Method for simultaneous processing of plastic pyrolysis oil and feedstock derived from renewable resources

Abstract

The present invention relates to a method for processing a feedstock comprising plastic pyrolysis oil and a feedstock derived from renewable resources, comprising: - a) an optional step of selective hydrogenation of the feedstock comprising plastic pyrolysis oil; - b) hydrodemetallization of the feedstock comprising plastic pyrolysis oil or the effluent from step a); - c) hydrotreatment of said effluent from step b), wherein said feedstock derived from renewable resources is introduced into step a) and / or step b) and / or step c), and the weight ratio of the flow rate of the feedstock comprising plastic pyrolysis oil to the flow rate of the introduced feedstock derived from renewable resources is between 0.05 and 20, and - d) separation in the presence of an aqueous stream.

Description

[Technical Field]

[0001] The present invention relates to a method for co-processing plastic pyrolysis oil and a feedstock derived from a renewable resource to obtain a hydrocarbon-based effluent that may be incorporated directly into a naphtha or diesel pool or upgraded as a feedstock to a steam cracking unit. More particularly, the present invention relates to a method for co-processing a feedstock derived from the pyrolysis of plastic waste and a feedstock derived from a renewable resource to at least partially remove impurities that may be present in relatively high amounts in these feedstocks. [Background technology]

[0002] The plastics obtained from the collection and sorting channels can be subjected to a process of pyrolysis to obtain, among other things, pyrolysis oils, which are generally incinerated to generate electricity and / or used as fuel in industrial or municipal heating boilers.

[0003] Another route to upgrading plastic pyrolysis oils is to use them as feedstock for steam cracking units to (re)produce olefins, which are the constituent monomers of certain polymers. However, plastic waste is generally a mixture of several polymers, such as polyethylene, polypropylene, polyethylene terephthalate, polyvinyl chloride, and polystyrene. Furthermore, depending on the application, plastics may contain other compounds in addition to polymers, such as plasticizers, pigments, dyes, or polymerization catalyst residues. Plastic waste may also contain small amounts of renewable resources, for example, originating from household waste. Waste treatment, especially storage, mechanical treatment, sorting, and pyrolysis on the one hand, and also the storage and transportation of pyrolysis oil on the other, can cause corrosion. As a result, the oil obtained from the pyrolysis of plastic waste often contains high levels of impurities, particularly diolefins, metals, metalloids, especially iron, silicon, or halogenated compounds, especially chlorinated compounds, heteroelements such as sulfur, oxygen, and nitrogen, and insoluble matter, which are incompatible with the steam cracking unit or units downstream of the steam cracking unit, especially polymerization and selective hydrogenation processes. These impurities can cause problems with operability, especially corrosion, coking, or catalyst deactivation, or incompatibility in the application of the target polymer. The presence of diolefins can also lead to instability problems in the pyrolysis oil, characterized by the formation of gums. The gums and insoluble materials that may be present in the pyrolysis oil can cause clogging problems in the process.

[0004] Furthermore, during the steam cracking process, the yield of light olefins, especially ethylene and propylene, desired for petrochemical applications, is highly dependent on the quality of the feedstock sent to the steam cracking process. The BMCI (Bureau of Mines Correlation Index) is often used to characterize hydrocarbon fractions. This index was developed for hydrocarbon-based products obtained from crude oil and is calculated from measurements of density and average boiling point: it is equal to 0 for normal paraffins and 100 for benzene. Therefore, if the analyzed product contains naphthenes, which are condensed aromatic structures with an intermediate BMCI between paraffins and aromatics, its value will be higher. Overall, a higher yield of light olefins occurs when the paraffin content increases, thereby decreasing the BMCI. Conversely, a higher yield of unwanted heavy compounds and / or coke occurs when the BMCI increases.

