PROCESS FOR TREATMENT OF PYROLYTIC OILS FOR VALORIZATION IN A CATALYTIC CRACKING UNIT OR HYDRO-REFINING UNITS

Abstract

A process for treating a feedstock comprising a pyrolysis oil from plastics and / or tires and / or solid recovered fuels containing halogenated compounds, comprising: a) a hydrotreating step to obtain a partially hydrotreated effluent having a reduced halogenated compound content, b) a separation step, fed by the hydrotreated effluent from step a) and an aqueous solution to obtain a gaseous effluent, an aqueous effluent and a partially hydrotreated hydrocarbon effluent, c) a fluidized bed catalytic cracking or hydrorefining step of a petroleum feedstock and / or a feedstock from biomass conversion in which the partially hydrotreated hydrocarbon effluent is introduced as a co-feedstock without undergoing another hydrotreating step carried out beforehand at higher temperature and / or pressure,the mixture of petroleum feedstock and / or biomass and partially hydrotreated hydrocarbon effluent having a halogenated compound content less than or equal to 10 ppm by weight.

Description

Title of the invention: METHOD FOR TREATMENT OF PYROLYZED OILS FOR VALORIZATION IN A CATALYTIC CRACKING UNIT OR HYDRO-REFINING UNITS technical field

[0001] The present invention relates to a process for treating pyrolysis oil from plastics and / or tires and / or solid recovered fuels (SRF) to obtain a partially hydrotreated pyrolysis oil that can be used as a co-feed with petroleum feedstocks and / or feedstocks from biomass conversion in a refinery unit such as a fluidized bed catalytic cracking unit or hydrogen-based hydrorefining units such as a hydrotreating, hydrocracking, or hydroconversion unit. More particularly, the present invention relates to a process for treating pyrolysis oil to remove its halogenated compounds so that this oil can be easily used in existing refinery units. Previous technique

[0002] Plastic waste is generally a mixture of several polymers, for example, mixtures of polyethylene, polypropylene, polyethylene terephthalate, polyvinyl chloride, and polystyrene. Furthermore, depending on their use, plastics may contain, in addition to polymers, other compounds such as plasticizers, pigments, dyes, or residues of polymerization catalysts. Plastic waste may also contain, in smaller quantities, biomass originating, for example, from household waste. Waste treatment, on the one hand, including storage, mechanical processing, sorting, pyrolysis, and also the storage and transport of pyrolysis oil, on the other hand, can also induce corrosion.

[0003] As for tires, they are mainly made of rubbers for their elastic properties (mixture of elastomers of the natural and synthetic cross-linked rubber type, with added additives of the silica type, resin, sulfur, zinc oxide, carbon black, etc.) and textile and metallic fibers for their reinforcing properties.

[0004] Solid recovered fuels (SRF), also called "refuse derived fuel" (RDF), or "solid recovered fuels" (SRF) according to Anglo-Saxon terminology, are non-hazardous solid wastes prepared for energy recovery, Whether they originate from household and similar waste, waste from economic activities, or construction and demolition waste, RDF (Refuse-Derived Fuel) is 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., used vehicles, WEEE), household and commercial waste, and residues from the recycling of various types of waste, including certain municipal waste, plastics, textiles, and wood, among others. RDF generally contains plastic waste.

[0005] Plastics from collection and sorting streams, recycled tires, or RDF can undergo a pyrolysis step to obtain, among other things, pyrolysis oils. These oils generally contain many impurities, in particular halogenated compounds, especially chlorine-based compounds, but also diolefins, olefins, metals, especially iron and silicon, heteroelements such as sulfur, oxygen, and nitrogen, and insolubles.

[0006] These pyrolysis oils from plastics and / or tires and / or RDF are generally burned to generate electricity and / or used as fuel in industrial or district heating boilers.

[0007] Another way to valorize pyrolysis oils is by using them as feedstock in a steam cracking unit to (re)create olefins, which are monomers that make up certain polymers. However, pyrolysis oils from plastics and / or tires often contain high levels of impurities that are incompatible with steam cracking units or downstream units, particularly polymerization and selective hydrogenation processes.

[0008] One way to remove these impurities contained in pyrolysis oils is to perform hydrotreating in the presence of catalysts. Steam cracking units require very high feedstock purities, particularly low levels of chlorine, diolefins, olefins, metals, and sulfur. Hydrotreating upstream of steam cracking is therefore often carried out in several stages and under fairly demanding conditions, particularly in terms of temperature and pressure, in order to achieve the required specifications. Such processes are described, for example, in WO2016 / 142808, WO2016 / 142809, WO2018 / 055555, WO2021 / 110395, or WO2021 / 165178.

[0009] Another way to valorize pyrolysis oils from plastics and / or tires is to use these pyrolysis oils as a feedstock in fluidized bed catalytic cracking (FCC) units to produce essentially gasoline. Such processes are by examples described in US10442997, WO2021 / 133893, WO2021 / 133889, WO2021 / 133895 and WO2021 / 201932.

[0010] Although the specification requirements are different and often less stringent in terms of purity for an FCC feedstock, the upstream hydrotreatments performed to remove the impurities described in the prior art are generally also carried out under fairly advanced conditions. Document WO2021 / 201932, for example, describes a pretreatment of FCC by hydrotreatment at a temperature between 349-415°C (660-780°F) and a pressure between 6.8 and 13.8 MPa (68-138 bar, 1000-2000 psi).

[0011] The present invention proposes a gentle hydrotreating process for a pyrolysis oil from plastics and / or tires and / or RDF, allowing in particular the reduction of its content of halogenated compounds, and in particular of chlorine, in order to obtain a pyrolysis oil free of most of the halogenated compounds and which can then be sent as a co-feed with petroleum feedstocks and / or feedstocks from biomass conversion in a refinery unit such as an FCC unit or a hydrorefining unit using hydrogen such as a hydrocracking, hydrotreating or hydroconversion unit.

[0012] Chlorine is generally the limiting contaminant for treating pyrolysis oils in existing refinery units. Indeed, chlorine, even at low concentrations (< 10 ppm wt., or even < 5 ppm wt.), is responsible for corrosion (in the form of HCl) which can occur in existing units whose metallurgy is generally not designed to withstand chlorine levels exceeding 10 ppm wt., or even 5 ppm wt. in the feedstock.

[0013] Unlike the hydrotreating processes described in the prior art, the process according to the invention aims at gentle hydrotreating, particularly at low pressure and moderate temperatures. The gentle operating conditions in the hydrotreating, combined with a separation step involving washing, make it possible to largely eliminate halogenated compounds while preserving as much as possible the diolefins and olefins, which can, for example, be recovered in FCC (for the production of propylene).

[0014] The process according to the invention is primarily focused on the removal of halogenated compounds to make the pyrolysis oil compatible as a feedstock in downstream units. The process according to the invention does not necessarily involve complete hydrotreating of the oil. Other impurities contained in pyrolysis oils (metals, silicon, nitrogen, etc.) are not necessarily completely removed during the process according to the invention, although the operating conditions allow for the removal of at least some of them. These impurities will eventually be converted or removed in the downstream units, the residual impurity levels being compatible with these units. units.

[0015] The "mild" hydrotreatment of the present invention is a hydrotreatment carried out under carefully chosen pressure, temperature, and hourly volumetric velocity conditions, generally more moderate than those of conventional hydrotreatments known in the prior art, aimed at removing all impurities. The hydrotreatment of the present invention makes it possible, in particular, to largely eliminate halogenated compounds while preserving as much as possible the diolefins and olefins.

[0016] The objective of the present invention is to provide a low-cost, easy-to-implement process for treating pyrolysis oils from plastics and / or tires, which can be readily integrated into existing refinery units. The use of mild operating conditions minimizes hydrogen consumption, thereby reducing the cost of this purification as well as operating and investment costs, while also minimizing chlorine content.

[0017] Furthermore, the process according to the invention can be carried out in a unit dedicated to pyrolysis oils, and therefore in a low-capacity unit making it possible to obtain a partially hydrotreated pyrolysis oil with a halogenated compound content sufficiently low to be sent directly for co-processing in an existing refinery unit. Existing units do not need to be modified.

[0018] The unit of the process according to the invention is easily integrable into refining units and can also use, thanks to the low pressure required, hydrogen supply units already existing in the refinery. Summary of the invention

[0019] More specifically, the invention relates to a process for treating a so-called pyrolysis feedstock, comprising a pyrolysis oil of plastics and / or tires and / or solid recovered fuels comprising halogenated compounds, said process comprising:

[0020] a) a hydrotreating step carried out in a hydrotreating reaction section comprising at least one hydrotreating catalyst, said hydrotreating reaction section being fed at least by the pyrolysis feed and a gas stream comprising hydrogen, said hydrotreating reaction section being carried out at an average temperature between 100 and 220°C, a partial pressure of hydrogen between 1.0 and 3.0 MPa abs. and an hourly volumetric velocity between 0.05 and 5 h1, the hydrogen coverage being between 5 and 50 Nm3 of hydrogen per m3 of pyrolysis feed, to obtain a partially hydrotreated effluent having hydrocarbon compounds with a reduced halogen content,

[0021] b) a separation step, fed by the partially hydrotreated effluent from step a) and an aqueous solution to obtain at least one gaseous effluent, one aqueous effluent and one partially hydrotreated hydrocarbon effluent,

[0022] c) a fluidized bed catalytic cracking or hydrorefining step of a petroleum feedstock and / or a feedstock from biomass conversion in which at least a portion of the partially hydrotreated hydrocarbon effluent from step b) is introduced as a co-feedstock, said partially hydrotreated hydrocarbon effluent from step b) being introduced without prior hydrotreating at a higher temperature and / or pressure than the temperature and / or pressure of step a), said mixture of said petroleum feedstock and / or said feedstock from biomass conversion and the partially hydrotreated hydrocarbon effluent from step b) having a halogen content of less than or equal to 10 ppm by weight.

[0023] According to one variant, the mass ratio between the flow rate of the partially hydrotreated hydrocarbon effluent from step b) and the flow rate of petroleum feed and / or feed from biomass conversion introduced in step c) is less than 1.

[0024] According to one variant, the pyrolysis charge consists of a pyrolysis oil of plastics and / or tires and / or solid recovered fuels.

[0025] According to one variant, the content of halogenated compounds of said pyrolysis charge is between 1 and 5000 ppm by weight.

[0026] According to one variant, said hydrotreating catalyst of step a) comprises a support selected from alumina, silica, silica-aluminas, magnesia, clays and mixtures thereof and a hydro-dehydrogenating function comprising either at least one element of group VIII and at least one element of group VIB, or at least one element of group VIII.

[0027] According to one variant, said process includes at least one step aO) of pretreatment of the pyrolysis feed comprising a pyrolysis oil of plastics and / or tires and / or RDF, said pretreatment step being carried out upstream of step a) and includes 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.

