Method for immobilizing heavy fossil fuel feedstock containing fractions of plastic pyrolysis oil

Abstract

The present invention relates to a method for processing a feedstock comprising a heavy fraction of fossil-derived hydrocarbons and a fraction of pyrolysis oil from plastics and / or tires and / or solid recovery fuels, wherein the pyrolysis oil fraction constitutes less than 50% by weight of the feedstock. a) A hydrogenation demetallation step carried out in a fixed-bed reaction section comprising at least two replaceable reactors, wherein the section is supplied by a gas stream containing at least feedstock and hydrogen in the presence of a hydrogenation demetallation catalyst, b) A hydrogenation step carried out in a reaction section comprising at least one fixed-bed reactor, wherein the section is supplied by a gas stream containing at least the effluent from step a) and optionally hydrogen, in the presence of a hydrogenation catalyst. c) A method comprising the step of separating the effluent resulting from step b).

Description

[Technical Field]

[0001] The present invention relates to the field of hydrogenation conversion of feedstocks comprising heavy fractions of fossil-derived hydrocarbons and trace fractions of plastics and / or tires and / or solid recovery fuel (SRF) pyrolysis oil containing impurities. The heavy fractions of hydrocarbons are heavy oil feedstocks of atmospheric residue and / or vacuum residue type.

[0002] In particular, the present invention relates to a method for processing such mixed feed materials in a fixed bed having a lower boiling point, for example for the purpose of producing fuel or chemicals, with the aim of producing higher quality materials while enabling the capture of impurities in plastics and / or tires and / or solid recovery fuel (SRF) pyrolysis oil. [Background technology]

[0003] For several years, the fuel and chemical industries have seen the incorporation of non-petroleum products, such as plastics or waste oil, as supplements or substitutes for fossil-derived products.

[0004] In particular, plastics obtained from the collection and sorting industries can undergo a pyrolysis step to obtain pyrolysis oil. These plastic pyrolysis oils are commonly incinerated to generate electricity and / or used as fuel for industrial or urban heating boilers.

[0005] Used tires often undergo the same processing.

[0006] Solid recovery fuel (SRF), also known as waste-derived fuel (RDF), is a solid, non-hazardous waste prepared for energy improvement, regardless of whether it originates from household and similar waste, waste from economic activities, or waste from construction and demolition. SRF is generally a mixture of any combustible waste, such as used tires, food by-products (fat, animal feed, etc.), viscose and wood waste, light fractions from shredders (e.g., from used cars, electrical and electronic equipment (WEEE)), household and commercial waste, particularly certain municipal waste, plastic waste, textiles, or wood. SRF generally includes plastic waste. Currently, SRF is primarily being improved as an energy source. They can be used directly as a substitute for fossil fuels in co-incineration facilities (coal and lignite power plants, cement plants, lime kilns) or household waste incineration units, or indirectly in pyrolysis units dedicated to energy quality improvement. Thus, SRF pyrolysis oil is commonly burned to generate electricity and is actually also used as fuel for industrial or urban heating boilers.

[0007] Plastics and / or tires and / or SRF pyrolysis oil can also be modified, optionally through refining methods, to produce various polymers for the chemical industry, as well as chemicals such as fuels, e.g., gasoline or diesel, and / or olefins.

[0008] However, this pathway for improving the quality of plastic and / or tire and / or SRF pyrolysis oils faces problems arising from the specific composition of these oils, particularly the impurities they contain, and the composition of these oils is itself related to the diversity of components in plastic waste, tires, and SRF.

[0009] This is because plastic waste, tires, or SRF are generally mixtures of several polymers, such as polyethylene, polypropylene, polyethylene terephthalate, polyvinyl chloride, and polystyrene. Furthermore, depending on the application, plastics may contain other compounds in addition to the polymer, such as plasticizers, pigments, dyes, or polymerization catalyst residues, as well as other highly diverse organic and mineral impurities derived from the separation operations of sorting centers, and the selectivity of these operations may not be 100%.

[0010] Therefore, oils resulting from thermal decomposition generally contain many diolefins and impurities, especially metals, silicon, or halogenated compounds, particularly chlorinated compounds, heteroatoms such as sulfur, oxygen, and nitrogen, and insoluble matter, often in high concentrations, and may not be compatible with some refining units.

[0011] The handling of these oils can present operational problems, particularly corrosion, coking, or catalyst deactivation, or incompatibility with the target polymer's application. For example, the presence of diolefins very often leads to instability issues in pyrolysis oils, characterized by gum formation. The gum and insoluble matter that may be present in the pyrolysis oils can cause clogging issues with equipment items.

[0012] One route to remove these impurities from plastics and / or tires and / or SRF pyrolysis oil is to perform hydrogenation in the presence of a catalyst.

[0013] International Publication No. 2018 / 055555 provides a very general and relatively complex overall method for recycling plastic waste, ranging from the actual stage of thermal decomposition of plastic waste to the steam decomposition stage, thereby enabling the production of highly refinable products in the petrochemical field, such as olefins and aromatic compounds. The method, in particular, preferably includes a step of hydrocracking of the liquid phase resulting directly from thermal decomposition, in a fixed bed.

[0014] French Patent Application Publication No. 3,107,530, French Patent Application Publication No. 3,113,060, and French Patent Application Publication No. 3,113,061 describe, inter alia, a method for treating plastic pyrolysis oil that includes a stage of selective hydrogenation of plastic pyrolysis oil and a hydrotreatment in a fixed bed of the hydrogenation effluent. A specific separation of the hydrotreated effluent by water, followed by a naphtha cut resulting from a fraction of the separated hydrocarbon stream, can be sent to a steam cracking unit or used as a fuel feedstock. According to French Patent Application Publication No. 3,113,060 and French Patent Application Publication No. 3,113,061, this method minimizes the yield of the heavy cut and maximizes the yield of the naphtha cut by converting the heavy cut, at least partially, to a naphtha cut by hydrocracking, which is a cut generally preferred for steam cracking units, by incorporating one or two stages of hydrocracking in a fixed bed after the hydrotreatment stage.

Prior Art Documents

Patent Documents

[0015]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Summary of the Invention

Means for Solving the Problems

[0016] <着 (Object and Outline of the Invention) The present invention relates to the field of improving fossil-derived heavy feedstocks, such as petroleum residues that are generally difficult to improve, containing high levels of impurities such as metals, sulfur, nitrogen, Conradson carbon, and asphaltenes, in order to convert heavy feedstocks into lighter products that can be improved as fuels, for example, to produce petroleum, diesel fuel, or bunker fuel oil, or starting materials for the petrochemical industry.

[0017] More specifically, the present invention relates to a method for processing a feedstock comprising a heavy fraction of fossil-derived hydrocarbons 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 fraction of plastics and / or tires and / or solid recovery fuel pyrolysis oil, wherein the pyrolysis oil fraction constitutes less than 50% by weight of the feedstock, and the method is a) A hydrogenation demetallation step carried out in a fixed-bed reaction section comprising at least two replaceable reactors, wherein the section is performed in the presence of at least one hydrogenation demetallation catalyst, at a temperature of 300-500°C, an absolute pressure of 5 MPa-35 MPa, and for 0.1-5.0 hours. -1 A hydrogenation demetallation step, supplied by a gas flow containing at least the supply material and hydrogen at a spatiotemporal velocity, b) A hydrogenation step carried out in a reaction section comprising at least one fixed-bed reactor, wherein the section is subjected to a temperature of 300-500°C, an absolute pressure of 5 MPa-35 MPa, and 0.1-5.0 h in the presence of at least one hydrogenation catalyst. -1 A hydrogenation treatment step, supplied by a gas stream containing the effluent generated from at least step a) and optionally hydrogen, at a spatiotemporal velocity, The present invention provides a method comprising: c) a step of separating the effluent resulting from step b) which is performed in a separation section that yields a gas fraction and at least one liquid product.

[0018] The inventors have demonstrated, surprisingly, that it is possible to incorporate trace fractions of plastics and / or tires and / or SRF pyrolysis oil containing impurities into fossil-derived heavy hydrocarbon feedstocks, typically atmospheric or vacuum residues conventionally treated by fixed-bed hydrogenation methods. Thus, by efficiently treating the present impurities and converting the feedstock into an improveable product, optimized processing of two challenging feedstocks is possible.

[0019] Accordingly, the present invention provides a method for the hydrogenation conversion of heavy feedstock of fossil origin hydrocarbons in a fixed bed, particularly heavy feedstock of atmospheric residue and / or vacuum residue type, said feedstock comprising trace fractions of plastics and / or tires and / or SRF pyrolysis oil, thus enabling the production of fuel stocks and other improveable hydrocarbons and / or feedstocks suitable for steam cracking units for the production of olefins and / or aromatics.

[0020] The presence of plastic pyrolysis oil allows for a significant increase in the yield of IP-180°C cut, while reducing the yield of heavy cut. One essential aspect of the present invention lies in the ability of a fixed-bed reactor(s) to at least partially convert pyrolysis oil to lighter products through a combination of high temperature and the presence of a catalyst that enables the hydrogenation of unsaturated molecules (olefins or aromatics). Thus, co-treatment of pyrolysis oil makes it possible to improve the yield of hydrogenated effluent, particularly specific cuts obtained in gasoline cut.

[0021] Furthermore, it has been demonstrated that, despite the presence of silicon in the pyrolysis oil, the product obtained by the method according to the present invention is substantially silicon-free, indicating that silicon was captured by the catalyst(s). Similarly, chlorine is substantially completely captured and / or converted (to HCl). Therefore, the product resulting from this stage is low in impurities.

[0022] Another advantage of the present invention is to limit the temperature rise between the inlet and outlet of the fixed-bed reactor caused by the heat released by the hydrogenation of diolefins or olefins contained in the pyrolysis oil fraction, which is partially absorbed by the heavy fraction of fossil hydrocarbons being processed at the same time. This results in an optimized method that limits the recycling of the effluent and / or the use of resources in gaseous and / or liquid cooling flows.

[0023] Another object of the present invention is to produce atmospheric distillates (naphtha, kerosene, diesel), vacuum distillates, marine fuels and / or light (C1-C4) gases by the same method.

[0024] According to the alternative, naphtha, kerosene, and diesel-type raw materials can be improved in refineries for the production of fuels for the automotive and aviation industries, such as premium grade gasoline, jet fuel, and diesel fuel.

[0025] According to another alternative, naphtha, kerosene, and diesel-type raw materials can be modified in a steam cracking unit to obtain particularly light olefins that can be used as monomers in the production of polymers.