[0005] The integration of new products of plant origin into refinery processes, derived from the conversion of lignocellulosic renewable resources or from the production of vegetable oils or animal fats, has experienced a significant resurgence of interest over the past few decades due to the rising cost of fossil materials and the desire to reduce the transportation carbon footprint. As a result, many biofuels (mainly ethanol, vegetable oil methyl esters, and hydrotreated vegetable oils) have gained a viable position as a petroleum-based supplement in the fuel pool.

[0006] Hydroprocessing of triglycerides and fatty acids derived from feedstocks of biological and / or animal origin makes it possible to obtain long-chain paraffins, which can optionally be hydroisomerized with the aim of incorporating them into fuel pools of the jet or diesel type.

[0007] However, the rapid electrification of land transport vehicles is likely to limit reliance on biogenic feedstocks in the coming years, so there is an advantage to finding new upgrade methods.

[0008] The document WO 02 / 04796 proposes a very general and relatively complex overall method for recycling plastic waste, which starts from the step of pyrolysis of plastic waste to the step of steam cracking. The method of WO 02 / 04796 comprises, inter alia, a step of hydrotreating the liquid phase obtained directly from the pyrolysis, preferably under very strict conditions, in particular with respect to temperature, for example at a temperature of 260-300°C, a step of separation of the hydrotreated effluent, and a subsequent step of hydrodealkylation of the separated heavy effluent, preferably at high temperatures, for example at 260-400°C.

[0009] Unpublished patent application FR 20 / 01758 describes a method for treating plastic pyrolysis oil, which method comprises the following steps: a) selectively hydrogenating said feedstock in the presence of hydrogen and a selective hydrogenation catalyst; obtaining a hydrogenated effluent; b) fixed-bed hydrotreating said hydrotreated effluent in the presence of hydrogen and a hydrotreating catalyst; obtaining a hydrotreated effluent; c) Separation of the hydroprocessing effluent in the presence of an aqueous stream at a temperature between 50 and 370°C to obtain a gaseous effluent, an aqueous liquid effluent and a hydrocarbon-based liquid effluent; d) optionally fractionating all or part of the hydrocarbon-based effluent obtained from step c) to obtain a gas stream and at least two hydrocarbon-based streams, which may be a naphtha fraction and a heavier fraction; e) a recycling step, comprising recovering a portion of the hydrocarbon-based effluent obtained from separation step c) or a portion of the hydrocarbon-based stream obtained from fractionation step d) and / or at least one of said hydrocarbon-based streams for recycling to selective hydrogenation step a) and / or hydrotreating step b).

[0010] Patent document 2 proposes a method for processing petroleum-based and biogenic feedstocks, in which the petroleum-based feedstock is injected into a catalyst section located upstream of the injection point of the biogenic feedstock. The solution proposed in Patent document 2 does not make it possible to process plastic pyrolysis oil in a mixture with biogenic feedstocks.

[0011] Therefore, the simultaneous processing of plastic pyrolysis oil and feedstocks derived from renewable resources allows for optimal processing of the two feedstocks by efficiently treating the impurities present and converting the feedstocks into upgradeable products. These products can be used, among other things, as feedstock for a steam cracking unit aimed at producing olefins, and after polymerization it will be possible to obtain not only recycled polymers due to the plastic origin of the pyrolysis oil, but also polymers with reduced environmental impact due to their biological origin. These products can be upgraded as a base in the fuel pool. [Prior art documents] [Patent documents]

[0012] [Patent Document 1] International Publication No. 2018 / 055555 [Patent Document 2] French Patent Application Publication No. 2910017 Summary of the Invention [Means for solving the problem]

