087] According to one or more embodiments, the heavy fraction of non-asphaltene hydrocarbons of the feedstock consists of one or more aromatic distillates extracted from lubricant production units.

[0088] According to one or more embodiments, the heavy fraction of non-asphaltene hydrocarbons of the feedstock comprises, and can consist of, FCC fluidized bed catalytic cracking effluents, such as heavy cycle oil (HCO) or light cycle oil (LCO).

[0089] The heavy fraction of non-asphaltene hydrocarbons of the feedstock can also be derived from direct coal liquefaction processes, for example VGO and / or DAO from such processes (for example H-Coal TM Processes).

[0090] According to one or more embodiments, the heavy fraction of non-asphaltene hydrocarbons of the feedstock is derived from direct liquefaction processes of lignocellulosic biomass, alone or mixed with coal and / or petroleum distillates, in particular VGO and / or DAO obtained from such processes.

[0091] According to one or more embodiments, the heavy fraction of non-asphaltene hydrocarbons of the feedstock is not derived from direct liquefaction processes of lignocellulosic biomass, alone or mixed with coal and / or petroleum distillates.

[0092] According to one or more embodiments, the heavy fraction of non-asphaltene hydrocarbons of the feedstock is derived from liquefaction processes of plastics and / or tires and / or solid recovered fuel (SRF), preferably pyrolysis, preferably VGO and / or DAO obtained from such processes.

[0093] Tires are generally composed mainly of rubber (elastomer, such as a mixture of crosslinked synthetic and natural rubber, with additives such as silica, resins, sulfur, zinc oxide, carbon black, etc.) providing elastic properties, and fabric and metal fibers providing reinforcing properties.

[0094] Solid Recovered Fuel (SRF), also known as Refuse Derived Fuel (RDF), is a solid non-hazardous waste prepared for energy upgrading, whether it comes from household waste and similar waste, from economic activity waste or from construction and demolition waste. SRF is usually a mixture of any combustible waste, such as old tires, food by-products (fats, animal meal, etc.), viscose and wood waste, light fractions from shredders (e.g. from old vehicles, WEEE), household and commercial waste, residues from recycling of various types of waste, including notably certain municipal waste, plastic waste, textiles or wood. SRF usually contains plastic waste.

[0095] The liquefaction process of the plastic and / or tire and / or SRF can be thermal pyrolysis, catalytic pyrolysis, hydro-pyrolysis (pyrolysis in the presence of a catalyst and hydrogen) or hydrothermal conversion.

[0096] All these heavy hydrocarbon fractions can be used, alone or as a mixture, to constitute the heavy fraction of non-asphaltene hydrocarbons of the feedstock treated according to the application.

[0097] According to one or more embodiments, the heavy fraction of non-asphaltene hydrocarbons is selected from the following fractions, alone or as a mixture: i) straight run from crude oil or vacuum distillate oil from other refining processes selected from cracking processes, preferably fluidized bed catalytic cracking processes or hydrocracking processes, thermal conversion processes, preferably coking processes or visbreaking processes, coal liquefaction processes, biomass liquefaction processes, liquefaction processes of plastic and / or tire and / or SRF, preferably pyrolysis, and / or ii) solvent deasphalted from solvent deasphalting processes, preferably solvent deasphalted from straight run residues of crude oil or deasphalted oils of other refining processes, and / or iii) one or more aromatic fractions extracted from a lubricant production unit.

[0098] The heavy fraction of non-asphaltene hydrocarbons of the feedstock treated according to the application usually contains impurities, such as sulfur and nitrogen. It can also contain Conradson Carbon Residue, or low contents of other impurities, such as metals, or, as mentioned above, a very small amount of asphaltene, in particular C7 asphaltene insoluble in heptane, the heavy hydrocarbon fraction being defined as "non-asphaltene".

[0099] The metal content, for example the cumulative nickel and vanadium content, or the cumulative nickel, vanadium and iron content, is preferably less than 100 ppm by weight, preferably less than 50 ppm by weight, or even less than 20 ppm by weight.

[0100] The sulphur content can be greater than or equal to 0.1 wt%, or even greater than or equal to 0.5% or 1%, and can be greater than or equal to 2 wt%. Typically, for VGO type feedstocks, the sulphur content is less than or equal to 5 wt%, or even less than or equal to 3 wt%.

[0101] The nitrogen content can be greater than or equal to 1 ppm by weight, or even greater than or equal to 500 ppm by weight or even 0.1 wt%. It is typically less than or equal to 1 wt%.

[0102] The Conradson carbon content can be greater than or equal to 1 wt%, or even up to 15 wt%, in particular for heavy fractions of non-asphaltene hydrocarbons of DAO type. As an indication, VGO can comprise between 1 wt% and 5 wt% of Conradson carbon, and DAO can comprise between 2 wt% and 15 wt% of Conradson carbon. The Conradson carbon content is defined by the standard ASTM D 482 and represents an evaluation of the amount of residual carbon produced after pyrolysis under standard temperature and pressure conditions, which is well known to the person skilled in the art.

[0103] These contents are expressed as wt% (ppm) relative to the total weight of the heavy fraction of non-asphaltene hydrocarbons of the feedstock.

[0104] (a) a step of conditioning the feedstock and injecting the feedstock into a first hydroconversion reactor The process according to the application comprises a step (a) of conditioning the feedstock and injecting the feedstock into a first hydroconversion section 20 comprising at least a first ebullated bed or hybrid bed reactor comprising a first porous supported hydroconversion catalyst.

[0105] The term "conditioning of the feedstock" means conditioning of the feedstock for the subsequent hydroconversion step (b) of the feedstock once it is introduced into the first hydroconversion reactor, that is to say, bringing the feedstock into a state suitable for the hydroconversion in the first hydroconversion reactor and under temperature and pressure conditions.

[0106] The plastic fraction of the feedstock can be introduced into the first hydroconversion reactor as a suspension or in a substantially liquid form, with or without premixing with the heavy fraction of non-asphaltene hydrocarbons of the feedstock.

[0107] The term "plastic fraction in a substantially liquid form" means that at least 80 wt% of the polymers of the plastic fraction are in a liquid form, preferably at least 90 wt%, more preferably at least 95 wt%, and even more preferably at least 98 wt%. The term "polymers of the plastic fraction in a liquid form" means polymers that are not in a solid form, the solid form being generally considered to correspond to the crystalline, semi-crystalline and amorphous states of the polymers.

[0108] The plastic fraction, in solid particles or in substantially liquid form, is preferably mixed with a diluent before its introduction into the first hydroconversion reactor, and, where appropriate, before its mixing with the heavy hydrocarbon fraction of the feedstock. Said diluent, referred to in the present description by the term "plastic diluent" (designated 107 in the attached figures), is formed by a hydrocarbon or mixture of liquid hydrocarbons of the same nature as the heavy fraction of non-asphaltene hydrocarbons, examples of which are not described here again, or consists of a lighter fraction of non-asphaltene hydrocarbons, such as light gas oil (which generally has a boiling range of 200°C to 360°C), lighter liquid hydrocarbons such as xylene, toluene, gasoline, mixtures thereof, etc. The plastic diluent 107 can act as a solvent for the plastic fraction, in particular for the polymers of the plastic fraction.

[0109] Different embodiments of step (a) are possible, distinguished at a first level by the way the feedstock is introduced into the first hydroconversion reactor: - According to a first embodiment of the application, referred to in the present description as "direct injection", the plastic fraction and the heavy fraction of non-asphaltene hydrocarbons are injected separately into the first hydroconversion reactor (i.e. without mixing them before their introduction into the hydroconversion reactor). This first embodiment makes it possible, among other things, to limit the risk of incompatibility between the heavy hydrocarbons of the feedstock and the plastic fraction, which can lead, for example, to the stratification or precipitation of asphaltenes. According to this first embodiment, different variants can be carried out, which are better described below in connection with Figure 1A , 1B , 1C and 1D. These variants are distinguished at a second level by the fact that the plastic fraction is introduced into the hydroconversion reactor in a predominantly liquid form ( Figure 1A and 1B ) or in a slurry form ( Figure 1C and 1D ). - According to a second embodiment of the application, referred to in the present description as "indirect injection", the plastic fraction and the heavy hydrocarbon fraction are mixed before their introduction into the hydroconversion reactor. The advantage of this second embodiment is that the dispersion / dissolution of the plastic fraction in the feedstock is significantly better, and this more homogeneous feedstock introduced into the reactor facilitates, for example, good fluidization of the catalyst and, in general, good hydrodynamic operation of the reactor. It can also allow the use of common equipment, such as furnaces, feedstock distributors, mixers of hydrogen with the feedstock, for example T-type mixers, which can contribute to reducing the investment cost. Likewise, according to this second embodiment, different variants can be carried out, which are better described below in connection with Figure 2A , 2B , 2C, 2D and 2E. These variants are distinguished at a second level by the fact that the plastic fraction, when mixed with the heavy fraction of non-asphaltene hydrocarbons, is in a solid or slurry form ( Figure 2A and 2B ) or in a substantially liquid form ( Figure 2C ,2D and the fact of differentiation between 2E).

[0110] In the drawings, the bold arrows represent the stream in which the plastic fraction is in a substantially liquid form (i.e. at least 90 wt%, preferably at least 95 wt%, more preferably at least 98 wt% of the plastic fraction is in liquid form) and the hatched rectangles represent the device in which the plastic fraction is heated so as to be melted.

[0111] Direct injection: separate injection of fractions into the hydroconversion reactor Step (al) Figure 1A Figure illustrates a first variant of the first embodiment in which the step (a) of conditioning and injecting the feedstock is a step (al) of extruding the plastic fraction and introducing said extruded plastic fraction into the first hydroconversion reactor of the first hydroconversion section 20. The plastic fraction is thus introduced into said reactor in a substantially liquid form.

[0112] The relevant steps and devices other than step (a) in the first embodiment will be described later in the description. Figure 1A

[0113] Extrusion is conventionally a process that enables the injection or shaping of polymers initially in solid state. According to one extrusion process, the material is conveyed, kneaded and heated by one or more screws, which enables its melting. At the same time, the screw conveys the material and increases its pressure, which enables its injection into a die or a mold.

[0114] According to this first variant of the first embodiment of the application, the extrusion of the plastic fraction is a means of introducing a plastic fraction that is solid at room temperature into a hydroconversion reactor operating at high pressure and high temperature. The extrusion thus makes it possible to heat to liquefy the plastic fraction and to pressurize the plastic fraction to the operating conditions of the first hydroconversion reactor operating in step (b).

[0115] The material is not injected into a die or a mold as in a conventional extrusion process, thus does not constitute a shaping process, but is directly injected into the first hydroconversion reactor of the first hydroconversion section 20.

[0116] According to this first variant of the first embodiment of the application, the plastic fraction 102 in the form of solid particles, preferably with a plastic diluent 107 as described above, is fed into an extruder 10 in which it is progressively heated to a temperature above the melting point of said plastic fraction, and is at the pressure of said first hydroconversion reactor during the conveyance preferably for a time of less than 15 minutes, and the plastic fraction 103 thus extruded is introduced into the first hydroconversion reactor of the first hydroconversion section 20.