[0026] In yet another alternative form, naphtha, kerosene, and diesel-type feedstocks can also be improved in fluidized bed catalytic cracking (FCC) units or hydrocracking units.

[0027] According to another alternative, vacuum distillates can be improved within a hydrocracking unit.

[0028] One advantage of the present invention is to provide a method that combines the conversion and refining of fossil-derived heavy feedstock for the production of marine fuel having a low sulfur content, while improving the co-feed feedstock for pyrolysis oil. The quality requirements for marine fuel are described in standard ISO 8217. The specifications regarding sulfur will be as follows: SO xLinked to emissions (Annex VI of the International Maritime Organization's MARPOL Convention), this is reflected in the recommended sulfur content of 0.5% by weight or less outside emission control areas (ECAs) and 0.1% by weight or less within emission control areas for 2020-2025. Another very restrictive recommendation is the content of aged precipitate according to ISO 10307-2 (also known as IP390), which must be 0.1% by weight or less. In addition, the viscosity of RMG380 grade bunker fuel oil must adhere to the viscosity limit of less than 380 cSt at 50°C.

[0029] The presence of pyrolysis oil as a co-supply in the processing of heavy raw materials of fossil origin makes it possible to directly obtain fuel oil that meets specifications in terms of sulfur, precipitate, and viscosity, particularly without the need to add flux. Flux is generally added to reduce the viscosity of bunker fuel oil to meet viscosity specifications. In fact, the presence of pyrolysis oil is generally lighter in terms of boiling point, which makes it possible to reduce the sulfur content and viscosity to achieve the required specifications. Therefore, the method according to the present invention has the advantage of making it possible to directly obtain bunker fuel oil that meets the required specifications (without the need to add flux, which is the conventional case, to meet the specifications), while at the same time being able to improve feedstocks that are difficult to improve, such as pyrolysis oil, and increase the yield of the desired distillate.

[0030] According to one or more embodiments of the present invention, the method according to the present invention comprises at least one step a0) of pretreatment of fractions of plastics and / or tires and / or solid recovered fuel pyrolysis oil, wherein the pretreatment step is performed upstream of step a) and comprises an adsorption step and / or a filtration step and / or a centrifugation step and / or an electrostatic separation step and / or an aqueous scrubbing step and / or a gas stripping step.

[0031] According to one or more embodiments of the present invention, the pyrolysis oil fraction constitutes 1% to 45% by weight of the feedstock, preferably 2% to 30% by weight, and preferably 2% to 25% by weight of the feedstock.

[0032] According to one or more embodiments of the present invention, the feedstock consists of a fraction of the pyrolysis oil and a heavy fraction of the hydrocarbon, wherein the pyrolysis oil fraction constitutes 1% to 45% by weight, preferably 2% to 30% by weight, and more preferably 2% to 25% by weight of the feedstock, and the heavy fraction of the hydrocarbon constitutes 55% to 99% by weight, preferably 70% to 98% by weight, and more preferably 75% to 98% by weight of the feedstock.

[0033] According to one or more embodiments of the present invention, the heavy hydrocarbon fraction is selected from a list consisting of crude oil, taken individually or as a mixture, atmospheric residue or vacuum residue from atmospheric and / or vacuum distillation of effluents from thermal conversion, hydrotreatment, hydrocracking or hydroconversion units, aromatic cuts extracted from lubricant production units, de-bitumen from de-bitumen units, asphalt from de-bitumen units, residual fractions from direct coal liquefaction, vacuum distillates from direct coal liquefaction, bitumen sand or derivatives thereof, oil shale or derivatives thereof, raw rock oil or derivatives thereof.

[0034] According to one or more embodiments of the present invention, the heavy hydrocarbon fraction is vacuum residue and / or atmospheric residue.

[0035] According to one or more embodiments of the present invention, the hydrogenation demetallation catalyst of step a) comprises, on a mineral support selected from the group consisting of alumina, silica, silica-alumina, magnesia, clay, and mixtures of at least two of these minerals, nickel represented as nickel oxide (NiO) in an amount of 0.5% to 10% by weight relative to the total weight of the catalyst, and molybdenum represented as molybdenum oxide (MoO3) in an amount of 1% to 30% by weight relative to the total weight of the catalyst.

[0036] According to one or more embodiments of the present invention, the hydrogenation catalyst of step b) comprises, on a mineral support selected from the group consisting of alumina, silica, silica-alumina, magnesia, clay, and mixtures of at least two of these minerals, nickel represented as nickel oxide (NiO) in an amount of 0.5% to 10% by weight relative to the total weight of the catalyst, and molybdenum represented as molybdenum oxide (MoO3) in an amount of 1% to 30% by weight relative to the total weight of the catalyst.

[0037] According to one or more embodiments of the present invention, the separation section in step c) includes means for scrubbing by contact with an aqueous solution.

[0038] According to one or more embodiments of the present invention, the separation section c) is c1) A first separation step carried out at a temperature higher than the precipitation temperature of ammonium halide in order to obtain at least one first gas fraction and one liquid effluent, c2) A second separation step comprising a second separation step supplied with the first gas fraction and at least a portion of the liquid effluent resulting from step c1) and an aqueous solution, wherein the second separation step is carried out at a temperature lower than the precipitation temperature of ammonium halide, in order to obtain at least one second gas fraction, one aqueous effluent and one liquid product.

[0039] According to one or more embodiments of the present invention, the method according to the present invention further comprises a step d) of subsequent treatment of at least one liquid product resulting from step c), the step d) comprising at least one step selected from the list of hydrogenation, steam cracking, fluidized bed catalytic cracking, hydrocracking, desying, and extraction of lubricating oil.

[0040] According to one or more embodiments of the present invention, in step a), the pyrolysis oil fraction and the heavy hydrocarbon fraction of the feedstock are premixed before being introduced into one of the replaceable reactors.

[0041] According to one or more embodiments of the present invention, in step a), the pyrolysis oil fraction of the feedstock is introduced into one of the replaceable reactors separately from the heavy hydrocarbon fraction.

[0042] According to one or more embodiments of the present invention, step a) includes preheating the heavy fraction of hydrocarbons to a temperature preferably between 280°C and 450°C, and preheating a fraction of pyrolysis oil at a lower temperature than that of the heavy fraction of hydrocarbons before introducing the feedstock into one of the replaceable reactors.

[0043] The present invention also relates to a preferred product that is easily obtained by the method according to the present invention.

[0044] Such products, in their free form, contain a silicon content of 10 ppm by weight or less and / or a chlorine element content of 10 ppm by weight or less, relative to the weight of the product.

[0045] Description of the Embodiment To better understand the present invention, some definitions are given below.

[0046] In this specification, the term “to comprise” is synonymous with “to include” and “to contain,” and is inclusive or non-exclusive, not excluding other elements not mentioned. The term “to comprise” is understood to include the exclusive and closed term “to consist.”

[0047] In this specification, the expression "between... and..." means that the interval limit falls within the range of values ​​specified, unless otherwise specified.

[0048] Within the scope of the present invention, various parameter ranges of a given stage, such as pressure ranges and temperature ranges, can be used individually or in combination. For example, within the scope of the present invention, a preferred range of pressure values ​​can be combined with a more preferred range of temperature values.

[0049] This specification may describe specific and / or preferred embodiments of the present invention. These may be used separately or together without limiting the combination, where technically feasible.

[0050] Next, the groups of chemical elements are given according to the CAS classification (CRC Handbook of Chemistry and Physics, published by CRC Press, edited by DRLide, 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 of the new IUPAC classification.

[0051] The metal content is measured using X-ray fluorescence.

[0052] The term "processing method" refers to a method that includes hydrogenation conversion and hydrogenation treatment reactions.

[0053] The term "hydrogenation conversion" refers to a method whose primary purpose is to reduce the boiling point range of the feedstock, in which a significant portion of the feedstock is converted into a product having a lower boiling point range than the starting material. Hydrogenation conversion generally involves the fragmentation of larger hydrocarbon molecules, yielding smaller molecular fragments with fewer carbon atoms and a higher hydrogen-to-carbon ratio. The reactions that occur during hydrogenation conversion allow for the reduction of hydrocarbon molecular size, primarily by cleaving carbon-carbon bonds in the presence of hydrogen to saturate the cleaved bonds and aromatic rings. The mechanism by which hydrogenation conversion occurs typically involves the formation of free radicals of the hydrocarbon during fragmentation, mainly by thermal decomposition, followed by the capping of the terminal or fragment of the free radicals with hydrogen in the presence of an active catalytic site. Of course, other reactions typically associated with hydrogenation treatment can be carried out during the hydrogenation conversion method, such as the removal of sulfur or nitrogen from the feedstock, or the saturation of olefins, which are defined more broadly below.

[0054] The term "hydrogenation," commonly referred to as "HDT," refers to a milder operation whose primary purpose is to remove impurities such as sulfur, nitrogen, oxygen, halides, and trace amounts of metals from the feedstock, to saturate the olefins, and / or to stabilize the free radicals of hydrocarbons by reacting them with hydrogen rather than with themselves. The main objective is not to alter the boiling point range of the feedstock. Thus, hydrogenation includes, in particular, hydrogenated desulfurization (commonly known as "HDS"), hydrogenated denitrification (commonly known as "HDN"), and hydrogenated demetallation (commonly known as "HDM"), and involves hydrogenation, hydrogenated deoxygenation (commonly known as "HDO"), hydrogenated dearomatization, hydrogenated dechlorination, hydrogenated isomerization, hydrogenated dealkylation, hydrogenolysis or hydrogenated desyringe reactions, and reduction of Conradson carbon.

[0055] In the remainder of this text, unless otherwise specified, the term “pyrolysis oil” is understood to mean oil resulting from the pyrolysis of plastics and / or tires and / or SRF. Also, for simplicity, unless otherwise specified, the term “heavy hydrocarbon fractions” of the feedstock means heavy hydrocarbon fractions of fossil origin.

[0056] feedstock According to an essential aspect of the present invention, the feedstock mainly comprises a heavy fraction of fossil-derived hydrocarbons and a trace fraction of plastics and / or tires and / or SRF pyrolysis oil.

[0057] According to a preferred embodiment of the present invention, the feedstock consists of the trace fraction of plastics and / or tires and / or SRF pyrolysis oil, as well as the major fraction of heavy hydrocarbons of fossil origin.

