Process for fixed bed treatment of heavy fossil-based feedstock comprising plastic pyrolysis oil component

Abstract

A process for the treatment of a feedstock comprising components of plastics and / or tyres and / or solid recovered fuel pyrolysis oil and a heavy hydrocarbon component of fossil origin, the pyrolysis oil component comprising less than 50% by weight of the feedstock, the process comprising: a) subjecting the feedstock to hydrodemetallization in the presence of a hydrodemetallization catalyst; a hydrodemetallization stage in a fixed bed reaction section comprising at least two displaceable reactors feeding at least the feedstock and a gas stream comprising hydrogen, b) a hydrotreating stage in the presence of a hydrotreating catalyst in a reaction section comprising at least one fixed bed reactor, feeding the effluent produced by stage a) and optionally a gas stream comprising hydrogen to said stage, c) a stage of separating the effluent produced by stage b).

Description

Technical Field

[0001] The present invention relates to the field of hydroconversion of raw materials, which mainly comprises heavy hydrocarbon components of fossil origin, as well as minor components of plastics and / or tires and / or pyrolysis oil of solid recovered fuel (SRF) containing impurities. The heavy hydrocarbon components are heavy oil raw materials of the atmospheric residue and / or vacuum residue type.

[0002] Specifically, the present invention relates to a method for treating such mixed raw materials in a fixed bed, aiming to produce higher-quality materials with lower boiling points, such as for the production of fuels or chemicals, while being able to capture impurities in plastics and / or tires and / or pyrolysis oil of solid recovered fuel (SRF). Prior Art

[0003] For many years, in the fuel and chemical industries, methods have emerged for introducing products other than traditional petroleum products (such as wastes like plastics or waste oils) as supplements or substitutes for fossil-source products.

[0004] In particular, plastics generated by the collection and sorting industries can undergo a pyrolysis stage to specifically obtain pyrolysis oil. These plastic pyrolysis oils are usually incinerated for power generation and / or used as fuel for industrial or urban heating boilers.

[0005] Waste tires usually undergo the same treatment.

[0006] Solid recovered fuel (SRF), also known as refuse-derived fuel (RDF), is a solid non-hazardous waste prepared for energy upgrading, regardless of whether it is derived from household and similar wastes, economic activity wastes, or construction and demolition wastes. SRF is usually a mixture of any combustible wastes, such as waste tires, food by-products (fats, animal powders, etc.), viscose and wood wastes, light components generated by shredders (such as light components from used cars, electrical and electronic equipment (WEEE)), household and commercial wastes, residues from various waste recycling, including certain municipal wastes, plastic wastes, textiles or wood etc. . SRF usually contains plastic wastes. Nowadays, SRF is mainly upgraded for energy. They can be directly used as substitutes for fossil fuels in co-incineration facilities (coal and lignite power plants, cement plants, lime kilns) or domestic waste incineration plants, or indirectly used in pyrolysis plants dedicated to energy upgrading: thus, SRF pyrolysis oil is usually burned for power generation and even used as fuel for industrial or urban heating boilers.

[0007] Plastics and / or tires and / or SRF pyrolysis oil can also be upgraded, optionally through refining processes, to produce fuels (such as gasoline or diesel) and / or chemicals (such as olefins) for the production of various polymers in the chemical industry.

[0008] However, this route of upgrading plastics and / or tires and / or SRF pyrolysis oil faces problems arising from the special composition of these oils, especially those caused by the impurities they contain. The composition of these oils is itself related to the compositional diversity of plastic waste, tires, and SRF.

[0009] This is because plastic waste, tires, or SRF are usually mixtures of several polymers, such as mixtures of polyethylene, polypropylene, polyethylene terephthalate, polyvinyl chloride, and polystyrene. In addition, depending on their use, plastics may contain other compounds in addition to polymers, such as plasticizers, pigments, dyes, or residues of polymerization catalysts, as well as other highly diverse organic and inorganic impurities resulting from the separation operations in sorting centers, and the selectivity of the separation operations in said sorting centers may not be 100%.

[0010] Therefore, the oils produced by pyrolysis usually contain many diolefins and impurities, especially metals, silicon, or also halides, especially chlorine-based compounds, heteroelements such as sulfur, oxygen, and nitrogen, and insolubles, the content of which is usually high and may be incompatible with some refining units.

[0011] The treatment of these oils can pose operational problems, and especially problems of corrosion, coking, or catalytic deactivation, or problems incompatible with the applications of the target polymers. For example, the presence of diolefins often leads to problems of instability of the pyrolysis oil, characterized by the formation of gums. The gums and insolubles that may be present in the pyrolysis oil can cause blockage problems in equipment items.

[0012] One way to remove these impurities contained in plastic and / or tire and / or SRF pyrolysis oil is to carry out hydrotreating in the presence of a catalyst.

[0013] For example, application WO2018 / 055555 provides a very general and relatively complex complete process for the recycling of plastic waste, covering from the actual pyrolysis stage of plastic waste to the steam cracking stage, so as to produce highly upgradable products in the petrochemical field, such as olefins and aromatic compounds. This process especially includes a stage of hydrocracking the liquid phase directly produced by pyrolysis, preferably carried out in a fixed bed.

[0014] Patent applications FR 3 107 530, FR 3 113 060 and FR 3 113 061 describe methods for treating pyrolysis oils from plastics, especially including a selective hydrogenation stage of the plastic pyrolysis oil and a hydrotreatment of the hydrogenation effluent in a fixed bed. The hydrotreated effluent is subjected to a specific separation with water, and then the separated hydrocarbon stream is fractionated. The resulting naphtha fraction can be sent to a steam cracking unit or used as a fuel feedstock. According to patent applications FR 3113 060 and FR 3 113 061, the process incorporates one or two stages of hydrocracking in a fixed bed after the hydrotreatment stage, aiming to minimize the yield of heavy components and maximize the yield of naphtha components by at least partially converting the heavy components into naphtha components (which are generally favored by steam cracking units) through hydrocracking.

[0015] Object and content of the invention The present invention relates to the field of upgrading heavy feedstocks of fossil origin that are difficult to upgrade, such as petroleum residues, which usually contain high levels of impurities such as metals, sulfur, nitrogen, Conradson carbon, and asphaltenes, in order to convert them into lighter products that can be upgraded as fuels, for example to produce gasoline, gas oil, or marine fuel oil, or raw materials for the petrochemical industry.

[0016] More specifically, the present invention provides a method for treating a feedstock that includes a heavy hydrocarbon fraction of fossil origin with an initial boiling point of at least 340 °C and a final boiling point of at least 550 °C and containing sulfur and nitrogen, as well as a pyrolysis oil component of plastics and / or tires and / or solid recovered fuel, where the pyrolysis oil component accounts for less than 50% by weight of the feedstock, the method comprising: a) A hydrodemetallization stage carried out in a fixed bed reaction section including at least two replaceable reactors in the presence of at least one hydrodemetallization catalyst at a temperature of 300 to 500 °C, an absolute pressure of 5 MPa to 35 MPa, and a space velocity of 0.1 to 5.0 h -1 , feeding at least the feedstock and a gas stream containing hydrogen to the section. b) A hydrotreatment stage carried out in a reaction section including at least one fixed bed reactor in the presence of at least one hydrotreatment catalyst at a temperature of 300 to 500 °C, an absolute pressure of 5 MPa to 35 MPa, and a space velocity of 0.1 to 5.0 h -1 , feeding at least the effluent produced in stage a) and optionally a gas stream containing hydrogen to the section. c) A separation stage of the effluent produced in stage b) in a separation section, producing a gas fraction and at least one liquid product.

[0017] The present inventors have surprisingly demonstrated that small amounts of components of plastics and / or tires and / or SRF pyrolysis oil containing impurities can be introduced into heavy hydrocarbon feedstocks of fossil origin, typically atmospheric residue or vacuum residue, and are usually processed in a fixed-bed hydroconversion process, thereby achieving optimized treatment of these two difficult feedstocks by effectively treating the impurities present and converting the feedstock into upgradable products.

[0018] Accordingly, the present invention provides a method for hydroconverting a heavy hydrocarbon feedstock of fossil origin (especially of the atmospheric residue and / or vacuum residue type) in a fixed bed, said feedstock comprising small amounts of components of plastics and / or tires and / or SRF pyrolysis oil, so that a fuel feedstock and other upgradable hydrocarbons and / or a feedstock for a steam cracker suitable for producing olefins and / or aromatics can be produced.

[0019] The presence of plastic pyrolysis oil results in a significant increase in the yield of the IP-180 °C fraction and a decrease in the yield of the heavy fraction. A key aspect of the present invention is that one or more fixed-bed reactors can utilize the combined action of high temperature and a catalyst to at least partially convert the pyrolysis oil into lighter products, and the catalyst can hydrogenate unsaturated molecules (olefins or aromatics). Therefore, the co-processing of pyrolysis oil can increase the yield of certain fractions in the hydrotreated effluent, especially the yield of the gasoline fraction.

[0020] It has also been demonstrated that, despite the presence of silicon in the pyrolysis oil, the products obtained by the method according to the present invention are substantially free of silicon, indicating that the silicon has been captured by one or more catalysts. Similarly, chlorine is substantially completely captured and / or converted (converted to HCl). Therefore, the products obtained at this stage have a low impurity content.

[0021] Another advantage of the present invention is that it limits the temperature rise between the inlet and the outlet of the fixed-bed reactor, which is especially caused by heat released by the hydrogenation of dienes or olefins contained especially in the pyrolysis oil components, and part of this heat is absorbed by the heavy hydrocarbon components of fossil origin being processed simultaneously. This optimizes the process flow and limits the heavy dependence on the recycle of the effluent and / or gaseous and / or liquid cooling streams.

[0022] Another object of the present invention is to produce atmospheric distillates (naphtha, kerosene, diesel), vacuum distillates, marine fuels, and / or light (C1 to C4) gases using the same method.

[0023] According to an alternative form, feedstocks of the naphtha, kerosene, and diesel types can be upgraded in a refinery to produce fuels for the automotive and aviation industries, such as premium gasoline, jet fuel, and gas oil.

[0024] According to another alternative form, naphtha, kerosene, and diesel - type feedstocks can be upgraded in a steam cracking unit in order to be able to obtain, in particular, light olefins, which can be used as monomers for manufacturing polymers.

[0025] According to yet another alternative form, naphtha, kerosene, and diesel - type feedstocks can be upgraded in a fluidized catalytic cracking (FCC) unit or a hydrocracking unit.

[0026] According to another alternative form, vacuum distillates can be upgraded in a hydrocracking unit.