[0117] ​During the extrusion, the plastic fraction is preferably gradually heated to a temperature above its melting point, so as to melt. Advantageously, at the end of the extrusion, at least 80% by weight of the plastic fraction is in liquid form (molten), very advantageously at least 90%, preferably at least 95%, or even 98% by weight. As mentioned above, the plastic fraction usually contains compounds other than polymers, in particular impurities of plastics. Some of these non-polymeric compounds, including impurities of plastics, can be insoluble and / or have a higher melting point than the polymers of the plastic fraction. Even if all polymers are molten, a part of the liquid fraction can thus still be in solid form, taking into account the non-polymeric compounds. This is the case for all the steps described below, in which heating leads to complete or almost complete liquefaction of the plastic fraction.

[0118] The extrusion temperature depends on the polymer composition of the plastic fraction (nature and proportions of polymers). It can also depend on the plastic diluent 107 added to the plastic fraction during the extrusion.

[0119] Preferably, the extruder 10 is operated at a temperature between 25°C below the melting point of the plastic fraction and 25°C above the melting point of the plastic fraction.

[0120] In the case where the plastic fraction comprises a mixture of polymers, the extruder 10 is operated at a temperature between 25°C below the melting point of the most easily melting polymer of the plastic fraction (i.e. which has the lowest melting point) and 25°C above the melting point of the most difficultly melting polymer of the plastic fraction (i.e. which has the highest melting point). Advantageously, the plastic fraction is preferably gradually heated in the extruder 10 to a temperature above the melting point of the polymer having the highest melting point.

[0121] As a guide, the melting point of polyethylene (PE) is between approximately 85°C and 140°C. The melting point of other polymers such as polypropylene (PP) is approximately 170°C, and the melting point of polystyrene is between approximately 240°C and 270°C.

[0122] The extrusion temperature is preferably such that it limits the thermal degradation of the polymers, which can lead to the formation of undesirable solids. For example, the extrusion temperature is advantageously less than 200°C.

[0123] Preferably, the extruder 10 is operated at a temperature between 60°C and 295°C, more preferably between 60°C and 195°C.

[0124] Advantageously, the extruder 10 is operated at a temperature between 60°C and 165°C, to melt a plastic fraction comprising mainly PE.

[0125] The operating temperature of the extruder is advantageously adjusted according to the composition of the plastic fraction.

[0126] Advantageously, the extruder 10 comprises at least one screw conveying section, called extrusion section, to which the plastic fraction is fed.

[0127] The residence time in this extrusion section, which is the volume of the section divided by the volumetric flow of the plastic fraction, is advantageously less than 15 minutes, preferably less than 10 minutes, and in a preferred manner less than 2 minutes.

[0128] Said extrusion section is advantageously connected to a vacuum extraction system to remove impurities that can be present in the plastic fraction, such as dissolved gases, light organic compounds and / or moisture.

[0129] Said extrusion section can also advantageously comprise a filtration system to remove solid particles of undesirable size, for example of size greater than 200 pm, preferably of size greater than 40 pm, such as sand particles. If a diluent is used to enable the viscosity to be reduced, it is possible to filter particles of smaller size, for example of size greater than 3 pm.

[0130] Within said extrusion section of the extruder 10, the plastic fraction is advantageously contacted with a hydrocarbon-based plastic diluent 107, originating or not from the hydroconversion process according to the application, preferably from the hydroconversion process.

[0131] The use of a plastic diluent has the following advantages: - reduction of the viscosity of the plastic fraction, which in particular allows the diluted plastic fraction to be easily transported over greater distances; - reduction of the operating temperature of the extruder 10, and optional limitation of the thermal degradation of the polymers in the plastic fraction. For example, it is possible to start the extrusion from a temperature of 25°C below the melting temperature of the plastic fraction, at least after the point of contact with the plastic diluent 107; - induction of the dispersion of the polymers of the plastic fraction in a low viscosity phase, to make them more easily mixable with the heavy fraction of non-asphaltene hydrocarbons within the first hydroconversion reactor of the first hydroconversion section 20.

[0132] Separately from the introduction of the extruded plastic fraction, diluted or not, the heavy fraction of non-asphaltene hydrocarbons 101 is introduced into the first hydroconversion reactor, and the hydroconversion step (b) is carried out as described below.

[0133] Before its introduction into the first hydroconversion reactor, the heavy fraction of non-asphaltene hydrocarbons 101 can be mixed with an entrained catalyst precursor 104, so that after the formation of the entrained catalyst, in particular by reaction with sulfur, this entrained catalyst comprises a colloidal or molecular catalyst dispersed in the feedstock.

[0134] The entrained catalyst precursor can be selected from any metal catalyst precursor known to the skilled person which 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 sulphur source and which is capable of effecting the hydroconversion of the feedstock after injection of the feedstock into the first hydroconversion reactor.

[0135] The catalyst precursor is advantageously an oil-soluble catalyst precursor containing at least one transition metal.

[0136] The catalyst precursor preferably comprises an oil-soluble organometallic compound or complex.

[0137] The catalyst precursor can comprise an oil-soluble organometallic or bimetallic compound or complex comprising one or both of the following metals: Mo, Ni, V, Fe, Co or W, or a mixture of these compounds / complexes.

[0138] The oil-soluble catalyst precursor preferably has a decomposition temperature in the range of 100°C to 350°C, more preferably in the range of 150°C to 300°C, most preferably in the range of 175°C to 250°C (below which temperature the catalyst precursor is essentially chemically stable).

[0139] The oil-soluble organometallic compound or complex is preferably selected from the group consisting of molybdenum 2-ethylhexanoate, molybdenum naphthenate, vanadium naphthenate, vanadium octoate, molybdenum hexacarbonyl, vanadium hexacarbonyl and iron pentacarbonyl. These compounds are non-limiting examples of oil-soluble catalyst precursors.

[0140] More preferably, the catalyst precursor comprises Mo and, for example, comprises a compound selected from the group consisting of molybdenum 2-ethylhexanoate, molybdenum naphthenate and molybdenum hexacarbonyl.

[0141] The presently preferred catalyst precursor comprises or consists of molybdenum 2-ethylhexanoate (also commonly known as molybdenum octoate). Typically, molybdenum 2-ethylhexanoate contains 15 wt% of molybdenum and has a sufficiently high decomposition temperature or decomposition temperature range to avoid significant thermal decomposition when mixed with heavy fractions of non-asphaltene hydrocarbons at temperatures below 250°C.

[0142] The skilled person can select a mixing temperature profile such that the selected precursors mix without significant thermal decomposition prior to colloidal or molecular catalyst formation.

[0143] As described in US2005 / 0241991, US10822553 or US10941353 and restated below, the catalyst precursor 104, preferably an oil-soluble catalyst precursor, can be pre-mixed with the hydrocarbon stream of diluent to form a diluted precursor mixture.

[0144] The catalyst precursor 104 can be premixed with the diluent to form a diluted precursor mixture, the premixing preferably being carried out at a temperature lower than the temperature at which a substantial portion of the catalyst precursor begins to decompose, preferably at room temperature, for example between 15°C and 300°C, more preferably between 15°C and 200°C, again more preferably between 50°C and 200°C, again more preferably between 75°C and 150°C, and again more preferably between 75°C and 100°C, advantageously for a period of 1 second to 30 minutes.

[0145] Generally, the diluent for the catalyst precursor is preferably a hydrocarbon oil of the same type as the heavy non-asphaltene hydrocarbon fraction of the feedstock, examples of which are not described herein, generally being a vacuum distillate oil.

[0146] Next, the diluted precursor can be mixed with the heavy non-asphaltene hydrocarbon fraction 101, preferably at ambient temperature, for example at a temperature between 15°C and 300°C, and advantageously mixed for a period of 1 second to 30 minutes, preferably 1 second to 10 minutes, and again more preferably in the range of 2 seconds to 3 minutes. In this specification, a mixing period (or residence time for mixing) of 1 second means instantaneous mixing.

[0147] The mass ratio of catalyst precursor 104 to hydrocarbon oil diluent is preferably in the range of about 1 :500 to about 1 : 1, more preferably in the range of about 1 : 150 to about 1 :2, again more preferably in the range of about 1 : 100 to about 1 :5 (for example 1 : 100, 1 :50, 1 :30 or 1 : 10).

[0148] If not mixed with a diluent, it is preferable to ensure that the components are mixed for a sufficient period of time to fully / closely mix the catalyst precursor into the heavy non-asphaltene hydrocarbon fraction prior to forming the entrained catalyst. However, a long mixing period, for example mixing for 24 hours, can be too expensive for certain industrial operations.

[0149] Premixing the catalyst precursor 104 with the hydrocarbon diluent greatly facilitates the thorough and intimate mixing of the precursor into the heavy non-asphaltene hydrocarbon fraction, particularly in the relatively short period of time required for economically viable large scale industrial operations.

[0150] The diluted precursor is preferably combined with the heavy hydrocarbon fraction and mixed for a sufficient time to disperse the catalyst precursor throughout the non-asphaltene heavy fraction, such that the catalyst precursor is in complete / intimate contact with the non-asphaltene hydrocarbon heavy fraction. To achieve sufficient mixing prior to colloid or molecular catalyst formation, the diluted precursor and non-asphaltene heavy fraction are more preferably mixed for a period of time ranging from 1 second to 10 minutes, and even more preferably from 2 seconds to 3 minutes. Increasing the vigor and / or shear energy of the mixing process generally decreases the time required to achieve complete / intimate mixing. Examples of mixing equipment that can be used to achieve complete / intimate mixing of the catalyst precursor 104 and heavy hydrocarbon fraction 101 include, but are not limited to, high shear mixing, such as in a pump with turbine mixer blades or rotors, multiple static inline mixers, multiple static inline mixers in combination with a high shear inline mixer, multiple static inline mixers in combination with a high shear inline mixer, multiple static inline mixers in combination with a high shear inline mixer, and subsequent recirculation pumping in a storage tank, combinations of the above, and subsequent one or more multi-stage centrifugal pumps.

[0151] The non-asphaltene heavy fraction 101 and the diluted precursor are preferably mixed and conditioned at a temperature ranging from 50°C to 200°C, and more preferably from 75°C to 175°C, prior to introduction of the non-asphaltene heavy fraction into the first hydroconversion reactor. Preferably, the pressure is between 0 MPa and 25 MPa, and more preferably between 0.01 MPa and 5 MPa.