[0058] Therefore, the method according to the present invention is specific to the hydrogenation conversion of mixtures of plastics and / or tires and / or SRF pyrolysis oils with low content, as well as the hydrogenation conversion of heavy fractions of fossil hydrocarbon origin.

[0059] The fraction of plastics and / or tires and / or SRF pyrolysis oil constitutes 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 another 2% to 25% by weight of the feedstock, more preferably another 3% to 20% by weight of the feedstock, and even more preferably 5% to 20% by weight of the feedstock, and in practice, an additional 5% to 15% by weight of the feedstock.

[0060] The feedstock can consist only of these two fractions, a pyrolysis oil fraction and a heavy hydrocarbon fraction, with the sum of the pyrolysis oil fraction and the heavy hydrocarbon fraction forming 100% by weight of the feedstock. Preferably, when the feedstock consists of the heavy hydrocarbon fraction and the pyrolysis oil fraction, the heavy hydrocarbon fraction can constitute 55% to 99% by weight of the feedstock, preferably 70% to 98% by weight, more preferably 75% to 98% by weight, more preferably 80% to 97% by weight, even more preferably 80% to 95% by weight, and in practice, even further 85% to 95% by weight of the feedstock.

[0061] According to the present invention, “plastic pyrolysis oil or tire pyrolysis oil or SRF pyrolysis oil” is an oil, advantageously in liquid form at ambient temperature, resulting from the pyrolysis of plastics, preferably particularly from the pyrolysis of plastic waste arising from collection and sorting channels, or from the pyrolysis of used tires, or from the pyrolysis of SRF. It comprises, in particular, a mixture of hydrocarbon compounds, especially paraffins, olefins (mono- and / or diolefins), naphthenes, and aromatics. At least 80% by weight of these hydrocarbon compounds have a boiling point preferably below 700°C, preferably below 550°C. In particular, depending on the origin of the pyrolysis oil, the pyrolysis oil may contain up to 70% by weight of paraffins, up to 90% by weight of naphthenes, up to 90% by weight of olefins, and up to 90% by weight of aromatic compounds, and it is understood that the sum of paraffins, naphthenes, olefins, and aromatic compounds is equal to 100% by weight of hydrocarbon compounds.

[0062] Pyrolytic oils may contain diolefins. The diolefin content is generally determined indirectly as the maleic anhydride value (MAV). This method is based on the Diels-Alder addition reaction between conjugated diolefins and maleic anhydride. The method for determining MAV is described by C. Lopez-Garcia et al. in 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. MAV is expressed as mg of maleic anhydride reacted with 1 g of sample (mg / g). MAV varies between 5 and 100 mg / g in pyrolytic oils.

[0063] The density of pyrolysis oil, measured at 15°C according to the ASTM D4052 method, is generally 0.75 g / cm³. 3 ~0.99 g / cm³ 3 Preferably 0.75 g / cm³ 3 ~0.95g / cm 3 That is the case.

[0064] Pyrolysis oil may contain, and usually contains, impurities such as metals, especially iron, silicon, or halogenated compounds, especially chlorinated compounds. These impurities may be present in high concentrations in the pyrolysis oil, for example, up to 500 ppm by weight, or up to 700 ppm by weight, actually further up to 1,000 ppm by weight, or even 5,000 ppm by weight, of halogenated elements (especially chlorine, but also bromine, fluorine, iodine, or astatine), generally in amounts of 1 to 1,000 ppm by weight, or 1 to 700 ppm by weight, or 1 to 500 ppm by weight. Pyrolysis oil may also contain chlorinated elements, generally in amounts of 1 to 1,000 ppm by weight, or 1 to 700 ppm by weight, or 1 to 500 ppm by weight, of chlorinated compounds contributing up to 500 ppm by weight or 700 ppm by weight, actually further up to 1,000 ppm by weight, or even 5,000 ppm by weight.

[0065] Oils can contain up to 200 ppm by weight, and in practice even more than 1500 ppm by weight, of metallic or metalloid elements, generally between 1 and 200 ppm by weight or 1 and 1500 ppm by weight. Alkali metals, alkaline earth metals, transition metals, post-transition metals, and metalloids can be placed in the same category as metallic contaminants called metals or metalloid elements. In particular, metals or metalloid elements include silicon, iron, or both of these elements. Pyrolysis oils can contain up to 200 ppm by weight or 1000 ppm by weight of silicon, generally between 1 and 200 ppm by weight or 1 and 1000 ppm by weight or 1 and 500 ppm by weight of silicon. Pyrolysis oils can contain up to 50 ppm by weight or 100 ppm by weight of iron, generally between 1 and 50 ppm by weight or 1 and 100 ppm by weight of iron. Pyrolysis oils can also contain phosphorus, sodium, calcium, potassium, and magnesium.

[0066] Pyrolytic oil may also contain other impurities, such as heteroatoms, particularly sulfur compounds, oxygen compounds, and / or nitrogen compounds, generally in amounts of less than 40,000 ppm by weight of heteroatoms, preferably less than 15,500 ppm by weight, and generally 1 to 40,000 ppm by weight or 1 to 15,500 ppm by weight of heteroatoms. Sulfur compounds are generally present in amounts of less than 15,000 ppm by weight, preferably less than 10,000 ppm by weight, and generally 1 to 15,000 ppm by weight or 1 to 10,000 ppm by weight of sulfur compounds.

[0067] Oxygen compounds are generally present in concentrations of less than 15,000 ppm by weight, preferably less than 10,000 ppm by weight, and generally between 1 and 15,000 ppm by weight or 1 and 10,000 ppm by weight.

[0068] Nitrogen compounds are generally present in concentrations of less than 10,000 ppm by weight, preferably less than 5,000 ppm by weight, and generally between 1 and 10,000 ppm by weight or 1 and 5,000 ppm by weight.

[0069] Pyrolysis oil may also contain other impurities such as heavy metals, e.g., mercury, arsenic, zinc, and lead, e.g., up to 100 ppb by weight of mercury or arsenic, or 200 ppb by weight of mercury or arsenic, and generally 1 to 200 ppb by weight of heavy metals or 1 to 100 ppb by weight.

[0070] The method according to the present invention, in combination with a heavy hydrocarbon feedstock, is particularly well suited for treating pyrolysis oil containing impurities, as defined in more detail below. The term “containing impurities” is understood to mean that the pyrolysis oil has the following properties:

[0071] - The aromatic compound content is 0% to 90% by weight, often 20% to 90% by weight, and may also be 50% to 90% by weight, or in practice, even more than 30% to 70% by weight; - A chlorine content of 2 ppm by weight to 5000 ppm by weight, often 200 ppm by weight to 5000 ppm by weight, and may also be 500 ppm by weight to 5000 ppm by weight; - A metallic element content ranging from -0 ppm by weight to 1500 ppm by weight, which may be 1 ppm by weight to 1100 ppm by weight; - Contains iron in concentrations of 0 ppm to 100 ppm by weight, often 5 ppm to 100 ppm by weight, and may also be 10 ppm to 100 ppm by weight; - A silicon content of 0 ppm by weight to 1000 ppm by weight, often 20 ppm by weight to 1000 ppm by weight, actually even more than 30 ppm by weight or 40 ppm by weight, and 1000 ppm by weight, which may also be 100 ppm by weight to 1000 ppm by weight.

[0072] Plastic and / or tire and / or SRF pyrolysis oils may be obtained from thermal or catalytic pyrolysis treatments, or prepared by hydrothermal decomposition (thermal decomposition in the presence of a catalyst and hydrogen).

[0073] The heavy fraction of fossil hydrocarbons used as feedstock in the method according to the present invention is a heavy fraction of hydrocarbons containing sulfur and nitrogen, having an initial boiling point of at least 340°C and a final boiling point of at least 550°C. Preferably, its initial boiling point is at least 350°C, preferably at least 375°C, and its final boiling point is at least 550°C, preferably at least 560°C, and more preferably at least 600°C.

[0074] The heavy hydrocarbon fractions of the feedstock may include, or consist of, atmospheric residue and / or vacuum residue resulting from atmospheric and / or vacuum distillation of crude oil.

[0075] The heavy fraction of hydrocarbons in the feedstock may also consist of atmospheric and / or vacuum residues resulting from thermal conversion, hydrotreatment, hydrocracking and / or atmospheric and / or vacuum distillation of effluents from hydroconversion units.

[0076] The heavy hydrocarbon fraction of the raw materials may also consist of aromatic cuts extracted from units for lubricant production, de-aging oil (raffinates from the de-aging units) resulting from de-aging units, or asphalt (residues from the de-aging units) resulting from de-aging units.

[0077] The heavy hydrocarbon fractions of the raw materials may also be residual fractions resulting from direct coal liquefaction (e.g., atmospheric and / or vacuum residues obtained from the H-Coal® method).

[0078] All of these fossil-derived fractions can be used individually or in mixtures to constitute heavy fractions of hydrocarbons of feedstock processed according to the present invention.

[0079] According to one or more embodiments, the heavy hydrocarbon fraction may consist of, alone or in a mixture of, at least one of the following feedstocks: atmospheric residue or vacuum residue resulting from atmospheric and / or vacuum distillation of crude oil or spills derived from thermal conversion, hydrotreatment, hydrocracking or hydroconversion units; aromatic cuts extracted from units for lubricant production; desynthesized oil resulting from desynthesized units; asphalt resulting from desynthesized units; or residual fractions resulting from direct coal liquefaction.

[0080] In the present invention, the heavy fraction of hydrocarbons to be treated is preferably atmospheric residue, vacuum residue, or a mixture thereof.

[0081] The heavy fraction of hydrocarbons of the feedstock processed according to the present invention contains impurities such as sulfur and nitrogen. It may also contain impurities such as metals insoluble in heptane, Conradson carbon, and asphaltenes, particularly C7 asphaltenes.

[0082] The sulfur content is 0.1% by weight or more, and may actually be 0.5% by weight or more, or 1% by weight or more, or even 2% by weight or more.

[0083] The nitrogen content is typically between 1 ppm by weight and 8,000 ppm by weight, more commonly between 200 ppm by weight and 8,000 ppm by weight, for example, 2,000 ppm by weight and 8,000 ppm by weight.

[0084] The metal content (especially Ni and V) may be 20 ppm by weight or more, preferably 100 ppm by weight or more.

[0085] The Conradson carbon content is 3% by weight or more, and in practice, it may be at least 5% by weight. The Conradson carbon content is defined by standard ASTM D482 and represents a well-known assessment of the amount of carbon residue produced after thermal decomposition under standard temperature and pressure conditions.