[0028] According to one variant, the petroleum feedstock is chosen from gasoline, gas oils, vacuum gas oils, atmospheric residues, vacuum residues, atmospheric distillates, vacuum distillates, heavy fuel oils, oils, waxes and paraffins, used oils, residues or deasphalted crudes, petroleum feedstocks from thermal or catalytic conversion processes, or mixtures of such feedstocks.

[0029] According to one variant, the feed from biomass is chosen from oils vegetable oils, algae or algal oils, fish oils, used food oils, and fats of vegetable or animal origin; methyl esters of fatty acids of vegetable and / or animal origin, methyl esters of fatty acids from used vegetable food oils, feedstocks from thermal or catalytic biomass conversion processes, or mixtures of such feedstocks.

[0030] According to one variant, the reaction section of step a) implements at least two reactors operating in switchable mode.

[0031] According to one variant, step c) of catalytic cracking in a fluidized bed is carried out in a reaction section of catalytic cracking in a fluidized bed in a substantially vertical reactor either in ascending or descending mode in the presence of a zeolite catalyst at a reactor temperature between 450°C and 600°C with a contact time in the reactor of less than 1 minute.

[0032] According to one variant, the hydrorefining step c) is a hydrotreating step carried out in a hydrotreating reaction section comprising at least one hydrotreating catalyst, said hydrotreating reaction section being fed by a gas stream comprising hydrogen, said hydrotreating reaction section being carried out at an average temperature between 180 and 480°C, a partial pressure of hydrogen between 0.5 and 25 MPa abs., an hourly volumetric velocity between 0.1 and 20 h1, and a hydrogen cover of between 50 and 5000 Nm3 of hydrogen per m3 of feed.

[0033] According to one variant, the hydrorefining step c) is a hydrocracking step carried out in a hydrocracking reaction section comprising at least one hydrocracking catalyst, said hydrocracking reaction section being supplied with a gaseous stream comprising hydrogen, said hydrocracking reaction section being carried out at an average temperature between 250 and 480°C, a partial pressure of hydrogen between 2 and 25 MPa abs., an hourly volumetric velocity between 0.5 and 40 h1, and a hydrogen cover of between 80 and 5000 Nm3 of hydrogen per m3 of feed.

[0034] According to one variant, the hydrorefining step c) is a hydroconversion step carried out in a hydroconversion reaction section comprising at least one hydroconversion catalyst, said hydroconversion reaction section being fed by a gaseous stream comprising hydrogen, said hydroconversion reaction section being carried out at an average temperature between 340 and 550°C, a partial pressure of hydrogen between 2 and 38 MPa abs., an hourly volumetric velocity between 0.05 and 10 h1, and a hydrogen cover of between 50 and 5000 Nm3 of hydrogen per m3 of feed.

[0035] In the following text, "pyrolysis oil" means an oil obtained from the pyrolysis of plastics and / or tires and / or RDF, unless otherwise indicated.

[0036] According to the present invention, the pressures are absolute pressures, also noted as abs., and are given in absolute MPa (or abs. MPa), unless otherwise indicated.

[0037] According to the present invention, 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.

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

[0039] In the following, particular and / or preferred embodiments of the invention may be described. They may be implemented separately or in combination with each other, without limitation of combination where technically feasible.

[0040] In the following, 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 IUP AC classification.

[0041] The metal content is measured by X-ray fluorescence. DETAILED DESCRIPTION The pyrolysis charge

[0042] According to the invention, a "plastic pyrolysis oil or tire pyrolysis oil or RDF pyrolysis oil" is an oil, advantageously in liquid form at room temperature, obtained from the pyrolysis of plastics, preferably plastic waste originating in particular from collection and sorting channels, or from the pyrolysis of used tires or from the pyrolysis of RDF. It comprises, in particular, a mixture of hydrocarbon compounds, notably paraffins, olefins (mono- and / or diolefins), naphthenes, and aromatics. At least 80% by weight of these hydrocarbon compounds preferably have a boiling point below 700°C, and more preferably below 550°C.In particular, depending on the origin of the pyrolysis oil, it may comprise up to 70% by weight in paraffins, up to 90% by weight in naphthenes, up to 90% by weight in olefins and up to 90% by weight in aromatics, it being understood that the sum of the paraffins, naphthenes, olefins and aromatics is equal to 100% by weight of the hydrocarbon compounds.

[0043] The pyrolysis oil may contain diolefins. The diolefin content is com The maleic anhydride value (MAV) is commonly determined indirectly. The method is based on the Diels-Alder addition reaction between conjugated diolefins and maleic anhydride. The method for determining the MAV is described in C. López-Garcia et al., "Near Infrared Monitoring of Low Conjugated Diolefins Content in Hydrotreated FCC Gasoline Streams," Oil & Gas Science and Technology - Rev. IFP, Vol. 62 (2007), No. 1, pp. 57-68. The MAV is expressed as mg of maleic anhydride that reacted with 1 g of sample (mg / g). The MAV varies between 5 and 100 mg / g in pyrolysis oils.

[0044] The density of the pyrolysis oil, measured at 15°C according to the ASTM D4052 method, is generally between 0.75 g / cm3 and 0.99 g / cm3, preferably between 0.75 g / cm3 and 0.95 g / cm3.

[0045] Pyrolysis oil may include, and most often does include, in addition to impurities such as metals, in particular iron, silicon, and halogenated compounds, in particular chlorinated compounds. These impurities may be present in the pyrolysis oil at high levels, for example up to 500 ppm by weight or even 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, iodine or astatine) supplied 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 even 700 ppm by weight or even 1000 ppm by weight and even 5000 ppm by weight of chlorine element supplied by chlorinated 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 chlorine element.

[0046] The oil may comprise up to 200 ppm by weight, or even 1500 ppm by weight, of elements Metallic or semi-metallic elements, typically containing between 1 and 200 ppm by weight or between 1 and 1500 ppm by weight of metallic or semi-metallic elements. Alkali metals, alkaline earth metals, transition metals, post-transition metals, and metalloids can be considered contaminants of a metallic nature, referred to as metallic or semi-metallic metals or elements. Specifically, metallic or semi-metallic metals or elements include silicon, iron, or both. Pyrolysis oil may contain up to 200 ppm by weight or even 1000 ppm by weight of silicon, typically containing between 1 and 200 ppm by weight or between 1 and 1000 ppm by weight or between 1 and 500 ppm by weight of silicon. Pyrolysis oil may also contain up to 50 ppm by weight or even 100 ppm by weight of iron, typically containing between 1 and 50 ppm by weight or between 1 and 100 ppm by weight of iron.Pyrolysis oil may also contain phosphorus, sodium, calcium, potassium, and magnesium.

[0047] The pyrolysis oil may also include other impurities such as hetero-elements supplied in particular by sulfur compounds, oxygenated compounds and / or nitrogenous compounds, at levels generally less than 40000 ppm weight of hetero-elements and preferably less than 15500 ppm weight of hetero-elements, and generally between 1 and 40000 ppm weight or between 1 and 15500 ppm weight of hetero-elements.

[0048] Sulphur compounds are generally present in a content of less than 15000 ppm by weight and preferably less than 10000 ppm by weight, and generally between 1 and 15000 ppm by weight or between 1 and 10000 ppm by weight of sulphur compounds.

[0049] Oxygenated compounds are generally present in a content of less than 15000 ppm by weight and preferably less than 10000 ppm by weight, and generally between 1 and 15000 ppm by weight or between 1 and 10000 ppm by weight of oxygenated compounds.

[0050] Nitrogen compounds are generally present in a content of less than 10000 ppm by weight and preferably less than 5000 ppm by weight, and generally between 1 and 10000 ppm by weight or between 1 and 5000 ppm by weight of nitrogen compounds.

[0051] The levels of sulfur, oxygen, and / or nitrogen compounds often depend on the origin of the oil. Thus, pyrolysis oils from tires generally contain more heteroatoms than pyrolysis oils from plastics, particularly sulfur compounds.

[0052] Pyrolysis oil may also include other impurities such as heavy metals like mercury, arsenic, zinc and lead, for example up to 100 ppb by weight or 200 ppb by weight of mercury or arsenic, and generally between 1 and 200 ppb by weight or between 1 and 100 ppb by weight of heavy metals.

[0053] The pyrolysis feed of the process according to the invention comprises at least one pyrolysis oil of plastics and / or tires and / or RDF. Said feed may consist solely of pyrolysis oil(s). Preferably, said feed comprises at least 50% by weight, preferably between 70% and 100% by weight, of pyrolysis oil relative to the total weight of the feed, i.e., preferably between 50% and 100% by weight, preferably between 70% and 100% by weight of plastic pyrolysis oil.

[0054] In a particularly preferred manner, the pyrolysis charge of the process according to the invention consists solely of pyrolysis oil(s) from plastics and / or tires and / or RDF.

[0055] In the case of a mixture of a plastics pyrolysis oil, a tire pyrolysis oil and / or a CSR pyrolysis oil, this mixture can be made in any proportion.

[0056] According to another embodiment, the pyrolysis feed of the process according to the invention introduced in step a) may comprise, in addition to the pyrolysis oil or oils, a conventional petroleum feed or a feed resulting from the conversion of biomass which is then co-treated with the pyrolysis oil from the feedstock.

[0057] The conventional petroleum feed introduced in step a) may advantageously be a cut or a mixture of cuts of the naphtha or diesel type.

[0058] The feedstock resulting from the conversion of the biomass introduced in step a) may advantageously be selected from vegetable oils, algae or algal oils, fish oils, used cooking oils, and fats of vegetable or animal origin; or mixtures of such feedstocks. Said vegetable oils may advantageously be crude or refined, wholly or partially, and derived from plants selected from rapeseed, sunflower, soybean, palm, olive, coconut, copra, castor, cottonseed, peanut, linseed, and crambe oils, and all oils derived, for example, from sunflower or rapeseed by genetic modification or hybridization, this list not being exhaustive. Said animal fats are advantageously selected from lard and fats composed of residues from the food industry or from the catering industry.Frying oils, various animal oils such as fish oil, tallow, and lard can also be used. The feedstock from biomass conversion can also advantageously be chosen from among methyl esters of fatty acids of vegetable and / or animal origin, or from methyl esters of fatty acids from used edible vegetable oils.

[0059] The feedstock resulting from biomass conversion can also be selected from feedstocks obtained from thermal or catalytic biomass conversion processes, such as oils produced from biomass, particularly lignocellulosic biomass, using various liquefaction methods, such as hydrothermal liquefaction or pyrolysis. The term "biomass" refers to material derived from recently living organisms, including plants, animals, and their by-products. The term "lignocellulosic biomass" refers to biomass derived from plants or their by-products. Lignocellulosic biomass is composed of carbohydrate polymers (cellulose, hemicellulose) and an aromatic polymer (lignin).

[0060] The feed from biomass conversion can also advantageously be chosen from feeds from the paper industry.

