Method for producing middle distillates and naphtha from a feedstock comprising an aromatic pyrolysis oil fraction

Abstract

The invention relates to a method for producing middle distillates and naphtha from a mixed feedstock comprising a heavy fraction of fossil hydrocarbons, of which at least 50% by weight of the compounds have an initial boiling point greater than 300°C and a final boiling point less than 700°C, and less than 50% by weight is a pyrolysis oil fraction of plastic and / or tyres and / or recovered solid fuels having an aromatic compound content greater than 30% by weight, the method comprising the following steps: a) a step of hydrotreating the mixed feedstock to obtain a hydrotreated effluent; b) a step of hydrocracking the hydrotreated effluent to obtain a hydrocracked effluent; c) a step of separating the hydrocracked effluent to produce at least one gaseous effluent comprising hydrogen and at least one liquid effluent; d) a fractionation step to produce a naphtha cut and a middle distillate cut.

Description

[0001] PROCESS FOR PRODUCING MIDDLE DISTILLERS AND NAPHTHA FROM A FEED COMPRISING AN AROMATIC PYROLYSIS OIL FRACTION

[0002] Technical field

[0003] The present invention relates to a process for producing middle distillates and naphtha comprising a hydrotreatment step and a hydrocracking step, said process being characterized by the use of a mixed feedstock comprising mainly a heavy fraction of hydrocarbons of fossil origin, in particular a heavy fraction of hydrocarbons of which at least 50% by weight of the compounds have an initial boiling point above 300°C and a final boiling point below 700°C, such as a vacuum distillate cut (VDC) or Vacuum Gas Oil (VGO) and a minor fraction of highly aromatic plastic and / or tire and / or solid recovered fuel (SRF) pyrolysis oil, loaded with impurities.

[0004] The objective of the process according to the invention is essentially the production of a middle distillate cut, comprising a kerosene cut having initial and final boiling points in a range of approximately 150 to 250°C and a diesel cut having initial and final boiling points in a range of approximately 250°C to 370°C. The process according to the invention also makes it possible to produce a naphtha cut having boiling points approximately below 150°C.

[0005] Prior art

[0006] The process for producing middle distillates, which includes a hydrocracking step for heavy petroleum fractions, is now an essential refining process that allows the production of lighter fractions such as gasoline (naphtha), kerosene and diesel from excess and low-value heavy feedstocks, which the refiner seeks to adapt its production to the structure of demand. Compared to catalytic cracking (FCC), the advantage of catalytic hydrocracking is that it provides very high-quality middle distillates. Conversely, the gasoline (naphtha) produced often has a low octane rating.For several years, we have seen the emergence of processes in the fuel and chemical sectors incorporating products other than traditional petroleum products, for example products of renewable origin such as vegetable oils and animal fats or waste such as used tires, plastics or used oils, in addition to or as a substitute for products of fossil origin.

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

[0008] Pyrolysis oils can also be recycled through refining processes to produce fuels, such as gasoline or diesel, and / or chemicals such as olefins for the production of various polymers in the chemical industry.

[0009] However, this other way of recovering pyrolysis oils is faced with the problems generated by the specific composition of these oils, in particular by the impurities they contain, the composition of these oils itself being linked to the diversity of the components of the waste.

[0010] Oils from the pyrolysis of plastics or tires or solid recovered fuels (SRF) generally contain a lot of diolefins and impurities, in particular metals, silicon, or halogenated compounds, including chlorine-based compounds, heteroelements such as sulfur, oxygen and nitrogen, insolubles, often at high levels and which may be incompatible with certain refining units, such as fixed-bed hydrotreatment units.

[0011] The processing of these oils can pose operability problems, including corrosion, coking, catalytic deactivation, and incompatibility problems in polymer applications. The presence of diolefins, for example, very often leads to problems of instability in the pyrolysis oil, characterized by the formation of gums. Gums and insolubles that may be present in the pyrolysis oil can cause clogging problems in the equipment. The presence of chlorine can lead to corrosion problems.

[0012] One way to remove these impurities from pyrolysis oils is to carry out hydrotreatment in the presence of catalysts. Such processes are described, for example, in documents WO2016 / 142808 or WO2016 / 142806.

[0013] Patent applications FR3107530, FR3113060 and FR31113061 describe processes for treating plastic pyrolysis oil, comprising, among other things, a selective hydrogenation step of the pyrolysis oil and a fixed-bed hydrotreatment of the hydrogenated effluent. The naphtha cut resulting from a water-specific separation of the hydrotreated effluent followed by a fractionation of the separated hydrocarbon stream can be sent to a steam cracker or be used as a fuel base. According to patent applications FR3113060 and FR31113061, the process integrates one or two fixed-bed hydrocracking steps after the hydrotreatment step, to minimize the yield of the heavy cut and maximize the yield of the naphtha cut by transforming the heavy cut at least in part into a naphtha cut by hydrocracking, a cut generally favored for a steam cracking unit.

[0014] Other processes involving a mixture of a fossil feedstock and a pyrolysis oil are also known, for example in document WO2015 / 128033 which describes a process for co-processing a pyrolysis oil low in aromatics and an unspecified hydrocracking feedstock in a hydrocracking step to increase the production of light compounds of the ethane and propane type, without disclosing a prior hydrotreatment step.

[0015] Document WO2023 / 002092 describes a process for producing hydrocarbons from a feedstock containing predominantly a fraction of hydrocarbons of fossil origin such as vacuum distillate or heavy diesel and, to a lesser extent, a fraction of pyrolysis oil comprising a hydrotreatment step and a hydrocracking step. The pyrolysis oil contains between 40 and 60% by weight of olefins and an aromatic content of less than 20% by weight. This document does not describe the use of a pyrolysis oil highly loaded with aromatics and its beneficial effect as a co-feedstock in the production of middle distillates and naphtha by hydrocracking a feedstock of vacuum distillate type. Objectives and Summary of the Invention

[0016] The present invention relates to the field of the recovery of heavy loads that are difficult to recover, such as vacuum distillates, which generally contain high levels of impurities such as metals, sulfur, and nitrogen, to convert them into lighter products that can be recovered as fuels, for example to produce gasoline (naphtha), kerosene and / or diesel.

[0017] The inventors have demonstrated that, surprisingly, it is possible to incorporate a minor fraction of plastic and / or tire pyrolysis oil and / or recovered solid fuels having a high content of aromatic compounds and loaded with impurities into a heavy hydrocarbon feedstock of fossil origin, typically a vacuum distillate, traditionally treated in a hydrocracking process, and thus to improve the production of basic fuels and / or other recoverable hydrocarbons in terms of yield but also in terms of quality.

[0018] Indeed, the process according to the invention makes it possible, on the one hand, to recover pyrolysis oil that is highly loaded with aromatic compounds, a product that is generally difficult to recover, which makes it possible to reduce dependence on fossil fuels and create a circular economy.

[0019] The process according to the invention makes it possible to produce middle distillates (in particular a kerosene cut and a diesel cut) meeting the specifications required respectively for these cuts and this despite the use of a pyrolysis oil containing many aromatic compounds and many impurities. It is indeed known that a high aromatic content in a middle distillate can be problematic in order to respect the maximum rate of aromatics allowed according to the specification, as well as the density specification, and the cetane index for diesel.

[0020] The process according to the invention makes it possible to produce, in particular by controlling the conversion rate during the hydrocracking step (i.e. between 50 and 95% by weight), a diesel cut meeting the specifications of density, sulfur content, cetane index and cloud point. The same applies to the specifications of density, sulfur content, freezing point and smoke point for a kerosene cut. If the high aromaticity of the pyrolysis oil is therefore rather a disadvantage for the production of middle distillates, it presents an advantage when it is desired to produce a naphtha cut, in particular when it is intended to be sent to a catalytic reforming process.The high aromatic content in the oil is found after the hydrotreatment and hydrocracking stages in the naphtha cut, which is thus very aromatic and naphthenic. This naphtha cut has a high octane number (RON / MON) and a high naphthenes and paraffins content and can therefore be sent to a catalytic reforming unit. The objective of catalytic reforming is to transform the naphthenic (low octane) constituents into high octane aromatic constituents used as a base for gasoline blending.

[0021] Another advantage of the present invention is the fact of observing an increase in the yield of middle distillate cut (kerosene and diesel), in particular when the conversion rate of the hydrocracking step is controlled (i.e. less than 85% by weight) compared to the yield of a feedstock of hydrocarbons of pure fossil origin. Indeed, since pyrolysis oil generally has compounds with boiling points in the middle distillate range, the addition of such a feedstock to the heavier feedstock of hydrocarbons of fossil origin intrinsically makes it possible to increase the yield of middle distillate if the conversion rate is controlled (in order to avoid overcracking).

[0022] The process according to the invention therefore takes advantage in particular of the chemical nature of the pyrolysis oil used as feedstock, in particular a pyrolysis oil having a high content of aromatic compounds, on the one hand compounds sought for example in a naphtha cut intended to be sent to a catalytic reforming process and on the other hand compounds tolerable in diesel and kerosene cuts.

[0023] The process according to the invention thus makes it possible to upgrade a pyrolysis oil while taking advantage of its chemical nature (high aromatic content) in order to produce fuel bases meeting specifications and having improved properties while increasing their yield. More particularly, the invention relates to a process for producing middle distillates and naphtha from a feedstock comprising a heavy fraction of hydrocarbons of fossil origin of which at least 50% by weight of the compounds have an initial boiling point above 300°C and a final boiling point below 700°C, and a fraction of plastic and / or tire and / or solid recovered fuel pyrolysis oil having an aromatic compound content above 30% by weight relative to the weight of the pyrolysis oil, said pyrolysis oil fraction constituting less than 50% by weight of said feedstock,said method comprising: a) a hydrotreatment step carried out in a hydrotreatment reaction section, using at least one fixed bed reactor having n catalytic beds, n being an integer greater than or equal to 1, each comprising at least one hydrotreatment catalyst, said hydrotreatment reaction section being supplied at least by said feedstock and a gas stream comprising hydrogen, said hydrotreatment reaction section being carried out at a temperature between 200 and 450°C, a pressure between 2.0 and 18.0 MPa abs. and an hourly volumetric flow rate between 0.1 and 6.0 h, -1and to a quantity of hydrogen introduced such that the volume ratio liter of hydrogen / liter of hydrocarbon is between 100 and 3000 NL / L, to obtain a hydrotreated effluent; b) a hydrocracking step carried out in a hydrocracking reaction section, using at least one fixed-bed reactor having n catalytic beds, n being an integer greater than or equal to 1, each comprising at least one hydrocracking catalyst, said hydrocracking reaction section being fed with at least a portion of said hydrotreated effluent from step a) and a gas stream comprising hydrogen, said hydrocracking reaction section being carried out at a temperature between 200 and 450°C, a pressure between 2.0 and 18.0 MPa abs. and an hourly volumetric flow rate between 0.1 and 12.0 h -1and to a quantity of hydrogen introduced such that the volume ratio liter of hydrogen / liter of hydrocarbon is between 100 and 3000 NL / L, to obtain a hydrocracked effluent; c) a separation step, fed with at least a portion of the hydrocracked effluent from step b), in a separation section, to produce at least one gaseous effluent comprising hydrogen, and at least one liquid effluent; d) a fractionation step, fed with at least a portion of the liquid effluent from step c), in a fractionation section, to produce at least one naphtha cut, at least one middle distillate cut and at least one unconverted heavy liquid cut.