[0013] (Summary of the Invention) The present invention relates to a method for processing feedstocks containing plastic pyrolysis oil and feedstocks derived from renewable resources, the method comprising the steps of: a) an optional selective hydrogenation step, in which the feedstock containing the plastic pyrolysis oil and a gas stream containing hydrogen are fed to a reaction section, in the presence of at least one selective hydrogenation catalyst, at a temperature of 80 to 280°C, a hydrogen partial pressure of 1.0 to 20.0 MPa (absolute), and an hourly space velocity of 0.3 to 10.0 h -1 obtaining a hydrogenated effluent; b) Hydrodemetallization step: This step is carried out in a hydrodemetallization reaction section containing at least one hydrodemetallization catalyst, and at least a feedstock containing plastic pyrolysis oil and / or a hydrogenated effluent obtained from step a) and a gas stream containing hydrogen are fed to the hydrodemetallization reaction section, and the average temperature during the hydrodemetallization reaction section is 140 to 400°C, the partial pressure of hydrogen is 1.0 to 20.0 MPa (absolute), and the hourly space velocity is 0.1 to 10.0 h -1 Obtaining a demetallized effluent, c) a hydrotreating step, which is carried out in a hydrotreating reaction section containing at least one hydrotreating catalyst, to which at least the demetallized effluent obtained from step b) and a gas stream containing hydrogen are fed, the hydrotreating reaction section being used at a temperature of 250 to 450°C, the hydrogen partial pressure being 1.0 to 10.0 MPa (absolute), and the hourly space velocity being 0.1 to 10.0 h -1 to obtain a hydrotreated effluent. wherein the feedstock derived from renewable resources is optionally introduced in step a) and / or step b) and / or step c) as a mixture with the feedstock comprising plastic pyrolysis oil, The weight ratio between the flow rate of the feedstock containing plastic pyrolysis oil and the flow rate of the introduced renewable resource-derived feedstock is 0.05 to 20; c') an optional hydrocracking step, carried out in a hydrocracking reaction section comprising at least one hydrocracking catalyst, to which at least the hydrotreated effluent from step c) and / or the fraction comprising compounds with a boiling point above 175°C from step e) and a gas stream comprising hydrogen are fed, the hydrocracking reaction section being used at an average temperature of 250 to 450°C, the hydrogen partial pressure being 1.5 to 20.0 MPa (absolute) and the hourly space velocity being 0.1 to 10.0 h -1 obtaining a hydrocracked effluent which is sent to separation step d); d) a separation step, wherein the hydrotreated effluent obtained from step c) and / or the hydrocracked effluent obtained from step c') and an aqueous solution are fed, said step being carried out at a temperature of 50 to 450°C; obtaining at least one gaseous effluent, an aqueous effluent and a hydrocarbon-based effluent; e) optionally fractionating all or part of the hydrocarbon-based effluent obtained from step d) to obtain at least one gaseous effluent, at least one fraction comprising compounds having a boiling point less than or equal to 175°C, and at least one hydrocarbon fraction comprising compounds having a boiling point greater than 175°C.

[0014] One advantage of the process according to the invention is that it allows the simultaneous purification of feedstocks comprising oil obtained from the pyrolysis of plastic waste and feedstocks derived from renewable resources to at least partially remove impurities, hydrogenating these feedstocks and upgrading the products thus obtained, in particular by incorporating them directly into the fuel pool and / or by adapting them for processing in a steam cracking unit, to obtain increased yields of light olefins which can be used in particular as monomers in the production of polymers.

[0015] The method according to the invention is particularly distinguished by its great flexibility in introducing the renewable resource-derived feedstock depending on the impurities in the various steps of the method. Indeed, if the renewable resource-derived feedstock contains many impurities, it can be introduced partially or entirely in steps a) and / or b). If such treatment is not required, the renewable resource-derived feedstock can also be introduced partially or entirely in step c).

[0016] Another advantage of the present invention is that it limits the temperature increase between the inlet and outlet of a plug flow reactor, e.g., a fixed bed, induced in particular by the heat generated by the hydroprocessing of renewable resource-derived feedstocks, where this heat is partially absorbed by the simultaneously processed plastic pyrolysis oil, resulting in an optimized process that limits significant reliance on effluent recycling and / or gaseous and / or liquid cooling streams.