[0061] The pyrolysis oil of plastics and / or tires and / or RDF can be obtained from a thermal pyrolysis treatment, catalytic or be prepared by hydropyrolysis (pyrolysis in the presence of a catalyst and hydrogen). Preprocessing (optional)

[0062] Said feed comprising a pyrolysis oil of plastics and / or tires and / or RDF may advantageously be pretreated in at least one optional pretreatment step a0), prior to step a) of hydrotreatment, to obtain a feed pre-treated which feeds into step a).

[0063] According to one embodiment, this optional pretreatment step aO) reduces the amount of contaminants and solid particles, in particular the amount of iron and / or silicon and / or chlorine, that may be present in the feed containing pyrolysis oil. This optional step aO) notably allows for the removal of sediments that may form due to the instability of pyrolysis oils and / or a compatibility issue between two different feeds. Thus, an optional pretreatment step aO) of the feed containing pyrolysis oil is advantageously carried out particularly when said feed contains more than 10 ppm by weight, in particular more than 20 ppm by weight, more particularly more than 50 ppm by weight of metallic elements and / or solid particles, and in particular when said feed contains more than 5 ppm by weight of silicon, more particularly more than 10 ppm by weight, or even more than 20 ppm by weight of silicon.Similarly, an optional pretreatment step aO) of the feed comprising a pyrolysis oil is advantageously carried out in particular when said feed comprises more than 10 ppm by weight, in particular more than 20 ppm by weight, more particularly more than 50 ppm by weight of chlorine.

[0064] Said optional pretreatment step aO) can be implemented by any method known to those skilled in the art that reduces the amount of contaminants. It may, in particular, include 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.

[0065] The optional pretreatment step aO) 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.

[0066] According to one embodiment, said optional pretreatment step aO) is carried out in an adsorption section operated in the presence of at least one adsorbent. The adsorbent may be selected from zeolite, activated carbon, clay, silica, or alumina. Preferably, the adsorbent is alumina, having a specific surface area greater than or equal to 100 m² / g, preferably greater than or equal to 200 m² / g. The specific surface area of ​​said at least one adsorbent is advantageously less than or equal to 600 m² / g, in particular less than or equal to 400 m² / g. The specific surface area of ​​the adsorbent is a surface area measured by the BET method, that is, the specific surface area determined by nitrogen adsorption in accordance with ASTM D 3663-78 established from the BRUNAUER-EMMETT-TELLER method described in the periodical 'The Journal of the American Chemical Society', 6Q, 309 (1938).

[0067] Advantageously, said adsorbent comprises less than 1% by weight of elements The adsorbent is preferably free of metallic elements. Metallic elements in the adsorbent are defined as those in groups 6 to 10 of the periodic table (new IUP-AC classification). The residence time of the charge in the adsorption section is generally between 1 and 180 minutes.

[0068] Said adsorption section of optional step aO) comprises at least one adsorption column, preferably comprising at least two adsorption columns, preferably between two and four adsorption columns, containing said adsorbent. When the adsorption section comprises two adsorption columns, one operating mode may be a so-called "swing" operation, in which one of the columns is online, i.e., in operation, while the other column is in reserve. When the adsorbent in the online column is depleted, this column is isolated while the reserve column is brought online, i.e., into operation. The depleted adsorbent can then be regenerated in situ and / or replaced with fresh adsorbent so that the column containing it can be brought online again once the other column has been isolated.

[0069] Another operating mode involves having at least two columns operating in series. When the absorbent in the leading column is depleted, this first column is isolated, and the spent absorbent is either regenerated in situ or replaced with fresh absorbent. The column is then placed back in the last position, and so on. This operation is called the permutable mode, or, in English, "PRS" for Permutable Reactor System, or "lead and lag" in the established English term. Combining at least two adsorption columns makes it possible to overcome the potential and potentially rapid poisoning and / or clogging of the adsorbent due to the combined action of metallic contaminants, diolefins, gums derived from diolefins, and insolubles that may be present in the pyrolysis oil being treated.The presence of at least two adsorption columns facilitates the replacement and / or regeneration of the adsorbent, advantageously without stopping the pretreatment unit, or even the process, thus reducing the risk of clogging and therefore avoiding unit shutdown due to clogging, controlling costs and limiting adsorbent consumption.

[0070] According to another embodiment, said optional pretreatment step aO) is carried out in a washing section with an aqueous solution, for example water or an acidic or basic solution. This washing section may include equipment for contacting the feed with the aqueous solution and separating the phases so as to obtain the pretreated feed on the one hand and the aqueous solution containing impurities on the other. This equipment may include, for example, a stirred reactor, a decanter, a mixer-decanter and / or a column of washing with co- or counter-current.

[0071] According to another embodiment, said optional pretreatment step aO) is implemented by filtration. The filtration step removes inorganic solids, sediments, and / or fines contained in the feed, in particular metals, metal oxides, and metal chlorides. A filter with a pore size (e.g., diameter or equivalent diameter) of less than 25 pm is generally used, preferably less than or equal to 10 pm, and even more preferably less than or equal to 5 pm. According to another embodiment, a filter with a pore size of less than 25 pm but greater than 5 pm may be used. Alternatively, a series of filters with different pore sizes may be used, in particular 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 examples. The dry extract can be measured, for example, by the Heptane Insolubles test, ASTM Method D-3279. The insolubles content in heptane must be reduced to less than 0.5% by weight, preferably less than 0.1%.

[0072] According to a particular embodiment, the pretreatment step aO) by filtration comprises at least one filter having a pore size of less than 10 microns, and preferably greater than 5 pm, optionally followed by a filtration system having a pore size of less than 2 pm and preferably less than 1 pm.

[0073] According to another particular embodiment, the pretreatment step aO) by filtration comprises at least one filter having a pore size of less than 10 pm, and preferably greater than 5 pm, followed by an electrostatic precipitation system.

[0074] According to another particular embodiment, the pretreatment step aO) by filtration comprises at least one filter having a pore size of less than 10 pm, and preferably greater than 5 pm, followed by a filter system(s) using filtration aids such as sand or diatomaceous earth.

[0075] According to another embodiment, said optional pretreatment step aO) is carried out by centrifugation. According to another embodiment, the pretreatment step aO) comprises centrifugation and filtration.

[0076] According to another embodiment, said optional pretreatment step aO) is carried out by decantation. According to another embodiment, the pretreatment step aO) comprises decantation and filtration.

[0077] According to another embodiment, said optional pretreatment step aO) is implemented by gas stripping, thereby reducing the oxygen content in the feed. Gas extraction can remove oxygen (O2) that may be dissolved in the feed, thus reducing the probability of free radical formation leading to polymerization in downstream steps. The process generally involves contacting The feed is sprayed with an extraction gas (e.g., H2, N2, or a mixture thereof), thereby transferring at least some of the dissolved oxygen from the feed to the extraction gas, followed by separation of the extraction gas from the feed. The volume of extraction gas relative to the volume of feed (both volumes measured under gas extraction conditions) is generally greater than 1, and preferably at least 3. In particular embodiments, the extraction gas may contain at least 60% (molar percent) H2. Any dissolved H2 remaining in the feed after the gas extraction step is not a problem, given the downstream hydrotreating. Preferably, the gas extraction step is completed before any (pre)heating of the feed, in order to minimize potential fouling.

[0078] Said optional pretreatment step aO) generally comprises one or more, preferably several, treatments described above. It may, in particular, comprise a sequence of a washing step using an aqueous solution and / or an adsorption step, followed by a gas stripping step, followed by a filtration step and / or a centrifugation step. All these steps are preferably carried out before any (pre)heating of the feed.

[0079] Said optional pretreatment step aO) thus makes it possible to obtain a pretreated feed which then feeds the mild hydrotreatment step a). Step a) of hydrotreatment

[0080] According to the invention, the process comprises a step a) carried out in a hydrotreating reaction section comprising at least one hydrotreating catalyst, said hydrotreating reaction section being fed at least by the pyrolysis feed and a gaseous stream comprising hydrogen, said hydrotreating reaction section being carried out at an average temperature between 100 and 220°C, a partial pressure of hydrogen between 1.0 and 3.0 MPa abs. and an hourly volumetric velocity between 0.05 and 5 h1, the hydrogen coverage being between 5 and 50 Nm3 of hydrogen per m3 of pyrolysis feed, to obtain a partially hydrotreated effluent having hydrocarbon compounds having a reduced halogen content.

[0081] Step a) is in particular carried out under mild hydrogen pressure and temperature conditions allowing in particular the elimination of halogens, and in particular chlorine, in order to make the pyrolysis oil compatible as a co-charge in the downstream units while preserving as much as possible the diolefins and olefins which are valuable in the FCC (for the production of propylene).

[0082] Other impurities contained in pyrolysis oils (metals, silicon, nitrogen, etc.) are not necessarily completely eliminated during the process according to the invention, although the operating conditions allow for the removal of at least some of them. Step a) thus mainly involves hydrogenation reactions of halogenated compounds, and to a lesser extent other reactions hydrotreating well known to those skilled in the art, particularly hydrotreating reactions such as aromatic hydrogenation, hydrodesulfurization and hydrodeazotation, as well as olefin and diolefin hydrogenation (although we seek to keep them in the oil).

[0083] Said hydrotreating reaction section is advantageously implemented at an average temperature (or WABT as defined below) of hydrotreating between 100 and 220°C, preferably between 120 and 200°C, at a partial pressure of hydrogen between 1.0 and 3.0 MPa abs., preferably between 1.0 and 2.4 MPa abs., preferably between 1.2 and 2.2 MPa abs., and at a volumetric hourly rate (WH) between 0.1 and 5 h1, preferably between 0.1 and 2 h1, preferably between 0.1 and 1.0 h1. The hydrogen coverage in step a) is advantageously between 5 and 50 Nm3 of hydrogen per m3 of fresh feed, and preferably between 10 and 40 Nm3 of hydrogen per m3 of fresh feed, preferably between 15 and 30 Nm3 of hydrogen per m3 of fresh feed.

[0084] According to the invention, the "average temperature" of a reaction section corresponds to the Weight Average Bed Temperature (WABT), a term well known to those skilled in the art. The average temperature is advantageously determined based on the catalytic systems, equipment, and their configuration used. The average temperature (or WABT) is calculated as follows:

[0085] [Math.l]

[0086] with Tinlet: the temperature of the flow at the inlet of the reaction section and Toutlet: the temperature of the effluent at the outlet of the reaction section. Unless otherwise specified, the "average temperature" of a reaction section is given at the start of the cycle.

[0087] The hourly volumetric velocity (WH) is defined here as the ratio between the hourly volumetric flow rate of the charge including the pyrolysis oil, possibly pre-treated, by the volume of catalyst(s).