[0152] The non-asphaltene heavy fraction 101, which can contain a diluted or undiluted entrained catalyst precursor, can be heated in at least one preheating device prior to introduction into the hydroconversion reactor. Such preheating can aid in achieving the target temperature in the first hydroconversion reactor in subsequent step (b). The preheating is preferably conducted at a temperature between 280°C and 450°C, and more preferably between 300°C and 400°C, and even more preferably between 320°C and 365°C. Such preheating can be conducted at a temperature that is 100°C, and preferably 50°C, lower than the hydroconversion temperature in the hydroconversion reactor. The absolute pressure during such preheating can range from atmospheric pressure (e.g., 0.101325 MPa) to 38 MPa, and preferably from 5 MPa to 25 MPa, and more preferably from 6 MPa to 20 MPa. The preheating advantageously causes the release of sulfur contained in the non-asphaltene heavy fraction, which can combine with the metals of the catalyst precursor. A colloid or molecular catalyst can form, or at least begin to form, in situ in the non-asphaltene heavy fraction during such preheating step. To form the colloid or molecular catalyst, sulfur must be available (e.g., as H2S) to combine with the metals of the dispersed catalyst precursor composition. The entrained catalyst can also form in the hydroconversion step (b).

[0153] In the case where the heavy fraction of non-asphaltic hydrocarbon contains a sufficient amount or an excess amount of sulfur, the final activated catalyst can be formed in situ by heating the heavy fraction of non-asphaltic hydrocarbon to a temperature sufficient to release sulfur therefrom. The source of sulfur can thus be H2S dissolved in the heavy fraction of non-asphaltic hydrocarbon, or H2S contained in the hydrogen gas recycled to the hydroconversion reactor, or H2S originating from sulfur-containing organic molecules present in the heavy fraction of non-asphaltic hydrocarbon or optionally previously introduced into the non-asphaltic heavy fraction (for example: any sulfur-containing hydrocarbon feedstock of the type injected dimethyl disulfide, thioacetamide, such as mercaptans, sulfides, sulfur-containing gasoline, sulfur-containing gas oil, sulfur-containing vacuum distillate oil, sulfur-containing residual oil).

[0154] Thus, the source of sulfur can be a sulfur compound in the heavy fraction of non-asphaltic hydrocarbon or a sulfur compound added to the heavy fraction.

[0155] The temperature during the preheating of the heavy hydrocarbon fraction and / or in step (b) is such that it enables the formation of a metal sulfide catalyst.

[0156] The metal concentration of the catalyst in the feedstock, i.e. the heavy fraction of non-asphaltic hydrocarbon together with the plastic fraction, preferably the concentration of Mo, is preferably comprised between 5 ppm by weight and 500 ppm by weight of the feedstock, more preferably between 10 ppm by weight and 300 ppm by weight, more preferably between 10 ppm by weight and 175 ppm by weight, again more preferably between 10 ppm by weight and 75 ppm by weight, and again more preferably between 10 ppm by weight and 50 ppm by weight.

[0157] Preferably, the colloidal or molecular catalyst comprises molybdenum disulfide.

[0158] Step (a2) Alternatively, in step (a), the plastic fraction in the form of solid microparticles can be mixed with a plastic diluent in the mixing section and heated in the heating section in order to obtain a substantially liquid plastic fraction before introducing it into the first hydroconversion reactor (for example at a temperature higher than the melting temperature of the plastic fraction, preferably between 60°C and 295°C), this heating step possibly being carried out before or after mixing with the plastic diluent, and preferably after mixing with the plastic diluent.

[0159] Thus, step (a) can be step (a2) of directly injecting the plastic fraction in a substantially liquid form after mixing the plastic fraction with a plastic diluent 107 to form a slurry, then heating it to obtain a substantially liquid plastic fraction.

[0160] Figure 1B This second variant of the first embodiment of the process according to the application is illustrated.

[0161] This variant has in particular the advantage of using simple low-cost equipment.

[0162] The plastic fraction 102 in the form of solid particles is first mixed in a mixing section 11 with a plastic diluent 107 to form a suspension 108, which is then sent to a heating section 12 to be heated to a temperature higher than the melting temperature of the plastic fraction, to melt the solid particles of the suspended plastic fraction, and to introduce the heated plastic fraction 109 into the first hydroconversion reactor of the first hydroconversion section 20. The mixing of the plastic diluent 107 and the particulate plastic fraction 102 in the mixing section 11 is preferably carried out at atmospheric pressure or close to atmospheric pressure.

[0163] Preferably, during the mixing step in the mixing section 11, the temperature is such that the suspension 108 has a kinematic viscosity of less than 0.3 x 10 -3 m 2 / s, which corresponds to the viscosity of a pumpable fluid. In case the mixing step is separate and precedes the heating step, the temperature of this step is preferably lower than the temperature at which the heating step is operated.

[0164] The mixing section 11 can comprise a mixing tank, which includes dynamic blending means for achieving the suspension, such as a stirrer and / or a recirculation pump.

[0165] At the end of the heating of the suspension 108, at least 90% by weight of the heated plastic fraction 109 is advantageously in liquid form, very advantageously at least 95% by weight, preferably at least 98% by weight.

[0166] The description already made in step (al) of the temperature conditions of the extruder 10 applies to the heating of the suspension in step (a2) and is therefore not repeated here.

[0167] However, it is again noted that the heating temperature can also depend on the plastic diluent 107 used, according to its nature, such a plastic diluent being in particular able to melt the suspended plastic fraction at a lower temperature.

[0168] The heating section 12 comprises any heating means known to the person skilled in the art able to heat the suspended plastic fraction 108. The heating section 12 can comprise an oven comprising at least one heating compartment, and / or a pipe in which the suspension 108 flows, any type of suitable heat exchanger, etc.

[0169] According to one configuration, the mixing section 11 and the heating section 12 can constitute part of the same device configured to carry out successively the mixing and then the heating of step (a2).

[0170] Before being introduced into the first hydroconversion reactor, the heated plastic fraction 109 is preferably pressurized to a pressure suitable for operation in the first hydroconversion reactor, for example by means of a suitable pump. It may also undergo a filtration step, which is intended, for example, to remove solid particles from the plastic fraction that can form part of the impurities in the plastic, such as sand, glass, metal, certain additives known as fillers, etc.

[0171] Separately from the introduction of the heated plastic fraction 109, the non-asphaltene hydrocarbon heavy fraction 101 is introduced into the first hydroconversion reactor of the first hydroconversion section 20, and the hydroconversion step (b) as described below is carried out.

[0172] Before introducing it into the first hydroconversion reactor, the heavy fraction 101 of non-asphaltene hydrocarbons can be mixed with the entrained catalyst precursor 104 so that, after the formation of the entrained catalyst (especially by reaction with sulfur), the entrained catalyst comprises a colloidal or molecular catalyst dispersed in the feedstock. The content described in step (a1) regarding this subject matter also applies here and will not be repeated.

[0173] In another variant (not shown) of the first embodiment of the method according to the invention, step (a) may be step (a'2) of directly injecting the plastic fraction in the form of a basic liquid after the plastic fraction has been heated to obtain a basic liquid plastic fraction and then mixed with plastic diluent 107 to form a diluted plastic fraction introduced into the first hydroconversion reactor.

[0174] According to another variant, the mixing step and the heating step are performed simultaneously, and the mixing and heating sections thus form part of the same device configured to perform mixing and heating simultaneously.

[0175] Step (a3) Alternatively, step (a) can be step (a3) ​​of directly injecting the suspended plastic fraction into the first hydroconversion reactor.

[0176] Figure 1C This third variant illustrates a first embodiment of the method according to the invention.

[0177] This variant is particularly advantageous due to its use of simple, low-cost equipment.

[0178] According to step (a3), the plastic fraction 102 in the form of solid particles is first fed to the mixer 13 to be mixed with the plastic diluent 107 to form a suspension 110, and then the plastic fraction in the form of suspension 110 is introduced into the first hydroconversion reactor of the first hydroconversion section 20.

[0179] The mixing of the plastic diluent 107 and the plastic fraction 102 in the mixer is preferably carried out at a temperature greater than or equal to room temperature, for example 15°C, and lower than the melting point of the plastic fraction (or, if the plastic fraction comprises a blend of polymers, lower than the melting point of the polymer having the lowest melting point). Temperatures slightly lower than the melting point of the plastic fraction can constitute the upper limit of the mixing temperature, since the plastic diluent 107 used has an influence on the temperature at which the plastic fraction can be solubilized (in the case where the plastic diluent acts as a solvent), according to its nature.

[0180] According to one configuration, the mixing can be carried out at a temperature greater than or equal to 50°C or even 75°C and less than 140°C, or also at a temperature greater than or equal to 50°C or even 75°C and less than 85°C, for example very suitable for using VGO as plastic diluent and a plastic fraction comprising mainly PE as polymer.

[0181] The mixing can be active or not. Examples of active mixing equipment that can be used include, but are not limited to, high shear mixing, such as mixing made in a pump with turbine mixer blades or rotors, multiple static inline mixers, multiple static inline mixers combined with high shear inline mixers, multiple static inline mixers combined with high shear inline mixers, multiple static inline mixers combined with high shear inline mixers and subsequent recirculation pumping in a storage tank, combinations of the above equipment and subsequent one or more multi-stage centrifugal pumps.

[0182] Separately from the introduction of the suspended plastic fraction 110, the heavy fraction of non-asphaltene hydrocarbons 101 is introduced into the first hydroconversion reactor of the first hydroconversion stage 20 and a hydroconversion step (b) is carried out as described below.

[0183] Before their introduction into the first hydroconversion reactor, the heavy fraction of non-asphaltene hydrocarbons 101 can be mixed with the entrained catalyst precursor 104 so that, after the formation of the entrained catalyst (in particular by reaction with sulfur), the entrained catalyst comprises a colloidal or molecular catalyst dispersed in the feedstock. What is described on this subject in step (al) applies equally here and is not repeated.

[0184] Before their introduction into the first hydroconversion reactor, the suspended plastic fraction 110 and the heavy fraction of non-asphaltene hydrocarbons 101 can be subjected to a pressurization step to a pressure suitable for the operation in the first hydroconversion reactor.

[0185] Step (a4) Alternatively, step (a) can be a step (a4) of direct injection of the plastic fraction in the form of a suspension into the hydroconversion reactor via means for injecting the porous supported hydroconversion catalyst into the hydroconversion reactor.

[0186] Figure 1D Figure illustrating this fourth variant of the first embodiment of the process according to the application.

[0187] This variant has in particular the advantage of injecting the plastic fraction of feedstock using existing particle injection means in the reactor (supported catalyst).

[0188] According to step (a4), the plastic fraction 102 in the form of solid particles is pre-mixed with the plastic diluent 107 and with the first porous supported hydroconversion catalyst in a distribution and mixing tank 14 to form a suspension 112, which is then introduced into the first hydroconversion reactor of the first hydroconversion section 20 via the means for injecting the catalyst into the reactor.

[0189] The distribution and mixing tank 14 constitutes part of the means for taking out and injecting the porous supported catalyst in the first hydroconversion reactor.

[0190] Preferably, the plastic fraction 102 in the form of solid particles is fed intermittently into the distribution and mixing tank 14.

[0191] The first hydroconversion reactor, like each ebullated bed or hybrid hydroconversion reactor used in the process according to the application, comprises means for injecting and taking out the supported catalyst in the reactor.