[0027] One advantage of the present invention is to provide a method that combines the conversion and purification of heavy feedstocks of fossil origin, which is used to produce marine fuels with a low sulfur content while upgrading the by - feedstock of pyrolysis oil. The quality requirements for marine fuels are described in the ISO 8217 standard. From now on, sulfur - related specifications will be related to SO x emissions (International Maritime Organization, MARPOL Convention, Annex VI), and are reflected in the fact that, during the period 2020 - 2025, the recommended sulfur content outside the Emission Control Areas (ECAs) is less than or equal to 0.5 wt%, and less than or equal to 0.1 wt% within the Emission Control Areas. Another very strict recommendation is that the sediment content after aging according to ISO 10307 - 2 (also known by the name IP390) must be less than or equal to 0.1 wt%. In addition, the viscosity of RMG 380 grade marine fuel oil must comply with the viscosity limit of less than 380 cSt at 50 °C.

[0028] When processing heavy feedstocks of fossil origin, there is pyrolysis oil as a by - feedstock. In particular, it is possible to directly obtain a fuel oil that meets the specifications in terms of sulfur, sediment, and viscosity without adding flux. Usually, flux is added to reduce the viscosity of marine fuel oil to meet the viscosity specification. In fact, it is precisely due to the presence of pyrolysis oil, which is generally lighter in terms of boiling point, that it is possible to reduce the sulfur content and viscosity, thus meeting the required specifications. Therefore, the method according to the present invention can directly obtain the following marine fuel oil, which meets the required specifications (without adding flux, which is usually added to meet the specifications), while also showing the advantage of being able to upgrade difficult - to - upgrade feedstocks (such as pyrolysis oil) and increasing the yield of the required distillate.

[0029] According to one or more embodiments of the present invention, the method according to the present invention includes at least one stage a0), which pre - treats fractions of plastic and / or tire and / or solid recovered fuel pyrolysis oil. The pre - treatment stage is carried out upstream of stage a) and includes an adsorption stage and / or a filtration stage and / or a centrifugation stage and / or an electrostatic separation stage and / or a stage of washing with an aqueous solution and / or a gas stripping stage.

[0030] According to one or more embodiments of the present invention, the pyrolysis oil component accounts for 1 wt% to 45 wt% of the feedstock, preferably 2 wt% to 30 wt% of the feedstock, more preferably 2 wt% to 25 wt% of the feedstock.

[0031] According to one or more embodiments of the present invention, the feedstock consists of the pyrolysis oil component and the heavy hydrocarbon component, the pyrolysis oil component accounts for 1 wt% to 45 wt% of the feedstock, preferably 2 wt% to 30 wt%, more preferably 2 wt% to 25 wt%, and the heavy hydrocarbon component accounts for 55 wt% to 99 wt% of the feedstock, preferably 70 wt% to 98 wt%, more preferably 75 wt% to 98 wt%.

[0032] According to one or more embodiments of the present invention, the heavy hydrocarbon component is selected from: atmospheric residue or vacuum residue obtained by atmospheric and / or vacuum distillation of crude oil or effluents from thermal conversion, hydrotreating, hydrocracking or hydroconversion units; aromatic fractions extracted from lubricant production units; deasphalted oil obtained from a deasphalting unit; asphalt obtained from a deasphalting unit; residue fractions obtained by direct coal liquefaction; vacuum distillates obtained by direct coal liquefaction; oil sands or their derivatives; oil shale or their derivatives; source rock oil or their derivatives, alone or in mixtures thereof.

[0033] According to one or more embodiments of the present invention, the heavy hydrocarbon component is vacuum residue and / or atmospheric residue.

[0034] According to one or more embodiments of the present invention, the hydrodemetallization catalyst in stage a) contains 0.5 wt% to 10 wt% nickel (expressed as nickel oxide NiO) relative to the total weight of the catalyst and 1 wt% to 30 wt% molybdenum (expressed as molybdenum trioxide MoO3) relative to the total weight of the catalyst, and the catalyst is supported on a mineral support selected from alumina, silica, silica-alumina, magnesia, clay and mixtures of at least two of these minerals.

[0035] According to one or more embodiments of the present invention, the hydrotreating catalyst in stage b) contains 0.5 wt% to 10 wt% nickel (expressed as nickel oxide NiO) relative to the total weight of the catalyst and 1 wt% to 30 wt% molybdenum (expressed as molybdenum trioxide MoO3) relative to the total weight of the catalyst, and the catalyst is supported on a mineral support selected from alumina, silica, silica-alumina, magnesia, clay and mixtures of at least two of these minerals.

[0036] According to one or more embodiments of the present invention, the separation section in stage c) includes means for washing by contacting with an aqueous solution.

[0037] According to one or more embodiments of the present invention, separation stage c) comprises: c1) a first separation stage carried out at a temperature higher than the ammonium halide precipitation temperature to obtain at least one first gas fraction and a liquid effluent, c2) a second separation stage fed with the first gas fraction obtained in stage c1) and at least a portion of the liquid effluent and the aqueous solution feed, said stage being carried out at a temperature lower than the ammonium halide precipitation temperature to obtain at least one second gas fraction, an aqueous effluent and a liquid product.

[0038] According to one or more embodiments of the present invention, the method according to the present invention further comprises stage d) for the subsequent treatment of at least one liquid product obtained in stage c), said stage d) comprising at least one stage selected from hydrotreating, steam cracking, fluidized bed catalytic cracking, hydrocracking, deasphalting and lubricating oil extraction.

[0039] According to one or more embodiments of the present invention, in stage a), the pyrolysis oil component and the heavy hydrocarbon component of the feedstock are pre-mixed before being introduced into one of the replaceable reactors.

[0040] According to one or more embodiments of the present invention, in stage a), the pyrolysis oil component and the heavy hydrocarbon component of the feedstock are introduced separately into one of the replaceable reactors.

[0041] According to one or more embodiments of the present invention, stage a) comprises a stage of preheating the heavy hydrocarbon component before introducing the feedstock into one of the replaceable reactors, preferably at a temperature of 280 °C to 450 °C, and a stage of preheating the pyrolysis oil component at a temperature lower than that of the heavy hydrocarbon component.

[0042] The present invention also relates to products that may be obtained by the method according to the present invention, and preferably products obtained by the method according to the present invention.

[0043] Advantageously, such products contain a silicon content less than or equal to 10 ppm by weight, and / or a chlorine element content less than or equal to 10 ppm by weight, relative to the weight of the product.

[0044] Detailed Embodiment Description For a better understanding of the present invention, some definitions are given below.

[0045] In this specification, the terms "comprises", "comprising" and "containing" are synonymous (denoting the same thing), and are inclusive or open-ended and do not exclude other elements not mentioned. The term "comprises" should be understood to include the exclusive and closed term "consisting of".

[0046] In this specification, the expression "between... and..." means that, unless otherwise specified, the limiting values of the interval are included within the described value range.

[0047] Within the meaning of the present invention, various parameter ranges of a specific stage, such as a pressure range and a temperature range, can be used alone or in combination. For example, within the meaning of the present invention, a preferred pressure value range can be combined with a more preferred temperature value range.

[0048] In this specification, specific and / or preferred embodiments of the present invention can be described. These embodiments can be used alone or can be combined together, without being limited by the combination as long as it is technically feasible.

[0049] Subsequently, the groups of chemical elements are given according to the CAS classification (CRC Handbook of Chemistry and Physics, published by CRC Press, edited by D.R. Lide, 81st edition, 2000 - 2001). For example, Group VIII (or VIIIB) according to the CAS classification corresponds to the metals in columns 8, 9, and 10 according to the new IUPAC classification.

[0050] The metal content is measured by X-ray fluorescence.

[0051] The term "treatment process" means a process including hydroconversion and hydrotreating reactions.

[0052] "Hydroconversion" means a process mainly aimed at reducing the boiling point range of the feedstock, and in which most of the feedstock is converted into products with a boiling point range lower than the starting feedstock. Hydroconversion generally involves the fragmentation of larger hydrocarbon molecules to obtain smaller molecular fragments with fewer carbon atoms and a higher hydrogen-to-carbon ratio. The reactions carried out during the hydroconversion process can reduce the size of hydrocarbon molecules, mainly by breaking carbon-carbon bonds in the presence of hydrogen and saturating the broken bonds and aromatic rings. The mechanism by which hydroconversion occurs generally involves the formation of hydrocarbon radicals during the fragmentation process (mainly through thermal cracking), and then capping the ends or fragments of the radicals with hydrogen in the presence of active catalyst sites. Of course, during the hydroconversion process, other reactions usually associated with hydrotreating can also occur, for example, especially removing sulfur or nitrogen from the feedstock, or saturating olefins, as more broadly defined below.

[0053] The term "hydrotreating" (commonly known as "HDT") is a relatively mild 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 olefins and / or hydrocarbon radicals with hydrogen rather than with themselves. The main purpose is not to change the boiling range of the feedstock. Thus, hydrotreating specifically includes hydrodesulfurization (commonly known as "HDS") reactions, hydrodenitrogenation (commonly known as "HDN") reactions, and hydrodemetallization (commonly known as "HDM") reactions, accompanied by hydrogenation, hydrodeoxygenation (commonly known as "HDO"), hydrodearomatization, hydrodechlorination, hydroisomerization, hydrodealkylation, hydrocracking, or hydrodewaxing reactions, and Conradson carbon reduction.

[0054] Hereinafter, the term "pyrolysis oil" is understood to mean oil produced by the pyrolysis of plastics and / or tires and / or SRF, unless otherwise specified. Similarly, for the sake of simplicity, unless otherwise specified, the "heavy hydrocarbon fraction" of the feedstock means the heavy hydrocarbon fraction of fossil origin.

[0055] Feedstock According to a basic aspect of the present invention, the feedstock mainly comprises a heavy hydrocarbon fraction of fossil origin and a small amount of plastics and / or tires and / or pyrolysis oil of SRF.

[0056] According to a preferred embodiment of the present invention, the feedstock consists of the small amount of plastics and / or tires and / or SRF pyrolysis oil fraction and a large amount of heavy hydrocarbon fraction of fossil origin.

[0057] Thus, the process of the present invention is specific to the hydroconversion of mixtures of low contents of plastics and / or tires and / or pyrolysis oil of SRF and heavy hydrocarbon fractions of fossil origin.

[0058] The components of plastics and / or tires and / or SRF pyrolysis oil account for less than 50% by weight of the feedstock (total weight of the feedstock), preferably 1% to 45% by weight of the feedstock, more preferably 2% to 30% by weight of the feedstock, more preferably 2% to 25% by weight of the feedstock, more preferably 3% to 20% by weight of the feedstock, and even more preferably 5% to 20% by weight of the feedstock, and in fact even 5% to 15% by weight of the feedstock.