[0086] The content of C7 asphaltenes (compounds insoluble in heptane according to standard ASTM D6560 and corresponding to standard NF T 60-115) can reach a minimum of 1% by weight, and is often 3% or more by weight (excluding heavy hydrocarbon fractions that essentially contain dehisced oil). C7 asphaltenes are compounds known to inhibit the conversion of residual cuts, both by their ability to form heavy hydrocarbon residues commonly known as coke, and by their tendency to produce precipitates that significantly limit the operability of hydrogenation and hydrogenation conversion units.

[0087] The content of sulfur, nitrogen, metals, Conradson carbon, and asphaltenes in the heavy hydrocarbon fraction is expressed as a weight percentage of the total weight of the heavy hydrocarbon fraction of the feedstock.

[0088] According to one or more embodiments, the feedstock for the method according to the present invention comprises a low content, typically 1% to 20% by weight of feedstock, actually further 1% to 10% of vegetable and / or animal fats and oils, and / or hydrocarbon fractions resulting from methods for the thermal and / or catalytic conversion of lignocellulosic biomass, such as oil produced from lignocellulosic biomass, obtained by various liquefaction methods such as hydrothermal liquefaction or pyrolysis, and then co-processed together with plastics and / or tires and / or SRF pyrolysis oil, and heavy fractions of fossil-derived hydrocarbons.

[0089] Oils and fats of plant and / or animal origin contain triglycerides and / or free fatty acids and / or esters. Vegetable oils can be advantageously crude, whole, or partially refined and may be derived from the following plants: rapeseed, sunflower, soybean, palm, palm kernel, olive, coconut, jatropha (French physic nut), castor oil plant, cotton, peanut, flax, or rugosa, but this list is not limiting. Algal oils or fish oils are also relevant. Oils / fats of plant and / or animal origin may be waste, e.g., waste cooking oil. Animal fats may consist of porcine fat or residues from the food industry or fats derived from the catering industry.

[0090] The term "lignocellulosic biomass" refers to compounds derived from plants or their by-products, and includes components selected from the group formed by cellulose, hemicellulose (carbohydrate polymers), and / or lignin (aromatic polymers).

[0091] According to one or more embodiments, the feedstock for the method according to the present invention does not contain plant and / or animal fat fractions, or hydrocarbon fractions resulting from methods for the thermal and / or catalytic conversion of lignocellulosic biomass, such as biomass pyrolysis oil.

[0092] ((a0) Pretreatment step for pyrolysis oil (optional)) The plastic and / or tire and / or SRF pyrolysis oil can be advantageously pretreated in at least one arbitrary pretreatment step a0) prior to the hydrodemetallation step a) in order to obtain a pretreated pyrolysis oil to be supplied to step a).

[0093] According to the alternative configuration, this optional pretreatment step a0) makes it possible to 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 step a0) makes it possible to remove precipitates that may form as a result of the unstable nature of the pyrolysis oil and / or compatibility issues between two different feedstocks. Therefore, any optional step a0) of pretreatment of pyrolysis oil is advantageously implemented in particular when the oil contains more than 10 ppm by weight, in particular more than 20 ppm by weight, more specifically more than 50 ppm by weight of metal elements and / or solid particles, and in particular when the oil contains more than 5 ppm by weight of silicon, more specifically more than 10 ppm by weight, and actually more than 20 ppm by weight of silicon. Similarly, any optional step a0) of pretreatment of pyrolysis oil is advantageously implemented in particular when the oil contains more than 10 ppm by weight, in particular more than 20 ppm by weight, more specifically more than 50 ppm by weight of chlorine.

[0094] The optional pretreatment step a0) can be carried out by any method known to those skilled in the art that allows for a reduction in the amount of contaminants. This may include, in particular, an adsorption step and / or a filtration step and / or a centrifugation step and / or an electrostatic separation step and / or an aqueous scrubbing step and / or a gas stripping step.

[0095] Any pretreatment step a0) is advantageously carried out at a temperature of 20 to 400°C, preferably 40 to 350°C, and a pressure of 0.15 to 10.0 MPa abs, preferably 0.2 to 7.0 MPa abs.

[0096] According to the alternative configuration, the optional pretreatment step a0) is carried out in an adsorption section operated in the presence of at least one adsorbent. The adsorbent may be selected from zeolite, activated carbon, clay, silica, or alumina.

[0097] Advantageously, the adsorbent contains less than 1% by weight of metallic elements, and preferably does not contain metallic elements. The term “metallic elements in the adsorbent” should be understood to mean elements in columns 6 through 10 of the periodic table (new IUPAC classification). The residence time of the feed material in the adsorption section is generally between 1 minute and 180 minutes.

[0098] The adsorption section of any stage a0) includes at least one adsorption column, preferably at least two, and preferably two to four, adsorption columns containing the adsorbent. If the adsorption section includes two adsorption columns, one of the operating modes can be a "swing" operation, with one column being online, i.e., in operation, and the other column being spare. When the adsorbent in the online column is consumed, this column is isolated, but the spare column is placed online, i.e., in operation. The used adsorbent can then be regenerated in situ and / or replaced with fresh adsorbent, so that when the other column is isolated, the column containing it can be brought back online.

[0099] Another mode of operation is to have at least two columns operating in series. When the adsorbent in the column positioned at the head is consumed, this first column is isolated, and the consumed adsorbent is regenerated in situ or replaced with fresh adsorbent. The column is then brought back online at its last position, and so on. This operation is also known as the replaceable mode, or according to the term PRS for replaceable reactor systems, or simply "lead and lag". The combination of at least two adsorption columns allows for overcoming the potential for potentially rapid poisoning and / or clogging of the adsorbent under the combined action of metal contaminants, diolefins, gums derived from diolefins, and insoluble substances that may be present in the pyrolysis oil being treated. This is because the presence of at least two adsorption columns makes it advantageous to replace and / or regenerate the adsorbent without stopping the pretreatment unit, and indeed even by further means, thus reducing the risk of clogging, thus avoiding unit shutdowns due to clogging, controlling costs, and limiting adsorbent consumption.

[0100] In another alternative configuration, the arbitrary pretreatment step a0) is carried out in a section for scrubbing with an aqueous solution, such as water, or an acidic or basic solution. This scrubbing section may include items of equipment that allow the feedstock to be brought into contact with the aqueous solution and the phases to be separated to obtain the pretreated feedstock on the one hand and the aqueous solution containing impurities on the other. These pieces of equipment may include, for example, a stirred reactor, a decanter, a mixer-decanter, and / or a parallel or countercurrent scrubbing column.

[0101] According to another alternative, the arbitrary pretreatment step a0) is carried out by filtration. The filtration step allows for the removal of inorganic solids, sediments and / or particulate matter contained in the oil, particularly metals, metal oxides and metal chlorides. Generally, filters are used, and the size of their pores (e.g., diameter or equivalent diameter) is less than 25 μm, preferably 10 μm or less, and more preferably 5 μm or less. According to another alternative, filters with pore sizes less than 25 μm but greater than 5 μm may be used. A series of filters with different pore sizes, particularly a series of filters with pore sizes decreasing in the direction of oil circulation, may be used. 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, for example, by the heptane insoluble matter test, ASTM D-3279 method. The insoluble matter content in heptane must be reduced to less than 0.5% by weight, preferably less than 0.1%.

[0102] According to a particular embodiment, step a0) of pretreatment by filtration includes at least one filter having a pore size of less than 10 μm, preferably greater than 5 μm, and optionally a subsequent filtration system having a pore size of less than 2 μm, preferably less than 1 μm.

[0103] According to another specific embodiment, step a0) of pretreatment by filtration includes at least one filter having a pore size of less than 10 μm, preferably greater than 5 μm, and a subsequent electrostatic precipitation system.

[0104] According to another specific embodiment, step a0) of pretreatment by filtration includes a system of at least one filter having a pore size of less than 10 μm, preferably greater than 5 μm, followed by a filter(s) using a filter aid such as sand or diatomaceous earth.

[0105] According to another alternative, the arbitrary pretreatment step a0) is carried out by centrifugation. According to another alternative, the pretreatment step a0) includes centrifugation and filtration.

[0106] According to another alternative embodiment, the arbitrary pretreatment step a0) is carried out by gas stripping, thereby reducing the oxygen content in the oil. Gas extraction can remove oxygen (O2) that may be dissolved in the feedstock, thus reducing the probability of free radical formation that would lead to polymerization in downstream steps. This method generally involves contacting the oil with an extraction gas (e.g., H2, N2, or a mixture thereof) to transfer at least some of the dissolved oxygen in the oil to the extraction gas, followed by the separation of the extraction gas from the oil. The volume of the extraction gas relative to the volume of the oil (two volumes measured under gas extraction conditions) is generally greater than 1, preferably at least 3. In certain embodiments, the extraction gas may contain at least 60% (mol percent) of H2. Dissolved H2 remaining in the feedstock after the gas extraction step is not a problem for downstream hydrodemetallation / hydrogenation treatment. Preferably, the gas extraction step is completed before any (pre)heating of the feedstock to minimize potential contamination.

[0107] The optional pretreatment step a0) generally includes one or more, preferably several, of the above-described steps. This may include, in particular, a series of scrubbing and / or adsorption steps using an aqueous solution, followed by a gas stripping step, followed by a filtration and / or centrifugation step. All of these steps are preferably performed before any (pre)heating of the feedstock.

[0108] Therefore, the optional pretreatment step a0) makes it possible to obtain pretreated pyrolysis oil to be supplied to the subsequent hydrodemetallation step a).

[0109] (a) Hydrogenation demetallation step in a replaceable reactor) According to the present invention, the method comprises step a) of hydrogenation demetallation carried out in a fixed-bed reaction section comprising at least two replaceable reactors, the section being supplied by at least the feedstock, in the presence of at least one hydrogenation demetallation catalyst, at a temperature of 300 to 500°C, an absolute pressure of 5 MPa to 35 MPa, and for 0.1 to 5.0 h-1 At a spatiotemporal velocity, the mixture comprises the heavy fraction of hydrocarbons of fossil origin, optionally a trace fraction of pyrolysis oil pretreated in step a0), and a gas stream containing hydrogen.

[0110] The pyrolysis oil fraction and the heavy hydrocarbon fraction can be produced in the hydrodemetallation step by different methods.

[0111] According to the first alternative, the pyrolysis oil fraction can be pre-mixed with the heavy hydrocarbon fraction of the feedstock before entering the reaction section of the hydrogenation demetallation step a).