[0192] In particular, one essential aspect of the operation of an ebullated bed or hybrid reactor is the continuous replacement of the supported catalyst. Catalyst replacement is generally required in all hydrocarbon hydroconversion processes, since the supported catalyst is deactivated mainly by deposition of the metals contained in the feedstock (for example in the form of vanadium sulphide and nickel sulphide) and by deposition of coke. In particular, although the ebullated bed technology, compared to other technologies such as fixed bed technology, enables an increase in the time between two conversion process stoppages by continuous catalyst renewal, it requires the implementation of a system for continuous catalyst renewal, in which for example the catalyst is taken out and replenished every day. The spent catalyst taken out of the reactor can be sent to a regeneration zone, in which the carbon and sulphur contained therein are removed. It is also possible to send the spent catalyst taken out of the reactor to a rejuvenation zone, in which most of the deposited metals are removed, and then to send the spent and rejuvenated catalyst to a regeneration zone, in which the carbon and sulphur contained therein are removed. The regenerated or rejuvenated catalyst can then be reintroduced into the reactor, optionally in combination with fresh catalyst, by means for injecting the catalyst.

[0193] Generally, the means for injecting and withdrawing the supported catalyst comprise at least one conduit leading into the expansion zone of the supported catalyst of the reactor for introducing fresh (and / or regenerated and / or rejuvenated) supported catalyst into the expansion zone of the supported catalyst of the reactor and withdrawing spent catalyst from said zone. The introduction and withdrawal can be carried out with the same conduit, or by means of separate conduits, thus requiring at least two conduits, i.e. an injection conduit for injecting the supported catalyst into the reactor and a conduit for withdrawing the spent catalyst.

[0194] According to step (a3), the suspension 112 formed by mixing the particulate plastic fraction 102, the supported catalyst 111 and the plastic diluent 107 in the distribution and mixing tank 14 is injected into the reactor via the supported catalyst injection means, in particular via a conduit connected at one end to said distribution and mixing tank 14 and leading at the other end to the supported catalyst expansion zone of the first hydroconversion reactor. Said conduit can comprise means for controlling the circulation of the injected slurry, such as valves and / or other elements, like pumps, tanks, etc. The means for injecting the supported catalyst into the first hydroconversion reactor are thus also means for injecting the plastic fraction into said first reactor as a suspension.

[0195] The heavy fraction of non-asphaltene hydrocarbons 101 is introduced into the first hydroconversion reactor of the first hydroconversion section 20 in a separate manner from the introduction of the suspension 112 comprising the plastic fraction and the first supported hydroconversion catalyst, and the hydroconversion step (b) is carried out as described below.

[0196] Before its introduction into the first hydroconversion reactor, the heavy fraction of non-asphaltene hydrocarbons 101 can be mixed with the entrained catalyst precursor 104 so that, after formation of the entrained catalyst, in particular by reaction with sulfur, the entrained catalyst comprises a colloidal or molecular catalyst dispersed in the feedstock. What is described on this subject in step (al) applies equally here and is not repeated.

[0197] Indirect injection: mixing of the fraction before injection into the hydroconversion reactor According to a second embodiment of the application, as an alternative to the first embodiment, in step (a), the plastic fraction of the feedstock (114, 117, 120, 122, 125) and the heavy fraction of non-asphaltene hydrocarbons are mixed and introduced into said at least one first hydroconversion reactor of the first hydroconversion section 20. The different variants can be implemented according to the alternative steps (a5) to (a9) described below. Figures 2A to 2E The different variants can be implemented according to the alternative steps (a5) to (a9) described below.

[0198] These variants are at a second level by the plastic fraction being in solid or slurry form (a5) when mixed with the heavy fraction of non-asphaltene hydrocarbons Figure 2A and 2B or in mainly liquid form (a6)Figure 2C , 2D and the fact of the differentiation of 2E).

[0199] Step (a5) Figure 2A Figure illustrates a first variant of the second embodiment, in which the step (a) of conditioning and injection of the feedstock is a step (a5) in which the plastic fraction is mixed in solid form with the non-asphaltene heavy fraction. The mixture then forms a suspension and constitutes the feedstock, which is heated before being introduced into the first hydroconversion reactor of the first hydroconversion section 20 to obtain a plastic fraction which is substantially liquid.

[0200] This variant has in particular the advantage of injecting into the first hydroconversion reactor a mixture comprising a plastic fraction which has been dispersed in the feedstock, to be able to achieve a good suspension of the plastic fraction by means of the heavy fraction of non-asphaltene hydrocarbons used for the suspension, and to increase the dissolution rate of the plastic fraction if appropriate.

[0201] According to step (a5), the plastic fraction 102 in the form of solid particles is first mixed in the mixing device 15 with the heavy fraction of non-asphaltene hydrocarbons 101 to form a suspension 113.

[0202] Said mixing in the mixing device 15 is preferably carried out at a temperature greater than or equal to room temperature, for example 15°C, and lower than the melting point of the plastic fraction (or, if the plastic fraction comprises a blend of polymers, lower than the melting point of the polymer with the lowest melting point).

[0203] Advantageously, this mixing can be carried out at a temperature greater than or equal to 50°C or even 75°C and less than 140°C, or at a temperature greater than or equal to 50°C or even 75°C and less than 85°C, for example very suitable for using a plastic fraction comprising mainly PE as polymer.

[0204] This mixing can be active or not. The same examples of active mixing equipment that can be used are, but are not limited to, those already described in connection with step (a3) for mixing the plastic component with the plastic diluent.

[0205] Before being introduced into the mixing device 15, the heavy fraction of non-asphaltene hydrocarbons 101 can be mixed with the entrained catalyst precursor 104, so that, after formation of the entrained catalyst (in particular by reaction with sulfur), this entrained catalyst comprises a colloidal or molecular catalyst dispersed in the feedstock. What is described on this subject in step (a1) applies equally here and is not repeated.

[0206] The suspension 113 is then heated in the heating device 16 to melt the solid particles of the plastic fraction. The suspension 113 is thus heated to a temperature above the melting point of the plastic fraction. At the end of the heating of the suspension 113, at least 90% by weight of the plastic fraction of the feedstock 114 is advantageously in liquid form, very advantageously at least 95% by weight, preferably at least 98% by weight.

[0207] Preferably, the suspension 113 is heated to reach the target temperature in the first reactor. The heating is preferably carried out at a temperature between 280°C and 450°C, again more preferably between 300°C and 400°C, and again more preferably between 320°C and 365°C. This preheating can be carried out at a temperature 100°C lower than the hydroconversion temperature in the hydroconversion reactor, preferably 50°C lower.

[0208] The heating section 16 comprises any heating device known to the person skilled in the art capable of heating the suspended plastic fraction 113. The heating section 16 can comprise an oven comprising for example at least one heating compartment, and / or a pipe in which the suspension flows, a mixer for mixing the feedstock with H2, any suitable type of heat exchanger, for example a pipe or spiral heat exchanger in which the suspension flows, etc.

[0209] According to one configuration, the mixing section 15 and the heating section 16 can constitute part of a similar configuration of device for carrying out successively the mixing and then the heating of step (a5).

[0210] The feedstock 114, which is substantially in liquid form and comprises the plastic fraction and the heavy fraction of non-asphaltene hydrocarbons as a mixture, is then introduced into the first hydroconversion reactor of the first hydroconversion section 20 and a hydroconversion step (b) is carried out as described below.

[0211] Preferably, a pressurization step is carried out after the heavy fraction of non-asphaltene hydrocarbons has been mixed with the plastic fraction and before the heating section, to adapt the feedstock 114 to the pressure at which the first hydroconversion reactor operates.

[0212] Step (a6) Alternatively, step (a) can be an indirect injection step (a6) in which the plastic fraction is first mixed with a diluent in solid form and then blended with the non-asphaltene heavy fraction. The final mixture then forms a suspension and constitutes a feedstock which is heated to obtain a plastic fraction which is substantially liquid before introducing it into the first hydroconversion reactor of the first hydroconversion section 20.

[0213] Figure 2B This second variant of the second embodiment of the process according to the application illustrated in Figure 2 thus differs from step (a5) only in that the fine plastic fraction 102 is pre-mixed with the plastic diluent 107 in the first mixer 17 to produce the first suspension 115.

[0214] This variant in particular offers the advantages mentioned for step (a5) and, where appropriate, also better dissolution of the liquid fraction.

[0215] The operating conditions for this premixing in the first mixer 17 as well as the mixing type and the associated devices are the same as those already described with respect to step (a3) for the mixing of the plastic fraction and the plastic diluent, and are not repeated here.

[0216] The first suspension 115 is then mixed in the second mixer 18 with the heavy fraction of non-asphaltene hydrocarbons 101 in the same way as described above in step (a5) to form a second suspension 116, and is not repeated here.

[0217] The heavy fraction of non-asphaltene hydrocarbons 101 can be mixed with the entrained catalyst precursor 104 before its introduction into the mixing device 15, so that after the formation of the entrained catalyst, in particular by reaction with sulfur, this comprises a colloidal or molecular catalyst dispersed in the feedstock. What is described in step (al) with respect to this subject matter also applies here and is not repeated.

[0218] The heating of the second suspension 116 in the heating device 19 is also carried out in the same way as described in step (a5) for the heating of the suspension 113 and enables the solid particles of the plastic fraction to be melted. At the end of the heating of the second suspension 116, at least 90% by weight of the plastic fraction of the feedstock is advantageously in liquid form, very advantageously at least 95%, preferably at least 98% by weight.

[0219] The feedstock 117 obtained from the heating of the second suspension 116 in the heating device 19, comprising the substantially liquid plastic fraction and the heavy fraction of non-asphaltene hydrocarbons as a mixture, is then introduced into the first hydroconversion reactor of the first hydroconversion stage 20 and the hydroconversion step (b) is carried out as described below.

[0220] Step (a7) Alternatively, step (a) can be an indirect injection step (a7) in which the plastic fraction is heated before mixing with the heavy fraction of non-asphaltene hydrocarbons so as to be in substantially liquid form.

[0221] Figure 2C This third variant of the second embodiment of the process according to the application is illustrated.

[0222] The advantages of this variant in particular lie in the fact that it avoids managing a suspension of the plastic fraction, in particular by dispensing with the need for associated mixing equipment.

[0223] According to step (a7), the plastic fraction 102 in the form of solid particles is first heated in a melting device 21 to melt said plastic fraction. To this end, the plastic fraction is heated to a temperature above the melting temperature of said plastic fraction. Advantageously, at the end of this heating, at least 80% by weight of the plastic fraction is in liquid form, very advantageously at least 90%, preferably at least 95%, or even 98% by weight.

[0224] The description already made in step (al) of the temperature conditions of the extruder 10 applies to the heating of the plastic fraction in the liquefaction device 21 in this step (a7), and is therefore not repeated here.

[0225] The melting device 21 comprises any heating device known to the person skilled in the art capable of melting a solid plastic fraction. The melting device 21 can comprise an oven, a heated tank, etc. The melting device 21 can comprise a mixing device for blending the existing phases during the melting.