[0059] The feedstock may consist of only the following two components: a pyrolysis oil component and a heavy hydrocarbon component, where the sum of the pyrolysis oil component and the heavy hydrocarbon component forms 100% by weight of the feedstock. Preferably, when the feedstock consists of the heavy hydrocarbon component and the pyrolysis oil component, the heavy hydrocarbon component may account for 55% to 99% by weight of the feedstock, preferably 70% to 98% by weight of the feedstock, more preferably 75% to 98% by weight of the feedstock, more preferably 80% to 97% by weight of the feedstock, and even more preferably 80% to 95% by weight of the feedstock, in fact even more preferably 85% to 95% by weight of the feedstock.

[0060] According to the present invention, "plastic pyrolysis oil or tire pyrolysis oil or SRF pyrolysis oil" is an oil produced by pyrolysis of plastics, preferably by pyrolysis of plastic waste (especially plastic waste from collection and sorting channels), or by pyrolysis of waste tires, or also by pyrolysis of SRF, which is advantageously in liquid form at ambient temperature. It particularly contains a mixture of hydrocarbon compounds, especially alkanes, olefins (monoolefins and / or diolefins), cycloalkanes and aromatics. At least 80% by weight of these hydrocarbon compounds preferably have a boiling point below 700 °C, and preferably below 550 °C. In particular, depending on the source of the pyrolysis oil, the pyrolysis oil may contain up to 70% by weight of alkanes, up to 90% by weight of cycloalkanes, up to 90% by weight of olefins and up to 90% by weight of aromatics, it being understood that the sum of alkanes, cycloalkanes, olefins and aromatics is equal to 100% by weight of the hydrocarbon compounds.

[0061] The pyrolysis oil may contain diolefins. The content of diolefins is generally determined indirectly in the form of the maleic anhydride value (MAV). The method is based on the Diels - Alder addition reaction between conjugated diolefins and maleic anhydride. The method for determining MAV is described in C. López - García et al., Near Infrared Monitoring of Low Conjugated Diolefins Content in Hydrotreated FCC Gasoline Streams, Oil&Gas Science and Technology–Rev. IFP, Vol. 62 (2007), No. 1, pp.57 - 68. The MAV is expressed as the number of mg of maleic anhydride reacting with 1 g of the sample (mg / g). The MAV in the pyrolysis oil varies between 5 and 100 mg / g.

[0062] The density of the pyrolysis oil measured at 15 °C according to the ASTM D4052 method is generally 0.75 g / cm 3 to 0.99 g / cm 3 and is preferably 0.75 g / cm 3to 0.95 g / cm 3 。

[0063] The pyrolysis oil may also contain (and typically contains) impurities such as metals (especially iron), silicon, or halides (especially chlorinated compounds). These impurities can be present in high amounts in the pyrolysis oil, such as up to 500 weight ppm, or up to 700 weight ppm, in fact even up to 1000 weight ppm, and even up to 5000 weight ppm of halogen elements contributed by halogenated compounds (especially chlorine, but also bromine, fluorine, iodine, or astatine), and typically 1 to 1000 weight ppm, or 1 to 700 weight ppm, or 1 to 500 weight ppm of halogen elements. The pyrolysis oil can contain up to 500 weight ppm or 700 weight ppm, in fact even 1000 weight ppm and even 5000 weight ppm of chlorine element contributed by chlorinated compounds, and typically contains 1 to 1000 weight ppm or 1 to 700 weight ppm or 1 to 500 weight ppm of chlorine element.

[0064] The oil can contain up to 200 weight ppm, even up to 1500 weight ppm of metal or metalloid elements, and typically contains 1 to 200 weight ppm or 1 to 1500 weight ppm of metal or metalloid elements. Alkali metals, alkaline earth metals, transition metals, post-transition metals, and metalloids can be grouped into the same category of metal-like contaminants (referred to as one or more metal or metalloid elements). In particular, one or more metal or metalloid elements include silicon, iron, or both. The pyrolysis oil can especially contain up to 200 weight ppm or 1000 weight ppm of silicon, and typically contains 1 to 200 weight ppm or 1 to 1000 weight ppm or 1 to 500 weight ppm of silicon. The pyrolysis oil can especially contain up to 50 weight ppm or 100 weight ppm of iron, and typically 1 to 50 weight ppm or 1 to 100 weight ppm of iron. The pyrolysis oil can also contain phosphorus, sodium, calcium, potassium, and magnesium.

[0065] Other impurities may also be contained in the pyrolysis oil, such as heteroelements, especially contributed by sulfur-containing compounds, oxygen-containing compounds, and / or nitrogen-containing compounds, in a content of usually less than 40,000 weight ppm of heteroatoms, and preferably less than 15,500 weight ppm of heteroatoms, and typically 1 to 40,000 weight ppm of heteroatoms or 1 to 15,500 weight ppm of heteroatoms. Sulfur-containing compounds are usually present in a sulfur-containing compound content of less than 15,000 weight ppm, and preferably less than 10,000 weight ppm, and typically 1 to 15,000 weight ppm or 1 to 10,000 weight ppm.

[0066] Oxygenates are usually present in an oxygenate content of less than 15,000 weight ppm, preferably less than 10,000 weight ppm, and usually from 1 to 15,000 weight ppm or 1 to 10,000 weight ppm.

[0067] Nitrogen compounds are usually present in a nitrogen compound content of less than 10,000 weight ppm, preferably less than 5000 weight ppm, and usually from 1 to 10,000 weight ppm or 1 to 5000 weight ppm.

[0068] The pyrolysis oil may also contain other impurities such as heavy metals such as mercury, arsenic, zinc, and lead, such as up to 100 weight ppb or 200 weight ppb of mercury or arsenic, and usually from 1 to 200 weight ppb or 1 to 100 weight ppb of heavy metals.

[0069] The process according to the invention is particularly suitable for treating pyrolysis oil containing impurities, as well as heavy hydrocarbon feedstocks which will be more particularly defined hereinafter. The term "containing impurities" is understood to mean that the pyrolysis oil has the following properties: - The content of aromatics is from 0 wt% to 90 wt%, usually from 20 wt% to 90 wt%, and it can be from 50 wt% to 90 wt%, in fact even from 30 wt% to 70 wt%; - The content of chlorine is from 2 weight ppm to 5000 weight ppm, usually from 200 weight ppm to 5000 weight ppm, and it can be from 500 weight ppm to 5000 weight ppm; - The content of metal elements is from 0 weight ppm to 1500 weight ppm, and it can be from 1 weight ppm to 1100 weight ppm; - The content of iron element includes: from 0 weight ppm to 100 weight ppm, usually from 5 weight ppm to 100 weight ppm, and it can be from 10 weight ppm to 100 weight ppm; - And the content of silicon element is from 0 weight ppm to 1000 weight ppm, usually from 20 weight ppm to 1000 weight ppm, in fact even from 30 weight ppm or 40 weight ppm to 1000 weight ppm, and it can also be from 100 weight ppm to 1000 weight ppm.

[0070] Plastic and / or tire and / or SRF pyrolysis oil can be obtained by pyrolysis or catalytic pyrolysis treatment, or can be prepared by hydro-pyrolysis (pyrolysis in the presence of a catalyst and hydrogen).

[0071] The feedstock for the process according to the invention - the heavy hydrocarbon fraction of fossil origin - is a heavy hydrocarbon fraction having an initial boiling point of at least 340 °C, a final boiling point of at least 550 °C and containing sulfur and nitrogen. Preferably, it has an initial boiling point of at least 350 °C, preferably at least 375 °C, and a final boiling point of at least 550 °C, preferably at least 560 °C, and more preferably at least 600 °C.

[0072] The heavy hydrocarbon fraction of the feedstock may comprise or consist of atmospheric residue and / or vacuum residue produced by atmospheric and / or vacuum distillation of crude oil.

[0073] The heavy hydrocarbon fraction of the feedstock may also consist of atmospheric and / or vacuum residue produced by atmospheric and / or vacuum distillation of the effluent from thermal conversion, hydrotreating, hydrocracking and / or hydroconversion units.

[0074] The heavy hydrocarbon fraction of the feedstock may also consist of an aromatic fraction extracted from a lubricating oil production unit, deasphalted oil (residue of the deasphalting unit) produced by a deasphalting unit or asphalt (residue of the deasphalting unit) produced by a deasphalting unit.

[0075] The heavy hydrocarbon fraction in the feedstock may also be a residue fraction (atmospheric residue and / or vacuum residue, for example produced by the H-Coal® process) produced by direct liquefaction of coal.

[0076] All these components of fossil origin may be used alone or as a mixture to constitute the heavy hydrocarbon fraction of the feedstock to be treated according to the invention.

[0077] According to one or more embodiments, the heavy hydrocarbon fraction comprises or may consist of at least one of the following feedstocks alone or as a mixture: atmospheric residue or vacuum residue produced by atmospheric and / or vacuum distillation of crude oil or the effluent from thermal conversion, hydrotreating, hydrocracking or hydroconversion units, an aromatic fraction extracted from a lubricating oil production unit, deasphalted oil produced by a deasphalting unit, asphalt produced by a deasphalting unit or a residue fraction produced by direct liquefaction of coal.

[0078] In the present invention, the heavy hydrocarbon fraction to be treated is preferably atmospheric residue or vacuum residue, or a mixture of these residues.

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

[0080] The sulfur content may be greater than or equal to 0.1% by weight, in fact even greater than or equal to 0.5% by weight or 1% by weight, and may be greater than or equal to 2% by weight.

[0081] The nitrogen content is generally from 1 weight ppm to 8000 weight ppm, more generally from 200 weight ppm to 8000 weight ppm, for example from 2000 weight ppm to 8000 weight ppm.

[0082] The content of metals (especially Ni and V) can be greater than or equal to 20 weight ppm, preferably greater than or equal to 100 weight ppm.

[0083] The content of Conradson carbon can be greater than or equal to 3 wt%, in fact even at least 5 wt%. The content of Conradson carbon is defined by the ASTM D482 standard, and for those skilled in the art, it represents a well-known assessment of the carbon residue produced after pyrolysis under standard temperature and pressure conditions.

[0084] The content of C7 asphaltenes (compounds insoluble in hexane, corresponding to the NF T60-115 standard according to the ASTM D6560 standard) can be minimized at 1 wt%, and is generally higher than or equal to 3 wt% (except for the heavy hydrocarbon components mainly containing deasphalted oil). C7 asphaltenes are compounds known to inhibit the conversion of residue fractions because they can form heavy hydrocarbon residues (usually called coke), and they tend to produce deposits that severely limit the operation of hydrotreating and hydroconversion units.