[0088] Hydrogen coverage is defined as the ratio of the volumetric flow rate of hydrogen taken under normal temperature and pressure conditions to the volumetric flow rate of "fresh" feed, i.e. the feed to be treated, possibly pre-treated, without taking into account a recycled fraction, at 15°C (in normal m3, noted Nm3, of H2 per m3 of feed).

[0089] The hydrogen-containing gas stream that feeds the hydrotreating reaction section may consist of hydrogen make-up and / or recycled hydrogen. Preferably, an additional hydrogen-containing gas stream is Advantageously introduced at the inlet of each reactor, particularly those operating in series, and / or at the inlet of each catalytic bed from the second catalytic bed in the reaction section, these additional gas flows are also called cooling flows. They allow for temperature control within the reactor, in which the reactions carried out are generally highly exothermic.

[0090] The gaseous stream comprising hydrogen can be from a fossil source or from a renewable source, for example from the gasification of plastic waste or produced by electrolysis.

[0091] Advantageously, the hydrogen-containing gas stream originates from a compressor used in the refinery to supply another hydrogen-using hydrorefining unit, such as a hydrocracking, hydrotreating, or hydroconversion unit. For example, the hydrogen-containing gas stream may originate from a compressor used to supply the vacuum gas oil hydrotreating (VGO) unit. This has the advantage of eliminating the need for a dedicated compressor to recycle hydrogen from step b), thus resulting in investment cost savings.

[0092] Optionally, the reaction section of said step a) may also be further supplied by a portion of the partially hydrotreated hydrocarbon effluent from step b) (recycle) as described below.

[0093] Preferably, the process according to the invention comprises a step a) of hydrotreating carried out in a hydrotreating reaction section, employing at least one fixed-bed reactor having n catalytic beds, n being an integer greater than or equal to 1, preferably between one and ten, preferably between two and five, each comprising at least one hydrotreating catalyst.

[0094] Said hydrotreating reaction section is fed at least by the pyrolysis feed, possibly pretreated, and a gaseous stream including hydrogen, advantageously at the first catalytic bed of the first operating reactor. Injection of at least a portion of the pyrolysis feed and / or at least a portion of hydrogen between the different catalytic beds is also possible.

[0095] The hydrotreating reaction section employing at least one fixed-bed reactor can operate with downward or upward flow of gas and liquid.

[0096] Advantageously, the reaction section of said step a) comprises between 1 and 5 reactors, preferably between 2 and 5 reactors, and particularly preferably comprises two reactors. The advantage of a hydrotreating reaction section comprising several reactors lies in optimized feedstock treatment, while reducing the risk of clogging of the catalytic bed(s) and thus preventing unit shutdown due to clogging.

[0097] According to this embodiment, the hydrotreating reaction section of step a) comprises two reactors operating in a switchable mode, referred to in English as "PRS" for Permutable Reactor System or "lead and lag". Combining at least two reactors in PRS mode allows one reactor to be isolated, the spent catalyst to be discharged, the reactor to be refilled with fresh catalyst, and the reactor to be restarted without interrupting the process. The PRS technology is described, in particular, in patent FR2681871.

[0098] According to another embodiment, said hydrotreating reaction section comprises a single fixed-bed reactor containing n catalytic beds, n being an integer greater than or equal to one, preferably between one and ten, preferably between two and five.

[0099] Advantageously, reactor internals, for example of the filter plate type, can be used to prevent clogging of the reactor(s). An example of a filter plate is described in patent FR3051375.

[0100] Preferably, step a) may implement upstream of the hydrotreating catalyst(s) at least one guard bed containing adsorbents of the type alumina, silica, silica-alumina, zeolite and / or activated carbon possibly containing metals of group VIB and / or VIII. A series of guard beds with particles of different diameters may also be used, in particular a series of guard beds having diameters decreasing in the direction of the flow of the charge (also called "grading" according to Anglo-Saxon terminology).

[0101] Advantageously, said hydrotreating catalyst comprises a support, preferably mineral, and a hydro-dehydrogenating function.

[0102] According to one embodiment, the hydro-dehydrogenating function comprises, in particular, at least one element from Group VIII, preferably selected from nickel and cobalt, and at least one element from Group VIB, preferably selected from molybdenum and tungsten. According to this embodiment, the total content, expressed as oxides of the metallic elements from Groups VIB and VIII, is preferably between 1% and 40% by weight, preferably from 5% to 30% by weight relative to the total weight of the catalyst. When the metal is cobalt or nickel, the metal content is expressed as CoO and NiO, respectively. When the metal is molybdenum or tungsten, the metal content is expressed as MoO3 and WO3, respectively.

[0103] The weight ratio expressed in metal oxide between the metal (or metals) of group VIB and the metal (or metals) of group VIII is preferably between 1 and 20, and preferably between 2 and 10.

[0104] According to this embodiment, the reaction section of said step a) comprises, for example, a hydrotreating catalyst comprising between 0.5% and 12% by weight of nickel, preferably between 0.9% and 10% by weight of nickel (expressed as nickel oxide NiO per relative to the weight of said catalyst), and between 1% and 30% by weight of molybdenum, preferably between 3% and 20% by weight of molybdenum (expressed as molybdenum oxide MoO3 relative to the weight of said catalyst) on a support preferably mineral, preferably on an alumina support.

[0105] According to another embodiment, the hydro-dehydrogenating function comprises, and preferably consists of, at least one element from Group VIII, preferably nickel. According to this embodiment, the nickel oxide content is preferably between 1 and 50% by weight, preferably between 10% and 30% by weight relative to the weight of said catalyst. This type of catalyst is preferably used in its reduced form, on a preferably mineral support, preferably an alumina support.

[0106] The support for said hydrotreating catalyst is preferably selected from alumina, silica, silica-aluminas, magnesia, clays, and mixtures thereof. This support may contain doping compounds, in particular oxides selected from boron oxide, especially boron trioxide, zirconia, cerium, titanium dioxide, phosphoric anhydride, and mixtures thereof. Preferably, said hydrotreating catalyst comprises an alumina support, optionally doped with phosphorus and optionally with boron. When phosphoric anhydride (P₂O₅) is present, its concentration is less than 10% by weight relative to the weight of the alumina and advantageously at least 0.001% by weight relative to the total weight of the alumina. When boron trioxide B2O3 is present, its concentration is less than 10% by weight relative to the weight of alumina and advantageously at least 0.001% relative to the total weight of alumina.The alumina used can be, for example, a y (gamma) or q (eta) alumina.

[0107] Said hydrotreating catalyst is for example in the form of extrudates or in the form of beads.

[0108] Preferably, step a) may implement, in addition to the hydrotreating catalyst(s) described above, at least one hydrotreating catalyst used in step a) comprising less than 1% by weight of nickel and at least 0.1% by weight of nickel, preferably 0.5% by weight of nickel, expressed as nickel oxide NiO by weight of said catalyst, and less than 5% by weight of molybdenum and at least 0.1% by weight of molybdenum, preferably 0.5% by weight of molybdenum, expressed as molybdenum oxide MoO3 by weight of said catalyst, on an alumina support. This low-metal content catalyst may preferably be placed upstream or downstream of the hydrogenation catalyst(s) described above, preferably upstream.

[0109] The preparation of the catalyst in step a) of hydrotreating is known and generally includes an impregnation step with metals from group VIII and group VIB when present, and optionally with phosphorus and / or boron on the support, followed by drying, and then possibly calcination. The catalyst in step a) can also be a catalyst used in its reduced form, thus implying a reduction step in its preparation.

[0110] Before their use in a process step, catalysts are generally subjected to sulfidation to form the active species. Depending on the sulfur compound content in the initial feed to be treated, a stream containing a sulfidating agent can be injected upstream of the optional pretreatment step a0) or the hydrotreating step a), preferably upstream of the hydrotreating step a), to ensure a sufficient quantity of sulfur to form the catalyst's active species (in sulfide form). This activation or sulfidation step is carried out using methods well known to those skilled in the art, and advantageously under a sulfur-reducing atmosphere in the presence of hydrogen and hydrogen sulfide.The sulfurizing agents are preferably hydrogen sulfide (H₂S), elemental sulfur, CS₂, mercaptans, sulfides and / or polysulfides, hydrocarbon fractions with a boiling point below 400°C containing sulfur compounds, or any other sulfur-containing compound used for activating hydrocarbon feedstocks to sulfide the catalyst. These sulfur-containing compounds are advantageously selected from alkyl disulfides such as dimethyl disulfide (DMDS), alkyl sulfides such as dimethyl sulfide, thiols such as n-butylmercaptan (or 1-butanethiol), and tertiononyl polysulfide compounds. The catalyst can also be sulfided by the sulfur contained in the feedstock to be desulfurized. Preferably, the catalyst is sulfided in situ in the presence of a sulfurizing agent and a hydrocarbon feedstock.Preferably, the catalyst is sulfided in situ in the presence of the added charge of dimethyl disulfide. The sulfiding agent can be injected continuously.

[0111] The partially hydrotreated effluent obtained at the end of step a) hydrogenation is sent, preferably directly, to step b) washing / separation. Step b) separation

[0112] According to the invention, the treatment process includes a separation step b), advantageously implemented in at least one washing / separation section, fed at least by the partially hydrotreated effluent from step a) and an aqueous solution, to obtain at least one gaseous effluent, one aqueous effluent and one partially hydrotreated hydrocarbon effluent.

[0113] This separation step b) 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 step a) which dissolve in the aqueous solution.

[0114] Step b) of separation is advantageously carried out at a temperature between between 20 and 200°C, preferably between 50 and 180°C, preferably between 80 and 150°C. Advantageously, separation step b) is carried out at a pressure close to that used in step a), preferably between 1.0 and 2.0 MPa, so as to facilitate hydrogen recycling if needed.

[0115] The separation step can advantageously be carried out by any method known to those skilled in the art, such as, for example, the combination of one or more separator(s) (balloon(s)) and / or one or more stripping column(s), this separator(s) (balloon(s)) and / or column(s) optionally being supplied with a stripping gas, for example, a hydrogen-rich gas stream. The washing / separation section of step c) can be at least partially carried out in common or separate washing and separation equipment.

[0116] Advantageously, the separation step b) includes an injection of an aqueous solution, preferably an injection of water, into the partially hydrotreated effluent from step a), upstream of the washing / separation section, so as to dissolve at least part and preferably all of the hydrogen halides (especially HCl) and any salts present.

[0117] The aqueous solution can be water. It can also be a basic aqueous solution (for example, by adding NaOH). Using a basic solution neutralizes hydrogen halides and any dissolved salts.