[0226] The melting device can be an extruder as described in step (al).

[0227] The melted plastic fraction 118 is then mixed in a mixer 22 with the heavy fraction of non-asphaltene hydrocarbons 101 to form a feedstock 119, which is then introduced into the first hydroconversion reactor of the first hydroconversion stage 20, and subjected to the hydroconversion step (b) as described below.

[0228] Said mixing in the mixer 22 is preferably carried out at a temperature between 85°C or even 100°C and 350°C, preferably between 150°C and 250°C. The temperature is advantageously adjusted according to the viscosity of the mixture.

[0229] Before its introduction into the mixing device 22, the heavy fraction of non-asphaltene hydrocarbons 101 can be mixed with the entrained catalyst precursor 104 so that, after the formation of the entrained catalyst, in particular by reaction with sulfur, the entrained catalyst comprises a colloidal or molecular catalyst dispersed in the feedstock. What is described in step (al) on this subject also applies here and is not repeated.

[0230] The entrained catalyst precursor 104 can also be mixed with the feedstock 119 from the mixer 22 before its introduction into the first hydroconversion reactor - in addition to or instead of the mixing with the heavy fraction of non-asphaltene hydrocarbons 101. In this case, the mixing is similar to what has been described for the mixing with the heavy fraction of non-asphaltene hydrocarbons 101.

[0231] Step (a8) Alternatively, step (a) can be an indirect injection step (a8) in which the plastic fraction is pre-mixed in solid form with a plastic diluent before being mixed with the heavy fraction of non-asphaltene hydrocarbons, then heated so as to be in substantially liquid form.

[0232] Figure 2D This fourth variant of the second embodiment of the process according to the application illustrated in the figure thus differs from step (a7) only in that the particulate plastic fraction 102 is premixed with the plastic diluent 107 in a premixer 17 to produce a suspension 120.

[0233] This variant has in particular the advantage of good dispersion and / or good dissolution of the plastic fraction and offers greater flexibility in mixing with the heavy fraction of non-asphaltene hydrocarbon, in particular in terms of target viscosity.

[0234] The operating conditions for this premixing in the premixer 17 as well as the type of mixing and associated devices are the same as those already described in connection with steps (a3) and (a6) regarding the mixing of the plastic fraction and the plastic diluent, and are not repeated here.

[0235] The suspension 120 is then heated in a heating device 23 to a temperature higher than the melting temperature of the plastic fraction to melt the solid particles of the suspended plastic fraction.

[0236] At the end of the heating of the suspension 120, at least 90% by weight of the plastic fraction is advantageously in liquid form, very advantageously at least 95%, preferably at least 98% by weight.

[0237] The description already made in step (al) of the temperature conditions of the extruder 10 applies to the heating of the suspension 120 in step (a8), which is not repeated here.

[0238] However, it is again noted that the heating temperature can also depend on the plastic diluent 107 used, such a plastic diluent being in particular able to melt the suspended plastic fraction at a lower temperature according to its nature.

[0239] The heating section 23 comprises any heating device known to the person skilled in the art able to heat the suspended plastic fraction 120. The heating section 23 can comprise an oven comprising at least one heating compartment, and / or a pipe in which the suspension 120 flows, any type of suitable heat exchanger, etc.

[0240] According to one configuration, the mixing section 17 and the heating section 23 can constitute part of the same device configured to carry out successively the mixing and then the heating of step (a8).

[0241] The melted diluted plastic fraction 121 is then mixed in a mixer 22 with the heavy fraction of non-asphaltene hydrocarbon 101 in the same way as described for the mixer 22 in step (a7) to form a feedstock 122 which is then introduced into the first hydroconversion reactor of the first hydroconversion section 20 and subjected to the hydroconversion step (b) described below.

[0242] The heavy fraction of non-asphaltene hydrocarbons 101 can be mixed with the entrained catalyst precursor 104 before it is introduced into the mixer 22 so that, after formation of the entrained catalyst, especially by reaction with sulfur, the entrained catalyst comprises a colloidal or molecular catalyst dispersed in the feedstock. What has been described in step (al) in this respect applies equally here and is not repeated.

[0243] The entrained catalyst precursor 104 can also be mixed with the feedstock 122 from the mixer 22 before it is introduced into the first hydroconversion reactor - in addition to or instead of the heavy fraction of non-asphaltene hydrocarbons 101. In this case, the mixing is similar to what has been described for the mixing with the heavy hydrocarbon fraction 101.

[0244] The entrained catalyst precursor 104 can also be mixed with the liquid plastic fraction 121 before it is mixed with the heavy hydrocarbon fraction in the mixer 22 - in addition to or instead of the heavy fraction of non-asphaltene hydrocarbons 101 or the mixing with the feedstock 122. In this case, the mixing is similar to what has been described for the mixing with the heavy fraction of non-asphaltene hydrocarbons 101.

[0245] Step (a9) Alternatively, step (a) can be an indirect injection step (a9) in which the plastic fraction is heated before mixing with the heavy fraction of non-asphaltene hydrocarbons so as to be in substantially liquid form, then mixed with the diluent.

[0246] Figure 2E This fifth variant of the second embodiment of the process according to the application is illustrated.

[0247] This variant offers in particular the advantage of good dispersion and / or good dissolution of the plastic fraction.

[0248] According to step (a9), the plastic fraction 102 in solid particulate form is first heated in the melting device 24 in the same way as described in step (a7) to melt said plastic fraction. To this end, the plastic fraction is heated to a temperature higher than the melting temperature of said plastic fraction. Advantageously, at the end of this heating, at least 80% by weight of the plastic fraction is in liquid form, very advantageously at least 90%, preferably at least 95%, or even 98% by weight.

[0249] What has been described in step (al) in respect of the temperature conditions of the extruder 10 applies to the heating of the plastic fraction in the melting device 24 in this step (a9) and is not repeated here.

[0250] The melting device 24 is the same as described in step (a7) for the melting device 21 and is not repeated here.

[0251] The molten plastic fraction 123 is then mixed in a first mixer 25 with a plastic diluent 107 to form a diluted molten plastic fraction 124.

[0252] The mixing in the first mixer 25 is preferably carried out at a temperature higher than the melting point of the plastic fraction, for example higher than 85°C or even higher than 100°C, and lower than or equal to 350°C, preferably between 150°C and 250°C.

[0253] The first mixer can comprise a static mixer or a dynamic mixer, such as a stirred tank, preferably a static mixer.

[0254] The diluted molten plastic fraction 124 is then mixed in a second mixer 26 with the heavy fraction of non-asphaltene hydrocarbons 101 to form a feedstock 125 which is then introduced into the first hydroconversion reactor of the first hydroconversion section 20 and subjected to a hydroconversion step (b) as described below.

[0255] The mixing in the mixer 26 is preferably similar to that described for the mixer 22 in step (a7).

[0256] Before its introduction into the mixing device 26, the heavy fraction of non-asphaltene hydrocarbons 101 can be mixed with the entrained catalyst precursor 104 so that, after the formation of the entrained catalyst, especially by reaction with sulfur, this entrained catalyst comprises a colloidal or molecular catalyst dispersed in the feedstock. What is described in step (al) on this subject also applies here and is not repeated.

[0257] The entrained catalyst precursor 104 can also be mixed with the diluted molten plastic fraction 124 before its mixing in the mixer 26 with the heavy hydrocarbon fraction - in addition to or instead of the mixing of this precursor with the heavy fraction of non-asphaltene hydrocarbons 101. In this case, the mixing is similar to that already described for the mixing with the heavy fraction of non-asphaltene hydrocarbons 101.

[0258] The entrained catalyst precursor 104 can also be mixed with the molten plastic fraction 123 before its mixing in the mixer 25 with the heavy fraction of non-asphaltene hydrocarbons 101 - in addition to or instead of the mixing of this precursor with the heavy fraction of non-asphaltene hydrocarbons 101. Figure 1A The hydrocarbon-based diluent mixing already described in relation to the catalyst precursor - in addition to or instead of the mixing of this precursor with the heavy fraction of non-asphaltene hydrocarbons 101 or with the diluted molten plastic fraction 124. In this case, the mixing is similar to that already described for the mixing with the heavy fraction of non-asphaltene hydrocarbons 101.

[0259] (b) First hydroconversion step The feedstocks (101, 102, 114, 117, 119, 122, 125) are introduced into the first hydroconversion reactor of the first hydroconversion section 20, either separately or mixed, with hydrogen. The first reactor contains a first porous supported hydroconversion catalyst.

[0260] The first hydroconversion step (b) is carried out under conditions providing a first hydroconversion effluent 105. The first hydroconversion effluent 105 contains conversion products; notably, the first effluent has a reduced content of hydrocarbons having a boiling point of at least 300°C. The first hydroconversion effluent 105 can also have a reduced content of sulfur, and / or metals, and / or nitrogen, and / or Conradson carbon, and / or asphaltenes, depending on the reactions carried out in the first hydroconversion reactor.

[0261] Step (b) is preferably carried out at a pressure between 2 MPa and 38 MPa, more preferably between 5 MPa and 25 MPa, and again more preferably between 6 MPa and 20 MPa, absolute, at a temperature between 350°C and 550°C, more preferably between 350°C and 500°C, and preferably between 370°C and 450°C.

[0262] The hourly space velocity (HSV) is preferably between 0.05 h -1 and 10 h -1 , relative to the volume of each reactor. According to one preferred embodiment, the HSV is between 0.1 h - 1 and 10 h -1 , more preferably between 0.1 h -1 and 5 h -1 , again more preferably between 0.15 h -1 and 2 h -1 , and again more preferably between 0.15 h -1 and 1 h -1 . According to another embodiment, the HSV is between 0.05 h -1 and 0.09 h -1 .

[0263] The amount of hydrogen mixed with the feedstock is preferably between 50 and 5000 normal cubic meters (Nm 3 ) per cubic meter (m 3 ) of liquid feedstock, preferably between 100 Nm 3 / m 3 and 2000 Nm 3 / m 3 , and very preferably between 200 Nm 3 / m 3 and 1000 Nm 3 / m3 between.

[0264] The first hydroconversion section 20 comprises one or more fluidized bed or hybrid bed reactors containing at least one first supported hydroconversion catalyst, which may be arranged in series and / or in parallel. In this step, at least the first supported hydroconversion catalyst is thus held in the reactor. According to one or more embodiments of the invention, the first hydroconversion section 20 includes reactors that can be arranged in series and / or in parallel, operating as a fluidized bed, such as for H-Oil. TM One or more hydroconversion reactors for the process, such as, for example, patents US 4,521,295, US 4,495,060, US 4,457,831, or US 4,354,852; paper Aiche, March 19-23, 1995, Houston, Texas, paper number 46d, “Secondgeneration ebullated bed technology”; or chapter 3.5, “Hydroprocessing and Hydroconversion of Residue Fractions,” in the book “Catalysis by Transition Metal Sulfides” published by Technip in 2013. According to this or these embodiments, each reactor operates as a fluidized bed, referred to as a boiling bed. Each reactor advantageously includes a recirculation pump, which enables the porous supported solid catalyst to be maintained as a boiling bed through continuous recirculation of at least a portion of the liquid fraction removed from the top of the reactor and reinjected into the bottom of the reactor.