[0085] These contents of sulfur, nitrogen, metals, Conradson carbon and asphaltenes in the heavy hydrocarbon components are expressed as weight % of the total weight of the heavy hydrocarbon components of the feedstock.

[0086] According to one or more embodiments, the feedstock for the process according to the invention may also contain low contents (generally from 1 wt% to 20 wt% of the feedstock, in fact even from 1 wt% to 10 wt%) of vegetable and / or animal oils or fats, and / or hydrocarbon components produced by the thermal and / or catalytic conversion of lignocellulosic biomass, such as oils produced from lignocellulosic biomass according to various liquefaction methods (such as hydrothermal liquefaction or pyrolysis), which are then co-processed with plastics and / or tires and / or SRF pyrolysis oil and heavy hydrocarbon components of fossil origin.

[0087] Oils / fats of plant and / or animal origin contain triglycerides and / or free fatty acids and / or esters. Vegetable oils can advantageously be crude or fully or partially refined, and can be derived from the following plants: rapeseed oil, sunflower oil, soybean oil, palm oil, palm kernel oil, olive oil, coconut oil, jatropha oil (French physic nut oil), castor oil vegetable oil, cottonseed oil, peanut oil, linseed oil or sea kale oil, this list is not restrictive. Algal oil or fish oil is also applicable. Vegetable and / or animal oils / fats can be waste, such as waste cooking oil. Animal fats can be selected from lard or oils produced from food industry residues or the catering industry.

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

[0089] According to one or more embodiments, the feedstock of the process according to the invention does not include oil or fat components of plants and / or animals, or hydrocarbon components produced by thermal and / or catalytic conversion processes of lignocellulosic biomass, such as pyrolysis oil of biomass.

[0090] (a0) Pyrolysis oil pretreatment stage (optional) Prior to the hydrodemetallation stage a), it may be advantageous to pretreat the plastic and / or tyre and / or SRF pyrolysis oil in at least one optional pretreatment stage a0) to obtain a pretreated pyrolysis oil fed to stage a).

[0091] According to an alternative form, the optional pretreatment stage a0) can reduce the amount of contaminants and solid particles that may be present in the pyrolysis oil, in particular the amount of iron and / or silicon and / or chlorine. This optional stage a0) can in particular remove deposits that can form due to the unstable nature of the pyrolysis oil and / or compatibility problems between two different feedstocks. Thus, the optional pyrolysis oil pretreatment stage a0) is advantageously carried out, in particular when the oil contains more than 10 weight ppm, especially more than 20 weight ppm, more especially more than 50 weight ppm of metal elements and / or solid particles, and in particular when the oil contains more than 5 weight ppm of silicon, more especially more than 10 weight ppm, in fact even more than 20 weight ppm of silicon. Similarly, the optional pretreatment stage a0) of the pyrolysis oil is advantageously carried out especially when the oil contains more than 10 weight ppm, especially more than 20 weight ppm, more especially more than 50 weight ppm of chlorine.

[0092] The optional pretreatment stage a0) can be carried out by any method known to those skilled in the art capable of reducing the amount of contaminants. It can in particular include an adsorption stage and / or a filtration stage and / or a centrifugation stage and / or an electrostatic separation stage and / or a washing stage with an aqueous solution and / or a gas stripping stage.

[0093] The optional pretreatment stage a0) is advantageously carried out at a temperature of from 20 to 400 °C, preferably from 40 to 350 °C, and at a pressure of from 0.15 to 10.0 MPa abs., preferably from 0.2 to 7.0 MPa abs.

[0094] According to an alternative form, the optional pretreatment stage a0) is carried out in an adsorption section in the presence of at least one adsorbent. The adsorbent can be selected from zeolites, activated carbon, clays, silica or alumina.

[0095] Advantageously, the adsorbent contains less than 1% by weight of metal elements and preferably contains no metal elements. The term "metal elements of the adsorbent" should be understood to mean the elements in columns 6 to 10 of the periodic table (new IUPAC classification). The residence time of the feedstock in the adsorption section is generally from 1 minute to 180 minutes.

[0096] The adsorption section of the optional stage a0) includes at least one adsorption tower, preferably at least two adsorption towers, preferably two to four adsorption towers, containing the adsorbent. When the adsorption section includes two adsorption towers, one operating mode can be "swing" operation, where one tower is in-line, i.e., in the operating state, while the other adsorption tower is in standby. When the adsorbent in the in-line tower is used up, this adsorption tower is isolated, and the standby tower is put in-line, i.e., into operation. Subsequently, the used-up adsorbent can be regenerated in-situ and / or replaced with fresh adsorbent, so that once another adsorption tower is isolated, the tower containing the adsorbent can be put back in-line again.

[0097] Another operating mode is to operate at least two towers in series. When the adsorbent at the top in the tower is used up, the first tower is isolated, and the used-up adsorbent is regenerated in-situ or replaced with fresh adsorbent. Subsequently, the tower is put back in the last position in-line, and so on. This operation is called the displacement mode, or according to the term, a displaceable reactor system, PRS or "lead and lag". The combination of at least two adsorption towers can overcome the possible and potential problem of rapid poisoning and / or blockage of the adsorbent under the combined action of metal contaminants, diolefins, gums produced by diolefins, and insolubles that may be present in the pyrolysis oil to be treated. The reason is that the presence of at least two adsorption towers is beneficial for the replacement and / or regeneration of the adsorbent, advantageously without shutting down the pretreatment device, and actually even the process, so that the risk of blockage can be reduced, and thus the shutdown of the device due to blockage can be avoided, the cost can be controlled, and the consumption of the adsorbent can be limited.

[0098] According to another alternative form, the optional pretreatment stage a0) is carried out in a section for washing with an aqueous solution (such as water or an acidic or alkaline solution). This washing section can include items of equipment for bringing the feedstock into contact with the aqueous solution and carrying out phase separation, so as to obtain on the one hand the pretreated feedstock and on the other hand an aqueous solution containing impurities. These items of equipment can include, for example, stirred reactors, decanters, mixer-decanters and / or co-current or counter-current washing towers.

[0099] According to another alternative form, the optional pretreatment stage a0) is carried out by filtration. The filtration stage can remove inorganic solids, sediments and / or fines in the oil, especially metals, metal oxides and metal chlorides. Filters with a pore size (e.g., diameter or equivalent diameter) less than 25 µm, preferably less than or equal to 10 µm, and even more preferably less than or equal to 5 µm are generally used. According to another alternative form, filters with a pore size less than 25 µm but greater than 5 µm can be used. A series of filters with different pore sizes can also be used, especially a series of filters with decreasing pore sizes along the oil circulation direction. These filtration media are well-known in industrial applications. For example, cartridge filters or self-cleaning filters are suitable. The solid content can be measured by, for example, the heptane insolubles test (ASTM D-3279 method). The content of insolubles in heptane must be reduced to less than 0.5 wt%, preferably less than 0.1 wt%.

[0100] According to a specific embodiment, the pretreatment stage a0) carried out by filtration includes at least one filter with a pore size less than 10 µm and preferably greater than 5 µm, optionally followed by a filtration system with a pore size less than 2 µm and preferably less than 1 µm.

[0101] According to another specific embodiment, the pretreatment stage a0) carried out by filtration includes at least one filter with a pore size less than 10 µm and preferably greater than 5 µm, followed by an electrostatic precipitation system.

[0102] According to another specific embodiment, the pretreatment stage a0) carried out by filtration includes at least one filter with a pore size less than 10 µm and preferably greater than 5 µm, followed by a system of one or more filters using filter aids (such as sand or diatomaceous earth).

[0103] According to another alternative form, the optional pretreatment stage a0) is carried out by centrifugation. According to another alternative form, the pretreatment stage a0) includes centrifugation and filtration.

[0104] According to another alternative form, the optional pretreatment stage a0) is carried out by gas stripping to reduce the oxygen content in the oil. Gas extraction can remove the oxygen (O2) that can be dissolved in the feedstock, thereby reducing the possibility of forming free radicals that cause polymerization in the downstream stage. The process generally includes contacting the oil with an extraction gas (such as H2, N2 or a mixture thereof), thereby transferring at least a part of the dissolved oxygen in the oil to the extraction gas, and then separating the extraction gas from the oil. The ratio of the volume of the extraction gas to the volume of the oil (the two volumes measured under the gas extraction conditions) is generally greater than 1, and preferably at least 3. In a specific embodiment, the extraction gas can contain at least 60% (mole percentage) of H2. Any dissolved H2 remaining in the feedstock after the gas extraction stage will not cause problems due to the downstream hydrodemetallization / hydrotreatment. Preferably, the gas extraction stage is completed before any (pre)heating of the feedstock to minimize potential fouling.

[0105] The optional pretreatment stage a0) generally includes one or more (preferably multiple) of the above-mentioned treatments. In particular, it can include the following series: a stage of washing with an aqueous solution and / or an adsorption stage, followed by a stripping stage, followed by a filtration stage and / or a centrifugation stage. All these stages are preferably carried out before any (pre)heating of the feedstock.

[0106] The optional pretreatment stage a0) thus makes it possible to obtain a pretreated pyrolysis oil, which is then fed to the hydrodemetallization stage a).

[0107] (a) Hydrodemetallization stage in a replaceable reactor According to the present invention, the method includes a hydrodemetallization stage a), in the presence of at least one hydrodemetallization catalyst, at a temperature of 300 to 500 °C, at an absolute pressure of 5 MPa to 35 MPa and at a space velocity of 0.1 to 5.0 h -1 , in a fixed bed reaction section including at least two replaceable reactors, the section being fed at least with the feedstock, which mainly contains the heavy hydrocarbon component of fossil origin and a small amount of pyrolysis oil component (the pyrolysis oil is optionally pretreated in stage a0), and a gas stream containing hydrogen.

[0108] The pyrolysis oil component and the heavy hydrocarbon component can enter the hydrodemetallization stage in different ways.

[0109] According to the first alternative form, the pyrolysis oil component can be premixed with the heavy hydrocarbon component of the feedstock before entering the reaction section of the hydrodemetallization stage a).

[0110] Another alternative form is to inject the pyrolysis oil component and the heavy hydrocarbon component into the reaction section of stage a) separately. This injection mode may be preferred to prevent any problems related to chemical incompatibility between the two components (e.g., the risk of phase separation or asphaltene precipitation), or also to prevent possible accelerated fouling of the preheating furnace (the high diolefin and olefin content in plastic and / or tire and / or SRF pyrolysis oil can lead to the formation of gum).