[0118] In a possible embodiment of the invention, step b) of separation comprises the injection of an aqueous solution into the partially hydrotreated effluent from step a), followed by the washing / separation section advantageously comprising a separation phase enabling the production of at least one aqueous effluent containing hydrogen halides (in particular HCl) and any dissolved salts, one washed partially hydrotreated effluent, and one partially washed gaseous effluent. Said aqueous effluent and the washed partially hydrotreated effluent can then be separated in a settling tank to obtain said washed partially hydrotreated effluent and said aqueous effluent.The partially washed gaseous effluent may simultaneously be introduced into a scrubbing column where it flows counter-currently to an aqueous stream, preferably of the same nature as the aqueous solution injected into the partially hydrotreated effluent. This allows for the removal, at least in part, and preferably in full, of the hydrochloric acid contained in the partially washed gaseous effluent, thus obtaining the gaseous effluent, preferably consisting essentially of hydrogen, and an acidic aqueous stream. The aqueous effluent from the settling tank may optionally be mixed with the acidic aqueous stream and used, possibly mixed with the acidic aqueous stream, in a water recycling circuit to supply step b) of separation into the aqueous solution upstream of the scrubbing / separation section and / or into the aqueous stream in the scrubbing column. The water recycling circuit may include a water top-up and / or a basic solution and / or a purge to remove impurities.

[0119] Step a) of hydrotreating mainly implements hydrogenation reactions of halogenated compounds, and to a lesser extent also other hydrotreating reactions such as hydrodeazotation which generates NH3 by hydrogenation of nitrogen compounds and hydrodesulfurization which generates H2S by hydrogenation of sulfur compounds.

[0120] When NH3 is present in the partially hydrotreated effluent from step a), the separation step b) also makes it possible to remove ammonium chloride salts, which are formed by reaction between chloride ions, released by the hydrogenation of chlorinated compounds in the form of HCl in particular during step a), and ammonium ions, generated by the hydrogenation of nitrogen compounds in the form of NH3 during step a) by dissolving them in the aqueous solution.

[0121] When H2S is present in the partially hydrotreated effluent from step a), the separation step b) also allows the removal of ammonium sulfide salts ((NH4)2S) which are formed by reaction between the H2S from the hydrodesulfurization of the sulfide compounds and NH3 by dissolving them in the aqueous solution.

[0122] According to one embodiment, and depending on the content of chlorinated compounds in the initial or pre-treated feed, a stream containing a nitrogenous compound such as ammonia or an amine, for example monoethanolamine, diethanolamine and / or monodie-ethanolamine, can be injected upstream of step a) of hydrotreating in order to ensure a sufficient quantity of ammonium ions to combine the chloride ions formed during the hydrotreating step in the form of ammonium chloride salts, thus limiting the formation of hydrochloric acid and thus limiting corrosion downstream of the separation section.

[0123] The gaseous effluent obtained at the end of step b) advantageously comprises hydrogen, preferably comprising at least 80% by volume, preferably at least 85% by volume, of hydrogen. The gaseous effluent obtained at the end of step b) contains very little chlorine, generally at a concentration of less than 5 ppm by weight of chlorine, which allows it to be sent to a refining unit requiring hydrogen.

[0124] According to one embodiment, said gaseous effluent can at least partly be recycled to step a) of hydrotreatment, the recycling system being able to include a purification section (for example for adsorption of heavy metals such as mercury).

[0125] According to another preferred embodiment, said gaseous effluent can at least partially be recycled upstream of a hydrogen compressor used to supply a hydrogen-based hydrorefining unit such as a hydrocracking unit, from the refinery's hydrotreating or hydroconversion process. This gaseous effluent can be recycled upstream of a compressor used to supply a vacuum diesel hydrotreating unit. This has the advantage of eliminating the need for a dedicated compressor to recycle hydrogen from step b), thus saving on investment costs.

[0126] As for the partially hydrotreated hydrocarbon liquid effluent from step b), and according to one variant, a portion of the partially hydrotreated hydrocarbon effluent from step b) can be recycled upstream of step a). Recycling a portion of the partially hydrotreated hydrocarbon effluent from step b) to or upstream of step a) advantageously allows, on the one hand, for the dilution of impurities and, on the other hand, for temperature control in step a), in which reactions can be highly exothermic. Diluting the impurities helps to limit undesirable reactions such as the polymerization of diolefins (gum formation) and / or coke formation.

[0127] Advantageously, the quantity of partially hydrotreated hydrocarbon effluent from step b) recycled, i.e. the recycled fraction of the product obtained, is adjusted so that the weight ratio between the recycle stream from step b) and the feed including pyrolysis oil, i.e. the feed to be treated supplying the overall process, is less than or equal to 10, preferably less than or equal to 7, and preferably greater than or equal to 0.001, preferably greater than or equal to 0.01, and preferably greater than or equal to 0.1. Preferably, the quantity of partially hydrotreated hydrocarbon effluent from step b) recycled is adjusted so that the weight ratio between the recycle stream and the feed including pyrolysis oil is between 0.01 and 10, preferably between 0.1 and 7, and particularly preferably between 0.2 and 5.This recycle rate allows, in particular, for the control of the temperature rise in step a). Indeed, when the recycle rate is high, the feed dilution rate is high, and the temperature rise at the beginning of the reaction section of step a) is thus controllable by the dilution effect. The injection of the partially hydrotreated hydrocarbon effluent from step b) can be carried out at the first catalytic bed of the reaction section of step a) or between the different catalytic beds. When the hydrotreating reaction section of step a) comprises two reactors operating in switchable mode, at least a portion of the partially hydrotreated hydrocarbon effluent from step b) can be recycled between the two reactors.

[0128] According to another preferred embodiment, the partially hydrotreated hydrocarbon effluent from step b) is sent partly, and preferably entirely, directly to the inlet of a refinery unit such as an FCC unit or hydrogen-using units such as a hydrocracking, hydrotreating, or hydroconversion as a co-charge. This has the advantage of not requiring a recycler compressor.

[0129] Said partially hydrotreated hydrocarbon effluent from step b) thus obtained by treatment according to steps a) and b) of the process of the invention has a composition compatible for being introduced as co-feed in an FCC unit or a hydrorefining unit of a petroleum feed and / or a feed from biomass.

[0130] The partially hydrotreated hydrocarbon effluent from step b) is in particular an effluent with a reduced content of halogenated compounds, and in particular of chlorine.

[0131] Preferably, at least 50%, and more preferably at least 75% of the halogenated compounds of the initial charge are eliminated during steps a) and b).

[0132] Preferably, at least 80%, and more preferably at least 90% of the olefins are retained during step a).

[0133] Preferably, at least 25%, and more preferably at least 40% of the diolefins are retained during step a).

[0134] The other impurities contained in pyrolysis oils (metals, silicon, nitrogen, etc.) are not necessarily completely eliminated during steps a) and b) of the process according to the invention, although the operating conditions allow for the removal of at least some of them. Indeed, pyrolysis oil, which is the partially hydrotreated hydrocarbon effluent, does not need to be fully hydrotreated to be introduced into downstream FCC-type refining or hydrorefining units; in particular, it does not need to undergo further hydrotreatment at higher temperatures and / or pressures prior to its introduction into a downstream unit. The remaining impurities will be converted or removed in the downstream units, as the residual impurity levels are compatible with these units.

[0135] Preferably, at least 50%, and more preferably at least 75% of the metallic elements of the initial charge are eliminated during steps a) and b).

[0136] Generally, at most 50%, and more preferably at most 25%, of the sulfur compounds of the initial charge are eliminated during steps a) and b).

[0137] Preferably, at least 25%, and more preferably at least 50% of the oxygenated compounds of the initial charge are eliminated during steps a) and b).

[0138] Generally, at most 30%, and more preferably at most 15% of the nitrogen compounds of the initial charge are eliminated during steps a) and b).

[0139] The content of heavy metals such as mercury, arsenic, zinc and lead remains substantially unchanged.

[0140] The contents are given in relative weight concentrations, percentage (%) by weight, part(s) per million (ppm) by weight or part(s) per billion (ppb) by weight, relative to the total weight of the stream considered. Step c) of FCC or hydrorefining

[0141] According to the invention, the process comprises a step c) of catalytic fluidized bed cracking or hydrorefining of a petroleum feedstock and / or a feedstock from biomass conversion in which at least a portion of the partially hydrotreated hydrocarbon effluent from step b) is introduced as a co-feedstock, said partially hydrotreated hydrocarbon effluent from step b) being introduced without prior undergoing another hydrotreatment step carried out at higher temperature and / or pressure than the temperature and / or pressure of step a), said mixture of said petroleum feedstock and / or said feedstock from biomass conversion and the partially hydrotreated hydrocarbon effluent from step b) having a halogen content less than or equal to 10 ppm by weight.

[0142] Thanks to step a) of hydrotreating allowing the release of halogenated compounds (for example chlorine) mainly in gaseous form (hydrogen halides of the type HCl in particular), followed by step b) of washing / separation allowing the dissolution and removal of hydrogen halides, the partially hydrotreated hydrocarbon effluent from step b) has a content of halogenated compounds sufficiently reduced to be able to be injected as a co-feed in a fluidized bed cracking, hydrocracking, hydrotreating or hydroconversion unit of petroleum feedstocks and / or feedstocks from biomass conversion.

[0143] Chlorine is indeed generally the limiting contaminant for treating pyrolysis oils in existing units. Chlorine, even at low concentrations (< 10 or even < 5 ppm w / w), is responsible for corrosion (in the form of HCl) which can occur in existing units whose metallurgy is generally not designed to withstand chlorine levels exceeding 10 or even 5 ppm w / w in the feed.

[0144] The partially hydrotreated hydrocarbon effluent from step b) is introduced into the fluidized bed catalytic cracking or hydrorefining unit of a petroleum feedstock and / or a biomass conversion feedstock in such a quantity that the chlorine content in the mixture of petroleum feedstock and / or biomass conversion feedstock and the partially hydrotreated hydrocarbon effluent from step b) is less than or equal to 10 ppm w / w, preferably less than or equal to 5 ppm w / w

[0145] Generally, the mass ratio between the flow rate of the partially hydrotreated hydrocarbon effluent from step b) (pyrolysis oil) and the flow rate of petroleum feed and / or feed from biomass conversion introduced into the unit of step c) in the process according to the invention is generally less than 1, and preferably between 0.01 and 0.9, and preferably between 0.02 and 0.5.

[0146] When the content of halogenated compounds is greater than 10, or even 5 ppm by weight in the partially hydrotreated hydrocarbon effluent from step b), the content of 10, up to 5 ppm of chlorine can be achieved by dilution at the unit inlet with the petroleum feed and / or the feed from biomass conversion.

[0147] In step c), the partially hydrotreated effluent from step b) is introduced as a co-feed into a fluidized bed catalytic cracking unit or into a hydrogen-based hydrorefining unit such as a hydrotreating, hydrocracking, or hydroconversion unit for petroleum feedstock and / or biomass conversion feedstock. Preferably, the partially hydrotreated effluent from step b) is injected as a co-feed into a fluidized bed catalytic cracking unit.