[0024] According to one variant, the pyrolysis oil fraction constitutes between 1% and 45% by weight of said charge, preferably between 2% and 30% by weight of said charge, preferably between 2% and 25% by weight of said charge, more preferably between 3% and 20% by weight of said charge.

[0025] According to one variant, the feedstock consists of said pyrolysis oil fraction and said heavy hydrocarbon fraction of fossil origin, said pyrolysis oil fraction constituting between 1% and 45% by weight, preferably between 2% and 30% by weight, of said feedstock and the heavy hydrocarbon fraction constituting between 55% and 99% by weight, preferably between 70% and 98% by weight, of the feedstock.

[0026] According to one variant, the pyrolysis oil fraction has an olefin and paraffin content of less than 30% by weight, preferably less than 25% by weight.

[0027] According to a variant, the heavy fraction of hydrocarbons of fossil origin is chosen from a vacuum distillate resulting from the direct distillation of crude oil or resulting from hydrotreatment, hydroconversion or hydrocracking processes of atmospheric or vacuum residues operating in a fixed bed, moving bed, ebullating bed or entrained bed; or a fraction resulting from conversion units such as a fluid catalytic cracking process; or a fraction resulting from a coking process; or a fraction resulting from a visbreaking process; or a fraction resulting from aromatic extraction units of lubricating oil bases; or a fraction resulting from solvent dewaxing of lubricating oil bases; or even be a deasphalted oil resulting from solvent deasphalting of residues; or even any mixture of the previously mentioned feedstocks.

[0028] Alternatively, the heavy fraction of fossil hydrocarbons is a vacuum distillate.

[0029] According to one variant, the pyrolysis oil is selected from a pyrolysis oil derived from polyethylene terephthalate, polystyrene and / or polyvinyl chloride, and / or a pyrolysis oil derived from tires. According to one variant, the pyrolysis oil comprises a biocarbon content according to ASTM D6866 of between 20-70% by weight.

[0030] According to a variant, said feed comprising said heavy fraction of hydrocarbons of fossil origin and said fraction of pyrolysis oil, or the pyrolysis oil alone, or the heavy feed of hydrocarbons of fossil origin alone is / are subjected to a pretreatment step, said pretreatment step being carried out upstream of step a) and comprises an adsorption step and / or a filtration step and / or a centrifugation step and / or a decantation step and / or an electrostatic separation step and / or a step of washing using an aqueous solution and / or a gas stripping step.

[0031] According to one variant, a filter tray is integrated at the inlet of step a) upstream of the first catalytic bed.

[0032] According to a variant, the process comprises a separation step in a separation section between the hydrotreatment step a) and the hydrocracking step b) separating part, or all, of the hydrotreated effluent, to produce at least two cuts, including a heavy cut boiling mainly at a temperature greater than or equal to 370°C.

[0033] According to a variant, the separation section of step c) and / or the separation section between the hydrotreatment step a) and the hydrocracking step b) comprises(s) means for washing at least one cut separated by contact with an aqueous solution.

[0034] According to one variant, the conversion rate in the hydrocracking step b) is between 50 and 95% by weight.

[0035] According to a variant, the method further comprises a second hydrocracking step carried out in a hydrocracking reaction section, using at least one fixed-bed reactor having n catalytic beds, n being an integer greater than or equal to 1, each comprising at least one hydrocracking catalyst, said hydrocracking reaction section being fed with at least a portion of the unconverted heavy cut and / or the middle distillate cut resulting from fractionation step d) and a gas stream comprising hydrogen, said hydrocracking reaction section being carried out at a temperature between 200 and 450°C, a pressure between 2.0 and 18.0 MPa abs. and an hourly volumetric flow rate between 0.1 and 12.0 h -1and to a quantity of hydrogen introduced such that the volume ratio liter of hydrogen / liter of hydrocarbon is between 100 and 3000 NL / L, to obtain a second hydrocracked effluent. According to a variant, the present invention also relates to the product obtained by the process.

[0036] Alternatively, the product includes a bio-based carbon content according to ASTM D6866 of between 3 and 35% by weight.

[0037] For the purposes of the present invention, the various embodiments presented can be used alone or in combination with each other, without limitation of combination.

[0038] For the purposes of the present invention, the different parameter ranges for a given step such as pressure ranges and temperature ranges may be used alone or in combination. For example, for the purposes of the present invention, a preferred range of pressure values ​​may be combined with a preferred range of temperature values.

[0039] According to the present invention, the pressures are absolute pressures, also noted abs., and are given in absolute MPa (or MPa abs.), unless otherwise indicated.

[0040] In the following text, the groups of chemical elements are given according to the CAS classification (CRC Handbook of Chemistry and Physics, publisher CRC press, editor-in-chief DR Lide, 81st edition, 2000-2001). For example, group VIII (or VIIIB) according to the CAS classification corresponds to the metals in columns 8, 9 and 10 according to the new IUPAC classification, and group VIB to the metals in column 6.

[0041] The metal content is measured by X-ray fluorescence.

[0042] In the remainder of the text, the term "pyrolysis oil" means an oil resulting from the pyrolysis of plastics and / or tires and / or CSR, unless otherwise indicated. Also for the sake of simplification, the term "heavy hydrocarbon fraction" of the feedstock means a heavy fraction of hydrocarbons of fossil origin, unless otherwise indicated. In the remainder of the text, the expressions "between ... and ..." and "between .... and ..." are equivalent and mean that the limit values ​​of the interval are included in the range of values ​​described. If this were not the case and the limit values ​​were not included in the range described, such clarification will be provided by the present invention.

[0043] In this description, the term "include" is synonymous with (means the same as) "include" and "contain", and is inclusive or open and does not exclude other elements not mentioned. It is understood that the term "include" includes the exclusive and closed term "consist".

[0044] List of figures

[0045] Figure 1 schematically illustrates an embodiment of the hydroconversion process according to the invention.

[0046] DETAILED DESCRIPTION

[0047] The fossil load

[0048] The feedstock treated in the process according to the invention comprises a heavy fraction of hydrocarbons of fossil origin.

[0049] The heavy fraction of hydrocarbons of fossil origin is a fraction of which at least 50% by weight of the compounds have an initial boiling point above 300°C, preferably above 320°C and a final boiling point below 700°C, preferably below 550°C.

[0050] Said heavy hydrocarbon fraction of fossil origin may advantageously be chosen from a VGO (Vacuum Gas Oil according to the English terminology or vacuum distillates (DSV) resulting from the direct distillation of crude (feed of the Straight Run Vacuum Gas Oil type according to the English terminology) or resulting from other processes, in particular resulting from hydrotreatment, hydroconversion or hydrocracking processes of atmospheric or vacuum residues operating in a fixed bed, moving bed, bubbling bed or entrained bed (slurry bed according to the English terminology); or a fraction resulting from conversion units such as a fluid catalytic cracking process (FCC or "Fluid Catalytic Cracking" according to the English terminology) such as for example a light cut (LCO or "Light Cycle Oil" according to the English terminology), a heavy cut (HCO or "heavy cycle oil" according to the English terminology) or a heavy cut (HCO or "heavy cycle oil" according to the English terminology). Anglo-Saxon terminology), a residue of FCC;or a fraction resulting from a coking process, in particular a light diesel fraction (CGC or "Coker Gas Oil" according to English terminology), a heavy diesel fraction (HCGO or "Heavy Coker Gas Oil" according to English terminology); or a fraction resulting from a visbreaking process; or a fraction resulting from aromatic extraction units from lubricating oil bases (aromatic extract oil type feedstock according to English terminology); or a fraction resulting from solvent dewaxing of lubricating oil bases; or be a deasphalted oil (DAO or Deasphalted Oil according to English terminology) resulting from solvent deasphalting of residues (from direct distillation or from conversion processes); or any mixture of the previously mentioned feedstocks.;

[0051] Said heavy hydrocarbon fraction of fossil origin does not comprise a very heavy hydrocarbon fraction, such as a vacuum residue (i.e. containing a portion of at least 50% by weight, or even at least 80% by weight, having a boiling temperature of at least 450°C, preferably at least 500°C, and even more preferably at least 540°C).

[0052] Preferably, said heavy fraction is a vacuum distillate. Very preferably, said heavy fraction is a mixture of vacuum distillates from the distillation of crude oil and vacuum distillates from residue conversion processes.

[0053] The nitrogen content of said heavy fraction of fossil origin treated in the process according to the invention is usually greater than or equal to 500 ppm by weight, preferably between 500 and 10,000 ppm by weight, more preferably between 700 and 4,000 ppm by weight and even more preferably between 1,000 and 4,000 ppm by weight. The sulfur content of said heavy fraction of fossil origin is usually between 0.01 and 5% by weight, preferably between 0.2 and 4% by weight and even more preferably between 0.5 and 3% by weight.

[0054] Said heavy fraction of fossil origin may optionally contain metals. The cumulative nickel and vanadium content of said heavy fraction of fossil origin is preferably less than 20 ppm by weight and more preferably less than 10 ppm by weight. Said heavy fraction of fossil origin may optionally contain asphaltenes. The asphaltene content of said heavy fraction of fossil origin is generally less than 4000 ppm by weight, more preferably less than 1000 ppm by weight, even more preferably less than 200 ppm by weight.

[0055] These contents of metals, sulfur, nitrogen, asphaltenes are expressed in % weight of the total weight of the heavy hydrocarbon fraction of the charge.

[0056] The pyrolysis oil charge

[0057] The feedstock treated in the process according to the invention also comprises a minor fraction of plastic and / or tire pyrolysis oil and / or solid recovered fuels having an aromatic compound content greater than 30% by weight relative to the weight of the pyrolysis oil.

[0058] Pyrolysis oil can be pyrolysis oil from plastics, tires and / or recovered solid fuels.

[0059] Plastic waste is generally a mixture of several polymers, which may include, alone or in combination, polyethylene (low and / or high density), polypropylene, polyethylene terephthalate, polyvinyl chloride and polystyrene. In addition, depending on the uses, plastics may contain, in addition to polymers, other compounds, such as plasticizers, pigments, dyes or even residues from polymerization catalysts. Plastic waste may also contain, to a minor extent, biomass from, for example, household waste.