[0111] According to these two alternative embodiments, i.e., mixing or not mixing the components before introducing them into the reaction section of the hydrodemetallization stage a), the feedstock, and in particular the heavy hydrocarbon component of the feedstock, is generally preheated to a temperature suitable for hydrodemetallization.

[0112] The preheating of the heavy hydrocarbon component is preferably carried out at a temperature between 280 °C and 450 °C, more preferably between 300 °C and 400 °C, and even more preferably between 320 °C and 365 °C.

[0113] This preheating may also include heating the pyrolysis oil component, especially when the component is injected separately from the heavy hydrocarbon component, but preferably at a temperature lower than that of the heavy hydrocarbon component to limit gum formation due to the presence of olefins and diolefins in the pyrolysis oil component and / or coking of the preheating equipment items (such as furnaces and heat exchangers). Advantageously, the pyrolysis oil component can be preheated at a temperature between ambient temperature (e.g., 15 °C) and 350 °C, preferably 100 °C to 350 °C, more preferably 100 °C to 250 °C, more preferably 100 °C to below 230 °C, and actually even 100 °C to below 200 °C. For example, the pyrolysis oil component can be preheated by a furnace or by mixing with a hotter gas stream containing hydrogen from hydrogen supplementation and / or hydrogen recovered from stage c) of the process according to the invention.

[0114] In the case of a mixture of the two components, the preheating can be carried out after, before, or during the mixing. In this case, the preheating of the mixture of the two components is preferably carried out at a temperature between 280 °C and 450 °C, more preferably 300 °C to 400 °C, and even more preferably 320 °C to 365 °C.

[0115] According to another embodiment, in which the heavy hydrocarbon component and the pyrolysis oil component are mixed, the pyrolysis oil component is indirectly heated by mixing with the heavy hydrocarbon component (i.e., heat exchange between the two components is carried out by bringing the two components at different temperatures into contact).

[0116] Any device capable of preheating the feedstock known to those skilled in the art can be used. At least one furnace, commonly referred to as a preheating furnace, can be used, which includes, for example, at least one heating chamber, and / or tubes (through which the feedstock flows), a mixer for the feedstock and H2, any suitable type of heat exchanger, such as a tubular or spiral heat exchanger through which the feedstock flows, etc.

[0117] Before introducing the feedstock into the reaction section of the hydrodemetallation stage a), the feedstock needs to go through a pressurization stage to adapt it to the operating pressure in the reaction section of the hydrodemetallation stage a), for example, using a suitable pump. This pressurization stage is preferably carried out before the preheating stage.

[0118] The purpose of this hydrodemetallation stage a) is to reduce the impurity content, especially the content of metals (especially silicon) and halogens (especially chlorine), as well as the content of diolefins and olefins. These impurities can come from fossil heavy components or pyrolysis oil, and thus protect the downstream hydrotreating stage b) from deactivation and blockage, hence the concept of protecting the reactor.

[0119] These hydrodemetallation protection reactors are used as replaceable reactors (PRS, replaceable reactor system technology), as described in patent FR 2 681 871.

[0120] The term "replaceable reactor" is understood to mean a component of at least two reactors, where one reactor can be shut down, usually for catalyst regeneration or replacement or for maintenance, while the other reactor (or reactors) is in operation.

[0121] These replaceable reactors are fixed beds, which are located upstream of the fixed bed hydrotreating section of stage b) and are equipped with pipelines and valves to switch between them. That is, for a system with two replaceable reactors Ra and Rb, Ra can be located upstream of Rb, and vice versa. Each reactor Ra and Rb can be taken offline to replace the catalyst without shutting down the rest of the device. This catalyst replacement (flushing, discharging, refilling, sulfiding) is usually achieved through an adjustment section (a set of equipment items outside the main high-pressure circuit). Subsequently, the reactor containing fresh catalyst is returned to the last position online, and so on. When the catalyst activity is no longer sufficient (metal poisoning and coking) and / or when blockage causes too high a pressure drop, catalyst replacement is required.

[0122] According to an alternative form, there can be more than 2 replaceable reactors in the hydrodemetallation section in the replaceable reactor.

[0123] In the hydrodemetallization stage a), a hydrodemetallization (commonly referred to as HDM) reaction occurs. Additionally, a hydrodesulfurization (commonly referred to as HDS) reaction, a hydrodenitrogenation (commonly referred to as HDN) reaction with hydrogenation, a hydrodechlorination, a hydrodeoxygenation, a hydrodearomatization, a hydroisomerization, a hydrodealkylation, a hydrocracking, or a hydrodeasphalting reaction, as well as the Conradson carbon reduction, take place. Stage a) is called the hydrodemetallization stage because it removes most of the metals from the feedstock.

[0124] Furthermore, the silicon contained in the feedstock is deposited on one or more catalysts during this stage. The same applies to chlorinated compounds, where a small portion (the mineral part) is deposited on the catalyst, while the organic chlorinated compounds are converted to HCl.

[0125] According to the present invention, in a replaceable reactor, the hydrodemetallization stage a) can be advantageously carried out at a temperature of 300 °C to 500 °C, preferably 350 °C to 430 °C, and an absolute pressure of 5 MPa to 35 MPa, preferably 11 MPa to 26 MPa, more preferably 14 MPa to 20 MPa. The temperature is usually adjusted according to the desired level of hydrodemetallization and the target treatment duration. The temperature is typically adjusted to remove most, and preferably all, of the metals, including silicon. Most commonly, the space velocity of the hydrocarbon feedstock, also known as the liquid hourly space velocity (LHSV) or the hourly space velocity (HSV), commonly referred to as HSV, and which is defined as the volumetric flow rate of the feedstock divided by the total volume of the catalyst, can be 0.1 h -1 to 5 h -1 , preferably 0.15 h -1 to 3 h -1 , and more preferably 0.2 h -1 to 2 h -1 .

[0126] The amount of hydrogen mixed with the feedstock can be 100 to 5000 standard cubic meters (Sm 3 ) per cubic meter (m 3 ) of liquid feedstock, preferably 200 Sm 3 / m 3 to 2000 Sm 3 / m 3 , and more preferably 300 Sm 3 / m 3 to 1000 Sm 3 / m 3 .

[0127] Industrially, the hydrodemetallation stage a) in the replaceable reactor is carried out in at least two fixed-bed reactors, and preferably with a downward-flowing liquid stream. Each replaceable reactor is a fixed-bed reactor having n catalytic beds, where n is an integer greater than or equal to 1, and each catalytic bed contains at least one hydrodemetallation catalyst.

[0128] According to one embodiment of the invention, at least one reactor of the hydrodemetallation stage a) or the hydrotreating stage b), and preferably all reactors, are equipped with filtration and distribution means, such as those described in patent applications FR 3 043 339 and FR 3 051375.

[0129] According to one embodiment of the invention, stage a) and / or stage b) may use at least one guard bed upstream of one or more hydrodemetallation or hydrotreating catalysts, which guard bed contains adsorbents of the alumina, silica, silica-alumina, zeolite and / or activated carbon type, optionally containing Group VIB and / or Group VIII metals. A series of guard beds with different particle diameters may also be used, in particular a series of guard beds with decreasing diameters in the direction of the feedstock circulation (also known as "graded").

[0130] The hydrodemetallation catalysts used are preferably known catalysts. They may be granular catalysts containing at least one metal or metal compound having a hydrogenation-dehydrogenation function on a support. These catalysts may advantageously be metals containing at least one Group VIII metal (usually selected from nickel and cobalt), and / or at least one Group VIB metal (preferably molybdenum and / or tungsten). For example, a catalyst containing 0.5 wt% to 10 wt% of nickel, preferably 1 wt% to 5 wt% of nickel (expressed as nickel oxide NiO), and 1 wt% to 30 wt% of molybdenum, preferably 3 wt% to 20 wt% of molybdenum (expressed as molybdenum trioxide MoO3) relative to the weight of the catalyst on a mineral support may be used. The total content of the oxides of Group VIB and Group VIII metals relative to the weight of the catalyst may be 5 wt% to 40 wt%, preferably 5 wt% to 30 wt%, and expressed as metal oxides, the weight ratio of (one or more) Group VIB metals to (one or more) Group VIII metals is generally 20 to 1, and most commonly 10 to 2.

[0131] The carrier can, for example, be selected from alumina, silica, silica-alumina, magnesia, clay, and mixtures of at least two of these minerals. Advantageously, the carrier can contain other doping compounds, in particular oxides selected from boron oxide, zirconium oxide, cerium dioxide, titanium oxide, phosphoric anhydride, and mixtures of these oxides. The most commonly used is the alumina carrier, and an alumina carrier doped with phosphorus and (optionally) boron is often used. When phosphorus pentoxide P2O5 is present, its concentration is less than 10% by weight of the alumina, and advantageously at least 0.001% by weight of the total weight of the alumina. When boron trioxide B2O5 is present, its concentration is less than 10% by weight of the alumina, and advantageously at least 0.001% by weight of the total weight of the alumina. The alumina used can be γ (gamma) or η (eta) alumina. The hydrodemetallization catalyst is, for example, in the form of an extrudate.

[0132] Catalysts that can be used in the hydrodemetallization stage a) in a replaceable reactor are, for example, shown in the patent documents EP 0 113 297, EP 0 113 284, US 5 221 656, US 5827 421, US 7 119 045, US 5 622616, and US 5 089 463.

[0133] The hydrodemetallization stage a) can obtain a hydrodemetallization effluent, that is, an effluent with a reduced content of metals (including silicon), a reduced chlorine content, and a reduced olefin (especially diolefin) content. Preferably, during stage a), at least 50%, and more preferably at least 75%, of the chlorine, silicon, metals, and diolefins in the initial feed are removed respectively.

[0134] At the end of the hydrodemetallization stage a), the contents of metals Ni and V are generally less than 20 ppm by weight, and preferably less than 10 ppm by weight, relative to the weight of the effluent.

[0135] At the end of the hydrodemetallization stage a), the silicon content is generally less than 10 ppm by weight, and preferably less than 5 ppm by weight, preferably less than or equal to 2 ppm by weight, and in fact even less than or equal to 1 ppm by weight, relative to the weight of the effluent.

[0136] At the end of the hydrodemetallization stage a), the chlorine content is generally less than 10 ppm by weight, and preferably less than 5 ppm by weight, preferably less than or equal to 2 ppm by weight, and in fact even less than or equal to 1 ppm by weight, relative to the weight of the effluent.

[0137] At the end of the hydrodemetallization stage a), the diolefin content expressed by the MAV value defined above is generally less than 5 mg / g, and preferably less than 1 mg / g.

[0138] The effluent obtained at the end of the hydrodemetallation stage a) is preferably sent directly to the hydrotreatment stage b).