[0265] The ebullated bed reactor preferably comprises at least one feed opening in the lower part of the reactor or in its vicinity, through which the feedstock is introduced together with hydrogen, in particular two feed openings in case the plastic fraction of the feedstock is introduced separately from the heavy fraction of the non-asphaltene hydrocarbons, and a discharge opening in the upper part of the reactor or in its vicinity, through which the first hydroconversion effluent 105 is withdrawn. The reactor also preferably comprises an inlet and an outlet for the supported catalyst as already described above in connection with the means for injecting and withdrawing the supported catalyst. The ebullated bed reactor also comprises an expanded catalyst zone comprising the porous supported catalyst. The ebullated bed reactor also comprises a lower zone free of supported catalyst below the expanded catalyst zone and an upper zone free of supported catalyst above the expanded catalyst zone. The feedstock is continuously recycled from the upper zone free of supported catalyst to the lower zone free of supported catalyst in the ebullated bed reactor by means of a recycle conduit in communication with the ebullating pump. Preferably, a funnel-shaped recycle pan is located in the upper part of the recycle conduit through which the feedstock is drawn from the upper zone free of supported catalyst. The internally recycled feedstock is mixed with "fresh" feedstock and additional hydrogen.

[0266] The first supported hydroconversion catalyst used in the first hydroconversion step (b) can contain one or more elements of Groups 4 to 12 of the Periodic Table of the Elements, which can or can not be deposited on a support. Catalysts comprising an amorphous support, such as silica, alumina, silica-alumina, titania or combinations of these structures, very preferably alumina, can be advantageously used.

[0267] The first supported catalyst can contain at least one Group VIII non-noble metal selected from the group consisting of nickel and cobalt, preferably nickel, said Group VIII element being preferably used in combination with at least one Group VIB metal selected from the group consisting of molybdenum and tungsten; preferably, the Group VIB metal is molybdenum.

[0268] In the present description, the groups of chemical elements are given according to the CAS classification (CRC Handbook of Chemistry and Physics, published by CRC Press, Editor D.R. Lide, 81st edition, 2000-2001). For example, the Group VIII (or VIIIB) according to the CAS classification corresponds to the metals of columns 8, 9 and 10 according to the new IUPAC classification.

[0269] Advantageously, the first supported hydroconversion catalyst used in the first hydroconversion step (b) comprises an alumina support and at least one Group VIII metal selected from the group consisting of nickel and cobalt, preferably nickel, and at least one Group VIB metal selected from the group consisting of molybdenum and tungsten, preferably molybdenum. Preferably, the first supported hydroconversion catalyst comprises nickel as Group VIII element and molybdenum as Group VIB element.

[0270] The content of Group VIII non-noble metals, in particular nickel, expressed by weight of metal oxide, in particular NiO, is advantageously between 0.5% and 10% and preferably between 1 and 6% by weight, and the content of Group VIB metals, in particular molybdenum, expressed by weight of metal oxide, in particular molybdenum trioxide M0O3, is advantageously between 1% and 30% and preferably between 4% and 20% by weight. The content of metals is expressed as weight percentage of metal oxide with respect to the weight of the catalyst.

[0271] This first supported catalyst is advantageously used in the form of extrudates or beads. The beads have a diameter for example between 0.4 mm and 4.0 mm. The extrudates have a cylindrical shape with a diameter for example between 0.5 mm and 4.0 mm and a length between 1 mm and 5 mm. The extrudates can also be objects with different shapes such as trilobes, regular or irregular tetralobes or other multilobes. Other forms of porous supported catalysts can also be used. The size of these various forms of porous supported catalysts can be characterized by the equivalent diameter. The equivalent diameter is defined as the six times ratio of the volume of the particle to the external surface area of the particle. The porous supported catalysts used in the form of extrudates, beads or other forms thus have an equivalent diameter between 0.4 mm and 4.4 mm. These catalysts are well known by the person skilled in the art.

[0272] According to one or more embodiments of the application, the first hydroconversion section 20 comprises one or more hybrid bed reactors (i.e. hybrid ebullated-entrained bed) comprising at the same time at least one first supported hydroconversion catalyst held in the reactor and at least one entrained catalyst which enters the reactor with the feedstock and is entrained out of the reactor with the effluent. In this case, as already described above in connection with step (a), the entrained catalyst precursor has been introduced before injecting the feedstock into the first hydroconversion reactor and the colloidal or molecular catalyst, also called dispersed, entrained or slurry catalyst, can have been formed upstream of the hybrid bed hydroconversion reactor or in situ. These entrained catalysts are well known by the person skilled in the art.

[0273] The hybrid bed reactor comprises a solid phase comprising a porous supported catalyst in the form of an expanded bed, a liquid hydrocarbon phase comprising the feedstock containing the colloidal or molecular catalyst dispersed therein, and a gas phase comprising hydrogen.

[0274] The hybrid bed reactor is an ebullated bed hydroconversion reactor as described above, but comprises in addition to the porous supported catalyst in the form of an expanded bed held in the reactor, molecular or colloidal catalysts which are entrained out of the reactor with the hydroconverted liquid effluent 105.

[0275] According to one or more embodiments, the functioning of the hybrid bed hydroconversion reactor is based on the functioning of the ebullated bed reactor already described, and in addition involves the dispersion of colloidal or molecular catalyst throughout the feedstock dispersed into the hybrid bed reactor, both in the expanded catalyst zone and in the zones of unsupported catalyst, thus made available to promote upgrading reactions in the zones that in the conventional ebullated bed reactor constitute zones free of catalyst.

[0276] The presence of colloidal or molecular catalyst in the hybrid bed reactor provides additional catalytic hydrogenation activity in the expanded catalyst zone, in the recirculation pipe, and in the lower and upper unsupported catalyst zones. The capping of free radicals outside the porous supported catalyst minimizes the formation of deposits and coke precursors, which are usually the cause of deactivation of the supported catalyst. This can result in a reduction in the amount of porous supported catalyst that would otherwise be required to carry out the desired hydroconversion reactions. This can also reduce the rate at which the porous supported catalyst needs to be withdrawn and replenished.

[0277] In one of the embodiments of the process according to the application, different first supported hydroconversion catalysts can be used in each reactor of the first hydroconversion stage, the supported catalyst specific to each reactor being adapted to the feedstock sent to this reactor. In one of the embodiments of the process according to the application, several types of first supported catalyst are used in each reactor.

[0278] As is known and described, for example, in patent FR 3 033 797, when the first supported hydroconversion catalyst is spent, it can be partially replaced by fresh supported catalyst, and / or by a supported catalyst that is spent but catalytically more active than the spent supported catalyst to be replaced, and / or by a regenerated supported catalyst, and / or by a rejuvenated supported catalyst (catalyst from a rejuvenation zone in which most of the deposited metals are removed, then the spent and rejuvenated catalyst is sent to a regeneration zone in which the carbon and sulfur contained in it are removed, thus increasing the activity of the catalyst) - by withdrawing the spent supported catalyst, preferably at the bottom of the reactor, and by introducing the replacement supported catalyst at the top or at the bottom of the reactor. This replacement of the spent supported catalyst is preferably carried out at regular time intervals, and preferably in batches or almost continuously. This withdrawal and replacement is carried out using withdrawal and injection means that advantageously enable the continuous operation of such a hydroconversion step. An example of such means has already been described in connection with step (a), which also enables the introduction of a plastic fraction according to a particular embodiment (see step (a4)).

[0279] With this supported catalyst take-on / take-off operating mode, it is thus not necessary to stop the unit to replace the spent catalyst nor to increase the reaction temperature along the cycle to compensate for deactivation. Moreover, working at constant operating conditions enables to obtain constant product yield and quality along the cycle. Thus, due to the fact that the supported catalyst is kept stirred by the significant recirculation of the liquid, the pressure drop over the reactor remains low and constant and the reaction heat is rapidly averaged over the catalyst bed, thus almost isothermal and does not require the injection of a cooling stream (quenching).

[0280] According to one or more embodiments, when step (b) is carried out in one or more hybrid bed reactors, the feedstock or the supported catalyst precursor can be pre-mixed with an organic additive prior to introducing the feedstock into the first hydroconversion reactor of the first hydroconversion section 20 to significantly minimize the fouling of the facility prior to hydroconversion in the hybrid bed reactor. Without being bound by any theory, but the organic additive, as a mixture with the feedstock, is able to improve the solubility of the catalyst precursor supported in the feedstock to avoid or reduce the fouling in the facility upstream of the hydroconversion reactor, such as in the heating device, particularly caused by metal deposits, and thus to improve the dispersion of the supported catalyst, thus increasing the availability of the metal active sites to promote the hydrogenation of free radicals, which are precursors of coke and deposits, and to significantly reduce the fouling of the facility. The organic additive, which is neither a catalyst nor a catalyst precursor (e.g. it does not contain metals), has at least one carboxylic acid function and / or at least one ester function and / or at least one acid anhydride function. It preferably comprises at least 6, or even at least 8 carbon atoms, and more preferably at least 8 carbon atoms. For example, the organic additive can be 2-ethylhexanoic acid, naphthenic acid, octanoic 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, octanoic anhydride and mixtures thereof. The organic additive is preferably added during the mixing step to have a molar ratio of the organic additive to the active metal (e.g. Mo) of the catalyst precursor composition between 0.1 : 1 and 20: 1, more preferably between 0.75: 1 and 7: 1, and again more preferably between 1 : 1 and 5: 1.

[0281] (c) Optional intermediate separation step According to one or more preferred embodiments, the process further comprises a separation step (c) which separates a part or all of the first hydroconversion effluent 105 to produce at least two fractions, one of which is a heavy fraction boiling mainly at a temperature greater than or equal to 350°C.

[0282] The other (or the others) of the fractions is one or more light fractions and a middle fraction. The light fraction thus separated contains mainly gases (H2, H2S, NH3and C1-C4), naphtha (a fraction boiling at a temperature lower than 150°C), kerosene (a fraction boiling between 150°C and 250°C) and at least some diesel (a fraction boiling between 250°C and 375°C). The light fraction can then be at least partially sent to a fractionation unit (not shown in the attached figures) where light gases are extracted from the light fraction, for example by passing through an expansion vessel. The hydrogen thus recovered, which can have been sent to a purification and compression facility, can advantageously be recycled to the first hydroconversion step (b), and / or to the second hydroconversion step (d) if it is carried out. The recovered hydrogen can also be used in other refinery facilities.

[0283] The optional separation step (c) is carried out in a separation section (not shown in the attached figures) comprising any separation device known to the person skilled in the art. The separation section can comprise one or more expansion vessels arranged in series, and / or one or more steam and / or hydrogen stripping columns, and / or atmospheric distillation columns, and / or vacuum distillation columns, and preferably consists of a single expansion vessel, commonly referred to as a "hot separator".