[0060] As for tires, they are mainly made of rubber for their elastic property (mixture of elastomers of the crosslinked natural and synthetic rubber type, added with additives of the silica, resin, sulfur, zinc oxide, carbon black, etc. type) and textile and metallic fibers for their reinforcing property.

[0061] Solid recovered fuels (SRF), also known as refuse derived fuel (RDF), or solid recovered fuels (SRF), are solid non-hazardous waste prepared for energy recovery, whether they come from household and similar waste, waste from economic activities or construction and / or demolition waste. SRF are generally a mixture of any combustible waste such as used tires, food by-products (fats, animal meal, etc.), viscose and wood waste, light fractions from shredders (e.g. from used vehicles, electrical and electronic equipment (WEEE), household and commercial waste, residues from the recycling of various types of waste, including certain municipal waste, plastic waste, textiles, wood among others. SRF generally contains plastic waste.

[0062] Pyrolysis oil can be produced by thermal or catalytic pyrolysis, or by hydropyrolysis (pyrolysis in the presence of a catalyst and hydrogen). It can also be produced by hydrothermal conversion. Pyrolysis oil is advantageously in liquid form at room temperature.

[0063] Pyrolysis oil is a fraction of which at least 50% by weight of the compounds have an initial boiling point above 100°C, preferably above 150°C and a final boiling point below 1000°C, preferably below 650°C.

[0064] The pyrolysis oil comprises in particular a content of aromatic compounds greater than 30% by weight, preferably greater than 40% by weight, and particularly preferably greater than 50% by weight relative to the weight of the pyrolysis oil. Aromatic compounds are understood to mean any aromatic compound including mono-, di-, tri- and / or polyaromatic compounds. The content of aromatic compounds in the pyrolysis oil is generally between 30 and 90% by weight, preferably between 40 and 85% by weight relative to the weight of the pyrolysis oil. Other compounds, such as paraffins (n- and i-paraffins), olefins (mono- and / or diolefins) and naphthenes are generally also present in the pyrolysis oil.In particular, depending on the origin of the pyrolysis oil, it may comprise, relative to the weight of the pyrolysis oil, up to 30% by weight of paraffins, preferably between 1 and 30% by weight, preferably between 1 and 25% by weight, up to 70% by weight of naphthenes, preferably between 1 and 50% by weight, preferably between 1 and 40% by weight, up to 30% by weight of olefins, preferably between 1 and 30% by weight, preferably between 1 and 25% by weight, it being understood that the sum of the paraffins, naphthenes, olefins and aromatics is equal to 100% by weight of the hydrocarbon compounds and that the pyrolysis oil comprises a content of aromatic compounds greater than 30% by weight. According to one variant, the pyrolysis oil preferably comprises an olefin and paraffin content of less than 30% by weight, preferably less than 25% by weight (in total, i.e. the sum of the olefins and paraffins) relative to the weight of the pyrolysis oil.

[0065] Pyrolysis oil may contain at least some compounds of biological origin, such as for example tire pyrolysis oil which is produced from natural rubber type elastomers. Depending on the origin of the pyrolysis oil, it may include a biological carbon content (according to the analytical method of radiocarbon isotope C 14 according to ASTM D6866) between 20-70% by weight, preferably between 30 and 60% by weight relative to the total weight of the pyrolysis oil. This makes it possible to incorporate a biological composition into the hydrocracking products. The production of biokerosene, also known as SAF in English terminology ("Sustainable Aviation Fuel"), is particularly sought after to decarbonize the aviation sector, whether civil or military.

[0066] A pyrolysis oil particularly suitable for the process according to the invention is a pyrolysis oil derived from plastics having a high aromaticity content, such as for example an oil derived from polyethylene terephthalate (PET), polystyrene (PS) or polyvinyl chloride (PVC for polyvinylchloride according to the English terminology). Another pyrolysis oil fraction particularly suitable for the process according to the invention is a pyrolysis oil derived from tires. The aromaticity of tire pyrolysis oils is due, on the one hand, to the aromatic nature of the source polymer material, styrene-butadiene rubber, and on the other hand, to the cyclization of the olefinic structures followed by dehydrogenation reactions during pyrolysis. Preferably, said pyrolysis oil fraction used in the process according to the invention is a pyrolysis oil derived from tires.

[0067] Pyrolysis oil may contain diolefins. The diolefin content is commonly determined indirectly as the maleic anhydride value (MAV). The method is based on the Diels-Alder addition reaction between conjugated diolefins and maleic anhydride. The method for determining MAV is described in C. Lépez-Garcîa et al., Near Infrared Monitoring of Low Conjugated Diolefins Content in Hydrotreated FCC Gasoline Streams, Oil & Gas Science and Technology - Rev. IFP, Vol. 62 (2007), No. 1, pp. 57-68. MAV is expressed as mg of maleic anhydride reacted with 1 g of sample (mg / g). MAV preferably ranges between 5 and 100 mg / g in pyrolysis oils.

[0068] The density of pyrolysis oil, measured at 15°C according to the ASTM D4052 method, is generally between 0.75 g / cm 3 and 1.05 g / cm 3 , preferably between 0.80 g / cm3 and 0.98 g / cm 3 .

[0069] Pyrolysis oil may include, and most often does include, additional impurities such as metals, in particular iron, silicon, halogenated compounds, in particular chlorinated compounds. These impurities may be present at high levels, for example up to 500 ppm by weight or 700 ppm by weight or even 1000 ppm by weight, and even 5000 ppm by weight, of halogenated elements (in particular chlorine but also bromine, fluorine or iodine) provided by halogenated compounds, and generally between 1 and 1000 ppm by weight or between 1 and 700 ppm by weight or between 1 and 500 ppm by weight of halogenated elements. Pyrolysis oil can contain up to 500 ppm by weight or 700 ppm by weight or even 1000 ppm by weight or even 5000 ppm by weight of chlorine element provided by chlorinated compounds, and generally between 1 and 1000 ppm by weight or between 1 and 700 ppm by weight or even between 1 and 500 ppm by weight of chlorine elements.

[0070] Pyrolysis oil may contain up to 200 ppm by weight, or even 1500 ppm by weight of metallic or semi-metallic elements, and generally between 1 and 1500 ppm by weight or between 1 and 200 ppm by weight of metallic or semi-metallic elements. Alkali metals, alkaline earth metals, transition metals, poor metals and metalloids may be considered as contaminants of a metallic nature, called metals or metallic or semi-metallic elements. In particular, metals or metallic or semi-metallic elements include silicon, iron or both of these elements. Pyrolysis oil may contain up to 200 ppm by weight or even 1000 ppm by weight of silicon, and generally between 1 and 1000 ppm by weight or between 1 and 500 ppm by weight or even between 1 and 200 ppm by weight of silicon. Pyrolysis oil can contain up to 50 ppm by weight or 100 ppm by weight of iron, and generally between 1 and 100 ppm by weight or between 1 and 50 ppm by weight of iron.Pyrolysis oil may also include phosphorus, sodium, calcium, potassium, and magnesium.

[0071] The pyrolysis oil may also include other impurities such as heteroelements provided in particular by sulfur compounds, oxygenated compounds and / or nitrogen compounds, at contents generally less than 40,000 ppm by weight of heteroelements and preferably less than 15,500 ppm by weight of heteroelements, and generally between 1 and 40,000 ppm by weight or between 1 and 15,500 ppm by weight of heteroelements.

[0072] The sulfur compounds are generally present in a content of less than 15,000 ppm by weight and preferably less than 10,000 ppm by weight, and generally between 1 and 15,000 ppm by weight or between 1 and 10,000 ppm by weight of sulfur compounds. The oxygen compounds are generally present in a content of less than 15,000 ppm by weight and preferably less than 10,000 ppm by weight, and generally between 1 and 15,000 ppm by weight or between 1 and 10,000 ppm by weight of oxygen compounds. The nitrogen compounds are generally present in a content of less than 10,000 ppm by weight and preferably less than 8,000 ppm by weight, and generally between 1 and 10,000 ppm by weight or between 1 and 8,000 ppm by weight of nitrogen compounds.

[0073] The content of sulfur, oxygenated and / or nitrogen compounds often depends on the origin of the oil. Thus, tire pyrolysis oils generally contain more heteroelements than plastic pyrolysis oils, particularly sulfur compounds.

[0074] Pyrolysis oil may also include other impurities such as heavy metals such as mercury, arsenic, zinc and lead, for example up to 500 ppb weight of heavy metals such as mercury or arsenic, and typically between 1 and 300 ppb weight or between 1 and 200 ppb weight of heavy metals.

[0075] According to a key aspect of the invention, the feedstock comprises mainly a heavy fraction of hydrocarbons of fossil origin and a minor fraction of plastic and / or tire and / or CSR pyrolysis oil having an aromatic compound content greater than 30% by weight relative to the weight of the pyrolysis oil. The fraction of plastic and / or tire and / or CSR pyrolysis oil constitutes less than 50% by weight of the feedstock (total weight of the feedstock), preferably between 1% and 45% by weight of the feedstock, more preferably between 2% and 30% by weight of the feedstock, even more preferably between 2% and 25% by weight of the feedstock, even more preferably between 3% and 20% by weight of the feedstock, and even more preferably between 5% and 20% by weight of the feedstock, or even between 5% and 15% by weight of the feedstock.

[0076] The heavy hydrocarbon fraction may constitute more than 50% by weight of the feedstock (total weight of the feedstock), preferably between 55% and 99% by weight of the feedstock, preferably between 70% and 98% by weight of the feedstock, more preferably between 75% and 98% by weight of the feedstock, even more preferably between 80% and 97% by weight of the feedstock, and even more preferably between 80% and 95% by weight of the feedstock, or even between 85% and 95% by weight of the feedstock.

[0077] According to a preferred embodiment, the feedstock consists of said minor fraction of pyrolysis oil and a heavy fraction of fossil hydrocarbons. According to this embodiment, said pyrolysis oil fraction constitutes between 1% and 45% by weight, preferably between 2% and 30% by weight, of said feedstock and the heavy fraction of hydrocarbons constitutes between 55% and 99% by weight, preferably between 70% and 98% by weight, of the feedstock.

[0078] According to one or more implementations, the feedstock of the process according to the invention may further comprise, at a low content, typically between 1% and 20% by weight of the feedstock, or even between 1% and 10% or between 1 and 5% by weight, a fraction of vegetable and / or animal oil or fat, and / or a hydrocarbon fraction resulting from thermal and / or catalytic conversion processes of lignocellulosic biomass, such as an oil produced from lignocellulosic biomass, according to various liquefaction methods such as hydrothermal liquefaction or pyrolysis, which is then co-treated with the pyrolysis oil from plastics and / or tires and / or CSR and the heavy fraction of hydrocarbons of fossil origin.