[0148] The petroleum feed used in the fluidized bed catalytic cracking unit or in the hydrorefining unit can be selected from gasoline, gas oils, vacuum gas oils, atmospheric residues, vacuum residues, atmospheric distillates, vacuum distillates, heavy fuel oils, oils, waxes and paraffins, used oils, residues or deasphalted crudes, petroleum feeds from thermal or catalytic conversion processes, or mixtures of such feeds.

[0149] The feedstock from biomass used in the fluidized bed catalytic cracking unit or in the hydrorefining unit may be selected from vegetable oils, algae or algal oils, fish oils, used edible oils, and fats of vegetable or animal origin; methyl esters of fatty acids of vegetable and / or animal origin, methyl esters of fatty acids from used edible vegetable oils, feedstocks from thermal or catalytic biomass conversion processes, or mixtures of such feedstocks. It may, in particular, be a feedstock such as that described in the pyrolysis oil feedstock section above. FCC

[0150] Fluidized bed catalytic cracking (FCC) is widely used in the refining industry for converting atmospheric diesel, vacuum diesel, and atmospheric residues, lignocellulosic feedstock, or more generally biomass feedstock, alone or in mixtures, into high-octane gasoline, light fuel oil, heavy fuel oil, light olefin-rich gas (propylene, butylene), and coke. The FCC unit uses a high-activity zeolite catalyst to crack the heavy hydrocarbon molecules. A conventional FCC unit is used. For example, a summary description of catalytic cracking (the first industrial implementation of which dates back to 1936 (HOUDRY process) or 1942 for the use of a catalyst in a fluidized bed) can be found in ULLMANS ENCYCLOPEDIA OF INDUSTRIAL CHEMISTRY VOLUME A 18, 1991, pages 61 to 64. The choice of catalyst and operating conditions depends on the products being processed. sought according to the charge treated as described for example in the article by M. MARCILLY pages 990-991 published in the journal of the French Petroleum Institute Nov.-Dec. 1975 pages 969-1006.

[0151] Step c) of fluidized bed catalytic cracking is generally carried out in a fluidized bed catalytic cracking reaction section in a substantially vertical reactor either in ascending mode (riser according to Anglo-Saxon terminology) or in descending mode (downer according to Anglo-Saxon terminology) in the presence of a feed selected from atmospheric diesel, vacuum diesel, atmospheric residue and a feed from biomass and a zeolite catalyst at a reactor temperature between 450°C and 600°C with a contact time in the reactor of less than 1 minute, often from 0.1 to 50 seconds.

[0152] A conventional zeolite catalyst comprising a matrix, optionally an additive, and at least one zeolite is usually used in the FCC process. The amount of zeolite is variable but usually ranges from 3 to 60% by weight, often from 6 to 50% by weight, and most often from 10 to 45% by weight relative to the weight of the catalyst. The zeolite is usually dispersed within the matrix. The amount of additive is usually from 0 to 30% by weight and often from 0 to 20% by weight relative to the weight of the catalyst. The amount of matrix represents the remainder to 100% by weight. The additive is generally selected from the group formed by the oxides of metals in Group IIA of the periodic table of elements, such as, for example, magnesium oxide or calcium oxide, rare-earth oxides, and titanates of Group IIA metals.The matrix is ​​most often silica, alumina, silica-alumina, silica-magnesia, clay, or a mixture of two or more of these products. The most commonly used zeolite is zeolite Y. Hydrorefining

[0153] Hydrorefining processes using hydrogen from petroleum feedstocks and / or feedstocks from biomass conversion are known to those skilled in the art and include processes such as hydrotreating, hydrocracking or hydroconversion. Hydrotreatment

[0154] The term "hydrotreating," commonly referred to as "HDT," refers to an operation whose main purpose is to remove impurities such as sulfur, nitrogen, oxygen, halides, and trace metals from the feed, and to saturate olefins and / or stabilize hydrocarbon free radicals by causing them to react with hydrogen rather than allowing them to react with themselves. The main purpose is not to change the boiling point range of the feed. Thus, hydrotreating includes, among other things, hydrodesulfurization reactions. (commonly referred to as "HDS"), hydrodeazotation reactions (commonly referred to as "HDN"), and hydrodemetallation reactions (commonly referred to as "HDM"), accompanied by hydrogenation, hydrodeoxygenation (commonly referred to as "HDO"), hydrodearomatization, hydroisomerization, and hydrodealkylation reactions. Hydrotreating is most often carried out using a fixed-bed reactor, although other reactors can also be used for hydrotreating, for example, a bubbling-bed hydrotreating reactor.

[0155] The feedstocks used in the hydrotreating process are, for example, gasoline, diesel fuel, vacuum diesel fuel, atmospheric residues, vacuum residues, atmospheric distillates, vacuum distillates, heavy fuel oils, oils, waxes and paraffins, used oils, residues or deasphalted crude oil, feedstocks from thermal or catalytic conversion processes, lignocellulosic feedstocks, or more generally, feedstocks derived from biomass, taken alone or in mixtures. The feedstocks that are treated, and in particular those mentioned above, generally contain heteroatoms such as sulfur, oxygen, and nitrogen, and, for heavy feedstocks, they most often also contain metals.

[0156] A hydrotreating process particularly suitable for introducing partially hydrotreated pyrolysis oil according to the process according to the invention is a hydrotreating process of a vacuum gas oil, diesel, kerosene or gasoline feed and / or a feed from biomass chosen from vegetable oils, algae or algal oils, fish oils, used cooking oils, and fats of vegetable or animal origin.

[0157] The operating conditions used in processes implementing the feed hydrotreating reactions described above are generally as follows: the average temperature is advantageously between 180 and 450°C, and preferably between 250 and 440°C; the pressure is advantageously between 0.5 and 30 MPa, and preferably between 1 and 18 MPa; the hourly volumetric rate is advantageously between 0.1 and 20 h₁ and preferably between 0.2 and 5 h₁; and the hydrogen cover is between 50 and 5000 Nm³ of hydrogen per m³ of feed, preferably between 80 and 2000 Nm³. The definitions of the average temperature (WABT), the WH, and the hydrogen cover correspond to those described above.

[0158] Conventional hydrotreating catalysts generally comprise an oxide support and an active phase based on metals from groups VIB and VIII in their oxide forms, as well as phosphorus. The group VIB metal present in the active phase of the catalyst is preferably chosen from molybdenum and tungsten. The group VIII metal present in the active phase of the catalyst is preferably The active phase of the catalyst is preferably chosen from the group formed by the combination of the elements nickel-molybdenum, cobalt-molybdenum, nickel-tungsten, nickel-molybdenum-tungsten and nickel-cobalt-molybdenum, and most preferably the active phase consists of cobalt and molybdenum, nickel and molybdenum, nickel and tungsten or a nickel-molybdenum-tungsten combination.

[0159] The Group VIII metal content is between 1 and 10 wt%, preferably between 1.5 and 9 wt%, and more preferably between 2 and 8 wt%, expressed as Group VIII metal oxide relative to the total weight of the catalyst. The Group VIB metal content is between 1 and 40 wt%, preferably between 1 and 35 wt%, and more preferably between 2 and 30 wt%, expressed as Group VIB metal oxide relative to the total weight of the catalyst. The Group VIII metal to Group VIB metal molar ratio of the fresh catalyst is generally between 0.1 and 0.8, preferably between 0.15 and 0.6.

[0160] Optionally, the hydrotreating catalyst may further have a phosphorus content generally between 0.1 and 20 wt% of P2O5 relative to the total weight of fresh catalyst, preferably between 0.2 and 15 wt% of P2O5, most preferably between 0.3 and 11 wt% of P2O5. Moreover, the phosphorus / (metal of group VIB) molar ratio is generally between 0.08 and 1, preferably between 0.1 and 0.9, and most preferably between 0.15 and 0.8.

[0161] The oxide support for the hydrotreating catalyst is usually a porous solid selected from the group consisting of: aluminas, silica, silica-alumina, or titanium or magnesium oxides used alone or in a mixture with alumina or silica-alumina. According to a particularly preferred embodiment, the oxide support consists of alumina, silica, or silica-alumina.

[0162] The catalyst may also further comprise at least one organic compound containing oxygen and / or nitrogen and / or sulfur before sulfidation. Such additives are known. Generally, the organic compound is chosen from a compound having one or more chemical functionalities selected from among a carboxyl group, alcohol, thiol, thioether, sulfone, sulfoxide, ether, aldehyde, ketone, ester, carbonate, amine, nitrile, imide, oxime, urea, and amide, or compounds including a furan ring, or sugars. The content of the organic compound(s) containing oxygen and / or nitrogen and / or sulfur in the catalyst is between 1 and 30 wt%, preferably between 1.5 and 25 wt%, and more preferably between 2 and 20 wt% relative to the total weight of the catalyst.

[0163] A hydrocracking process makes it possible to convert petroleum fractions, by In particular, vacuum distillates (VDS) are converted into lighter and more valuable products (gasoline, middle distillates). Other reactions, such as the hydrogenation of olefins and aromatics, hydrometallation, hydrodesulfurization, hydrodeazotation, etc., are also carried out.

[0164] Hydrocracking is most often carried out using a fixed bed reactor.

[0165] The charge used in a hydrocracking process is generally a hydrocarbon charge of which at least 50% by weight of the compounds have an initial boiling point above 300°C and a final boiling point below 650°C.It can be chosen from HCOs (Heavy Cycle Oil, according to Anglo-Saxon terminology (heavy gas oils from a catalytic cracking unit)), vacuum distillates, for example gas oils from the direct distillation of crude oil or from conversion units such as catalytic cracking, coking, or visbreaking, feedstocks from aromatic extraction units, lubricating oil bases or from the solvent dewaxing of lubricating oil bases, distillates from desulfurization or hydroconversion processes in fixed or bubbling beds of atmospheric residues and / or vacuum residues and / or deasphalted oils, or the feedstock can be a deasphalted oil or include vegetable oils or even come from the conversion of feedstocks from biomass. It can also be paraffins from the Fischer-Tropsch process.The hydrocarbon feedstock treated according to the hydrocracking process of the invention may also be a mixture of the aforementioned feedstocks. Preferably, the feedstock is a vacuum distillate.

[0166] A hydrocracking process particularly suitable for introducing partially hydrotreated pyrolysis oil according to the process according to the invention is a vacuum hydrotreating process of a diesel feedstock.

[0167] Hydrocracking processes are generally carried out at an average temperature of between 250 and 480°C, advantageously between 320 and 450°C, preferably between 330 and 435°C, under a pressure of between 2 and 25 MPa, preferably between 3 and 20 MPa, the volumetric flow rate of the feed relative to the volume of each catalyst (WH) is advantageously between 0.1 and 40 h⁻¹, preferably between 0.2 and 12 h⁻¹, most preferably between 0.4 and 6 h⁻¹, and a hydrogen cover of between 50 and 5000 Nm³ of hydrogen per m³ of feed, preferably between 100 and 2000 Nm³. The definitions of the average temperature (WABT), WH, and hydrogen cover correspond to those described above.