[0017] The process of the present invention thus makes it possible to obtain a hydrocarbon-based effluent obtained from plastic pyrolysis oil and from feedstocks derived from renewable resources, from which starting impurities have been at least partially removed, thereby limiting operability problems that these impurities may cause, such as corrosion, coking or catalyst deactivation, in particular in the steam cracking unit and / or units located downstream of the steam cracking unit, especially in the polymerization unit and hydrogenation unit. The removal of at least a portion of the impurities from the oil obtained from the pyrolysis of plastic waste and from feedstocks derived from renewable resources also makes it possible to broaden the range of applications of the target polymer, reducing its incompatibility with the application.

[0018] According to one variant, the process according to the invention comprises a fractionation step e).

[0019] According to one variant, the process according to the invention comprises a hydrocracking step c').

[0020] According to one variant, the process according to the invention comprises said selective hydrogenation step a).

[0021] According to one variant, the feedstock derived from renewable resources is a feedstock comprising oils and / or fats of plant and / or animal origin.

[0022] According to one variant, at least part of the feedstock derived from renewable resources is introduced into step c).

[0023] According to one variant, the temperature in the reaction section of step c) is higher than the temperature in the hydrodemetallization reaction section of step b).

[0024] According to one variant, at least part of the hydrocarbon-based effluent obtained from the separation step d) or at least part of the naphtha fraction comprising compounds with a boiling point below 175° C. obtained from the fractionation step e) is sent as a recycle stream to the selective hydrogenation step a) and / or the hydrodemetallization step b) and / or the hydrotreating step c).

[0025] According to one variant, at least part of the fraction comprising compounds with a boiling point above 175° C. obtained from fractionation step e) is sent as a recycle stream to the hydrodemetallization step b) and / or the hydrotreating step c) and / or the hydrocracking step c′).

[0026] According to one variant, the weight ratio between the recycled stream and the feedstock comprising plastic pyrolysis oil and the feedstock from renewable sources is less than or equal to 10.

[0027] According to one variant, the process according to the invention comprises a step a0) of pretreating the feedstock, said pretreatment step being carried out upstream of the selective hydrogenation step a) and comprising a filtration step and / or an electrostatic separation step and / or a step of washing with an aqueous solution and / or an adsorption step.

[0028] According to one variant, the hydrocarbon-based effluent obtained from the separation step d) or at least one of the two liquid hydrocarbon-based streams obtained from step e) is sent, in whole or in part, to a steam cracking step f), which is carried out in at least one pyrolysis furnace, the temperature being between 700 and 900°C and the pressure being between 0.05 and 0.3 MPa (relative).

[0029] According to one variant, the selective hydrogenation catalyst comprises a support selected from alumina, silica, silica-alumina, magnesia, clay and mixtures thereof, and a hydrodehydrogenation functional group comprising either at least one Group VIII element and at least one Group VIB element, or at least one Group VIII element.

[0030] According to one variant, the hydrodemetallization catalyst and the hydrotreating catalyst comprise a support selected from the group consisting of alumina, silica, silica-alumina, magnesia, clay and mixtures thereof, and a hydrodehydrogenation functional group comprising at least one Group VIII element and / or at least one Group VIB element.

[0031] According to one variant, the process according to the invention also comprises a second hydrocracking step c''), which is carried out in a hydrocracking reaction section comprising at least one hydrocracking catalyst, said hydrocracking reaction section being fed with the fraction comprising compounds with a boiling point above 175°C obtained from step e) and a gas stream comprising hydrogen, said hydrocracking reaction section being used at a temperature between 250 and 450°C, with a partial pressure of hydrogen between 1.5 and 20.0 MPa (absolute) and an hourly space velocity between 0.1 and 10.0 h -1 to obtain a hydrocracked effluent, which is sent to the separation step d).

[0032] According to one variant, the hydrocracking catalyst comprises a support selected from halogenated alumina, a combination of oxides of boron and aluminum, amorphous silica-alumina and zeolites, and a hydrodehydrogenation functional group containing at least one Group VIB metal selected from chromium, molybdenum and tungsten, alone or in mixtures, and / or at least one Group VIII metal selected from iron, cobalt, nickel, ruthenium, rhodium, palladium and platinum.