[0079] Oils / fats of vegetable and / or animal origin contain triglycerides and / or free fatty acids and / or esters. Vegetable oils can advantageously be crude or refined, totally or partially, and can be derived from the following plants: rapeseed, sunflower, soybean, palm, palm kernel, olive, coconut, jatropha (purjay), castor oil, cotton, peanuts, flax, crambe, this list not being exhaustive. Algal or fish oils are also relevant. Oils / fats of vegetable and / or animal origin can be used, for example used cooking oils. Animal fats can be chosen from lard or fats composed of residues from the food industry or from the catering industries.

[0080] Oils / fats of vegetable and / or animal origin are generally very rich in paraffins. These paraffins have a low density and a good cetane number. The addition of such a charge in the feedstock of said process (fossil fraction and / or highly (or too) aromatic pyrolysis oil fraction) thus makes it possible to achieve the density specification for the desired product of said process. Similarly, the addition of such a charge makes it possible to improve the cetane number of a diesel cut.

[0081] The term "lignocellulosic biomass" means compounds derived from plants or their by-products, and includes constituents selected from the group consisting of cellulose, hemicellulose (carbohydrate polymers) and / or lignin (aromatic polymer).

[0082] According to one or more implementations, the feedstock of the process according to the invention does not comprise a fraction of vegetable and / or animal oil or fat, or a hydrocarbon fraction resulting from thermal and / or catalytic conversion processes of lignocellulosic biomass such as biomass pyrolysis oil.

[0083] Pre-treatment (optional)

[0084] Said feedstock comprising said heavy fraction of hydrocarbons of fossil origin and said fraction of pyrolysis oil, or the pyrolysis oil alone, or the heavy feedstock of hydrocarbons of fossil origin alone may advantageously be pretreated in an optional pretreatment step, prior to step a) of hydrotreatment, to obtain a pretreated mixed feedstock or a pretreated pyrolysis oil or a pretreated fossil feedstock which feeds step a).

[0085] According to a variant, this optional pretreatment step makes it possible to reduce the quantity of contaminants and solid particles. This optional pretreatment step allows in particular the elimination of sediments which can form due to the unstable nature of the pyrolysis oils and / or a compatibility problem between two different loads. Said optional pretreatment step can be implemented by any method known to those skilled in the art making it possible to reduce the quantity of contaminants. It can in particular comprise an adsorption step and / or a filtration step and / or a centrifugation step and / or a decantation step and / or an electrostatic separation step and / or a washing step using an aqueous solution and / or a gas stripping step.

[0086] The optional pretreatment step is advantageously carried out at a temperature between 20 and 400°C, preferably between 40 and 350°C, and at a pressure between 0.15 and 10.0 MPa abs, preferably between 0.2 and 7.0 MPa abs.

[0087] According to a variant, said optional pretreatment step is implemented in an adsorption section operated in the presence of at least one adsorbent. The adsorbent may be chosen from a zeolite, activated carbon, a clay, a silica or an alumina. Advantageously, said adsorbent comprises less than 1% by weight of metallic elements, preferably is free of metallic elements. By metallic elements of the adsorbent, it is meant the elements of groups VIB, VI IB and VIII. In the case where said heavy fraction of fossil origin contains metals and / or compounds of the resin and / or asphaltene type, it is advantageous to first pass the feed comprising said heavy fraction of fossil origin over a catalyst or adsorbent bed different from the hydrotreatment or hydrocracking catalyst, for example over a hydrodemetallization catalyst bed.Adsorption can also be carried out on the pyrolysis oil feed alone or on the mixed feed.

[0088] According to another variant, said optional pretreatment step is implemented in a washing section with an aqueous solution, for example water or an acidic or basic solution. This washing section may comprise equipment for bringing the mixed feedstock or the pyrolysis oil or the fossil feedstock into contact with the aqueous solution and for separating the phases so as to obtain the pretreated mixed feedstock or the pyrolysis oil or the fossil feedstock on the one hand and the aqueous solution comprising impurities on the other hand. Among this equipment, there may be for example a stirred reactor, a decanter, a mixer-decanter and / or a co- or counter-current washing column. According to another variant, said optional pretreatment step is implemented by filtration.The filtration step removes inorganic solids, sediments and / or fines contained in the mixed feedstock or pyrolysis oil or fossil feedstock, including metals, metal oxides and metal chlorides. A filter is generally used whose pore size (e.g. diameter or equivalent diameter) is less than 50 μm, preferably less than or equal to 30 μm. Alternatively, a filter may be used whose pore size is less than or equal to 5 μm. A series of filters with different pore sizes may also be used, including a series of filters with decreasing pore sizes in the direction of feed flow. These filter media are well known for industrial applications. Cartridge filters and self-cleaning filters are suitable, for example.

[0089] According to another variant, said optional pretreatment step is implemented by centrifugation, by decantation or by electrostatic separation.

[0090] In another variant, said optional pretreatment step is implemented by gas stripping, thereby reducing the oxygen content in the feedstock. Gas stripping may remove oxygen (O2) that may be dissolved in the mixed feedstock or pyrolysis oil or fossil feedstock thereby reducing the likelihood of free radical formation leading to polymerization in downstream steps. The process typically involves contacting with a stripping gas (e.g. H2, N2 or a mixture thereof), thereby transferring at least some of the dissolved oxygen from the feedstock to the stripping gas, followed by separation of the stripping gas from the mixed feedstock or pyrolysis oil or fossil feedstock. Any dissolved H2 remaining in the mixed feedstock or pyrolysis oil or fossil feedstock after the gas stripping step is not a concern, given the hydrotreatment step typically performed downstream.

[0091] Said optional pre-treatment step generally comprises one or more, preferably several treatments described above.

[0092] Said optional pretreatment step thus makes it possible to obtain a pretreated feedstock comprising said pyrolysis oil fraction or a pretreated pyrolysis oil or the pretreated fossil feedstock which can then feed the hydrotreatment step a). The two fractions of the feedstock can be preheated beforehand, individually or together, to ensure that they are in the liquid state before entering the hydrotreatment reactor, by means of any heating device known to those skilled in the art. Alternatively, only the heavy hydrocarbon fraction can be preheated, in particular if the pyrolysis oil fraction is liquid and pumpable at ambient temperature. The preheating is generally carried out at a temperature between 50 and 150°C, preferably between 60 and 100°C.

[0093] After the optional preheating step of at least one of the two fractions, heating can be carried out before entering the hydrotreatment reactor by any means known to a person skilled in the art. The heating can be carried out either on the fossil fraction alone, or on the pyrolysis oil fraction alone, or on the mixture of the two fractions. According to a variant, the pyrolysis oil fraction can be heated indirectly by mixing with the heavy hydrocarbon fraction heated beforehand (i.e. heat exchange between the two fractions by bringing said two fractions which have different temperatures into contact) so as to limit the formation of gums and / or the coking of the heating equipment.

[0094] According to one possibility, the pyrolysis oil fraction can be premixed with the heavy hydrocarbon fraction of the feedstock, possibly preheated, before entering the hydrotreatment reactor. Another possibility is the separate injection of the pyrolysis oil fraction and the heavy hydrocarbon fraction into the hydrotreatment reactor. This injection method may be preferred to avoid any problem that would be linked to a chemical incompatibility between the two fractions (risk of demixing or precipitation of asphaltenes for example), or to avoid possible accelerated fouling of the heating furnace (the high diolefin and olefin contents of the pyrolysis oil can lead to the formation of gum).

[0095] Before its introduction into the hydrotreatment reaction section, the feedstock undergoes a pressurization step to be adapted to the pressure operated in the hydrotreatment step. This pressurization step is preferably carried out before the heating step. Hydrotreatment step a)

[0096] According to the invention, the method comprises a hydrotreatment step a) carried out in a hydrotreatment reaction section, using at least one fixed bed reactor having n catalytic beds, n being an integer greater than or equal to 1, each comprising at least one hydrotreatment catalyst, said hydrotreatment reaction section being supplied at least by said feedstock and a gas stream comprising hydrogen, said hydrotreatment reaction section being carried out at a temperature between 200 and 450°C, a pressure between 2.0 and 18.0 MPa abs. and an hourly volumetric flow rate between 0.1 and 6.0 h -1and to a quantity of hydrogen introduced such that the volume ratio liter of hydrogen / liter of hydrocarbon is between 100 and 3000 NL / L, to obtain a hydrotreated effluent.

[0097] Advantageously, step a) implements hydrotreatment reactions well known to those skilled in the art, and more particularly hydrotreatment reactions such as the hydrogenation of aromatics, hydrodesulfurization and hydrodenitrogenation, the hydrogenation of olefins and halogenated compounds as well as hydrodemetalation.

[0098] Preferably, the hydrotreatment step according to the invention operates at a temperature between 200 and 450°C, preferably between 250 and 450°C, very preferably between 300 and 430°C, under a pressure between 2.0 and 18.0 MPa abs, preferably between 3 and 16 MPa abs, at a space velocity between 0.1 and 6.0 IT 1 'preferably between 0.2 and 5 h' 1, very preferably between 0.5 and 2 h -1 and to a quantity of hydrogen introduced such that the volume ratio liter of hydrogen / liter of hydrocarbon is between 100 and 3000 NL / L, preferably between 300 and 1500 NL / L.

[0099] According to the invention, the "temperature" of a reaction section corresponds to the Weight Average Bed Temperature (WABT) according to the established Anglo-Saxon term, well known to those skilled in the art. Unless otherwise indicated, the "average temperature" of a reaction section is given at cycle start conditions. The hourly volumetric flow rate (WH) is defined here as the ratio between the hourly volumetric flow rate of the feedstock, possibly pretreated, by the volume of catalyst(s).

[0100] Hydrogen coverage is defined as the ratio of the volume flow rate of hydrogen taken under normal temperature and pressure conditions to the volume flow rate of "fresh" feedstock, i.e. the feedstock to be treated, possibly pre-treated, without taking into account a recycled fraction, at 15°C (in normal m 3 , noted Nm 3 , of H2 per m 3 dump).

[0101] Advantageously, said hydrotreatment step is carried out in a hydrotreatment reaction section comprising at least one, preferably between one and five, fixed bed reactor(s) having n catalytic beds, n being an integer greater than or equal to one, preferably between one and ten, more preferably between two and five, said bed(s) each comprising at least one, and preferably not more than ten, hydrotreatment catalyst(s).

[0102] The hydrotreatment reaction section using at least one fixed bed reactor can operate with a descending or ascending flow of gas and liquid.

[0103] The gas stream comprising hydrogen, which feeds the hydrotreatment reaction section, may consist of hydrogen makeup and / or recycled hydrogen. The gas stream comprising hydrogen may come from a fossil source or a renewable source, for example from the gasification of plastic waste or produced by electrolysis.