[0112] Another alternative is to inject the pyrolysis oil fraction and the heavy hydrocarbon fraction separately into the reaction section of step a). This injection mode may also be preferred to prevent problems associated with chemical incompatibility between the two fractions (e.g., the risk of phase separation or precipitation of asphaltenes) or to prevent possible accelerated contamination of the preheating oven (gum formation may occur if the diolefin and olefin content of plastics and / or tires and / or SRF pyrolysis oil is high).

[0113] According to these two alternative embodiments, namely, the mixing or non-mixing of the fractions before they are introduced into the reaction section of step a), the feedstock, in particular the heavy fraction of hydrocarbons of the feedstock, is generally preheated to a temperature suitable for hydrogenation.

[0114] Preheating of the heavy hydrocarbon fraction is preferably carried out at a temperature of 280°C to 450°C, more preferably 300°C to 400°C, and more preferably 320°C to 365°C.

[0115] This preheating may also include heating of the pyrolysis oil fraction to limit gum formation and / or coking of items in the preheating equipment (e.g., ovens and heat exchangers) as a result of the presence of olefins and diolefins in the pyrolysis oil fraction, particularly apart from, but preferably at a lower temperature than, the heavy hydrocarbon fraction. Advantageously, the pyrolysis oil fraction can be preheated at ambient temperature, e.g., 15°C to 350°C, preferably 100°C to 350°C, more preferably 100°C to 250°C, even more preferably 100°C to less than 230°C, and actually even further 100°C to less than 200°C. The pyrolysis oil fraction may be preheated, for example, by an oven or by mixing with a higher temperature gas stream containing hydrogen derived from hydrogen replenishment and / or recycling from step c) of the method according to the present invention.

[0116] In the case of a mixture of two fractions, preheating can be performed after mixing, before mixing, or during mixing. In this case, preheating of the mixture of the two fractions is preferably carried out at a temperature of 280°C to 450°C, more preferably 300°C to 400°C, and more preferably 320°C to 365°C.

[0117] In another embodiment in which a heavy hydrocarbon fraction and a pyrolysis oil fraction are mixed, the pyrolysis oil fraction is indirectly heated by mixing with the heavy hydrocarbon fraction (i.e., heat exchange between the two fractions by bringing the two fractions at different temperatures into contact).

[0118] Any means known to those skilled in the art that can preheat the feedstock can be used. For example, at least one furnace generally known as a preheating furnace can be used, comprising at least one heating compartment and / or a tube through which the feedstock flows, a mixer of the feedstock and H2, and any suitable type of heat exchanger, such as a tubular or spiral heat exchanger through which the feedstock flows.

[0119] Before being introduced into the reaction section of hydrogenation step a), the feedstock is subjected to a pressurization step, for example using a suitable pump, to suit the pressure to be operated at in the reaction section of hydrogenation step a). This pressurization step is preferably performed before the preheating step.

[0120] The purpose of this hydrogenation demetallation step a) is to reduce the content of impurities, particularly metals, especially silicon, and halogens (especially chlorine), as well as the content of diolefins and olefins that may result from fossil heavy fractions or pyrolysis oils, and thus protect the downstream hydrogenation step b) from deactivation and clogging, and thus from the concept of a guard reactor (notion).

[0121] These hydrogenation demetallization guard reactors are used as replaceable reactors (replaceable reactors, in the case of technology, PRS) as described in French Patent No. 2 681 871.

[0122] The term “substitutable reactor” is understood to mean an assembly of at least two reactors, one of which can generally be shut down for catalyst regeneration, replacement, or maintenance, while the other (or any other) remains in operation.

[0123] These replaceable reactors are fixed beds located upstream of the fixed-bed hydrogenation section of step b) and equipped with lines and valves to allow switching between them; that is, in a system with two replaceable reactors Ra and Rb, Ra may be upstream of Rb and vice versa. Each reactor Ra and Rb can be placed offline to change the catalyst without stopping the rest of the unit. This catalyst change (rinsing, discharge, recharging, sulfidation) is generally enabled by a regulating section (a set of equipment items outside the main high-pressure loop). The reactor with the new catalyst is then brought back online in the final position, and so on. Permutations for catalyst change occur when the catalyst is no longer sufficiently active (poisoning and coking with metal) and / or clogging results in an excessively high pressure drop.

[0124] In another form, the section for hydrogenation demetallation in a replaceable reactor may contain more than two replaceable reactors.

[0125] During step a), hydrogenation (commonly known as HDM) reactions occur, but hydrogenation (commonly known as HDS) reactions, hydrogenation

[0126] Furthermore, silicon contained in the raw materials is deposited on the catalyst(s) during this stage. The same applies to chlorinated compounds; a small portion (mineral portion) is deposited on the catalyst, but organochlorinated compounds are converted to HCl.

[0127] The hydrodemetallation step a) in the replaceable reactor can preferably be carried out at a temperature of 300 °C to 500 °C, preferably 350 °C to 430 °C, and at an absolute pressure of 5 MPa to 35 MPa, preferably 11 MPa to 26 MPa, and preferably 14 MPa to 20 MPa in a preferred method. The temperature is usually adjusted according to the desired level of hydrodemetallation and the target duration of the treatment. The temperature is generally adjusted to remove most, preferably all, of the silicon-containing metals. Most frequently, the space velocity of the hydrocarbon feedstock, also known as the liquid hourly space velocity (LHSV) or hourly space velocity (HSV), which is generally known as HSV and is defined as the flow rate by volume of the feedstock divided by the total volume of the catalyst, can range from 0.1 h -1 ~5 h -1 Preferably 0.15 h -1 ~3 h -1 More preferably 0.2 h -1 ~2 h -1 and can be within the range.

[0128] The amount of hydrogen mixed with the feedstock is 100 to 5000 standard cubic meters (Sm 3 ) per cubic meter (m 3 ) of the liquid feedstock, preferably 200 Sm 3 / m 3 ~2000 Sm 3 / m 3 More preferably 300 Sm 3 / m 3 ~1000 Sm 3 / m 3 and can be.

[0129] The hydrodemetallation step a) in the replaceable reactor is carried out industrially in at least two fixed-bed reactors, preferably with a downward liquid flow. Each replaceable reactor is a fixed-bed reactor having n catalyst beds, where n is an integer greater than or equal to 1, and each contains at least one hydrodemetallation catalyst.

[0130] According to one embodiment of the present invention, at least one reactor, preferably all reactors, in the hydrogenation demetallation step a) or the hydrogenation treatment step b) is equipped with a filtration dispensing device, such as the device described in French Patent Application No. 3 043 339 and French Patent Application No. 3 051 375.

[0131] According to one embodiment of the present invention, steps a) and / or b) may optionally use at least one guard bed containing an activated carbon-type adsorbent comprising alumina, silica, silica-alumina, zeolite, and / or metals of group VIB and / or group VIII, upstream of the hydrogenation or hydrogenation catalyst(s). A series of guard beds having particles of different diameters, in particular a series of guard beds having diameters that decrease in the direction of the circulation of the feed material (also called "grading") may also be used.

[0132] The hydrogenation demetallation catalyst used is preferably a known catalyst. These may be granular catalysts containing at least one metal or metal compound having hydrogenation dehydrogenation function on a support. These catalysts may advantageously contain at least one metal from Group VIII, selected generally from the group consisting of nickel and cobalt, and / or at least one metal from Group VIB, preferably molybdenum and / or tungsten. For example, a catalyst may be used that contains 0.5% to 10% by weight of nickel, preferably 1% to 5% by weight of nickel (represented as nickel oxide NiO), and 1% to 30% by weight of molybdenum, preferably 3% to 20% by weight of molybdenum (represented as molybdenum oxide MoO3), on a mineral support. The total content of metal oxides from groups VIB and VIII may be 5% to 40% by weight, preferably 5% to 30% by weight, relative to the weight of the catalyst, and the weight ratio of group VIB metals (or multiple metals) to group VIII metals (or multiple metals), expressed as metal oxides, is generally 20 to 1, most frequently 10 to 2.

[0133] The support can be selected from the group consisting of, for example, alumina, silica, silica-alumina, magnesia, clay, and mixtures of at least two of these minerals. Advantageously, the support may contain other doping compounds, particularly oxides selected from the group consisting of boron oxide, zirconia, ceria, titanium oxide, phosphoric anhydride, and mixtures of these oxides. In most cases, an alumina support is used, and very often, alumina supports doped with phosphorus and optionally boron are used. If phosphorus pentoxide (P2O5) is present, its concentration is less than 10% by weight of alumina, and advantageously less than 0.001% by weight of the total weight of alumina. If boron trioxide (B2O5) is present, its concentration is less than 10% by weight of alumina, and advantageously less than 0.001% of the total weight of alumina. The alumina used may be gamma (γ) or eta (η) alumina. The hydrogenation demetallation catalyst is, for example, in the form of an extruded product.

[0134] Catalysts that can be used in step a) of hydrogenation demetallation in a replaceable reactor are shown, for example, in European Patent No. 0113297, European Patent No. 0113284, U.S. Patent No. 5221656, U.S. Patent No. 5827421, U.S. Patent No. 7119045, U.S. Patent No. 5622616 and U.S. Patent No. 5089463.

[0135] The hydrogenation demetallation step a) makes it possible to obtain a hydrogenation demetallation effluent, i.e., an effluent in which the metal content of silicon-containing chlorine is reduced and the content of olefins, particularly diolefins, is reduced. Preferably, at least 50%, more preferably at least 75%, of the chlorine, silicon, metals, and diolefins in the initial feedstock are removed during step a).

[0136] At the end of the hydrogenation demetallation step a), the content of metallic Ni and V is generally less than 20 ppm by weight, preferably less than 10 ppm by weight, relative to the weight of the effluent.

[0137] At the end of the hydrogenation demetallation step a), the silicon content is generally less than 10 ppm by weight, preferably less than 5 ppm by weight, preferably 2 ppm by weight or less, and in practice even less than 1 ppm by weight, relative to the weight of the effluent.

[0138] At the end of the hydrogenation demetallation step a), the chlorine content is generally less than 10 ppm by weight, preferably less than 5 ppm by weight, preferably 2 ppm by weight or less, and in practice even less than 1 ppm by weight, relative to the weight of the effluent.

[0139] At the end of the hydrogenation demetallation step a), the diolefin content, expressed as the MAV value defined above, is generally less than 5 mg / g, preferably less than 1 mg / g.