[0033] According to one variant, the feedstock has the following characteristics: - the content of aromatic compounds is 0 to 90% by weight; - the content of halogenated compounds is 2 to 5000 ppm by weight; - The content of metallic elements is 10 to 10,000 ppm by weight; - Contains iron element, the content of which is 0 to 100 ppm by weight; The silicon content is 0 to 1000 ppm by weight.

[0034] The present invention also relates to products that may be obtained via the process according to the invention.

[0035] According to one variant, the product comprises, relative to the total weight of the product: - metallic elements with a total content of 5.0 ppm by weight or less, - Contains iron element, the content of which is 100 ppb by weight or less; - elemental silicon with a content of not more than 1.0 ppm by weight, - sulfur content not exceeding 500 ppm by weight, - nitrogen with a content of not more than 100 ppm by weight, - Elemental chlorine with a content of not more than 10 ppm by weight.

[0036] According to the invention, pressure is absolute pressure, also expressed as abs. (absolute) and is given in MPa (absolute pressure) (or MPa (absolute)), unless otherwise indicated.

[0037] According to the present invention, the expressions "comprised between ... and ..." and "between ... and ..." are equivalent and mean that both limits of the interval are included within the range of values ​​stated. If this is not the case and if both limits are not included within the range stated, such clarification is provided by the present invention.

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

[0039] In the following text, specific and / or preferred embodiments of the present invention may be described, which may be implemented separately or combined together, without limitation to the combination where the combination is technically feasible.

[0040] Subsequently, the groups of chemical elements are given according to the CAS classification (CRC Handbook of Chemistry and Physics, published by CRC Press, editor-in-chief DR Lide, 81st edition, 2000-2001). For example, group VIII according to the CAS classification corresponds to the metals in columns 8, 9 and 10 according to the new IUPAC classification.

[0041] The metal content is measured by X-ray fluorescence. DETAILED DESCRIPTION OF THE INVENTION

[0042] (Detailed explanation) (Feed material) According to the invention, the feedstocks treated in the method according to the invention are feedstocks comprising plastic pyrolysis oil and feedstocks derived from renewable resources.

[0043] "Plastic pyrolysis oil" is an oil derived from the pyrolysis of plastics, preferably plastic waste, particularly originating from the collection and sorting industries. It contains a mixture of hydrocarbon-based compounds, in particular paraffins, mono- and / or diolefins, naphthenes, and aromatic compounds. At least 80% by weight of these hydrocarbon-based compounds preferably have a boiling point below 700°C, preferably below 550°C. In particular, depending on the origin of the pyrolysis oil, the oil may contain up to 70% by weight of paraffins, up to 90% by weight of olefins, and up to 90% by weight of aromatic compounds, the sum of which is understood to be 100% by weight of the hydrocarbon-based compounds.

[0044] The density of pyrolysis oil is generally 0.75 to 0.99 g / cm, measured at 15°C according to ASTM D4052 method. 3 , preferably 0.75 to 0.95 g / cm 3 is.

[0045] Pyrolysis oil can further contain, and usually contains, impurities such as metals, especially iron, silicon, or halogenated compounds, especially chlorinated compounds. These impurities may be present in high concentrations in plastic pyrolysis oil, for example, up to 350 ppm by weight, even up to 700 ppm by weight, or even up to 1000 ppm by weight of halogen elements (especially chlorine) provided by halogenated compounds, and up to 100 ppm by weight, or even up to 200 ppm by weight of metallic or semi-metallic elements. Alkali metals, alkaline earth metals, transition metals, post-transition metals, and metalloids may be likened to metallic contaminants called metals or metallic or semi-metallic elements. In particular, metals or metallic or semi-metallic elements that may be contained in oil obtained from the pyrolysis of plastic waste include silicon, iron, or both of these elements. The plastic pyrolysis oil may also contain other impurities, such as heteroelements provided in particular by sulfur compounds, oxygen compounds and / or nitrogen compounds, generally in a content of less than 10,000 ppm by weight of heteroelements, preferably less than 4,000 ppm by weight of heteroelements.