[0104] Preferably, an additional gas stream comprising hydrogen is advantageously introduced at the inlet of each reactor, in particular operating in series, and / or at the inlet of each catalytic bed from the second catalytic bed of the reaction section. These additional gas streams are also called cooling streams. They make it possible to control the temperature in the reactor in which the reactions carried out are generally very exothermic.

[0105] Preferably, step a) may use upstream of the hydrotreatment catalyst(s) at least one guard bed containing adsorbents and / or catalysts of the alumina, silica-alumina, zeolite and / or activated carbon type possibly containing metals from group VIB and / or VIII. It is also possible to use a series of guard beds (catalysts) with particles of different diameters, in particular a series of guard beds having decreasing diameters in the direction of flow of the feedstock (also called "grading" according to English terminology). The main task of the guard beds is to protect the catalysts of the main reactors of step a) downstream by carrying out part of the demetallation and by filtering the particles contained in the feedstock which can lead to clogging.Said catalysts may comprise at least one support comprising a porous refractory oxide, at least one metal from group VIB, and at least two metals from group VIII. This (these) catalyst(s) has (have) a content of metal(s) from group VIB of between 2 and 9% by weight of trioxide of the metal(s) from group VIB relative to the total mass of the catalyst, and the sum of the contents of metals from group VIII is between 0.3 and 2% by weight of the oxide of the metals from group VIII relative to the total mass of the catalyst.

[0106] According to a variant, the feed passes through a filter distributor tray at the inlet of each guard zone, which tray is composed of a single stage or two successive stages, said tray being located upstream of the catalytic beds, preferably upstream of each catalytic bed. This filter distributor tray, described for example in document US2009177023, makes it possible to trap the clogging particles contained in the feed by means of a specific distributor tray comprising a filtering medium. Thus, the filter tray makes it possible to increase the cycle time savings in the process according to the invention. This filter tray makes it possible to simultaneously distribute the gas phase (hydrogen and the gaseous part of the feed) and the liquid phase (the liquid part of the feed) feeding the reactor while ensuring a filtration function with respect to the impurities contained in the feed.Likewise, the filter tray ensures a more homogeneous distribution of the mixture over the entire surface of the catalytic bed and limits problems of maldistribution during the clogging phase of the tray itself.

[0107] More specifically, the filter tray is a filtration and distribution device, said device comprising a tray located upstream of the catalytic bed, said tray consisting of a substantially horizontal base plane secured to the walls of the reactor and to which are fixed substantially vertical chimneys, open at their upper end for the admission of gas, and at their lower end for the evacuation of the gas-liquid mixture intended to feed the catalytic bed located downstream, said chimneys being pierced over a certain fraction of their height with a continuous lateral slot or lateral orifices for the admission of liquid, said tray supporting a filtration bed surrounding the chimneys, and said filtration bed consisting of at least one layer of particles of a size less than or equal to the size of the particles of the catalytic bed.The filtration bed consists of generally inert particles but can also include at least one layer of catalyst identical to or belonging to the same family as the catalyst of the catalytic bed. This latter variant makes it possible to reduce the volume of catalytic beds in the reactor.

[0108] The filter distributor tray can also comprise two stages and be composed of two successive trays: the first tray supporting a guard bed composed of internal particles and at least one layer of catalyst identical to or belonging to the same family as the catalyst of the catalytic bed. This tray is described in document US2009177023. The bed is arranged on a grid, the liquid phase flows through the guard bed and the gas through chimneys passing through the guard bed and the first tray. At the end of clogging, the liquid and the gas flow simultaneously through the chimneys while allowing the second tray to continue to perform its distribution function. The second tray ensures the gas and liquid distribution function: it can be composed of chimneys with lateral perforations for the passage of the liquid or composed of bubble caps.

[0109] Conventional hydrotreatment catalysts may advantageously be used in supported or unsupported form, preferably containing at least one amorphous support and at least one hydro-dehydrogenating element chosen from at least one non-noble element from groups VIB and VIII, and most often at least one element from group VIB (from molybdenum or tungsten taken alone or in a mixture) and at least one non-noble element from group VIII (from nickel or cobalt taken alone or in a mixture). Preferably, the hydrotreatment catalyst comprises a support chosen from alumina, silica, silica-aluminas, magnesia, clays and their mixtures and a hydro-dehydrogenating function comprising either at least one element from group VIII and at least one element from group VIB, or at least one element from group VIII.The reaction section of said hydrotreatment step comprises, for example, a hydrotreatment catalyst comprising between 0.5% and 12% by weight of nickel or cobalt, preferably between 0.9% and 10% by weight of nickel or cobalt (expressed as NiO or CoO oxide relative to the weight of said catalyst), and between 1% and 30% by weight of molybdenum and / or tungsten, preferably between 3% and 20% by weight of molybdenum and / or tungsten (expressed as MoOs or WO3 oxide relative to the weight of said catalyst) on an amorphous support, preferably on an alumina support. The hydrotreatment catalyst may comprise phosphorus. When phosphorus is present, its concentration is less than 10% by weight (expressed as P2O5) relative to the weight of said catalyst and advantageously at least 0.001% by weight relative to the total weight of said catalyst.

[0110] Preferably, the amorphous support is alumina or silica-alumina.

[0111] Preferred catalysts are selected from NiMo, NiW, NiMoW or C0M0 catalysts supported on alumina and NiMo, NiW or NiMoW catalysts supported on silica-alumina.

[0112] According to another aspect of the invention, the hydrotreatment catalyst further comprises one or more organic compounds containing oxygen and / or nitrogen and / or sulfur. Such a catalyst is often referred to as an "additive catalyst". Generally, the organic compound is chosen from a compound comprising one or more chemical functions chosen from a carboxylic function, alcohol, thiol, thioether, sulfone, sulfoxide, ether, aldehyde, ketone, ester, carbonate, amine, nitrile, imide, oxime, urea and amide or compounds including a furan cycle or sugars.

[0113] Advantageously, the hydrotreatment step a) allows the hydrogenation of at least 80%, and preferably of all of the olefins (mono- and diolefins) and halogenated compounds, but also the conversion at least in part of other impurities / compounds present in the feedstock, such as aromatic compounds, metallic compounds, sulfur compounds, nitrogen compounds, oxygenated compounds.

[0114] Preferably, the nitrogen content at the outlet of step a) is between 5 and 500 ppm, and preferably between 10 and 40 ppm by weight.

[0115] Preferably, the sulfur content at the outlet of step d) is less than 200 ppm by weight, and preferably less than 150 ppm by weight. Step a) can also make it possible to reduce the contaminant content, such as that of metals, in particular the silicon content. Preferably, the metal content at the outlet of step a) is less than 10 ppm by weight, and preferably less than 2 ppm by weight, and the silicon content is less than 5 ppm by weight.

[0116] Preferably, the halogen element content at the outlet of step a) is less than 2 ppm by weight.

[0117] Optional intermediate separation step

[0118] The process according to the invention can advantageously comprise a separation step between the hydrotreatment step and the hydrocracking step.

[0119] According to one or more preferred embodiments, the method according to the invention further comprises a separation step, which separates part, or all, of the hydrotreated effluent, to produce at least two cuts, including a heavy cut boiling mainly at a temperature greater than or equal to 370°C.

[0120] The other cut(s) are one or more light and intermediate cut(s). The light cut thus separated mainly contains gases (H2, HCl, H2S, NH3, and C1-C4), naphtha (or gasoline, cut which boils at a temperature below 150°C), kerosene (fraction which boils between 150°C and 280°C), and at least part of the diesel (fraction which boils between 280°C and 370°C). The light cut can then be sent at least partially to a fractionation unit where the light gases are extracted from said light cut, for example by passing through an expansion drum. This fractionation unit can be that of the fractionation step described below (in section separation step d).

[0121] The hydrogen gas thus recovered, which may have been sent to a purification and compression facility, can advantageously be recycled to the hydrotreatment stage a), to the hydrocracking stage b), and / or to a second hydrocracking stage if one is implemented. The recovered hydrogen gas can also be used in other facilities of the refinery.

[0122] This separation step is advantageously implemented when the pyrolysis oil from the feedstock is highly chlorine-laden. The most problematic impurities contained in pyrolysis oils are often halides, and more specifically chlorine. Indeed, chlorine is generally the limiting contaminant for treating pyrolysis oils in existing refinery units. Chlorine, even at low levels (e.g., <5 ppm by weight), is responsible for corrosion (in the form of HCl), which can occur in existing units whose metallurgy is generally not designed to withstand even low chlorine levels.Another problem related to the presence of halides in pyrolysis oils, and in particular chlorine, is the formation of ammonium chloride salts which are formed by reaction between chloride ions, released by hydrodechlorination in the form of HCl and ammonium ions, generated by the hydrogenation of nitrogen compounds (hydrodenitrogenation) in the form of NH3 during the hydrotreatment step. It is known that these ammonium chloride salts precipitate at a relatively low temperature (e.g. below 280°C) which creates clogging problems particularly in transfer lines and / or in sections of a process downstream of a hydrotreatment.

[0123] This separation step (hot) makes it possible in particular to eliminate halogens (chlorine) in the form of hydrogen halides (HCl in particular) formed by the reaction of hydrogen ions and halide ions released by the hydrogenation of halogenated compounds during the hydrotreatment step and to avoid the precipitation of ammonium chloride salt which is formed by reaction between chloride ions and ammonium ions and which can dissolve in an aqueous solution. The separation step thus makes it possible to recover a heavy cut boiling mainly at a temperature greater than or equal to 370°C for hydrocracking, freed from most of the impurities such as chlorine, but also from the H2S and NH3 formed during hydrotreatment.

[0124] Another advantage of the separation stage is the ability to extract naphtha, kerosene and at least part of the diesel (mainly from pyrolysis oil) before the hydrocracking stage and thus avoid overcracking in the naphtha and gas cuts, particularly when seeking to maximize the kerosene and diesel cuts.

[0125] The optional separation step is carried out in a separation section, which comprises any separation means known to a person skilled in the art. Said separation section may comprise one or more flash drums arranged in series, and / or one or more steam and / or hydrogen stripping columns, and / or an atmospheric distillation column, and / or a vacuum distillation column, and preferably consists of a single flash drum, commonly referred to as a "hot separator".

[0126] The optional separation step is generally carried out at high temperature and high pressure operating under a pressure between 8 and 25 MPa and at a temperature between 200 and 450°C, preferably between 250 and 350°C.

[0127] The separation section may also comprise means for washing at least one separated cut by contact with an aqueous solution, in particular the light cut containing mainly gases.