[0139] (b) Hydrotreatment stage According to the present invention, the treatment method includes a hydrotreatment stage b), in the presence of at least one hydrotreatment catalyst, at a temperature of 300 to 500 °C, at an absolute pressure of 5 MPa to 35 MPa, and at a space velocity of 0.1 to 5.0 h -1 in a reaction section including at least one fixed-bed reactor, feeding at least the effluent produced by stage a) and optionally a gas stream containing hydrogen to said section.

[0140] The hydrotreatment stage b) includes hydrotreatment reactions and also includes hydroconversion reactions as defined in the "Definition" section above.

[0141] In the hydrotreatment stage b), the conversion rate is moderate, in fact even low, usually below 45% at the end of the cycle, most usually below 35%, and below 25% at the start of the cycle. The conversion rate usually changes during the cycle as a result of increasing the temperature to compensate for catalyst deactivation. The conversion rate is defined as the weight fraction of organic compounds with a boiling point above 520 °C in the feedstock at the inlet of the reaction section minus the weight fraction of organic compounds with a boiling point above 520 °C in the effluent at the outlet of the reaction section, and then divided as a whole by the weight fraction of organic compounds with a boiling point above 520 °C in the feedstock at the inlet of the reaction section.

[0142] According to a preferred alternative form, the hydrotreatment stage b) includes: a first hydrodemetallation (HDM) stage b1), which is carried out in one or more hydrodemetallation zones in a fixed bed; and a subsequent second hydrodesulfurization (HDS) stage b2), which is carried out in one or more hydrodesulfurization zones in a fixed bed. In the first hydrodemetallation stage b1), the effluent from stage a) is contacted with a hydrodemetallation catalyst under hydrodemetallation conditions; and then in the second hydrodesulfurization stage b2), the effluent from the first hydrodemetallation stage b1) is contacted with a hydrodesulfurization catalyst under hydrodesulfurization conditions. This method is known under the name Hyvahl-F™ and is described, for example, in patent US 5 417 846.

[0143] Those skilled in the art can easily understand that in the hydrodemetallation stage b1), hydrodemetallation reactions are carried out, and at the same time, a part of other hydrotreatment reactions are also carried out, and in particular hydrodesulfurization and hydrocracking reactions. Similarly, in the hydrodesulfurization stage b2), hydrodesulfurization reactions are carried out, and at the same time, a part of other hydrotreatment reactions are also carried out, and in particular hydrodemetallation and hydrocracking reactions.

[0144] Those skilled in the art sometimes define a transition zone where all types of hydrotreating reactions take place. According to another alternative form, the hydrotreating stage b) includes a first hydrodemetallization stage b1) carried out in one or more hydrodemetallization zones of a fixed bed, followed by a second transition stage b2) carried out in one or more transition zones of the fixed bed, and then a third hydrodesulfurization stage b3) carried out in one or more hydrodesulfurization zones of the fixed bed. In the first hydrodemetallization stage b1), the effluent from stage a) is contacted with a hydrodemetallization catalyst under hydrodemetallization conditions; then in the second transition stage b2), the effluent from the first hydrodemetallization stage b1) is contacted with a transition catalyst under transition conditions; and then in the third hydrodesulfurization stage b3), the effluent from the second transition stage b2) is contacted with a hydrodesulfurization catalyst under hydrodesulfurization conditions.

[0145] When the hydrodemetallization carried out during stage a) is insufficient to protect the catalysts in stage b), especially the hydrodesulfurization catalyst, in addition to the hydrodemetallization stage a) in the replaceable protection reactor, it is reasonable to have the hydrodemetallization stage b1) according to the above alternative form.

[0146] Each fixed bed reactor includes n catalytic beds, where n is an integer greater than or equal to 1, and each catalytic bed includes at least one hydrotreating catalyst.

[0147] The hydrotreating stage b) according to the present invention is carried out under hydrotreating conditions. It can advantageously be carried out at a temperature of 300 °C to 500 °C, preferably 350 °C to 430 °C, and an absolute pressure of 5 MPa to 35 MPa, preferably 11 MPa to 26 MPa, more preferably 14 MPa to 20 MPa. The temperature is usually adjusted according to the required level of hydrotreating and the target treatment duration. Most commonly, the space velocity of the feedstock, also known as the liquid hourly space velocity (LHSV) or the hourly space velocity (HSV), usually referred to as HSV, and which is defined as the volumetric flow rate of the feedstock divided by the total volume of the catalyst, can range from 0.1 h -1 to 5 h -1 , preferably 0.1 h -1 to 2 h -1 , and more preferably 0.1 h -1 to 1 h -1 . The amount of hydrogen mixed with the feedstock can be 100 to 5000 standard cubic meters (Sm 3 ) per cubic meter (m 3 ) of liquid feedstock, preferably 200 Sm 3 / m 3 to 2000 Sm 3 / m 3, and more preferably 300 Sm 3 / m 3 to 1500 Sm 3 / m 3 The hydrotreating stage b) can be carried out industrially in one or more reactors with a downward liquid stream.

[0148] The hydrotreating catalysts used are preferably known catalysts. They can be granular catalysts containing at least one metal or metal compound with a hydrogenation - dehydrogenation function on a support. These catalysts can advantageously be catalysts containing at least one Group VIII metal (usually selected from nickel and cobalt), and / or at least one Group VIB metal (preferably molybdenum and / or tungsten). For example, a catalyst can be used that contains 0.5 wt% to 10 wt% of nickel, preferably 1 wt% to 5 wt% of nickel, expressed as nickel oxide NiO, and 1 wt% to 30 wt% of molybdenum, preferably 3 wt% to 20 wt% of molybdenum, expressed as molybdenum trioxide MoO3, relative to the weight of the catalyst. The support can be selected, for example, from alumina, silica, silica - alumina, magnesia, clay, and mixtures of at least two of these minerals.

[0149] Advantageously, the support can contain other doping compounds, especially oxides selected from the following: boron oxide, zirconium oxide, cerium dioxide, titanium oxide, phosphoric anhydride, and mixtures of these oxides. Alumina supports are most commonly used, and more commonly alumina supports doped with phosphorus and optionally boron are used. When phosphorus pentoxide P2O5 is present, its concentration is less than 10 wt% of the weight of the alumina, and advantageously at least 0.001 wt% of the total weight of the alumina. When boron trioxide B2O5 is present, its concentration is less than 10 wt% of the weight of the alumina, and advantageously at least 0.001% of the total weight of the alumina. The alumina used can be γ (gamma) or η (eta) alumina. The catalyst is usually in the form of an extrudate. The total content of the oxides of Group VIB and Group VIII metals, relative to the weight of the catalyst, can be 3 wt% to 40 wt%, and usually 5 wt% to 30 wt%, and expressed as metal oxides, the weight ratio of one or more Group VIB metals to one or more Group VIII metals is usually 20 to 1, and most commonly 10 to 2.

[0150] In a hydrotreating stage comprising a hydrodemetallization (HDM) stage b1) and a subsequent hydrodesulfurization (HDS) stage b2), specific catalysts suitable for each stage are preferably used. Catalysts that can be used for the hydrodemetallization stage b1) are shown, for example, in the documents of patents EP 0 113 297, EP 0 113 284, US 5 221 656, US 5 827 421, US 7119 045, US 5622 616 and US 5 089 463. Catalysts that can be used for the hydrodesulfurization stage b3) are shown, for example, in the documents of patents EP 0 113 297, EP 0 113 284, US 6 589 908, US 4 818 743 and US 6332 976. Mixed catalysts can also be used as described in patent FR 2 940 143, which is also called a transition catalyst and is active in both hydrodemetallization and hydrodesulfurization, and both are used in the hydrodemetallization section b1) and the hydrodesulfurization section b2).

[0151] In the case of a hydrotreating stage comprising a hydrodemetallization (HDM) stage b1), then a transition stage b2), and then a hydrodesulfurization (HDS) stage b3), specific catalysts suitable for each stage are preferably used. Catalysts that can be used for the hydrodemetallization stage b1) are shown, for example, in the documents of patents EP 0 113 297, EP 0 113 284, US 5 221656, US 5 827 421, US 7119 045, US 5 622 616 and US 5 089 463. Catalysts that can be used for the transition stage b2) are as described, for example, in the document of patent FR 2 940 143, which is active in both hydrodemetallization and hydrodesulfurization. Catalysts that can be used for the hydrodesulfurization stage b3) are shown, for example, in the documents of patents EP 0 113 297, EP 0 113 284, US 6589 908, US4 818 743 and US 6332 976. The transition catalyst described in the document of patent FR 2 940 143 for sections b1), b2) and b3) can also be used.

[0152] The hydrotreating stage b) is carried out under conditions capable of obtaining a hydrotreating effluent, that is to say, having a reduced content of sulfur, nitrogen, asphaltenes and Conradson carbon.

[0153] At the end of the hydrotreating stage b), the sulfur content is generally less than 0.5 wt% (5000 ppm), and preferably less than 0.48 wt% (4800 ppm), relative to the weight of the effluent.

[0154] At the end of the hydrotreating stage b), the nitrogen content is generally less than 3500 weight ppm, preferably less than 3000 weight ppm, relative to the weight of the effluent.

[0155] At the end of the hydrotreating stage b), the content of C7 asphaltenes is generally less than 2 wt%, preferably less than 1 wt%, relative to the weight of the effluent.

[0156] At the end of the hydrotreating stage b), the content of Conradson carbon is generally less than 8 wt%, preferably less than 6 wt%, relative to the weight of the effluent.

[0157] The effluent resulting from the hydrotreating stage b) contains conversion products; in particular, the effluent has a reduced content (relative to the feedstock) of hydrocarbons having an initial boiling point of at least 340 °C, or at least 350 °C, 375 °C, 450 °C, 460 °C, 500 °C or 600 °C, depending on the nature of the feedstock.

[0158] (c) Separation stage According to the invention, the process further comprises a separation stage c), which separates part or all of the effluent from stage b) in a separation section, thereby producing a gaseous effluent and at least one liquid product.

[0159] This separation stage c) separates part or all of the said effluent into several components, including at least one liquid product, which can be a light fraction (naphtha, diesel, kerosene), an intermediate fraction (vacuum distillate) or a heavy fraction (vacuum residue).

[0160] The separation stage c) is carried out in a separation section, which comprises any separation device known to those skilled in the art. The separation section may comprise one or more flash drums arranged in series, and / or one or more steam stripping columns and / or hydrogen stripping columns, and / or an atmospheric distillation column, and / or a vacuum distillation column.

[0161] According to one or more embodiments, this separation stage c) is carried out by a series of at least two consecutive flash drums.