[0046] Plastic pyrolysis oil may be obtained from a thermal catalytic pyrolysis process or alternatively may be prepared by hydropyrolysis (thermal cracking in the presence of a catalyst and hydrogen).

[0047] Feedstocks treated in the method according to the invention also include feedstocks derived from renewable resources.

[0048] According to a first variant, the feedstock derived from renewable resources is advantageously selected from oils or fats of vegetable and / or animal origin. The vegetable and / or animal origin oils or fats used in the present invention contain triglycerides and / or free fatty acids and / or esters. The vegetable oils may advantageously be crude or fully or partially refined oils and may be derived from rapeseed, sunflower, soybean, palm, palm kernel, olive, coconut, or jatropha, but this list is not limiting. Algae oils or fish oils are also suitable. The animal fats are advantageously selected from fats composed of lard or residues from the food industry or catering industry. It is selected from fats consisting of blubber and residues from the food industry or residues resulting from the catering industry.

[0049] These feedstocks essentially contain triglyceride-type chemical structures, also known to those skilled in the art as fatty acid triesters and / or free fatty acids. Fatty acid triesters are therefore composed of three fatty acid chains. These fatty acid chains, in triester or free fatty acid form, generally have 0-3 unsaturations per chain (also known as the number of carbon-carbon double bonds per chain), although this can be higher, especially in the case of oils derived from algae, which generally have 5-6 unsaturations per chain.

[0050] Thus, the molecules present in the feedstocks containing oils or fats or of plant and / or animal origin used in the present invention advantageously have a number of unsaturations per molecule between 0 and 18. In these feedstocks, the ratio between the sum of the number of unsaturations of all molecules and the number of molecules is advantageously between 0 and 6.

[0051] According to a second variant, the feedstock derived from renewable resources is advantageously selected from lignocellulosic biomass, for example, feedstocks originating from processes for the thermal and / or catalytic conversion of oils produced from lignocellulosic biomass by various liquefaction processes, for example, hydrothermal liquefaction or pyrolysis. The term "biomass" refers to materials derived from recently living organisms, including plants, animals, and their by-products. The term "lignocellulosic biomass" refers to renewable resources derived from plants or their by-products. Lignocellulosic renewable resources are composed of carbohydrate polymers (cellulose, hemicellulose) and aromatic polymers (lignin).

[0052] These feedstocks derived from renewable resources may be crude feedstocks or refined or semi-refined feedstocks, which also contain impurities, especially phospholipids, alkali metals, alkaline earth metals, especially iron, phosphorus, sodium, calcium, magnesium.

[0053] Preferably, the renewable resource derived feedstock is a feedstock comprising oils or fats of plant and / or animal origin.

[0054] The feedstock for the process according to the invention comprises at least one plastic pyrolysis oil and at least one feedstock derived from renewable resources. The feedstock may consist exclusively of plastic pyrolysis oil(s) and feedstock(s) derived from renewable resources. Preferably, the feedstock comprises at least 50% by weight, preferably 75% to 100% by weight, of plastic pyrolysis oil(s) and feedstock(s) derived from renewable resources, i.e. preferably 50% to 100% by weight, preferably 70% to 100% by weight, of plastic pyrolysis oil and feedstock(s) derived from renewable resources.

[0055] The weight ratio between the flow rate of the feedstock comprising plastic pyrolysis oil and the flow rate of the feedstock(s) derived from renewable resources introduced into the process according to the invention is generally between 0.02 and 50, usually between 0.05 and 20, preferably between 0.1 and 10. The term "weight ratio" is intended to mean the total weight ratio introduced into the process according to the invention, regardless of the step in which the feedstock derived from renewable resources is introduced.

[0056] The feedstock for the process according to the invention may comprise a conventional petroleum-based feedstock, which is then co-processed with the plastic pyrolysis oil and the feedstock derived from renewable resources. The conventional petroleum-based feedstock may advantageously be a fraction or a mixture of fractions of the naphtha, gas oil or vacuum gas oil type. In this case, the petroleum-based feedstock may be injected in steps a) and / or b) and / or c) and / or c'), preferably in step c).