[0284] (d) Optional second hydroconversion step According to one or more preferred embodiments (not shown in the attached figures), the process further comprises a second hydroconversion step of a part or all of the first effluent 105 obtained from step (b) or optionally of the heavy fraction from step (c) in the presence of hydrogen in at least one second ebullated bed or hybrid bed reactor comprising a second porous supported catalyst. This second hydroconversion step is carried out to produce a second hydroconversion effluent. The second hydroconversion effluent advantageously contains a greater amount of conversion products than the first hydroconversion effluent, and a significantly lower content of hydrocarbons having a boiling point of at least 300°C. The second hydroconversion effluent can have a reduced Conradson carbon residue and optionally a reduced amount of sulfur, and / or nitrogen, and / or metals, and / or asphaltenes.

[0285] The second hydroconversion step is carried out in a similar manner as described for the first hydroconversion step (b), and is not repeated here. This applies in particular to the operating conditions, the equipment used and the porous supported hydroconversion catalyst used, with the exception of the details mentioned below.

[0286] As for the first hydroconversion step (b), the second hydroconversion step is carried out in at least a second ebullated bed or hybrid bed reactor. If the first hydroconversion step is also carried out in one or more ebullated bed reactors, it is preferably carried out in one or more ebullated bed reactors, and if the first hydroconversion step is carried out in one or more hybrid bed reactors, it is preferably carried out in one or more hybrid bed reactors.

[0287] In this second hydroconversion step, the operating conditions can be similar or different from those in hydroconversion step (d), with the temperature kept between 350°C and 550°C, preferably between 350°C and 500°C, more preferably between 370°C and 450°C, more preferably between 400°C and 440°C, and again more preferably between 410°C and 435°C, and the amount of hydrogen introduced into the reactor kept between 50 Nm 3 / m 3 to 5000 Nm 3 / m 3 between the liquid feedstocks, preferably between 100 Nm 3 / m 3 to 3000 Nm 3 / m 3 and again more preferably between 200 Nm 3 / m 3 to 2000 Nm 3 / m 3 . Other pressures and HSV parameters are in the same ranges as those described for hydroconversion step (d).

[0288] The operating temperature in the second hydroconversion step (d) can be higher than the operating temperature in the first hydroconversion step (b). This can allow a more complete conversion of the feedstocks that have not yet been converted. The hydroconversion of the liquid products from the first hydroconversion step and the conversion of the feedstocks are enhanced, as are the hydroprocessing reactions, especially for example hydrodesulfurization and hydrodenitrogenation. The operating conditions are chosen so as to minimize the formation of solids, for example coke.

[0289] The second porous supported hydroconversion catalyst used in the second hydroconversion reactor can be the same as the one used in the first hydroconversion reactor of the first hydroconversion section 20, or can be another porous supported catalyst that is also suitable for the hydroconversion of the feedstocks treated, as defined for the first supported catalyst used in the first hydroconversion step (b).

[0290] (e) fractionation step The first hydroconversion effluent 105 from the hydroconversion step (b), or from the second hydroconversion step (d) if such a step is performed, is then at least partially subjected to a fractionation step (e) in the fractionation section 30.

[0291] This fractionation step (e) separates a part or all of the hydroconversion effluent into several fractions, including at least one liquid product 106a boiling mainly at a temperature lower than 350°C. These are mainly naphtha fractions (fractions boiling at a temperature lower than 150°C), kerosene fractions (fractions boiling between 150°C and 250°C) and at least a part of diesel (fractions boiling between 250°C and 375°C).

[0292] This fractionation step also makes it possible to separate other products, such as a heavy liquid product 106b containing a fraction boiling mainly at a temperature greater than or equal to 350°C, for example containing a fraction boiling at a temperature higher than 540°C, called residual fraction (or vacuum residue). The heavy liquid product can contain a part of gas oil fractions boiling between 250°C and 375°C (gas oil, heavy, minor amount) and a fraction boiling between 375°C and 540°C (also called vacuum distillate oil).

[0293] This fractionation step thus provides at least two products, including a liquid product 106a as described above (which includes light fractions and intermediate fractions, which can themselves be separated during this fractionation step) and other products 106b (which include in particular heavier fractions). Light products are also generally obtained in the form of gases during this fractionation step.

[0294] The fractionation section 30 comprises any separation device known to those skilled in the art.

[0295] The fractionation section 30 can thus comprise one or more of the following separation equipment items: one or more flash vessels arranged in series, preferably a succession of at least two successive flash vessels, one or more steam and / or hydrogen stripping columns, atmospheric distillation columns, vacuum distillation columns.

[0296] According to one or more embodiments, this fractionation step (e) is carried out by a succession of at least two successive flash vessels.

[0297] According to one or more other embodiments, this fractionation step (e) is carried out by one or more steam and / or hydrogen stripping columns.

[0298] According to one or more preferred embodiments, this fractionation step (e) is carried out by an atmospheric distillation column, more preferably by an atmospheric distillation column and a vacuum column receiving the atmospheric residue.

[0299] According to the most preferred embodiment, 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.

[0300] In addition to a portion or all of the hydroconversion liquid effluent, fractionation section 30 can also receive one or more additional streams, such as one or more hydrocarbon feedstocks external to the process (e.g., atmospheric and / or vacuum distillate oil, atmospheric and / or vacuum residue), a portion of the heavy fraction from separation step (c) if performed.

[0301] (f) Subsequent processing steps One or more subsequent processing steps (f) can be performed on the product obtained from fractionation step (e).

[0302] The various hydrocarbon-based products that can result from fractionation step (e) in fractionation unit 30 can be sent to various processes in a refinery, represented in the figure by the general reference numeral 40, and the details of these post-processing are not described here as they are well known to those skilled in the art. For example, the gas fraction, naphtha, middle distillate, VGO can be sent to hydrotreatment, steam cracking, fluid catalytic cracking (FCC), hydrocracking, lube extraction, etc. processes. Residuum (atmospheric or vacuum) can also be post-processed, or used for other applications, such as gasification, asphalt production, heavy fuel oil, etc. The heavy fraction (product 106b or a fraction of said product), including the residuum, can also be recycled to the hydroconversion process, for example to the hydroconversion reactor in step (b) or (d).

[0303] When it is desirable to recycle a portion of the heavy residue fraction (e.g., a portion of the heavy liquid product 106b) to the hydroconversion system (e.g., to the first hydroconversion reactor or upstream thereof), it can be advantageous to leave the entrained catalyst in the residue in the case of a hybrid bed reactor operation. The recycle stream can be purged, typically to prevent excessive accumulation of certain compounds. Example

[0304] The following example is intended to demonstrate certain performance qualities of the process according to the present application.

[0305] These examples illustrate the possibility of chemical recycling of plastics in a hydroconversion process, in particular a H-Oil TM type ebullated bed process, which converts the plastics into lighter hydrocarbons that in turn can act as raw materials for new plastics or as a base for the manufacture of fuels, lubricants or any other products derived from petroleum refining. The process of incorporating these plastics, which are initially in the form of solid particles, which are dispersed, melted and dissolved in a mixer before the reaction, is also illustrated. The experiments in this example were performed in a closed (“batch”) reactor representative of a H-Oil TM process.

[0306] Example 1 is an illustration of the performance of a hydroconversion process for a feedstock of the vacuum distillate oil type, free of plastic materials, as defined hereafter, in particular in a ebullated bed, like H-oil TM Performance of the process.

[0307] Example 2 illustrates a hydroconversion process using a feedstock comprising a plastic fraction and a non-asphaltene heavy distillate fraction, as defined hereafter, in particular in a ebullated bed, like H-oil TM Performance of the process, wherein a dispersion / dissolution preliminary step is implemented in order to convert said plastics into light hydrocarbons of the light distillate oil, middle distillate oil or vacuum distillate oil type, which can be upgraded in a refinery.

[0308] By way of comparison, Examples 3 and 4 illustrate the performance of a hydroconversion process for a feedstock comprising a heavy asphaltene fraction of the vacuum residue type, like H-oil TM Performance of the process, which can be compared to the performance of the process according to Example 2 of the application.

[0309] Example 3 is an illustration of the performance of a hydroconversion process for a feedstock of the vacuum residue type, free of plastic materials, as defined hereafter, in particular in a ebullated bed, like H-oil TM Performance of the process.

[0310] Example 4 illustrates a hydroconversion process (H-oil TM type) fed with a feedstock comprising the same vacuum residue type fraction as Example 3 and a plastic fraction, as defined hereafter.

[0311] Feedstock: The distillate fraction (I) of the feedstock is a vacuum distillate oil (VGO). The plastic fraction (II) of the feedstock is a plastic mixture obtained from a conventional sorting channel, i.e. containing low density polyethylene (65%) as well as some high density polyethylene (35%). It is in the form of solid particles of size 500 pm to at most 1 cm. The heavy fraction (III) of the feedstock is a "straight-run" vacuum residue (SR-VR) directly derived from the distillation of a crude oil.

[0312] The main characteristics of these fractions of the feedstock are shown in Table 1 below.

[0313] Table 1

[0314] The operating conditions used for these four examples are summarized in Table 2 below.

[0315] Table 2

[0316] Procedure for Example 1: A batch reactor was loaded with 100% VGO (Fraction I of the feedstock) preheated to 100°C to make it less viscous. The reactor was closed, purged with nitrogen, purged with hydrogen and then pressurized with hydrogen to a pressure of about 3 MPa. The reactor was then heated to 100°C. At this temperature, stirring was started at 500 rpm. The temperature was gradually increased from 100°C to the reaction temperature while the stirring was gradually increased from 500 rpm to 1000 rpm. When the reaction temperature was reached, the pressure in the reactor was immediately adjusted to the target value by addition of H2. At this point, the reaction time was counted down. At the end of the experimental time, the reactor was rapidly cooled to stop the reaction, the stirring was stopped when the reactor was at room temperature and the liquid effluent and gases were collected for analysis.

[0317] Procedure of Example 2: A batch reactor was first loaded with 90% VGO (Fraction I of the feedstock) and then 10% plastic (Fraction II of the feedstock) was added and manually dispersed in the VGO preheated to 100°C to make it less viscous for a few seconds. To ensure complete homogeneity of the mixture, the reactor was closed, purged with nitrogen, purged with hydrogen and then pressurized with hydrogen to a pressure of about 3 MPa. The reactor was then heated to 100°C. At this temperature, stirring was started at 500 rpm. The temperature was gradually increased from 100°C to 200°C while the stirring was gradually increased from 500 rpm to 1000 rpm. At 200°C, the pressure in the reactor was 4 MPa. Following a 1 hour stabilization phase at this temperature to ensure good dissolution and dispersion of the plastic (feedstock Fraction II) in the VGO (feedstock Fraction I), the batch reactor was heated to the reaction temperature at which the pressure in the reactor was immediately adjusted to the target value by addition of H2. At this point, the reaction time was counted down. At the end of the experimental time, the reactor was rapidly cooled to stop the reaction, the stirring was stopped when the reactor was at room temperature and the liquid effluent and gases were collected for analysis.