[0162] According to one or more other embodiments, this separation stage c) is carried out by one or more steam stripping columns and / or hydrogen stripping columns.

[0163] According to one or more preferred embodiments, this separation stage c) is carried out by an atmospheric distillation column, and more preferably by an atmospheric distillation column and a vacuum column receiving the atmospheric residue.

[0164] According to one or more most preferred embodiments, this separation stage c) is carried out by one or more flash drums, an atmospheric distillation column and a vacuum column receiving the atmospheric residue.

[0165] The gaseous effluent especially contains H2, H2S, NH3 and C1-C4 hydrocarbons. This gaseous effluent can be separated from the effluent obtained at the end of stage b) using separation devices well-known to those skilled in the art, in particular using one or more liquid separation tanks that can operate at different pressures and temperatures, optionally combined with a steam or hydrogen stripping device and one or more distillation columns. The effluent obtained at the end of the hydrotreating stage b) is preferably separated in at least one liquid separation tank into at least one gaseous effluent and at least one liquid product. These separators can be, for example, high-pressure high-temperature (HPHT) separators and / or high-pressure low-temperature (HPLT) separators.

[0166] After optional cooling, this gaseous effluent is preferably treated in a hydrogen purification device to recover the hydrogen not consumed in the hydrodemetallization and hydrotreating reactions. The hydrogen purification device can be an amine scrubber, a membrane, a PSA-type system or several such devices arranged in series. The purified hydrogen, after optional recompression, can be advantageously recycled in the process according to the invention. Hydrogen can be introduced at the inlet of the hydrodemetallization stage a) and / or at different positions during the hydrotreating stage b). The hydrogen (which is hot as it is discharged from stage c)) can also be used to preheat the pyrolysis oil component introduced separately from the heavy components. The recovered gaseous hydrogen can also be used in other units of the refinery.

[0167] The separation stage c) can also include atmospheric distillation and / or vacuum distillation. Advantageously, the separation stage c) also includes at least one atmospheric distillation, in which the liquid effluent obtained after gas / liquid separation is fractionated by atmospheric distillation to obtain at least one atmospheric distillate fraction and at least one atmospheric residue fraction.

[0168] Furthermore, the separation stage c) according to the process of the invention can advantageously additionally include at least one vacuum distillation, in which the liquid effluent obtained after gas / liquid separation and / or the atmospheric residue fraction obtained after atmospheric distillation is fractionated by vacuum distillation to obtain at least one vacuum distillate fraction and at least one vacuum residue fraction. Preferably, the separation stage c) first includes an atmospheric distillation, in which the liquid effluent obtained after gas / liquid separation is fractionated by atmospheric distillation to obtain at least one atmospheric distillate fraction and at least one atmospheric residue fraction; and then includes a vacuum distillation, in which the atmospheric residue fraction obtained after atmospheric distillation is fractionated by vacuum distillation to obtain at least one vacuum distillate fraction and at least one vacuum residue fraction. The vacuum distillate fraction usually contains fractions of the vacuum gas oil type.

[0169] Advantageously, the separation section can also include means for washing at least one separation fraction by contact with an aqueous solution.

[0170] This washing can in particular remove ammonium chloride salts coming mainly from the pyrolysis oil fraction. These salts are formed by the reaction of chloride ions with ammonium ions, the chloride ions being released in the form of HCl by the hydrogenation of chlorinated compounds during stages a) and b), then being dissolved in water; the ammonium ions being produced in the form of NH3 by the hydrogenation of nitrogen-containing compounds during stages a) and b), and / or caused by the injection of amines, then being dissolved in water. Thus, the washing can reduce the risk of blockage caused by the precipitation of ammonium chloride salts, especially in the transport pipelines and / or in the sections of the process according to the invention. The washing can also remove hydrochloric acid formed by the reaction of hydrogen ions and chloride ions, and thus limit the corrosion of downstream equipment items.

[0171] According to a preferred embodiment, the separation stage c) comprises: c1) a first separation stage carried out at a temperature above the precipitation temperature of ammonium halides, to obtain at least one first gas fraction and a liquid effluent, c2) a second separation stage fed with the first gas fraction obtained from stage c1) and at least a portion of the liquid effluent and the aqueous solution, said stage being carried out at a temperature below the precipitation temperature of ammonium halides, to obtain at least one second gas fraction, an aqueous effluent and a liquid product.

[0172] This separation, by combining a thermal separation stage c1) followed by a cold separation / washing stage c2), aims to remove chlorine in the form of ammonium chloride salts.

[0173] During stages a) and b) (hydrodechlorination), the chloride ions released by the hydrogenation of chlorinated compounds in the form of HCl, and during stage b) (especially hydrodenitrogenation), the ammonia produced by the hydrogenation of nitrogen-containing compounds in the form of NH3, are mostly retained in the gaseous effluent by the thermal separation of stage c1). This is because the high temperature of this separation stage c1) prevents the precipitation of ammonium chloride salts formed by the reaction of chloride ions with ammonium ions. In stage c2), the gaseous effluent and a portion of the liquid effluent are separated at a lower temperature, causing these ammonium chloride salts to precipitate. In this stage c2), washing with an aqueous solution (usually water) or an alkaline aqueous solution (such as a sodium hydroxide solution, one or more amine solutions) can dissolve these salts in the aqueous effluent. A chlorine-free hydrocarbon effluent is thus obtained.

[0174] The "precipitation temperature" of the term ammonium halide is understood to mean the temperature at which, under specific conditions, such as concentration and pressure, gaseous ammonia and hydrogen halide precipitate, said precipitation being either by reaction to form solid crystals of ammonium halide or by dissolution in water. According to the principles of thermodynamics, the precipitation temperature depends on the concentration and pressure of the halide. Under the operating conditions of the present process, the precipitation temperature of ammonium halides is generally between 150 and 300 °C.

[0175] The separation equipment item or separation tank may include, at the bottom, a zone that can separate the sedimented hydrocarbon components and the aqueous components containing chloride salts, or may also include a column for washing the gas by contact with water or an alkaline solution.

[0176] (d) One or more subsequent treatment stages (optional) One or more subsequent treatment stages d) may be carried out on one or more liquid products obtained from the separation stage c).

[0177] This stage d) may include at least one stage selected from hydrotreating, steam cracking, fluidized bed catalytic cracking, hydrocracking, deasphalting, and lubricating oil extraction. These examples of subsequent treatments are not exhaustive.

[0178] This is because the various hydrocarbon products that can be produced in the separation stage c) can be sent to different processes in a refinery, and the details of all these post-treatments are not described here as they are well known to those skilled in the art.

[0179] According to an alternative form, feedstocks of the naphtha, kerosene, and diesel types can be upgraded directly in a refinery or after optional hydrotreating to produce fuels for the automotive and aviation industries, such as premium gasoline, jet fuel, and gas oil.

[0180] According to another alternative form, a portion of the gas containing hydrocarbons having 2 to 4 carbon atoms, naphtha, kerosene, and diesel-type feedstocks can be upgraded in a steam cracking unit in order to obtain, in particular, light olefins that can be used as monomers for manufacturing polymers.

[0181] According to yet another alternative form, feedstocks of the naphtha, kerosene, and diesel types can be upgraded in a fluid catalytic cracking (FCC) unit or a hydrocracking unit.

[0182] According to another alternative form, the vacuum distillate can be upgraded in a hydrocracking unit.

[0183] According to another alternative form, the atmospheric residue and / or the vacuum residue (unconverted) can be sent to a fluid catalytic cracking (FCC) process, hydrocracking, or deasphalting.

[0184] According to another alternative form, the atmospheric residue component and / or the vacuum residue component can be used as marine fuels with low sulfur content, in particular distillates for marine use and / or residue fuels for marine use, commonly known as marine fuel oil. Specifically, a residue fuel for marine use with low sulfur content can be produced without adding a flux. Fluxes are generally selected from light component oils from catalytic cracking (light cycle oil, LCO according to FCC terminology), heavy component oils from catalytic cracking (heavy cycle oil, HCO according to FCC terminology), catalytic cracking residues, kerosene, gas oil, vacuum distillates, and / or decant oils, which are generally added to reduce the viscosity of marine fuel oil. When processing heavy feedstocks of fossil origin, pyrolysis oil is present as an auxiliary feedstock, and in particular, a fuel oil that meets the specifications in terms of sulfur, sediment, and viscosity can be directly obtained without adding a flux. The specification of the fuel oil in terms of sulfur is a sulfur content of less than 0.5 wt% / ppm (ISO 8217). According to the ISO 8217 standard, RMG 380 is the most common marine fuel oil grade, and the specification of the marine fuel oil in terms of viscosity is a viscosity of less than 380 cST at 50 °C. Another very strict recommendation is that according to the ISO 10307-2 standard (also known by the name IP390), the sediment content after aging must be less than or equal to 0.1%.

[0185] List of drawings Figure 1 Schematically shows an embodiment of the method according to the present invention.

[0186] Figure 1 The schematic diagram of the embodiment of the reactor series of the present invention is described, but its scope is not limited. For simplicity, only the reactor is shown, but it should be understood that all the equipment items required for operation (drums, pumps, exchangers, furnaces, towers, etc.) are present. Only the main stream containing hydrocarbons is shown, but it should be understood that a hydrogen-rich gas stream (make-up or recycle) can be injected at the inlet of each catalytic bed or between two catalytic beds.

[0187] The feedstock contains a heavy hydrocarbon component 1 and a minor component 2 of plastic and / or tyre and / or SRF pyrolysis oil. Optionally pretreated (not shown), it enters a fixed-bed reaction unit including a replaceable protective reactor composed of reactors Ra and Rb to carry out the hydrodemetallation stage a). The pyrolysis oil component can be premixed with the feedstock heavy hydrocarbon component before entering the first hydrodemetallation reactor. Another alternative is to inject the pyrolysis oil component and the heavy hydrocarbon component separately into the first hydrodemetallation reactor (injection not shown). The effluent 3 from the hydrodemetallation stage a) in the replaceable protective reactor is sent to a fixed-bed reaction section composed of reactors R1, R2 and R3 to carry out the hydrotreating stage b). The fixed-bed hydrotreating reactors can be loaded with, for example, a hydrodemetallation catalyst, a transition catalyst and a hydrodesulfurization catalyst respectively. The effluent 4 from the fixed-bed hydrotreating stage is sent to a separation section 5 to enter the separation stage and separate out a gaseous effluent 6 and at least one liquid product 7.