[0140] The effluent obtained at the end of hydrogenation demetallation step a) is preferably sent directly to hydrogenation step b).

[0141] ((b) Hydrogenation stage) According to the present invention, the treatment method is a hydrogenation treatment step b) carried out in a reaction section including at least one fixed-bed reactor, wherein the section is subjected to at least one hydrogenation catalyst, at a temperature of 300 to 500°C, an absolute pressure of 5 MPa to 35 MPa, and for 0.1 to 5.0 h -1 The process includes a hydrogenation step b), supplied at a spatiotemporal velocity by a gas stream containing at least the effluent from step a) and optionally hydrogen.

[0142] Hydrogenation step b) includes not only the hydrogenation reaction but also the hydrogenation conversion reaction as defined above in the "Definitions" section.

[0143] In hydrogenation stage b), the conversion rate is moderate, and in practice even lower, generally less than 45% at the end of the cycle, most frequently less than 35%, and less than 25% at the start of the cycle. The conversion rate generally changes during the cycle as a result of rising temperatures to compensate for catalyst deactivation. The conversion rate is defined as the weight fraction of organic compounds with boiling points above 520°C in the feed material at the inlet of the reaction section minus the weight fraction of organic compounds with boiling points above 520°C in the effluent at the outlet of the reaction section, divided by the weight fraction of organic compounds with boiling points above 520°C in the feed material at the inlet of the reaction section.

[0144] According to a preferred alternative embodiment, the hydrogenation step b) comprises a first hydrometallation (HDM) step b1) carried out in one or more hydrometallation zones of a fixed bed, and a subsequent second hydrodesulfurization (HDS) step b2) carried out in one or more hydrodesulfurization zones of a fixed bed. During the first hydrometallation step b1), the effluent from step a) is brought into contact with a hydrometallation catalyst under hydrometallation conditions, and then during the second hydrodesulfurization step b2), the effluent from the first hydrometallation step b1) is brought into contact with a hydrodesulfurization catalyst under hydrodesulfurization conditions. This method is known by the designation Hyvahl-F® and is described, for example, in U.S. Patent No. 5,417,846.

[0145] Those skilled in the art will readily understand that in the hydrogenation demetallation step b1), the hydrogenation demetallation reaction takes place, but simultaneously, parts of other hydrogenation reactions, particularly hydrogenation desulfurization and hydrogenolysis, also take place. Similarly, in the hydrogenation desulfurization step b2), the hydrogenation desulfurization reaction takes place, but simultaneously, parts of other hydrogenation reactions, particularly hydrogenation demetallation and hydrogenolysis, also take place.

[0146] Those skilled in the art may define transition zones in which all types of hydrogenation reactions occur. According to another alternative form, hydrogenation step b) includes a first hydrogenation step b1) carried out in one or more hydrogenation zones of a fixed bed, a subsequent second transition step b2) carried out in one or more transition zones of a fixed bed, and a subsequent third hydrogenation step b3) carried out in one or more hydrogenation zones of a fixed bed. During the first hydrogenation step b1), the effluent from step a) is brought into contact with a hydrogenation catalyst under hydrogenation conditions; then, during the second transition step b2), the effluent from the first hydrogenation step b1) is brought into contact with a transition catalyst under transition conditions; and then, during the third hydrogenation step b3), the effluent from the second transition step b2) is brought into contact with a hydrogenation catalyst under hydrogenation conditions.

[0147] In addition to the hydrogenation demetallation step a) in a replaceable guard reactor, the need for the hydrogenation demetallation step b1) in the alternative form described above is justified when the hydrogenation demetallation performed during step a) is insufficient to protect the catalyst in step b), particularly the hydrogenation desulfurization catalyst.

[0148] Each fixed-bed reactor contains n catalyst beds, where n is an integer greater than or equal to 1, and each bed contains at least one hydrogenation catalyst.

[0149] The hydrogenation treatment step b) according to the present invention is carried out under hydrogenation treatment conditions. This can be advantageously carried out at a temperature of 300°C to 500°C, preferably 350°C to 430°C, and under an absolute pressure of 5 MPa to 35 MPa, preferably 11 MPa to 26 MPa, and preferably 14 MPa to 20 MPa. The temperature is usually adjusted according to the desired level of hydrogenation treatment and the target duration of the treatment. Most frequently, the space velocity of the feed material, also known as the liquid-time-space velocity (LHSV) or time-space velocity (HSV), is generally known as HSV and is defined as the flow rate by the volume of feed material divided by the total volume of catalyst, when 0.1h -1 ~5h -1 Preferably 0.1h -1 ~2h -1 Comfortably 0.1h-1 ~1h -1 It can be within a range of 1 cubic meter (m³) of liquid feedstock. 3 ) 100-5000 standard cubic meters (Sm 3 ), 200Sm 3 / m 3 ~2000 Sm 3 / m 3 , with a higher priority, 300Sm 3 / m 3 ~1500Sm 3 / m 3 This is possible. Hydrogenation step b) can be carried out industrially in one or more reactors having a downward liquid flow.

[0150] The hydrogenation catalyst used is preferably a known catalyst. These may be granular catalysts containing at least one metal or metal compound having hydrogenation-dehydrogenation function on a support. These catalysts may advantageously contain at least one metal from Group VIII, generally selected from the group consisting of nickel and cobalt, and / or at least one metal from Group VIB, preferably molybdenum and / or tungsten. For example, a catalyst can be used that contains 0.5% to 10% by weight of nickel, preferably 1% to 5% by weight of nickel (represented as nickel oxide NiO), and 1% to 30% by weight of molybdenum, preferably 3% to 20% by weight of molybdenum (represented as molybdenum oxide MoO3), on a mineral support. The support can be selected from the group consisting of, for example, alumina, silica, silica-alumina, magnesia, clay, and mixtures of at least two of these minerals.

[0151] Advantageously, this support may contain other doping compounds, particularly oxides selected from the group consisting of boron oxide, zirconia, ceria, titanium oxide, phosphoric anhydride, and mixtures thereof. In most cases, alumina supports are used, and very often, phosphorus and optionally boron-doped alumina supports are used. If phosphorus pentoxide (P2O5) is present, its concentration is less than 10% by weight of alumina, and advantageously less than 0.001% by weight of the total weight of alumina. If boron trioxide (B2O5) is present, its concentration is less than 10% by weight of alumina, and advantageously less than 0.001% of the total weight of alumina. The alumina used may be gamma (γ) or eta (η) alumina. This catalyst is most often in the form of an extruded form. The total content of metal oxides from groups VIB and VIII can be 3% to 40% by weight, generally 5% to 30% by weight, relative to the weight of the catalyst, and the weight ratio of group VIB metals (or multiple metals) to group VIII metals (or multiple metals), expressed as metal oxides, is generally 20 to 1, most frequently 10 to 2.

[0152] In the case of a hydrogenation treatment stage including a hydrogenation demetallation (HDM) stage b1) followed by a hydrogenation desulfurization (HDS) stage b2), it is preferable to use a specific catalyst suitable for each stage. Catalysts that can be used in the hydrogenation demetallation stage b1) are shown, for example, in European Patent Nos. 0113297, 0113284, U.S. Patent Nos. 5,221,656, 5,827,421, 7,119,045, 5,622,616, and 5,089,463. Catalysts that can be used in the hydrogenation desulfurization stage b3) are shown, for example, in European Patent Nos. 0113297, 0113284, U.S. Patent Nos. 6,589,908, 4,818,743, and 6,332,976. As described in French Patent No. 2 940 143, a mixed catalyst, also known as a transition catalyst, which is active in both the hydrometallation section b1) and the hydrodesulfurization section b2), may be used.

[0153] In the case of a hydrogenation treatment step comprising a hydrogenation demetallation (HDM) step b1), followed by a transition step b2), and then a hydrogenation desulfurization (HDS) step b3), it is preferable to use a specific catalyst suitable for each step. Catalysts that can be used in the hydrogenation demetallation step b1) are shown, for example, in European Patent Nos. 0113297, 0113284, U.S. Patent Nos. 5221656, 5827421, 7119045, 5622616, and 5089463. Catalysts that can be used in the transition step b2) are active in hydrogenation demetallation and hydrogenation desulfurization and are described, for example, in French Patent No. 2940143. Catalysts that can be used in the hydrogenodesulfurization step b3) are shown, for example, in European Patent No. 0113297, European Patent No. 0113284, U.S. Patent No. 6,589,908, U.S. Patent No. 4,818,743 and U.S. Patent No. 6,332,976. Transition catalysts, such as those described in French Patent No. 2,940,143 for sections b1), b2), and b3), may also be used.

[0154] The hydrogenation treatment step b) is carried out under conditions that allow for the acquisition of a hydrogenated effluent, i.e., by reducing the content of sulfur, nitrogen, asphaltene, and Conradsonian carbon.

[0155] At the end of hydrogenation stage b), the sulfur content is generally less than 0.5% by weight (5000 ppm), preferably less than 0.48% by weight (4800 ppm), relative to the weight of the effluent.

[0156] At the end of hydrogenation stage b), the nitrogen content is generally less than 3500 ppm by weight, preferably less than 3000 ppm by weight, relative to the weight of the effluent.

[0157] At the end of hydrogenation stage b), the C7 asphaltene content is generally less than 2% by weight, preferably less than 1% by weight, relative to the weight of the spill.

[0158] At the end of hydrogenation stage b), the Conradson carbon content is generally less than 8% by weight, preferably less than 6% by weight, relative to the weight of the effluent.

[0159] The effluent generated from hydrogenation stage b) contains conversion products, and 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 properties of the feedstock.

[0160] ((c) separation stage) According to the present invention, the method further includes a separation step c) which separates some or all of the effluent resulting from step b) in a separation section that yields a gaseous effluent and at least one liquid product.

[0161] This separation step c) separates part or all of the spillage into several fractions, each containing at least one liquid product which may be a light cut (naphtha, diesel fuel, kerosene), an intermediate cut (vacuum distillate), or a heavy cut (vacuum residue).

[0162] The separation step c) is carried out in a separation section comprising any separation means known to those skilled in the art. The separation section may include one or more flash drums arranged in series, and / or one or more steam stripping and / or hydrogen stripping columns, and / or atmospheric distillation columns, and / or vacuum distillation columns.

[0163] According to one or more embodiments, this separation step c) is performed by a series of at least two consecutive flash drums.

[0164] According to one or more other embodiments, this separation step c) is carried out by one or more steam stripping and / or hydrogen stripping columns.