[0128] According to a preferred embodiment, the optional separation step comprises a hot separator operated at a temperature greater than or equal to 300°C, or even 350°C, so as to avoid the formation of ammonium chloride salts in the liquid phase. The gas phase of the hot separator or at least one of the phases resulting from the subsequent separation of the gas phase of the hot separator, is advantageously brought into contact with water or a basic aqueous solution (soda or amine solution(s) for example) in order to at least partially eliminate the hydrogen chloride (HCl) and / or to at least partially dissolve the ammonium chloride salts. The separation equipment or tanks may comprise at the bottom a zone allowing the separate decantation of a hydrocarbon fraction and an aqueous fraction comprising chloride salts, or even comprise a column for washing the gases by bringing them into contact with water or a basic solution.

[0129] In another embodiment, the process according to the invention does not include a separation step between the hydrotreatment step and the hydrocracking step.

[0130] Hydrocracking stage b)

[0131] According to the invention, the process comprises a hydrocracking step b) carried out in a hydrocracking reaction section, using at least one fixed bed reactor having n catalytic beds, n being an integer greater than or equal to 1, each comprising at least one hydrocracking catalyst, said hydrocracking reaction section being fed with at least a portion of said hydrotreated effluent from step a) and a gas stream comprising hydrogen, said hydrocracking reaction section being carried out at a temperature between 200 and 450°C, a pressure between 2.0 and 18.0 MPa abs. and an hourly volumetric flow rate between 0.1 and 12.0 h -1and to a quantity of hydrogen introduced such that the volume ratio liter of hydrogen / liter of hydrocarbon is between 100 and 3000 NL / L, to obtain a hydrocracked effluent.

[0132] Advantageously, the hydrocracking step b) implements the hydrocracking reactions well known to those skilled in the art, and more particularly makes it possible to convert heavy compounds, for example compounds having a boiling point above 370°C contained in the hydrotreated effluent from step a). Other reactions, such as the hydrogenation of olefins, aromatics, hydrodemetallation, hydrodesulfurization, hydrodenitrogenation, etc. can continue.

[0133] Preferably, the hydrocracking step according to the invention operates at a temperature of between 200 and 450°C, preferably between 250 and 450°C, very preferably between 300 and 430°C, under a pressure of between 2 and 18 MPa abs., preferably between 3 and 16 MPa abs., at an hourly volumetric flow rate of between 0.1 and 12.0 h -1 , preferably between 0.4 and 10 h -1 , very preferably between 0.8 and 3 h -1 and to a quantity of hydrogen introduced such that the volume ratio liter of hydrogen / liter of hydrocarbon is between 100 and 3000 NL / L, preferably between 300 and 1500 NL / L.

[0134] The definitions of mean temperature (WABT), WH and hydrogen coverage correspond to those described above.

[0135] These operating conditions used in the hydrocracking stage generally make it possible to achieve conversions per pass, into products having boiling points below 340°C, and better still below 370°C, of ​​greater than 15% by weight and even more preferably between 50 and 95% by weight relative to the feedstock introduced into the hydrocracking stage.

[0136] Depending on the product sought, the conversion rate can be adapted.

[0137] When it is desired to promote the production of a naphtha cut, the conversion rate is preferably greater than or equal to 80%, and preferably between 80 and 95% by weight. When it is desired to promote the production of a middle distillate cut, for example a kerosene cut or a diesel cut, the conversion rate is preferably less than 90% by weight, preferably between 50 and 85% by weight. Indeed, since the feedstock is a mixture of a heavy feedstock of fossil origin and a lighter feedstock of highly aromatic pyrolysis oil (therefore comprising compounds which have a boiling point in the middle distillate range), the conversion rate in the hydrocracking stage must be moderate in order to avoid overcracking and therefore the formation of compounds lighter than the middle distillate cut.

[0138] Advantageously, said step b) is carried out in a hydrocracking reaction section comprising at least one, preferably between one and five, fixed bed reactor(s) having n catalytic beds, n being an integer greater than or equal to one, preferably between one and ten, preferably between two and five, said bed(s) each comprising at least one, and preferably not more than ten, hydrocracking catalyst(s).

[0139] The hydrocracking reaction section using at least one fixed bed reactor can operate with a descending or ascending flow of gas and liquid.

[0140] The hydrotreatment step and the hydrocracking step can advantageously be carried out in the same reactor or in different reactors. In the case where they are carried out in the same reactor, the reactor comprises several catalytic beds, the first catalytic beds comprising the hydrotreatment catalyst(s) and the following catalytic beds comprising the hydrocracking catalyst(s).

[0141] The hydrocracking catalyst(s) used in the hydrocracking step are conventional hydrocracking catalysts known to those skilled in the art, of the bifunctional type combining an acid function with a hydro-dehydrogenating function and optionally at least one binding matrix. The acid function is provided by supports with a large surface area (150 to 1000 m 2 / g generally) with surface acidity, such as halogenated aluminas (chlorinated or fluorinated in particular), combinations of boron and aluminum oxides, amorphous silica-aluminas and zeolites, and preferably aluminas or silica-aluminas, alone or in a mixture. The hydro-dehydrogenating function is provided by at least one metal from group VIB of the periodic table and / or at least one metal from group VIII.

[0142] Preferably, said hydrocracking catalyst comprises a support chosen from halogenated aluminas, combinations of boron and aluminum oxides, amorphous silica-aluminas and zeolites and a hydro-dehydrogenating function comprising at least one metal from group VIB chosen from chromium, molybdenum and tungsten, alone or as a mixture, and preferably from molybdenum and tungsten, and / or at least one metal from group VIII chosen from iron, cobalt, nickel, ruthenium, rhodium, palladium and platinum, and preferably from cobalt and nickel. Hydro-dehydrogenating functions of the NiMo, NiMoW, NiW type are preferred.

[0143] Preferably, the content of group VIII metal in the hydrocracking catalyst(s) is advantageously between 0.5 and 15% by weight and preferably between 1 and 10% by weight, the percentages being expressed as a percentage by weight of oxides relative to the total weight of the catalyst (in NiO or CoO for example).

[0144] Preferably, the content of group VIB metal in the hydrocracking catalyst(s) is advantageously between 5 and 35% by weight, and preferably between 10 and 30% by weight, the percentages being expressed as a percentage by weight of oxides relative to the total weight of the catalyst (in M0O3 or WO3 for example).

[0145] The hydrocracking catalyst(s) may also optionally comprise at least one promoter element deposited on the catalyst and selected from the group formed by phosphorus, boron and silicon, optionally at least one element from group VI IA (chlorine, fluorine preferred), optionally at least one element from group VI IB (manganese preferred), and optionally at least one element from group VB (niobium preferred).

[0146] One type of conventional hydrocracking catalyst is based on moderately acidic amorphous oxides, such as silica-aluminas. These systems are used to produce good quality middle distillates and, eventually, oil bases. The disadvantage of these amorphous-supported catalysts is their low activity.

[0147] Catalysts containing, for example, Y zeolite, or catalysts containing, for example, Beta zeolite, have a catalytic activity higher than that of silica-aluminas, but generally have lower selectivities for middle distillates (jet fuels and diesels).

[0148] Preferably, the hydrocracking catalyst(s) also optionally comprise a zeolite chosen from Y zeolites, preferably from USY zeolites, alone or in combination, with other zeolites from beta zeolites, ZSM-12, IZM-2, ZSM-22, ZSM-23, SAPO-11, ZSM-48, ZBM-30, alone or as a mixture.

[0149] In the case where said catalyst comprises a zeolite, the zeolite content in the hydrocracking catalyst(s) is advantageously between 0.1 and 80% by weight, preferably between 3 and 70% by weight, the percentages being expressed as a percentage of zeolite relative to the total weight of the catalyst.

[0150] A preferred catalyst comprises, and preferably consists of, at least one Group VIB metal and optionally at least one non-noble Group VIII metal, at least one promoter element, and preferably phosphorus, at least one Y zeolite and at least one alumina binder.

[0151] An even more preferred catalyst comprises, and preferably consists of, nickel, molybdenum, phosphorus, a USY zeolite, and optionally also a beta zeolite, and alumina.

[0152] Another preferred catalyst comprises, and preferably consists of, nickel, tungsten, alumina and silica-alumina.

[0153] Another preferred catalyst comprises, and preferably consists of, nickel, tungsten, USY zeolite, alumina and silica-alumina.

[0154] Said hydrocracking catalyst is for example in the form of extrudates.

[0155] According to another aspect of the invention, the hydrocracking catalyst as described above further comprises one or more organic compounds containing oxygen and / or nitrogen and / or sulfur. Such a catalyst is often referred to as an "additive catalyst". Generally, the organic compound is chosen from a compound comprising one or more chemical functions chosen from a carboxylic function, alcohol, thiol, thioether, sulfone, sulfoxide, ether, aldehyde, ketone, ester, carbonate, amine, nitrile, imide, oxime, urea and amide or compounds including a furan cycle or sugars.

[0156] The preparation of the catalysts of steps a) and b) is known and generally comprises a step of impregnation of the metals of group VIII and group VIB when present, and possibly phosphorus and / or boron on the support, followed by drying, then possibly calcination. In the case of an additive catalyst, the preparation is generally carried out by simple drying without calcination after introduction of the organic compound. Here, calcination is understood to mean a heat treatment under a gas containing air or oxygen at a temperature greater than or equal to 200°C. Before their use in a step of the process, the catalysts are generally subjected to sulfurization in order to form the active species.

[0157] Advantageously, hydrocracking step b) allows the conversion of the remaining impurities in the hydrotreated effluent, such as aromatic compounds, metallic compounds, sulfur compounds, nitrogen compounds, oxygenated compounds.

[0158] Preferably, the nitrogen content at the outlet of step b) is less than 300 ppm, preferably less than 100 ppm by weight, and preferably less than 50 ppm by weight.

[0159] Separation step c)

[0160] According to the invention, the process comprises a separation step c), fed with at least a portion, preferably all of the hydrocracked effluent from step b), in a separation section, to produce at least one gaseous effluent comprising hydrogen and at least one liquid effluent.

[0161] The separation, or at least one of the separations when there are several, aims to separate a liquid effluent comprising hydrocarbons on the one hand, and a gaseous effluent comprising unreacted hydrogen on the other hand, so as to recover / continue the treatment of the hydrocarbons, and, if necessary, to be able to recycle the unreacted hydrogen. In this case, the gaseous effluent comprising the (unreacted) hydrogen may have to be treated in order to be recycled. This involves in particular a purification treatment, such as washing with amines.

[0162] The separation means may operate at high pressure and use separation means such as, for example, a series of high-pressure separator drums operating between 2 and 25 MPa.

[0163] Their goal is to produce:

[0164] - a hydrogen stream, which is preferably recycled via a compressor to at least one of steps a), b) (or to the second hydrocracking step if the process, in another variant, is of the two-step hydrocracking type), or to other installations of the refinery.