[0168] Vacuum hydrocracking processes for distillates cover the pressure and conversion ranges from mild hydrocracking to high-pressure hydrocracking. Mild hydrocracking is defined as hydrocracking leading to moderate conversions, generally less than 40%, and operating at low pressure, generally between 2 MPa and 6 MPa.

[0169] The hydrocracking process can be a so-called "one-step" hydrocracking process or a so-called "two-step" hydrocracking process. A "one-step" hydrocracking process generally involves, firstly and generally, advanced hydrotreatment aimed at achieving advanced HDN, HDS, and HDA of the feed before it is sent to the hydrocracking catalyst(s). A "two-step" hydrocracking process includes a first step which, as in the "one-step" process, aims to perform hydrotreatment of the feed, but also to achieve a conversion rate of the feed, generally on the order of 40 to 60%. The effluent from the first step then undergoes separation, generally by distillation, most often called intermediate separation, which aims to separate the conversion products from the unconverted fraction.In the second stage of the two-stage hydrocracking process according to the invention, only the fraction of the feed not converted in the first stage is treated.

[0170] Hydrocracking catalysts are bifunctional: they combine an acid function with a hydro-dehydrogenating function. The acid function is provided by porous supports with surface areas generally ranging from 150 to 800 m².g⁻¹ and exhibiting surface acidity, such as halogenated aluminas (particularly chlorinated or fluorinated), combinations of boron and aluminum oxides, amorphous or crystalline mesoporous aluminosilicates, and zeolites dispersed in an oxide binder. The hydro-dehydrogenating function is provided by the presence of an active phase based on at least one metal from group VIB and possibly at least one metal from group VIII of the periodic table. The most common formulations are nickel-molybdenum (NiMo) and nickel-tungsten (NiW), and more rarely cobalt-molybdenum (CoMo).

[0171] The metal contents are generally as described for hydrotreating catalysts.

[0172] Hydrocracking catalysts may also contain phosphorus and / or an organic compound containing oxygen and / or nitrogen and / or sulfur in amounts such as those described for hydrotreating catalysts. Hydroconversion

[0173] The term "hydroconversion" refers to a process whose main purpose is to reduce the boiling point range of a feed comprising at least 50% of a heavy hydrocarbon fraction having a boiling point of at least 300°C, or even at least 450°C, and in which a substantial portion of the feed is converted into products having lower boiling point ranges than the original feed. Hydroconversion generally involves the fragmentation of larger hydrocarbon molecules into smaller molecular fragments with a smaller number of carbon atoms and a higher hydrogen-to-carbon ratio.

[0174] The feedstock used in a hydroconversion process is generally a heavy hydrocarbon fraction containing at least 50% by weight having a boiling point of at least 300°C, preferably at least 350°C, and even more preferably at least 375°C. Advantageously, the heavy hydrocarbon fraction of the feedstock consists of one or more vacuum residues. The vacuum residues may come directly from crude oil or from other refining units, such as, among others, tailings hydrotreating, tailings hydrocracking, and tailings visbreaking. Preferably, the vacuum residues are vacuum residues from the vacuum distillation column of primary crude oil fractionation (known as "straight run," or "SR" for short, according to Anglo-Saxon terminology).

[0175] The heavy hydrocarbon fraction of the feed can also consist of aromatic cuts extracted from a lubricant production unit, deasphalted oils from a deasphalting unit (refinates from the deasphalting unit), asphalts from a deasphalting unit (residues from the deasphalting unit).

[0176] The heavy hydrocarbon fraction of the feed can also consist of a settling oil or a recycling oil (which typically has a boiling range of 360°C to 550°C), for example a fluidized bed catalytic cracking effluent as a heavy cycle oil (HCO) or a slurry-like oil (SLO).

[0177] The heavy hydrocarbon fraction comprises, and may consist of, at least one of the following feedstocks, alone or in mixture: crude oil, topped-off crude oil, atmospheric residue or vacuum residue from atmospheric or vacuum distillation of crude oil (preferably from primary fractionation of crude oil), atmospheric residue or vacuum residue from atmospheric or vacuum distillation obtained during a direct coal liquefaction process, and preferably is vacuum residue from vacuum distillation of crude oil (preferably from primary fractionation of crude oil).

[0178] A hydroconversion process particularly suitable for introducing partially hydrotreated pyrolysis oil according to the process according to the invention is a hydroconversion process of a residual feedstock under vacuum.

[0179] Hydroconversion processes are generally carried out at an average temperature between 340 and 550°C, more preferably between 350 and 500°C, preferably between 360 and 450°C, under pressure The volumetric flow rate (WH) of the feed relative to the volume of each catalyst is advantageously between 2 and 38 MPa, more preferably between 5 and 25 MPa, and even more preferably between 6 and 20 MPa. The hourly volumetric velocity of the feed relative to the volume of each catalyst is advantageously between 0.05 and 10 h₁, preferably between 0.1 and 5 h₁, even more preferably between 0.15 and 2 h₂, and even more preferably between 0.15 and 1 h₁. The hydrogen coverage is between 50 and 5000 Nm³ of hydrogen per m³ of feed, preferably between 100 and 2000 Nm³, and most preferably between 200 and 1000 Nm³. The definitions of the mean average temperature (WABT), WH, and hydrogen coverage correspond to those described above.

[0180] The hydroconversion section may include one or more bubbling or hybrid (bubbling and entrained bed) reactors, containing at least one supported hydroconversion catalyst, the reactors being able to be arranged in series and / or in parallel, as used for the H-Oil® process, as described, for example, in patents US4521295 or US4495060 or US4457831 or US4354852, in the article Aiche, March 19-23, 1995, Houston, Texas, article number 46d, "Second generation bubbling bed technology", or in chapter 3.5 "Hydroprocessing and Hydroconversion of Residue Fractions" of the book "Catalysis by Transition Metal Sulphides", Éditions Technip, 2013.

[0181] The hydroconversion section may also include one or more driven bed reactors, also called 'slurry' reactors (three-phase reactors - liquid, gas, solid - in which the solid and liquid phases can behave as a homogeneous phase) or moving bed reactors (three-phase reactors with downward movement of the solid catalyst and upward or downward flow of liquid and gas) or fixed bed reactors (three-phase reactors with downward trickling of liquid feed onto a fixed bed of catalyst supported with hydrogen typically flowing simultaneously with the liquid, but possibly counter-currently in some cases).

[0182] The hydroconversion catalyst generally comprises an alumina support and at least one metal from Group VIII selected from nickel and cobalt, preferably nickel, and at least one metal from Group VIB selected from molybdenum and tungsten, preferably molybdenum. Preferably, the hydroconversion catalyst comprises nickel as a Group VIII element and molybdenum as a Group VIB element.

[0183] The metal contents are generally as described for hydrotreating catalysts.

[0184] Hydroconversion catalysts may also contain phosphorus and / or an organic compound containing oxygen and / or nitrogen and / or sulfur in amounts such as are described for hydrotreating catalysts. Analytical methods used

[0185] The analytical methods and / or standards used to determine the characteristics of the various flows, in particular the load to be treated and the effluents, are known to those skilled in the art. They are listed below for information purposes in Table 1. Other methods considered equivalent may also be used, in particular equivalent IP, EN or ISO methods:

[0186] [Tables 1] Description Methods Density @15°C ASTM D4052 Sulfur Content ISO 20846 Nitrogen Content ASTM D4629 Acid Value ASTM D664 Bromine Value ASTM DI 159 Maleic Anhydride Value (MAV) MAV Method (1) Oxygen Content Combustion + Infrared Paraffin Content UOP990-11 Naphthenes and Olefins Content UOP990-11 Aromatics Content UOP990-11 Halogen Content ASTM D7359 Chlorine Content ASTM D7536 Metal Content: ASTM D5185 P Fe Si Na B Simulated Distillation ASTM D2887

[0187] (1) MAV method described in the article: C. Lôpez-Garcla et al., Near Infrared Mo- nitoring 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 LIST OF FIGURES

[0188] Mention of the elements referenced in Figures 1 to 2 allows for a better understanding of the invention, without the latter being limited to the particular embodiments illustrated in Figures 1 to 2. The different embodiments presented can be used alone or in combination with each other, without limitation of combination. [Fig 1]

[0189] Figure 1 shows a diagram of a general embodiment of the process of the present invention, comprising:

[0190] - a step a) hydrotreating a pyrolysis oil 1 in the presence of a rich gas in hydrogen 2 and possibly an amine supplied by stream 3 and possibly a sulfurating agent by stream 4;

[0191] -a separation / washing step b) fed by the partially hydrotreated effluent 5 from the hydrotreatment step a) and in the presence of an aqueous solution 6 to obtain at least a gaseous effluent 7, an aqueous effluent 8 and a partially hydrotreated hydrocarbon effluent 9, of which part 9a can be recycled in step a);

[0192] - a step c) of catalytic cracking in a fluidized bed or hydrorefining of a petroleum feedstock and / or a feedstock from biomass conversion 10 in which at least part and preferably all of the partially hydrotreated hydrocarbon effluent from step b) 9 is introduced as a co-feedstock, said partially hydrotreated hydrocarbon effluent from step b) 9 being introduced without undergoing a further hydrotreatment step carried out at higher temperature and / or pressure beforehand, so as to increase the yield of the product(s) 11 (in particular propylene in the case of FCC) from step c). [Fig 2]

[0193] Figure 2 shows a diagram of a particular embodiment of the process of the present invention which is based on the diagram in Figure 1. This diagram shows the integration of the process according to the invention into an existing refinery comprising vacuum hydrotreating of diesel fuel, followed by separation of the hydrotreated diesel fuel under vacuum and then its introduction into a fuel cell converter (FCC) in order to produce, among other things, gasoline and olefins.

[0194] Step a) hydrotreatment and step b) separation / washing are carried out as described in [Fig.1].

[0195] A vacuum diesel fuel 12 is introduced into a hydrotreating unit 13 in the presence of fresh hydrogen 14 pressurized by a compressor 15 to reach the required pressure. The compressor 15 is also supplied, optionally after a purification step (not shown), by the gaseous effluent 7 from the separation step b) of the process according to the invention which essentially contains hydrogen.

[0196] The flow comprising hydrogen 2 supplying step a) of hydrotreating the pyrolysis oil of the process according to the invention can come from the compressor 15. This allows the use of a single hydrogen compressor.

[0197] The hydrotreated effluent 16 is then subjected to a separation 17 allowing recovery of at least a light cut 18 (gas and naphtha), a medium cut 19 (diesel oil) and a hydrotreated vacuum diesel cut 10.

[0198] The hydrotreated vacuum diesel cut 10 is then introduced into the catalytic cracking unit of step c), mixed with the partially hydrotreated hydrocarbon effluent 9 from step b).