[0165] According to one or more preferred embodiments, this separation step c) is carried out by an atmospheric distillation column, more preferably by an atmospheric distillation column and a vacuum column that accepts atmospheric residue.

[0166] In the most preferred embodiment(s), this separation step c) is carried out by one or more flash drums, atmospheric distillation columns, and atmospheric residue receiving vacuum columns.

[0167] The gaseous effluent contains, in particular, H2, H2S, NH3, and C1-C4 hydrocarbons. This gaseous effluent can be separated from the effluent obtained at the end of step b) using separation devices well known to those skilled in the art, in particular using one or more knockout drums that can operate at different pressures and temperatures, optionally in combination with vapor or hydrogen stripping means and one or more distillation columns. The effluent obtained at the end of hydrogenation step b) is advantageously separated into at least one gaseous effluent and at least one liquid product in at least one knockout drum. These separators may be, for example, high-pressure high-temperature (HPHT) separators and / or high-pressure low-temperature (HPLT) separators.

[0168] After any cooling, the gaseous effluent is preferably treated with a hydrogen purification means to recover hydrogen not consumed during the hydrometallation and hydrotreatment reactions. The hydrogen purification means may be amine, membrane, PSA-type systems, or scrubbing with some of these means arranged in series. The purified hydrogen can then be advantageously reused in the manner according to the present invention after any recompression. The hydrogen can be introduced at the inlet of the hydrometallation stage a) and / or at various locations during the hydrotreatment stage b). The hydrogen (high temperature as it exits stage c) can also be used to preheat the pyrolysis oil fraction if the pyrolysis oil is introduced separately from the heavy fraction. The recovered gaseous hydrogen can also be used in other equipment of the refinery.

[0169] Separation step c) may also include atmospheric distillation and / or vacuum distillation. Advantageously, separation step c) may further include at least one atmospheric distillation, and the liquid effluent obtained after gas-liquid separation is fractionated by atmospheric distillation to obtain at least one atmospheric distillation fraction and at least one atmospheric residual oil fraction.

[0170] Furthermore, separation step c) of the method according to the present invention may advantageously further include at least one vacuum distillation, in which case the liquid effluent obtained after gas-liquid separation and / or the atmospheric residual oil fraction obtained after atmospheric distillation are fractionally distilled by vacuum distillation to obtain at least one vacuum distillation fraction and at least one vacuum residual oil fraction. Preferably, separation step c) includes first atmospheric distillation to fractionate the liquid effluent obtained after gas-liquid separation by atmospheric distillation to obtain at least one atmospheric distillation fraction and at least one atmospheric residual oil fraction, and then vacuum distillation to fractionate the atmospheric residual oil fraction obtained after atmospheric distillation by vacuum distillation to obtain at least one vacuum distillation fraction and at least one vacuum residual oil fraction. The vacuum distillation fraction typically includes a vacuum diesel type fraction.

[0171] Advantageously, the separation section may also include means for scrubbing at least one cut separated by contact with an aqueous solution.

[0172] This scrubbing, in particular, allows for the removal of ammonium chloride salts that essentially originate from the pyrolysis oil fraction. These salts are formed by the reaction between chloride ions released by the hydrogenation of the chlorinated compound in HCl form during steps a) and b) and ammonium ions produced by the hydrogenation of the nitrogen compound in NH3 form during steps a) and b) and / or contributed by the injection of amines, followed by dissolution in water. Therefore, scrubbing allows for the limitation of the risk of blockage, particularly in the transfer lines and / or sections of the method of the present invention, due to the precipitation of ammonium chloride salts. It also allows for the removal of hydrochloric acid formed by the reaction of hydrogen ions and chloride ions, and thus can limit corrosion in items downstream of the equipment.

[0173] According to a preferred embodiment, separation step c) is c1) A first separation step carried out at a temperature higher than the precipitation temperature of ammonium halide in order to obtain at least one first gas fraction and one liquid effluent, c2) A second separation step comprising a first gas function and a second separation step supplied by at least a portion of the liquid effluent resulting from step c1) and an aqueous solution, wherein the second separation step is carried out at a temperature lower than the precipitation temperature of ammonium halide, in order to obtain at least one second gas fraction, one aqueous effluent and one liquid product.

[0174] The purpose of this separation, which combines a high-temperature separation step c1) with a subsequent low-temperature separation / scrubbing step c2), is to remove chlorine in the form of ammonium chloride salts.

[0175] Chloride ions released by the hydrogenation (hydrogen-dechlorination) of chlorinated compounds in HCl form between steps a) and b), and ammonia produced by the hydrogenation (particularly hydrogen-denitrification) of nitrogen compounds in NH3 form during step b), are largely retained in the gaseous effluent by the high-temperature separation in step c1). This is because the high temperature in this separation step c1) prevents the precipitation of ammonium chloride salts formed by the reaction of chloride ions with ammonium ions. The lower-temperature separation of the gaseous effluent and a portion of the liquid effluent in step c2) results in the precipitation of these ammonium chloride salts. By scrubbing with an aqueous solution (generally water) or a basic aqueous solution (e.g., a sodium hydroxide solution of amines) in step c2), these salts can be dissolved in the aqueous effluent. Thus, a chlorine-free hydrocarbon effluent is obtained.

[0176] The term "precipitation temperature" for ammonium halides is understood to mean the temperature at which gaseous ammonia and hydrogen halides precipitate by reacting to form solid crystals of ammonium halide or by dissolving in water (under given conditions such as concentration and pressure). The precipitation temperature depends on the concentration of the halide and the pressure according to thermodynamic principles. The precipitation temperature of ammonium halides is generally between 150°C and 300°C under the conditions used in this method.

[0177] The separation device or separation drum may have a zone at the bottom that allows for the separation and sedimentation of aqueous fractions containing hydrocarbon fractions and chloride salts, or it may also have a column for scrubbing the gas by contacting it with water or a basic solution.

[0178] ((d) Subsequent processing steps (multiple possible) (optional)) One or more of the subsequent processing steps d) of the liquid product(s) resulting from separation step c) can be performed.

[0179] Such step d) may include at least one step selected from the list consisting of hydrocracking, steam cracking, fluidized bed catalytic cracking, hydrocracking, desilicate, and extraction of lubricating oil. These examples of subsequent treatments are not exhaustive.

[0180] This is because the various hydrocarbon products that may result from separation step c) can be sent to different methods in the purification plant, and the details of all these post-treatments are not described here and are generally known to those skilled in the art.

[0181] According to alternative methods, naphtha, kerosene, and diesel-type raw materials can be improved directly or after any hydrogenation treatment in refineries for the production of fuels for the automotive and aerospace industries, such as premium grade gasoline, jet fuel, and diesel fuel.

[0182] According to another alternative, a portion of the gas containing hydrocarbons having 2 to 4 carbon atoms, naphtha, kerosene, and diesel-type feedstocks can be modified in a steam cracking unit so that light olefins, which can be used as monomers in the production of polymers in particular, can be obtained.

[0183] In yet another alternative form, naphtha, kerosene, and diesel-type feedstocks can also be improved in fluidized bed catalytic cracking (FCC) units or hydrocracking units.

[0184] According to another alternative, vacuum distillates can be improved within a hydrocracking unit.

[0185] According to another alternative, atmospheric residue and / or vacuum residue (unconverted) can be sent to a catalytic cracking (FCC), hydrocracking, or de-cracking method.

[0186] According to another alternative, atmospheric residual fractions and / or vacuum residual fractions can be used as marine fuels with low sulfur content, particularly as distillates for marine use and / or residual fuels for marine use, commonly known as bunker fuel oil. In particular, it is possible to produce residual fuels for marine use with low sulfur content without the need to add flux. Generally, fluxes selected from light cut oil from catalytic cracking (LCO for light cycle oil in FCC terminology), heavy cut oil from catalytic cracking (HCO for heavy cycle oil in FCC terminology), catalytic cracking residues, kerosene, diesel fuel, vacuum distillates and / or decanted oils are generally added to reduce the viscosity of bunker fuel oil. The presence of pyrolysis oil as a co-supplied raw material in the processing of heavy raw materials of fossil origin makes it possible to directly obtain fuel oil that complies with specifications in terms of sulfur, precipitate and viscosity, in particular, without the need to add flux. The standard for sulfur equivalent of fuel oil is a sulfur content of less than 0.5% by weight / ppm (ISO 8217). RMG380 is the most common grade of bunker fuel oil according to standard ISO 8217, and the viscosity specification for RMG380 grade bunker fuel oil is a viscosity of less than 380 cST at 50°C. Another very restrictive recommendation is the content of precipitate after aging according to ISO 10307-2 (also known as IP390), which must be 0.1% or less. [Modes for carrying out the invention]

[0187] (List of drawings) Figure 1 schematically shows one embodiment of the method according to the present invention.

[0188] Figure 1 shows a simplified diagram for the implementation of a series of reactors according to the present invention, without limiting its scope. For simplicity, only the reactor is shown, but it is understood that all the equipment necessary for its function (drum, pump, exchanger, oven, column, etc.) is present. Only the hydrocarbon-containing mainstream is shown, but it is understood that a hydrogen-rich gas stream (for replenishment or recycling) can be injected into the inlet of each catalyst bed or between two beds.

[0189] A feedstock comprising a heavy fraction of hydrocarbon 1 and optionally a trace fraction of pre-treated (not shown) plastics and / or tires and / or SRF pyrolysis oil 2 enters a fixed-bed reaction unit equipped with a replaceable guard reactor consisting of reactors Ra and Rb to carry out hydrometallation step a). The pyrolysis oil fraction can be pre-mixed with the heavy fraction of hydrocarbons of the feedstock before entering the first hydrometallation reactor. Another alternative is to inject the pyrolysis oil fraction and the heavy fraction of hydrocarbons separately into the first hydrometallation reactor (injection not shown). The effluent 3 from hydrometallation step a) in the replaceable guard reactor is sent to a fixed-bed reaction section consisting of reactors R1, R2 and R3 to carry out hydrotreatment step b). The fixed-bed hydrotreatment reactor may be charged with, for example, hydrometallation, transition and hydrodesulfurization catalysts, respectively. The effluent 4 from the fixed-bed hydrogenation stage proceeds to the separation stage and is sent to the separation section 5 to separate the gaseous effluent 6 and at least one liquid product 7.