[0165] - and a liquid effluent produced in hydrocracking step b), which is preferably sent to a steam stripping step preferably operating at a pressure of between 0.5 and 2 MPa, to separate the hydrogen sulfide (H2S) dissolved in said liquid effluent.

[0166] Step c) thus allows the production of a liquid hydrocarbon effluent which can then be sent to the fractionation step d). This sequence of separator drums and a stripping column can be carried out according to the teaching of patent EP 3 184 607, which uses a hot separator drum at high pressure, a cold separator drum at high pressure, a compression zone, a hot separator drum at low pressure and a stripping column: reference should be made to the patent in question for further details.

[0167] The separation section may also comprise means for washing at least one separated section by contact with an aqueous solution.

[0168] According to a preferred embodiment, the separation step comprises a hot separator operated at a temperature greater than or equal to 300°C, or even 350°C, so as to avoid the formation of ammonium chloride salts in the liquid phase; the gas phase of the hot separator or at least one of the phases resulting from the subsequent separation of the gas phase of the hot separator, as well as at least a portion of the liquid phase of the hot separator or at least one of the phases resulting from the subsequent separation of the liquid phase of the hot separator, are advantageously brought into contact with water or a basic aqueous solution (soda solution, amine(s) solution for example) in order to eliminate at least part of the hydrogen chloride (HCl) and / or to dissolve at least part of the ammonium chloride salts.This alternative is particularly interesting when there has been no separation, possibly completed with washing, between the hydrotreatment stage a) and the first hydrocracking stage b). The separation equipment or tanks may include at the bottom a zone allowing the separate decantation of a hydrocarbon fraction and an aqueous fraction comprising chloride salts, or even include a column for washing the gases by bringing them into contact with water or a basic aqueous solution.

[0169] Step d) of splitting

[0170] According to the invention, the process comprises a fractionation step d), fed with at least part and preferably all of the liquid effluent from step c), in a fractionation section, to produce at least one naphtha cut, at least one middle distillate cut and at least one unconverted heavy liquid cut.

[0171] Fractionation step d) is carried out in at least one distillation column.

[0172] The distillation column operates at a pressure between 0.1 and 0.4 MPa absolute.

[0173] Step d) of fractionation by distillation makes it possible in particular to extract:

[0174] - possibly a gaseous fraction,

[0175] - at least one naphtha cut,

[0176] - at least one middle distillate cut, and

[0177] - an unconverted heavy liquid fraction, having a boiling point above 370°C, said fraction being withdrawn at the lower end of the column.

[0178] The term "naphtha cut" means a hydrocarbon cut comprising compounds having a boiling point generally less than or equal to 150°C, in particular between 80 and 150°C. The term "middle distillate cut" means a hydrocarbon cut comprising compounds having a boiling point generally between 150 and 370°C. The middle distillate cut generally comprises a kerosene cut having a boiling point between 150 and less than 250°C and / or a diesel cut having a boiling point between 250 and 370°C.

[0179] The term "unconverted heavy liquid fraction" means a hydrocarbon fraction comprising compounds with a boiling point above 370°C which presents the unconverted portion of the charge (also called UCO for Unconverted Oil in English terminology).

[0180] Depending on the destination or use of the cuts from the fractionation step, the person skilled in the art will adjust the cut points in the separation and / or distillation operations. For example, it may be necessary to adjust the end point of the naphtha cut to 125, 150, 175, 180 or 200°C.

[0181] The naphtha cut, the kerosene cut and / or the diesel cut can be sent to a fuel storage unit, for example a naphtha storage unit, a kerosene storage unit or a diesel storage unit, derived from conventional petroleum feedstocks.

[0182] The product obtained by the process, which can therefore be a naphtha cut, a middle distillate cut (kerosene cut and / or diesel cut) or even the unconverted heavy liquid cut, can include a biological carbon content according to ASTM D6866 of between 3 and 35% by weight.

[0183] According to a variant, at least a portion of the naphtha cut can be sent to an aromatic complex comprising at least one step of reforming the naphtha in order to produce aromatic compounds.

[0184] The high content of aromatic compounds in the pyrolysis oil is found after the hydrotreatment and hydrocracking stages in the products obtained, and thus makes it possible to obtain in particular a very aromatic naphtha cut. This naphtha cut has a high octane number (RON / MON high (RON = Research Octane Number and Motor Octane Number according to the Anglo-Saxon terminology) and a high content of naphthenes and paraffins and can therefore be sent to a catalytic reforming unit. The objective of catalytic reforming is to transform the naphthenic constituents (with a low octane number) into aromatic constituents with a high octane number serving as a base for the gasoline blend. According to another variant, at least a part of the naphtha cut can be sent to a steam cracking unit, at the end of which olefins can be (re)formed to participate in the formation of polymers.

[0185] According to a preferred variant, at least part and preferably all of the kerosene cut and / or the diesel cut are sent to a respective fuel pool.

[0186] As for the content of aromatic compounds in the middle distillate cut (kerosene cut or diesel cut), which is relatively high by the nature of the heavy fossil feedstock, it increases following the addition of pyrolysis oil to the feedstock. However, it remains below 25% volume, which is particularly important for the kerosene cut, which has a specification of 25% volume maximum.

[0187] The specifications for density, sulfur content, cetane number, and cloud point of a diesel cut are met. The same applies to the specifications for density, sulfur content, freezing point, and smoke point of a kerosene cut.

[0188] According to yet another variant, part of the kerosene and / or diesel cut can be sent to a steam cracking unit.

[0189] As for the unconverted heavy liquid fraction, it can be recycled at least in part in the hydrotreatment stage a) and / or in the hydrocracking stage b) and / or even in a second hydrocracking stage.

[0190] Second hydrocracking stage (optional)

[0191] The process according to the invention may further comprise a second hydrocracking step of at least a portion of the unconverted heavy cut and / or the middle distillate cut(s) from fractionation step d), in the presence of hydrogen and at least one hydrocracking catalyst, to obtain a second hydrocracked effluent. When it is desired to promote the production of a middle distillate cut, for example a kerosene cut or a diesel cut, the second hydrocracking step is fed with at least a portion of the unconverted heavy cut.

[0192] When it is desired to promote the production of a naphtha cut, the second hydrocracking stage is fed with at least part of the middle distillate cut and possibly with at least part of the unconverted heavy cut.

[0193] The second hydrocracking stage is carried out in a manner similar to that described for the first hydrocracking stage b). This applies in particular to the operating conditions, the equipment used, the porous supported hydroconversion catalysts used, and the conversion rate.

[0194] In this second hydrocracking stage, the operating conditions may be similar or different from those in the first hydrocracking stage.

[0195] The hydrocracking catalyst used in said second hydrocracking step may be the same as or different from that used in said first hydrocracking step b), and preferably different.

[0196] The second hydrocracked effluent is preferably sent at least in part to separation step c).

[0197] According to the invention, this second hydrocracking step is carried out in a hydrocracking reaction section, using at least one fixed-bed reactor having n catalytic beds, n being an integer greater than or equal to 1, each comprising at least one hydrocracking catalyst, said hydrocracking reaction section being fed with at least a portion of the unconverted heavy cut and / or the middle distillate cut from fractionation step d) and a gas stream comprising hydrogen, said hydrocracking reaction section being carried out at a temperature between 200 and 450°C, a pressure between 2.0 and 18.0 MPa abs. and an hourly volumetric flow rate between 0.1 and 12.0 h' 1 and to a quantity of hydrogen introduced such that the volume ratio liter of hydrogen / liter of hydrocarbon is between 100 and 3000 NL / L, to obtain a second hydrocracked effluent.

[0198] Preferably, the second hydrocracking stage according to the invention operates at a temperature of between 200 and 450°C, preferably between 250 and 450°C, very preferably between 300 and 430°C, under a pressure of between 2 and 18 MPa abs., preferably between 3 and 16 MPa abs., at an hourly volumetric flow rate of between 0.1 and 12.0 h' 1 , preferably between 0.4 and 10 h -1 , very preferably between 0.8 and 3 h -1 and to a quantity of hydrogen introduced such that the volume ratio liter of hydrogen / liter of hydrocarbon is between 100 and 3000 NL / L, preferably between 300 and 1500 NL / L.

[0199] Figure 1 represents the diagram of a particular embodiment of the method of the present invention, comprising:

[0200] - an optional pretreatment step (1) of the pyrolysis oil (2), for example by filtration and / or nitrogen stripping so as to obtain a pretreated oil (3);

[0201] - a step a) of hydrotreatment (4) of a feedstock comprising a minority fraction of the pretreated pyrolysis oil (3) and a heavy majority fraction of hydrocarbons of fossil origin (5), in the presence of a hydrogen-rich gas (6), carried out in at least one fixed-bed reactor comprising at least one hydrotreatment catalyst, to obtain a hydrotreated effluent (7);

[0202] - a step b) of hydrocracking (8) at least part of the hydrotreated effluent (7) from step a), in the presence of hydrogen (9) carried out in at least one fixed-bed reactor comprising at least one hydrocracking catalyst, to obtain a hydrocracked effluent (10);

[0203] - a step c) of separation (11) of the hydrocracked effluent (10) optionally carried out in the presence of an aqueous washing solution (12) and making it possible to obtain at least one gaseous effluent comprising hydrogen (13), at least one liquid effluent (14) and optionally an aqueous effluent (15) containing dissolved salts.

[0204] - a fractionation step (16) of the liquid effluent (14) making it possible to obtain at least a naphtha cut (17), a kerosene cut (18), a diesel cut (19) and an unconverted heavy liquid cut having a boiling point above 370°C (20).

[0205] Optionally, the unconverted heavy liquid cut having a boiling point above 370°C (20) can be recycled in the hydrotreatment step a) and / or in the hydrocracking step b) (not shown). Optionally, the unconverted heavy liquid cut having a boiling point above 370°C (20) can be sent to a second hydrocracking step (21) which is carried out in at least one fixed-bed reactor comprising at least one hydrocracking catalyst and is supplied with hydrogen (22). The second hydrocracked effluent (23) is sent to the separation step c) (11).

[0206] Only the main steps, with the main flows, are shown in Figure 1, in order to allow a better understanding of the invention. It is understood that all the equipment necessary for operation is present (balloons, pumps, exchangers, furnaces, columns, etc.), even if not shown. It is also understood that hydrogen-rich gas flows (make-up or recycle), as described above, can be injected at the inlet of each reactor or catalytic bed or between two reactors or two catalytic beds. Means well known to those skilled in the art for purifying and recycling hydrogen can also be implemented.

[0207] Examples

[0208] The examples below aim to show certain performances of the method according to the invention.

[0209] These examples illustrate the possibility of co-processing tire pyrolysis oil in a process for producing middle distillates and naphtha comprising a hydrotreatment step and a hydrocracking step. The ability of the catalysts present in the hydrotreatment and hydrocracking steps to capture impurities present in the pyrolysis oil and thus obtain products meeting specifications is also demonstrated.