[0318] Procedure of Example 3: The procedure of Example 3 was identical to Example 1 but the batch reactor was loaded with 100% SR-VR (Fraction III of the feedstock).

[0319] Procedure of Example 4: The procedure of Example 4 was identical to Example 2 but the batch reactor was loaded with 95% SR-VR (Fraction III of the feedstock) and 5% plastic (Fraction II of the feedstock).

[0320] Results and overall performance quality: The results on the overall liquid effluent quality and hydroconversion performance of the examples are detailed in Table 3 below.

[0321] Table 3

[0322] The conversion of the 350°C+ fraction is calculated by the mass difference between the feedstock and the total liquid effluent as follows: .

[0323] The plastic conversion is obtained by the mass difference between the plastic of the feedstock and the remaining plastic in the total liquid effluent as follows: .

[0324] The mass of plastic in the feedstock is perfectly known, it is an operating data. The mass of non-converted plastic in the effluent is obtained by DSC (Differential Scanning Calorimetry), a calorimetry method suitable for the plastic qualification and quantification.

[0325] The principle is as follows: all crystalline or semi-crystalline materials (like most plastics) have a first order change of state (melting and crystallization). Therefore, the melting temperature and the associated enthalpy of the change of state can be determined, notably by DSC calorimetry analysis. All amorphous materials and liquids (like SR-VR and hydroconversion effluent) do not have a melting type transition and do not give any response in DSC.

[0326] Therefore, the DSC measurement of a mixture of plastic and hydrocarbon (feedstock or effluent) has the thermal signature of a semi-crystalline material only if there is remaining non-converted plastic. In this case, from the distillation yield of the 350°C+ fraction of the effluent, the DSC measurement of this fraction and the DSC measurement of pure plastic, the amount of non-converted plastic remaining in the effluent can be determined. Otherwise, if the DSC does not show any specific signature, the plastic has been completely converted.

[0327] In these examples, the plastic used is semi-crystalline: DSC is therefore a suitable analytical tool for determining its conversion.

[0328] The comparison of the results of examples 2 and 4 shows that under these same operating conditions, the plastic is converted to the same extent, 65%, whether it is combined with a non-asphaltene heavy distillate of VGO type (example 2) or with a heavy asphaltene fraction of vacuum residue type. However, the refiner naturally wishes to maximize the plastic conversion, thus making the operating conditions more severe. To achieve this, it is necessary to increase the temperature and the residence time. It is now known to the person skilled in the art that the higher the operating conditions, the more difficult the operation of the process due to the formation of deposits. When a certain threshold is exceeded, the person skilled in the art knows that the hydroconversion process is no longer operable.

[0329] The operating conditions of the hydroconversion process using a mixed VGO / high density and low density PE type plastic feedstock can be more severe to promote the conversion of plastics. In particular, as shown in Example 2, at a hydroconversion operating temperature of 430°C, the deposit content is very low, so there is a large margin with respect to deposit generation.

[0330] On the other hand, the results of Example 3 show that even without plastics in the feedstock, the deposit content is already very high from 430°C. In this case, there is little margin to make the operating conditions more severe. Moreover, the addition of plastics with the hydrocarbon feedstock (Example 4) increases the deposit content to values considered unacceptable for the operability of the process, indicating that the hydroconversion process in which the plastic fraction of high density and low density PE type is co-processed with a heavy hydrocarbon fraction of the type of vacuum residue is difficult to make more severe, the conversion of plastics being therefore limited.

[0331] It is also worth noting that the deposit content in Example 2 is lower than in Example 4, while in Example 2 the plastic fraction in the feedstock is 10% by weight, higher than 5% by weight in Example 4.

[0332] In summary, these examples clearly demonstrate the interest of the hydroconversion process according to the application for a mixed feedstock comprising a heavy fraction of non-asphaltene hydrocarbons and a plastic fraction of high density and low density PE type, to maximize the conversion of plastics into fractions that can be upgraded in a refinery (for example for fuel production) or in a petrochemical plant (for example for plastic production).

Claims

1. A feedstock hydroconversion process comprising the following successive steps: (a) conditioning the feedstock and introducing the feedstock into a first hydroconversion section (20) comprising at least a first ebullated bed or hybrid ebullated- entrained bed hydroconversion reactor, said reactor comprising a first porous supported hydroconversion catalyst; the feedstock comprising a minor fraction of plastic containing at least 70 wt% of polyethylene in high density form and / or in low density form, and mainly comprising a heavy fraction of non-asphaltene hydrocarbons containing at least 90 wt% of a fraction having a boiling point of at least 300°C and containing less than 1 wt% of asphaltenes; (b) a first step of hydroconversion of the feedstock in the presence of hydrogen in the first hydroconversion section (20) to obtain a first hydroconversion effluent (105); (c) optionally, a step of separating a part or all of the first effluent obtained from step (b) to form at least one heavy fraction boiling mainly at a temperature greater than or equal to 350°C; (d) optionally, a second hydroconversion step of a part or all of the first effluent obtained from step (b) or optionally of the heavy fraction obtained from step (c) in a second hydroconversion section comprising at least a second ebullated bed or hybrid ebullated-entrained bed hydroconversion reactor, said second hydroconversion reactor comprising a second porous supported catalyst and operating in the presence of hydrogen, to produce a second hydroconversion effluent; Step (b) and optional step (d) are carried out at an absolute pressure of between 2 MPa and 38 MPa, at a temperature of between 350°C and 550°C, at a weight hourly space velocity of between 0.05 h -1 to 10 h -1 relative to the volume of each hydroconversion reactor and at a hydrogen amount of between 50 Nm 3 / m 3 and 5000 Nm 3 / m 3 . (e) a step of fractionating all or a part of the first hydroconversion effluent from step (b) or of the second hydroconversion effluent from step (d) in a fractionation section (30) to produce at least one liquid product (106a) boiling mainly at a temperature lower than 350°C.

2. The process according to claim 1, wherein the heavy fraction of non-asphaltene hydrocarbons is selected from the following fractions, alone or as a mixture: i) straight run from crude oil or vacuum distillate oil from other refining processes selected from cracking processes, preferably fluidized bed catalytic cracking processes or hydrocracking processes, thermal conversion processes, preferably coking processes or visbreaking processes, coal liquefaction processes, biomass liquefaction processes, liquefaction processes of plastics and / or tires and / or solid recovered fuel, preferably pyrolysis, and / or ii) solvent deasphalting from solvent deasphalting processes, preferably from solvent deasphalting of straight run residues of crude oil or deasphalted oils of other refining processes, and / or iii) one or more aromatic fractions extracted from a lubricant production unit.

3. The process according to claim 2, wherein the heavy fraction of non-asphaltene hydrocarbons is a vacuum distillate oil containing at least 90 wt% of a fraction having a boiling point of at least 300°C and at most 20 wt% of a fraction having a boiling point of at least 540°C.

4. The process according to claim 2 or 3, wherein the heavy fraction of non-asphaltene hydrocarbons is of fossil origin.

5. The process according to claim 4, wherein the heavy fraction of non-asphaltene hydrocarbons is a vacuum distillate oil obtained from vacuum distillation of crude oil or a deasphalted oil obtained from solvent deasphalting processes of straight run residues of crude oil.

6. The process according to one of the preceding claims, wherein the plastic fraction contains at least 80 wt%, preferably at least 90 wt%, preferably at least 95 wt% of polyethylene in high density form and / or in low density form.

7. The process according to one of the preceding claims, wherein the plastic fraction contains from 50 wt% to 95 wt% of low density polyethylene and from 5 wt% to 50 wt% of high density polyethylene, in particular from 55 wt% to 70 wt% of low density polyethylene and from 30 wt% to 45 wt% of high density polyethylene.

8. The process according to one of the preceding claims, wherein the feedstock comprises: - between 0.1 wt% and 49 wt%, preferably between 0.5 wt% and 45 wt%, preferably between 1 wt% and 30 wt%, preferably between 2 wt% and 25 wt% or even between 2.5 wt% and 20 wt% of the plastic fraction, and - between 51 wt% and 99.9 wt%, preferably between 55 wt% and 99.5 wt%, preferably between 70 wt% and 99 wt%, preferably between 75 wt% and 98 wt%, or even between 80 wt% and 97.5 wt% of the heavy fraction of non-asphaltene hydrocarbons.

9. The process according to one of the preceding claims, wherein in step (a) the plastic fraction and the heavy fraction of non-asphaltene hydrocarbons of the feedstock (114, 117, 120, 122, 125) are mixed and introduced into the at least one first hydroconversion reactor of the first hydroconversion section (20).

10. The process according to claim 9, wherein in step (a) the plastic fraction (102) in the form of solid particles, optionally premixed with a diluent (107), is mixed with the heavy fraction of non-asphaltene hydrocarbons (101) to form a suspension (113, 116) in such a way that the suspension (113, 116) is heated to a temperature above the melting point of the plastic fraction to form the feedstock (114) introduced into the first hydroconversion reactor.

11. The process according to any one of claims 1 to 8, wherein in step (a) the plastic fraction (103, 109, 110, 112) and the heavy fraction of non-asphaltene hydrocarbons (101) of the feedstock are introduced separately into the at least one first hydroconversion reactor of the first hydroconversion section (20).

12. The process according to claim 11, wherein in step (a) the plastic fraction in the form of solid particles is mixed with a diluent (107) in a mixing section (11) and heated to a temperature above the melting point of the plastic fraction, preferably between 60°C and 295°C, in a heating section (12) before being introduced into the first hydroconversion reactor, the heating step possibly being carried out before or after mixing with the diluent and preferably after mixing with the diluent.

13. The process according to any one of the preceding claims, comprising a separation step (c) which separates a part or all of the first hydroconversion effluent (105) from step (b) to produce at least a heavy fraction boiling mainly at a temperature greater than or equal to 350°C, and a second step (d) of hydroconversion of said heavy fraction.

14. The process according to any one of the preceding claims, wherein the hydroconversion reactors of the first hydroconversion section (20) in step (b) and optionally in hydroconversion step (d) are hybrid boiling-entrained bed reactors, the process further comprising a step of introduction of a catalyst precursor (104), preferably molybdenum 2-ethylhexanoate, before introduction of the feedstock into the at least first hybrid boiling-entrained bed reactor of the first hydroconversion section (20), in such a way that a colloidal or molecular catalyst, which preferably comprises molybdenum disulfide, is formed upon reaction of said catalyst precursor with sulfur.

15. The process according to any one of the preceding claims, wherein the first hydroconversion catalyst and optionally the second hydroconversion catalyst contain at least one Group VIII non-noble metal selected from nickel and cobalt, preferably nickel, and at least one Group VIB metal selected from molybdenum and tungsten, preferably molybdenum, and comprise an amorphous support, preferably alumina.

Images