[0199] Only the main stages, with the principal flows, are shown in Figures 1 and 2, to facilitate a better understanding of the invention. It is understood that all the equipment necessary for operation is present (tanks, pumps, heat 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. EXAMPLES

[0200] The pyrolysis feed treated in the process is a plastics pyrolysis oil (i.e. comprising 100% by weight of said plastics pyrolysis oil) having the characteristics indicated in Table 2.

[0201] Table 2: Characteristics of the pyrolysis charge

[0202] [Tables2] Description Methods Unit Charge Density @15°C ASTM D4052 g / cm3 0.820 Sulfur Content ISO 20846 ppm by weight 320 Nitrogen Content ASTM D4629 ppm by weight 730 Acid Value ASTM D664 mg KOH / g 1.5 Bromine Value ASTM DI 159 g / 100g 80 Maleic Anhydride Value MAV Method mg / 100g 10 Oxygen Content Combustion + Infrared % by weight 1.0 Paraffin Content UOP990-11 % by weight 45 Naphthene Content UOP990-11 % by weight 20 Olefin Content UOP990-11 % by weight 25 Aromatic Content UOP990-11 % by weight 10 Halogen Content ASTM D7359 ppm by weight Chlorine Content (ASTM D7536 ppm by weight) 97 Metal Content (ASTM D5185): P ppm by weight 10 Fe ppm by weight 25 Si ppm by weight 45 Na ppm by weight 2 B ppm by weight 2 Simulated Distillation (ASTM D2887): 0% °C 40 10% °C 98 30% °C 161 50% °C 232 70% °C 309 90% °C 394 100% °C 432

[0203] The pyrolysis charge is subjected to a step a) of hydrotreating carried out in a fixed bed reactor and in the presence of hydrogen and a NiMo type hydrotreating catalyst on Alumina under different operating conditions and indicated in Table 3.

[0204] Table 3: Conditions of step a) hydrotreatment

[0205] [Tables3] Example 1 (non-compliant) Example 2 (compliant) Example 3 (compliant) Average Temperature °C 230 140 140 Partial Pressure of Hydrogen MPa abs 3 3 2 h2 / hc (Volume coverage of hydrogen relative to the charge volume) NmVm3 5 5 5 WH (Volume flow rate of charge / volume of catalysts) h1 0.5 0.5 0.35

[0206] At the end of step a) of hydrogenation, the conversion rates (= (initial concentration - final concentration) / initial concentration) observed in chlorine, diolefins and olefins are indicated in Table 4.

[0207] Table 4: Species conversions during step a) of hydrotreatment

[0208] [Tables4] Example 1 (non-compliant) Example 2 (compliant) Example 3 (compliant) Chlorine conversion rate % 90 82 75 Diolefin conversion rate % 60 21 12 Olefin conversion rate % 18 0 0 H2 consumption % weight relative to fresh load weight 0.18 0.01 0.01

[0209] The effluent from step a) of hydrotreatment is subjected to a step b) of separation: a stream of water is injected into the effluent from step a) of hydrotreatment; the mixture is then treated in an acid gas scrubbing column and separator tanks.

[0210] The yields of the different fractions obtained after separation are shown in Table 5 (the yields correspond to the ratios of the mass quantities of the different products obtained to the mass of feed upstream of step a), expressed as a percentage and noted % w / w).

[0211] Table 5: Yields of the different products obtained after separation

[0212] [Tables5] Gas fraction (NH3 + H2S + H2O + C1-C4) % m / m 2.42 Liquid fraction % m / m 99.31

[0213] The characteristics of the liquid fraction obtained after separation step b) are presented in Table 6:

[0214] Table 6: Liquid fraction characteristics

[0215] [Tableauxô] Description Methods Unit Example 1 (non-compliant) Example 2 (compliant) Example 3 (compliant) Sulfur Content ISO 20846 ppm weight 250 279 286 Nitrogen Content ASTM D4629 ppm weight 725 730 730 Bromine Value ASTM D1159 g / 100g 76.1 80 80 Maleic Anhydride Value MAV Method (1) mg / 100g 4 7.9 8.8 Chlorine Content ASTM D7536 ppm weight 10 17 24 Simulated Distillation ASTM D2887 0% °C 60 65 63 10% °C 98 99 98 30% °C 161 162 160 50% °C 232 231 231 70% °C 309 308 309 90% °c 394 393 394 100% °c 432 434 433

[0216] The effluent from step b) is then mixed with a petroleum feedstock for FCC having a chlorine content of 1 ppm wt. In a mass ratio of 10% oil / 90% petroleum feedstock, a mixture is obtained containing less than 5 ppm wt of chlorine (for all examples) which can be introduced into a fluidized bed catalytic cracking unit without fear of corrosion problems related to the chlorine content.

[0217] However, in the cases of Examples 2 and 3 according to the invention, the olefins and diolefins are preserved, which is advantageous because they are valuable compounds in the FCC for the production of propylene. Furthermore, less energy is used according to the process of the invention (temperatures of step a)) and less hydrogen (H2 consumption).

[0218] Example 3, carried out under very mild temperature and pressure conditions, shows that it is possible to obtain an oil sufficiently free of chlorine while preserving as much of the olefins and diolefins as possible and while using less pressure (and therefore less energy) than in example 2.

Claims

Demands

1. A process for treating a so-called pyrolysis feed, comprising a pyrolysis oil of plastics and / or tires and / or solid recovered fuels comprising halogenated compounds, said process comprising: a) a hydrotreating step carried out in a hydrotreating reaction section comprising at least one hydrotreating catalyst, said hydrotreating reaction section being fed at least by the pyrolysis feed and a gaseous stream comprising hydrogen, said hydrotreating reaction section being carried out at an average temperature between 100 and 220°C, a partial pressure of hydrogen between 1.0 and 3.0 MPa abs. and an hourly volumetric velocity between 0.05 and 5 h1, the hydrogen coverage being between 5 and 50 Nm3 of hydrogen per m3 of pyrolysis feed, to obtain a partially hydrotreated effluent having hydrocarbon compounds with a reduced halogen content,b) a separation step, fed by the partially hydrotreated effluent from step a) and an aqueous solution to obtain at least one gaseous effluent, one aqueous effluent and one partially hydrotreated hydrocarbon effluent, the separation step b) being carried out at a temperature between 20 and 200°C, c) a fluidized bed catalytic cracking or hydrorefining step of a petroleum feedstock and / or a feedstock from biomass conversion in which at least a portion of the partially hydrotreated hydrocarbon effluent from step b) is introduced as a co-feedstock, said partially hydrotreated hydrocarbon effluent from step b) being introduced without prior hydrotreatment at a higher temperature and / or pressure than the temperature and / or pressure of step a),said mixture of said petroleum feedstock and / or said feedstock resulting from the conversion of biomass and partially hydrotreated hydrocarbon effluent from step b) having a halogen content less than or equal to 10 ppm by weight.

2. A method according to the preceding claim, wherein the mass ratio between the flow rate of the partially hydrotreated hydrocarbon effluent from step b) and the flow rate of petroleum feed and / or feed from the conversion of biomass introduced in step c) is less than 1.

3. A method according to any one of the preceding claims, wherein the pyrolysis charge consists of a pyrolysis oil of plastics and / or tires and / or solid recovered fuels.

4. A method according to any one of the preceding claims, wherein the halogenated compound content of said pyrolysis charge is between 1 and 5000 ppm by weight.

5. A method according to any one of the preceding claims wherein a stream containing a nitrogen compound and / or a sulfur compound is injected upstream of step a).

6. A process according to any one of the preceding claims, wherein said hydrotreating catalyst of step a) comprises a support selected from alumina, silica, silica-aluminas, magnesia, clays and mixtures thereof and a hydro-dehydrogenating function comprising either at least one element of Group VIII and at least one element of Group VIB, or at least one element of Group VIII.

7. A process according to any one of the preceding claims, comprising at least one pretreatment step aO) of the feed comprising a pyrolysis oil of plastics and / or tires and / or RDF, said pretreatment step being carried out upstream of step a) and comprising 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.

8. A method according to any one of the preceding claims, wherein the petroleum feedstock is selected from gasoline, gas oils, vacuum gas oils, atmospheric residues, vacuum residues, atmospheric distillates, vacuum distillates, heavy fuel oils, oils, waxes and paraffins, used oils, residues or deasphalted crudes, petroleum feedstocks from thermal or catalytic conversion processes, or mixtures of such feedstocks.

9. A method according to any one of the preceding claims, wherein the biomass feedstock is selected from vegetable oils, algae or algal oils, fish oils, used edible oils, and fats of vegetable or animal origin; methyl esters of fatty acids of vegetable and / or animal origin, methyl esters of fatty acids from used edible vegetable oils, charges originating from thermal or catalytic biomass conversion processes, or mixtures of such charges.

10. A method according to any one of the preceding claims wherein the reaction section of step a) implements at least two reactors operating in switchable mode.

11. A process according to any one of the preceding claims wherein step c) of fluidized bed catalytic cracking is carried out in a fluidized bed catalytic cracking reaction section in a substantially vertical reactor either in upstream or downstream mode in the presence of a zeolite catalyst at a reactor temperature between 450°C and 600°C with a contact time in the reactor of less than 1 minute.

12. A process according to any one of claims 1 to 10, wherein the hydrorefining step c) is a hydrotreating step carried out in a hydrotreating reaction section comprising at least one hydrotreating catalyst, said hydrotreating reaction section being fed by a gas stream comprising hydrogen, said hydrotreating reaction section being carried out at an average temperature between 180 and 480°C, a partial pressure of hydrogen between 0.5 and 25 MPa abs., an hourly volumetric velocity between 0.1 and 20 h1, and a hydrogen cover of between 50 and 5000 Nm3 of hydrogen per m3 of feed.

13. A process according to any one of claims 1 to 10, wherein the hydrorefining step c) is a hydrocracking step carried out in a hydrocracking reaction section comprising at least one hydrocracking catalyst, said hydrocracking reaction section being fed by a gas stream comprising hydrogen, said hydrocracking reaction section being carried out at an average temperature between 250 and 480°C, a partial pressure of hydrogen between 2 and 25 MPa abs., an hourly volumetric velocity between 0.5 and 40 h1, and a hydrogen blanket of between 80 and 5000 Nm3 of hydrogen per m3 of feed.

14. A process according to any one of claims 1 to 10, wherein the hydrorefining step (c) is a hydroconversion step carried out in a hydroconversion reaction section comprising at least one hydroconversion catalyst, said hydroconversion reaction section being fed by a gas stream comprising hydrogen, said hydroconversion reaction section being implemented at an average temperature between 340 and 550°C, a partial pressure of hydrogen between 2 and 38 MPa abs., an hourly volumetric velocity between 0.05 and 10 h*, and a hydrogen blanket between 50 and 5000 Nm3 of hydrogen per m3 of charge.

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