[0210] Example 1 is a comparative example illustrating the performance of a process comprising a hydrotreatment step and a hydrocracking step for a reference feedstock (vacuum distillate) without tire pyrolysis oil.

[0211] Example 2 illustrates the performance of a process according to the invention comprising a hydrotreatment step and a hydrocracking step with a feed comprising a fraction of tire pyrolysis oil and a fraction of the reference feed (vacuum distillate) used in Example 1. The mixture was used during a pre-step of homogenization of the medium (optional step). Feed:

[0212] Fraction (I) of the feedstock is a vacuum distillate called straight-run (VGO-SR) coming directly from the distillation of a crude oil. The tire pyrolysis oil fraction (II) of the feedstock is a pyrolysis oil from a tire mixture and containing a significant level of impurities.

[0213] The main characteristics of these two fractions of the load are presented in Table 1 below.

[0214] The analysis methods and / or standards used to determine the characteristics of the various flows, in particular the load to be treated and the effluents produced, are known to those skilled in the art. They are listed below for information purposes. Other methods deemed equivalent may also be used, in particular equivalent IP, EN or ISO methods.

[0215] Table 1 Operating conditions:

[0216] The feedstock is injected into a preheating stage and then into a first hydrotreatment reactor whose operating conditions are summarized in Table 2 below. Table 2

[0217] (*) NC: Not Concerned

[0218] The feedstock is hydrotreated with a NiMo on alumina hydrotreatment catalyst, under operating conditions allowing a nitrogen content of 16 ppm to be obtained in the hydrotreated feedstock, i.e., at the inlet of the hydrocracking catalytic beds.

[0219] All of the hydrotreated effluent from the hydrotreatment section is then sent directly to the hydrocracking section without any intermediate separation step. The temperatures of the hydrocracking catalysts are controlled to achieve a total conversion of the 370°C+ cut of 69% by weight.

[0220] The operating conditions of the hydrocracking stage are summarized in Table 3 below.

[0221] Table 3

[0222] (*) NC: Not Concerned

[0223] Results and overall performance: The yields obtained following the sequence of hydrotreatment and hydrocracking stages, expressed as a mass percentage relative to the fresh feedstock, are presented in Table 4.

[0224] Table 4

[0225] At 69% iso-conversion, the feedstock consisting of a mixture of 90% VGO volume + 10% tire pyrolysis oil volume leads to a yield gain of 1% by weight on the kerosene cut and 1.1% by weight on the diesel cut compared to the test with 100% VGO volume. A smaller gain is also obtained on the naphtha cut (+0.2% by weight). Thanks to the presence of compounds of biological origin in the tire pyrolysis oil, the co-treatment of a mixture of 90% VGO volume with 10% tire pyrolysis oil volume allows the incorporation of part of the biological compounds into the products (Table 5). Table 5

[0226] The properties of the naphtha cut (C5-150°C) are detailed in Table 6.

[0227] Table 6 The properties of the naphtha obtained from the 90% VGO volume + 10% tire pyrolysis oil volume mixture are better with an N+2A index (naphthene content + 2 times aromatic content in % weight) of 55.2 compared to 53.6 for the naphtha obtained from a 100% VGO feedstock, this being mainly linked to a higher aromatic content of 4.4% weight compared to 3.5% weight. This cut can be sent to the catalytic reforming unit to transform the naphthenic constituents (with a low octane number) into high octane aromatic constituents to be added to the gasoline mixture or to supply the petrochemical industry with aromatic hydrocarbons.

[0228] The properties of the heavy naphtha cut (80-150°C) are detailed in Table 7. Table 7

[0229] The heavy naphtha fraction (80-150°C) has an even higher N+2A index, reaching a value of 73.6 for the feedstock consisting of the mixture 90% volume VGO + 10% volume tire pyrolysis oil compared to 69.0 for the feedstock consisting of 100% volume VGO. This fraction of the heavier naphtha, richer in naphthenic molecules, constitutes a very good feedstock for the catalytic reforming unit.

[0230] The properties of the kerosene cut (150 - 250°C) are detailed in Table 8.

[0231] Table 8 The kerosene produced from the feedstock consisting of the mixture 90% volume VGO + 10% volume tire pyrolysis oil meets the specifications of JET A1 in terms of density, sulfur content, aromatics and naphthalenes content and properties such as freezing point and smoke point.

[0232] The properties of the diesel cut (250 - 370°C) are detailed in Table 9.

[0233] Table 9 The diesel produced with the charge consisting of the mixture 90% volume VGO + 10% volume tire pyrolysis oil meets the specifications in terms of sulfur content, density, cetane index, cloud point and filterability temperature.

Claims

Claims 1. Process for producing middle distillates and naphtha from a feedstock comprising a heavy fraction of hydrocarbons of fossil origin of which at least 50% by weight of the compounds have an initial boiling point above 300°C and a final boiling point below 700°C, and a fraction of pyrolysis oil from plastic and / or tires and / or solid recovered fuels having an aromatic compound content above 30% by weight relative to the weight of the pyrolysis oil, said pyrolysis oil fraction constituting less than 50% by weight of said feedstock, said process comprising: a) a hydrotreatment step carried out in a hydrotreatment reaction section, using at least one fixed bed reactor having n catalytic beds, n being an integer greater than or equal to 1, each comprising at least one hydrotreatment catalyst,said hydrotreatment reaction section being fed at least by said feedstock and a gas stream comprising hydrogen, said hydrotreatment reaction section being operated at a temperature between 200 and 450°C, a pressure between 2.0 and 18.0 MPa abs. and an hourly volumetric flow rate between 0.1 and 6.0 h, -1and to a quantity of hydrogen introduced such that the volume ratio liter of hydrogen / liter of hydrocarbon is between 100 and 3000 NL / L, to obtain a hydrotreated effluent; b) a hydrocracking step carried out in a hydrocracking reaction section, using at least one fixed-bed reactor having n catalytic beds, n being an integer greater than or equal to 1, each comprising at least one hydrocracking catalyst, said hydrocracking reaction section being fed with at least a portion of said hydrotreated effluent from step a) and a gas stream comprising hydrogen, said hydrocracking reaction section being carried out at a temperature between 200 and 450°C, a pressure between 2.0 and 18.0 MPa abs. and an hourly volumetric flow rate between 0.1 and 12.0 h' 1and to a quantity of hydrogen introduced such that the volume ratio liter of hydrogen / liter of hydrocarbon is between 100 and 3000 NL / L, to obtain a hydrocracked effluent; c) a separation step, fed with at least part of the hydrocracked effluent from step b), in a separation section, to produce at least one gaseous effluent comprising hydrogen, at least one liquid effluent; d) a fractionation stage, fed with at least part of the liquid effluent from stage c), in a fractionation section, to produce at least one naphtha cut, at least one middle distillate cut and at least one unconverted heavy liquid cut.

2. Method according to claim 1, in which the pyrolysis oil fraction constitutes between 1% and 45% by weight of said feedstock.

3. A process according to any one of the preceding claims, wherein the feedstock consists of said pyrolysis oil fraction and said heavy hydrocarbon fraction of fossil origin, said pyrolysis oil fraction constituting between 1% and 45% by weight of said feedstock and the heavy hydrocarbon fraction constituting between 55% and 99% by weight of said feedstock.

4. A method according to any one of the preceding claims, wherein the pyrolysis oil fraction has a paraffin content of less than 30% by weight.

5. Process according to any one of the preceding claims, in which the heavy fraction of hydrocarbons of fossil origin is chosen from a vacuum distillate resulting from the direct distillation of crude oil or resulting from hydrotreatment, hydroconversion or hydrocracking processes of atmospheric or vacuum residues operating in a fixed bed, moving bed, ebullating bed or entrained bed; or a fraction resulting from conversion units such as a fluid catalytic cracking process; or a fraction resulting from a coking process; or a fraction resulting from a visbreaking process; or a fraction resulting from units for extracting aromatics from lubricating oil bases; or a fraction resulting from solvent dewaxing of lubricating oil bases; or else be a deasphalted oil resulting from solvent deasphalting of residues; or else any mixture of the previously mentioned feedstocks.

6. Process according to claim 5, in which the heavy fraction of hydrocarbons of fossil origin is a vacuum distillate.

7. Method according to any one of the preceding claims, in which the pyrolysis oil is chosen from a pyrolysis oil derived from polyethylene terephthalate, polystyrene and / or polyvinyl chloride, and / or a pyrolysis oil derived from tires.

8. A method according to any preceding claim, wherein the pyrolysis oil comprises a biocarbon content according to ASTM D6866 of between 20-70% by weight.

9. Process according to any one of the preceding claims, in which said feed comprising said heavy fraction of hydrocarbons of fossil origin and said fraction of pyrolysis oil or the pyrolysis oil alone or the heavy feed of hydrocarbons of fossil origin alone is / are subjected to a pretreatment step, said pretreatment step being carried out upstream of step a) and comprises an adsorption step and / or a filtration step and / or a centrifugation step and / or a decantation step and / or an electrostatic separation step and / or a step of washing using an aqueous solution and / or a gas stripping step.

10. Method according to any one of the preceding claims, in which a filter tray is integrated at the inlet of step a) upstream of the first catalytic bed.

11. Process according to any one of the preceding claims, which comprises a separation step in a separation section between the hydrotreatment step a) and the hydrocracking step b) separating part, or all, of the hydrotreated effluent, to produce at least two cuts, including a heavy cut boiling mainly at a temperature greater than or equal to 370°C.

12. Process according to any one of the preceding claims, in which the separation section of step c) and / or the separation section between the hydrotreatment step a) and the hydrocracking step b) comprises means for washing at least one cut separated by contact with an aqueous solution.

13. Process according to any one of the preceding claims, in which the conversion rate in the hydrocracking step b) is between 50 and 95% by weight.

14. Process according to one of the preceding claims, which further comprises a second hydrocracking step is carried out in a hydrocracking reaction section, using at least one fixed bed reactor having n catalytic beds, n being an integer greater than or equal to 1, each comprising at least one hydrocracking catalyst, said hydrocracking reaction section being fed with at least a portion of the unconverted heavy cut and / or the middle distillate cut from fractionation step d) and a gas stream comprising hydrogen, said hydrocracking reaction section being carried out at a temperature between 200 and 450°C, a pressure between 2.0 and 18.0 MPa abs. and an hourly volumetric flow rate between 0.1 and 12.0 h' 1and to a quantity of hydrogen introduced such that the volume ratio liter of hydrogen / liter of hydrocarbon is between 100 and 3000 NL / L, to obtain a second hydrocracked effluent.

15. Product obtained by the process according to one of claims 1 to 14.

16. Product according to claim 15 comprising a biological carbon content according to ASTM D6866 of between 3 and 35% by weight.

Images