[0190] The operation of the replaceable reactor is as follows: Each reactor Ra and Rb can be positioned offline to change the catalyst without stopping the rest of the unit. This catalyst change (rinsing, discharge, recharging, sulfidation) is generally enabled by adjustment sections not shown. In sequence 1, the feed material passes through reactors Ra and Rb, and then through R1, R2, and R3. If the catalyst in reactor Ra is no longer sufficiently active (metal poisoning and coking) and / or clogging reaches an excessively high pressure drop, a permutation for catalyst change occurs. In sequence 2, reactor Ra is positioned offline, and the feed material enters reactor Rb directly, and then passes through R1, R2, and R3. During this sequence 2, the spent catalyst is discharged from reactor Ra, and a new catalyst is recharged into reactor Ra. In sequence 3, reactor Ra, with a fresh catalyst, is positioned online so that the feed material first passes through reactor Rb, which contains a partially spent catalyst, then through reactor Ra, and then through R1, R2, and R3. If the catalyst in reactor Rb is no longer sufficiently active, and / or clogging reaches an excessively high pressure drop, another permutation for catalyst replacement occurs. During this sequence 4, the spent catalyst is discharged from reactor Rb, a new catalyst is recharged into reactor Rb, and the feed material enters reactor Ra directly, then passes through R1, R2 and R3. In sequence 5, reactor Rb, containing the fresh catalyst, is positioned online so that the feed material first passes through reactor Ra, containing the partially spent catalyst, then through reactor Rb, and then through R1, R2 and R3. Since sequence 5 is identical to sequence 1, this demonstrates the periodicity of the proposed operation.

[0191] Examples of sequences that can be generated according to Figure 1 are shown in the table below:

[0192] [Table 1]

[0193] Similarly, the section for hydrogenation in a replaceable reactor may have more than two replaceable reactors. Likewise, there may be more or fewer than three reactors for hydrogenation in a fixed bed, and the representations R1, R2, and R3 are given purely as examples.

[0194] (Analysis method used) Analytical methods and / or standards used to determine the characteristics of various flows, particularly the feedstocks being processed and the resulting effluents, are known to those skilled in the art. These are specifically listed in Table 2 below for informational purposes. Other methods said to be equivalent, particularly equivalent IP, EN, or ISO methods, may also be used.

[0195] [Table 2]

[0196] (Examples) The following examples are intended to demonstrate specific performance qualities of the method according to the present invention.

[0197] These examples demonstrate the potential for simultaneous treatment of plastic pyrolysis oil in Hyvahl®-type treatment methods that remove naturally occurring impurities from fossil-derived heavy feedstocks. The hydrogenated effluent can be used as a raw material for producing fuels, lubricants, or any other products conventionally arising from oil refining. The ability of supported catalysts in the Hyvahl® method to capture impurities present in the pyrolysis oil and thus improve the feedstock is also demonstrated, while facilitating the post-treatment of effluents resulting from the hydrogenation of heavy feedstocks meeting the sulfur (0.5 wt%) and viscosity (380 cSt at 50°C) specifications required by standard ISO 8217 for RMG380 type bunker fuel oil.

[0198] Example 1 is a comparative example demonstrating the performance quality of a treatment method for a standard feed material (vacuum residue oil) that does not contain plastic pyrolysis oil.

[0199] Example 2 demonstrates the performance quality of a processing method using feedstocks that include the fraction of plastic pyrolysis oil used in Example 1 and the fraction of standard feedstock (vacuum residue). The mixture was used during the pre-homogenization stage (any stage) of the culture medium.

[0200] (Feed material) The heavy fraction (I) of the feedstock is vacuum residue directly resulting from the distillation of crude oil ("straight run" (SR-VR)). The plastic pyrolysis oil (II) fraction of the feedstock is pyrolysis oil resulting from a mixture of plastics and containing high levels of impurities.

[0201] The main characteristics of these two fractions of the raw materials are shown in Table 3 below.

[0202] [Table 3]

[0203] The treatment method involves the use of two replaceable reactors Ra and Rb in the first hydrodemetallation (HDM) step upstream of a hydrogenation section consisting of four fixed-bed reactors (R1, R2, R3, and R4). The operating conditions are similar for both embodiments and are summarized in Table 4 below.

[0204] [Table 4]

[0205] (Overall results and performance quality) The results regarding the processing performance quality of VR supply raw materials that do not contain plastic pyrolysis oil (Example 2) or (Example 1) are described in detail in Table 5 below.

[0206] [Table 5]

[0207] The presence of plastic pyrolysis oil is observed to eliminate the need to add flux cut to achieve the sulfur and viscosity specifications imposed by standard ISO 8217 for RMG380 type bunker fuel oil. Furthermore, in the simultaneous processing of plastic pyrolysis oil in Example 2, the bunker fuel oil formulation does not require the use of all of the [180~350°C] cut, unlike that observed in Example 1. Therefore, this "excess" cut can be sent to a steam cracker with IP-180°C cut or used as a raw material for other fuel formulations.

[0208] The total effluent resulting from the hydrogenation treatment of a mixture of VR cut and plastic pyrolysis oil may also be observed to have Si and Cl content below the analytical detection limit, indicating that the catalyst and operating conditions used in the treatment method are suitable for removing impurities. [Brief explanation of the drawing]

[0209] [Figure 1] An embodiment of the method according to the present invention is illustrated.

Claims

1. A method for processing a feedstock comprising a heavy fraction of fossil-derived hydrocarbons 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 fraction of pyrolysis oil from plastics and / or tires and / or solid recovery fuels, wherein the pyrolysis oil fraction constitutes less than 50% by weight of the feedstock, and the method a) A hydrogenation demetallation step carried out in a fixed-bed reaction section comprising at least two replaceable reactors, wherein the section is performed in the presence of at least one hydrogenation demetallation catalyst, at a temperature of 300 to 500°C, an absolute pressure of 5 MPa to 35 MPa, and for 0.1 to 5.0 hours. －１ A hydrogenation demetallation step is performed, supplied by a gas flow containing at least the feed material and hydrogen at a spatiotemporal velocity, b) A hydrogenation step carried out in a reaction section comprising at least one fixed-bed reactor, the section being performed in the presence of at least one hydrogenation catalyst, at a temperature of 300 to 500°C, an absolute pressure of 5 MPa to 35 MPa, and for 0.1 to 5.0 hours. －１ A hydrogenation treatment step, supplied by a gas stream containing at least the effluent from step a) and optionally hydrogen, at a spatiotemporal velocity, c) A step of separating the effluent resulting from step b), which is carried out in a separation section that yields a gas fraction and at least one liquid product. Methods that include...

2. The method according to claim 1, comprising at least one step a0) of pretreatment of the pyrolysis oil fraction of plastics and / or tires and / or solid recovery fuels, wherein the pretreatment step is performed upstream of step a) and comprises an adsorption step and / or a filtration step and / or a centrifugation step and / or an electrostatic separation step and / or an aqueous scrubbing step and / or a gas stripping step.

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

4. The method according to any one of claims 1 to 3, wherein the supply material consists of a fraction of the pyrolysis oil and a heavy fraction of the hydrocarbon, the fraction of the pyrolysis oil constitutes 1% to 45% by weight, preferably 2% to 30% by weight, more preferably 2% to 25% by weight of the supply material, and the heavy fraction of the hydrocarbon constitutes 55% to 99% by weight, preferably 70% to 98% by weight, more preferably 75% to 98% by weight of the supply material.

5. The method according to any one of claims 1 to 4, wherein the heavy fraction of the hydrocarbon is selected from a list consisting of crude oil, or atmospheric residue or vacuum residue resulting from atmospheric and / or vacuum distillation of spills originating from thermal conversion, hydrotreatment, hydrocracking or hydroconversion units, aromatic cuts extracted from units for lubricant production, desynthesized oil resulting from desynthesized units, asphalt resulting from desynthesized units, or residual fractions resulting from direct coal liquefaction.

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

7. The hydrogenation demetallation catalyst of step a) is provided on a mineral support selected from the group consisting of alumina, silica, silica-alumina, magnesia, clay, and a mixture of at least two of these minerals, containing nickel represented as nickel oxide (NiO) in an amount of 0.5% to 10% by weight relative to the total weight of the catalyst, and molybdenum oxide (MoO) in an amount of 1% to 30% by weight relative to the total weight of the catalyst. ３ The method according to any one of claims 1 to 6, comprising molybdenum represented as:

8. The hydrogenation catalyst of step b) is provided on a mineral support selected from the group consisting of alumina, silica, silica-alumina, magnesia, clay, and a mixture of at least two of these minerals, containing nickel represented as nickel oxide (NiO) in an amount of 0.5% to 10% by weight relative to the total weight of the catalyst, and molybdenum oxide (MoO) in an amount of 1% to 30% by weight relative to the total weight of the catalyst. ３ The method according to any one of claims 1 to 7, comprising molybdenum represented as:

9. The method according to any one of claims 1 to 8, wherein the separation section of step c) includes means for scrubbing by contact with an aqueous solution.

10. The separation step c) is, c1) A first separation step performed at a temperature higher than the precipitation temperature of ammonium halide in order to obtain at least one first gas fraction and one liquid effluent, c2) The method according to claim 9, comprising a second separation step supplied by a first gas fraction and at least a portion of the liquid effluent resulting from step c1) and an aqueous solution, to obtain at least one second gas fraction, one aqueous effluent and one liquid product, wherein the second separation step is carried out at a temperature lower than the precipitation temperature of ammonium halide.

11. The method according to any one of claims 1 to 10, further comprising step d) of subsequent processing of the at least one liquid product resulting from step c), wherein step d) comprises at least one step selected from the list of hydrotreatment, steam cracking, fluidized bed catalytic cracking, hydrocracking, desying and lubricating oil extraction.

12. The method according to any one of claims 1 to 11, wherein in step a), the pyrolysis oil fraction and the heavy hydrocarbon fraction of the feedstock are premixed before being introduced into one of the replaceable reactors.

13. The method according to any one of claims 1 to 11, wherein in step a), the fraction of the pyrolysis oil of the supply material is introduced into one of the replaceable reactors separately from the heavy fraction of the hydrocarbon.

14. The method according to claim 13, wherein step a) includes preheating the heavy fraction of the hydrocarbon to a temperature preferably between 280°C and 450°C, and preheating the pyrolysis oil fraction at a temperature lower than that of the heavy fraction of the hydrocarbon before introducing the feed material into one of the replaceable reactors.

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

16. The product according to claim 15, wherein silicon is contained in an amount of 10 ppm by weight or less relative to the weight of the product and / or chlorine is contained in an amount of 10 ppm by weight or less.

Images