[0188] The operation of the replaceable reactor is as follows: Both reactors Ra and Rb can be put offline to replace the catalyst without shutting down the rest of the unit. The replacement of the catalyst (flushing, discharging, refilling, sulfiding) is usually achieved through an adjustment section not shown. In sequence 1, the feedstock flows through reactors Ra and Rb, and then through R1, R2 and R3. When the catalyst in reactor Ra no longer has sufficient activity (metal poisoning and coking) and / or when blockage causes too high a pressure drop, a catalyst replacement will be carried out. In sequence 2, reactor Ra is put offline, and the feedstock directly enters reactor Rb, and then flows through R1, R2 and R3. During this sequence 2, the spent catalyst in reactor Ra is discharged, and reactor Ra is refilled with fresh catalyst. In sequence 3, reactor Ra containing fresh catalyst is put online, so that the feedstock first flows through reactor Rb containing some spent catalyst, then through reactor Ra, and then through R1, R2 and R3. When the catalyst activity in reactor Rb is insufficient and / or blockage causes too high a pressure drop, another catalyst replacement will be carried out. In this sequence 4, the spent catalyst in reactor Rb is discharged, and reactor Rb is refilled with fresh catalyst; the feedstock directly enters reactor Ra, and then flows through R1, R2 and R3. In sequence 5, reactor Rb containing fresh catalyst is put online, so that the feedstock first flows through reactor Ra containing some spent catalyst, then through reactor Rb, and then through R1, R2 and R3. Since sequence 5 is the same as sequence 1, this proves the cyclic nature of the proposed operation.

[0189] The following table gives examples of sequences according to Figure 1 that can be generated: Similarly, in the replaceable reactor, the hydrodemetallization section may have more than 2 replaceable reactors. Similarly, there may be more or less than 3 reactors for hydrotreating in the fixed bed, and R1, R2, and R3 are shown by way of example only.

[0190] Analysis methods used Analysis methods and / or standards for determining the characteristics of various streams (especially the feedstock to be treated and the produced effluent) are known to those skilled in the art. They are specifically listed in Table 2 below as information. Other methods considered equivalent may also be used, especially equivalent IP, EN, or ISO methods.

[0191] Table 2 （1） The MAV method described in the following paper: C. López-García et al., Near Infrared Monitoring of Low Conjugated Diolefins Content in Hydrotreated FCC Gasoline Streams, Oil&Gas Science and Technology – Rev. IFP, Vol. 62 (2007), No. 1, pp. 57-68.

[0192] Examples The following examples are intended to demonstrate certain performance qualities of the method according to the present invention.

[0193] In these examples, the possibility of co-processing plastic pyrolysis oil in a Hyvahl® type treatment process is shown, which removes naturally occurring impurities in heavy feedstocks of fossil origin. The hydrotreated effluent can be used as a feedstock for producing fuels, lubricating oils, or any other products conventionally obtained from petroleum refining. The supported catalyst present in the Hyvahl® process also shows the ability to capture the impurities present in the pyrolysis oil and thus upgrade the feedstock, while facilitating the post-treatment of the heavy feedstock hydrotreated to obtain the effluent, which is within the specifications of the ISO 8217 standard for sulfur (0.5 wt%) and viscosity (380 cSt at 50 °C) of RMG 380 type marine fuel oil.

[0194] Example 1 is a comparative example, showing the performance quality of the treatment process of a reference feedstock (vacuum residue) without plastic pyrolysis oil.

[0195] Example 2 shows the performance quality of a treatment process using a process stream that contains a portion of pyrolysis oil from plastics and a portion of the reference feedstock (vacuum residue) used in Example 1. This mixture is used in the pre-stage (optional stage) of media homogenization.

[0196] Feedstock: The heavy fraction (I) of the feedstock is a vacuum residue directly from crude oil distillation ("straight run" (SR-VR)). The pyrolysis oil fraction (II) in the feedstock is pyrolysis oil produced from a plastic mixture and contains a large amount of impurities.

[0197] Table 3 below lists the main characteristics of these two feedstock components.

[0198] Table 3 (*) DL: Detection limit The treatment process includes using two replaceable reactors Ra and Rb in a first hydrodemetallization (HDM) stage upstream of a hydrotreating section consisting of four fixed-bed reactors (R1, R2, R3, and R4). The operating conditions of the two examples are similar and are summarized in Table 4 below.

[0199] Table 4 (**) MOR = Middle of Run Overall results and performance quality: Table 5 below details the results related to the treatment performance quality of VR feedstock with (Example 2) or without (Example 1) pyrolysis oil from plastics.

[0200] Table 5 (*) DL: Detection limit It was observed that the presence of pyrolysis oil from plastics allows the sulfur and viscosity specifications of ISO 8217 for marine fuel oil of the RMG 380 type to be achieved without the addition of a fluxing component. Additionally, in the co-processing of pyrolysis oil from plastics in Example 2, the formulation of marine fuel oil does not require the use of all [180 - 350°C] components, which is different from what was observed in Example 1. Therefore, these "excess" components can be sent to a steam cracking unit together with the IP-180°C component or used as a feedstock for formulating other fuels.

[0201] It was also observed that the total effluent produced by the hydrotreating of the mixture of VR component and pyrolysis oil from plastics exhibits Si and Cl contents below the analytical detection limit, indicating that the catalysts and operating conditions employed in the treatment process are suitable for removing impurities.

Claims

1. A method for treating a feedstock, the feedstock comprising a heavy hydrocarbon component of fossil origin having an initial boiling point of at least 340 °C and a final boiling point of at least 550 °C and containing sulfur and nitrogen, and a pyrolysis oil component of plastics and / or tires and / or solid recovered fuels, the pyrolysis oil component accounting for less than 50% by weight of the feedstock, the method comprising: a) In the presence of at least one hydrodemetallization catalyst, at a temperature of 300 to 500 °C, an absolute pressure of 5 MPa to 35 MPa, and a space velocity of 0.1 to 5.0 h -1 -1, the hydrodemetallization stage is carried out in a fixed-bed reaction section comprising at least two replaceable reactors, and at least the feedstock and a gas stream containing hydrogen are fed to the section, b) In the presence of at least one hydrotreating catalyst, at a temperature of 300 to 500 °C, an absolute pressure of 5 MPa to 35 MPa, and a space velocity of 0.1 to 5.0 h -1 , the hydrotreating stage is carried out in a reaction section comprising at least one fixed-bed reactor, and at least the effluent produced in stage a) and optionally a gas stream containing hydrogen are fed to said section. c) A separation stage of the effluent produced in stage b) in the separation stage, producing a gas component and at least one liquid product.

2. The method according to claim 1, comprising at least one stage a0) for pretreating the components of plastics and / or tires and / or solid recovered fuels pyrolysis oil, the pretreatment stage being upstream of stage a) and comprising an adsorption stage and / or a filtration stage and / or a centrifugation stage and / or an electrostatic separation stage and / or a stage of washing with an aqueous solution and / or a gas stripping stage.

3. The method according to any one of the preceding claims, wherein the pyrolysis oil component accounts for 1% to 45% by weight of the feedstock, preferably 2% to 30% by weight of the feedstock, preferably 2% to 25% by weight of the feedstock.

4. The method according to any one of the preceding claims, wherein the feedstock consists of the pyrolysis oil component and the heavy hydrocarbon component, the pyrolysis oil component accounting for 1% to 45% by weight of the feedstock, preferably 2% to 30% by weight, more preferably 2% to 25% by weight, and the heavy hydrocarbon component accounting for 55% to 99% by weight of the feedstock, preferably 70% to 98% by weight, more preferably 75% to 98% by weight.

5. The method according to any one of the preceding claims, wherein the heavy hydrocarbon component is selected from: atmospheric residue or vacuum residue produced by atmospheric and / or vacuum distillation of an effluent produced by a crude oil or by a thermal conversion, hydrotreating, hydrocracking or hydroconversion unit, an aromatic component extracted from a lubricating oil production unit, deasphalted oil produced by a deasphalting unit, asphalt produced by a deasphalting unit, or a residue fraction produced by direct coal liquefaction.

6. The method according to claim 5, wherein the heavy hydrocarbon component is vacuum residue and / or atmospheric residue.

7. The method according to any one of the preceding claims, wherein the hydrodemetallization catalyst of stage a) comprises nickel in an amount of 0.5% to 10% by weight of the total weight of the catalyst, expressed as nickel oxide NiO, and molybdenum in an amount of 1% to 30% by weight of the total weight of the catalyst, expressed as molybdenum trioxide MoO3, and the catalyst is supported on a mineral support selected from alumina, silica, silica-alumina, magnesia, clay and a mixture of at least two of these minerals.

8. The method according to any one of the preceding claims, wherein the hydrotreating catalyst in stage b) comprises from 0.5% to 10% by weight of nickel, expressed as nickel oxide NiO, and from 1% to 30% by weight of molybdenum, expressed as molybdenum oxide MoO3, based on the total weight of the catalyst, and the catalyst is supported on a mineral support selected from alumina, silica, silica - alumina, magnesia, clay, and mixtures of at least two of these minerals.

9. The method according to any one of the preceding claims, wherein the separation section in stage c) comprises means for washing by contact with an aqueous solution.

10. The method according to claim 9, wherein the separation stage c) comprises: c1) a first separation stage carried out at a temperature higher than the ammonium halide precipitation temperature to obtain at least a first gas fraction and a liquid effluent, c2) a second separation stage, into which the first gas fraction obtained from stage c1), at least a portion of the liquid effluent, and an aqueous solution are fed, the stage being carried out at a temperature lower than the ammonium halide precipitation temperature to obtain at least a second gas fraction, an aqueous effluent, and a liquid product.

11. The method according to any one of the preceding claims, further comprising stage d) for the subsequent treatment of at least one liquid product produced in stage c), said stage d) comprising at least one stage selected from hydrotreating, steam cracking, fluidized bed catalytic cracking, hydrocracking, deasphalting, and lubricating oil extraction.

12. The method according to any one of the preceding claims, wherein in stage a), the pyrolysis oil component of the feedstock is premixed with the heavy hydrocarbon component before introduction into one of the replaceable reactors.

13. The method according to any one of claims 1 to 11, wherein in stage a), the pyrolysis oil component of the feedstock and the heavy hydrocarbon component are introduced separately into one of the replaceable reactors.

14. The method according to claim 13, wherein stage a) comprises a stage of preheating the heavy hydrocarbon component before introducing the feedstock into one of the replaceable reactors, preferably at a temperature of from 280°C to 450°C, and a stage of preheating the pyrolysis oil component at a temperature lower than that of the heavy hydrocarbon component.

15. A product obtained by the method according to any one of claims 1 to 14.

16. The product according to claim 15, which comprises a silicon content of less than or equal to 10 weight ppm and / or a chlorine element content of less than or equal to 10 weight ppm relative to the weight of the product.

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