[0057] (Preprocessing (optional)) Said feedstock comprising plastic pyrolysis oil and / or feedstock derived from renewable resources may advantageously be pretreated in an optional pretreatment step a0) prior to the selective hydrogenation step a) to obtain at least one pretreated feedstock, which is fed to step a) or step b).

[0058] The feedstock to be pretreated in optional step a0) may comprise, inter alia: - a mixture of plastic pyrolysis oil and feedstock derived from renewable resources; - Feedstocks containing plastic pyrolysis oil and not having feedstocks derived from renewable resources; - Feedstock derived from renewable resources and free of plastic pyrolysis oils; - two different streams; one containing plastic pyrolysis oil and the other containing feedstock derived from renewable resources, which are treated in parallel in a pretreatment step a0) under different treatment conditions and operations.

[0059] If the feedstock to be pretreated in optional step a0) is a feedstock comprising plastic pyrolysis oil and does not have a feedstock derived from renewable resources, the feedstock derived from renewable resources can be introduced into step a) and / or step b) and / or step c), while the pretreated feedstock comprising plastic pyrolysis oil is introduced into optional step a) or step b).

[0060] If the feedstock to be pretreated in optional step a0) is a renewable resource derived feedstock and does not have plastic pyrolysis oil, a feedstock comprising plastic pyrolysis oil may be introduced into optional step a) or step b), while the pretreated renewable resource derived feedstock may be introduced into step a) and / or step b) and / or step c).

[0061] This optional pretreatment step a0) makes it possible to reduce the amount of contaminants, in particular iron and / or silicon and / or chlorine and / or phosphorus and / or sodium and / or calcium, that may be present in the feedstock containing pyrolysis oil and / or the feedstock derived from renewable resources. Therefore, the optional pretreatment step a0) of the feedstock containing pyrolysis oil and / or the feedstock derived from renewable resources is advantageously carried out in particular when the feedstock contains more than 10 ppm by weight, in particular more than 20 ppm by weight, and more particularly more than 50 ppm by weight of metallic elements, and in particular when the feedstock 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. Similarly, the optional pretreatment step a0) is advantageously carried out in particular when the feedstock contains more than 10 ppm by weight, in particular more than 20 ppm by weight, and more particularly more than 50 ppm by weight of chlorine. Likewise, the optional pretreatment step a0) is advantageously carried out in particular when the feedstock contains more than 100 ppm by weight, in particular more than 200 ppm by weight, more particularly more than 500 ppm by weight of phosphorus. Likewise, the optional step a0) of pretreatment of the feedstock is advantageously carried out in particular when the feedstock contains acidic species resulting in a TAN (Total Acid Number) value of more than 1 mg KOH / g, even more than 3 mg KOH / g, or even more than 6 mg KOH / g.

[0062] Said optional pretreatment step a0) may be carried out by any method known to those skilled in the art making it possible to reduce the amount of contaminants, and it may in particular comprise a filtration step and / or an electrostatic separation step and / or a step of washing with an aqueous solution and / or an adsorption step.

[0063] The optional pretreatment step a0) is advantageously carried out at a temperature of 0 to 150°C, preferably 5 to 100°C, and at a pressure of 0.15 to 10.0 MPa (absolute), preferably 0.2 to 1.0 MPa (absolute).

[0064] According to one variant, the optional pretreatment step a0) is carried out in an adsorption section operated in the presence of at least one adsorbent, preferably of the alumina type, which has a specific surface area of ​​at least 100 m 2 / g or more, preferably 200m 2 The specific surface area of ​​said at least one adsorbent is advantageously 600 m 2 / g or less, especially 400m 2 The specific surface area of ​​the adsorbent is the surface area measured by the BET method, i.e., the specific surface area determined by nitrogen adsorption according to standard ASTM D 3663-78, which was established from the Brunauer-Emmett-Teller method described in The Journal of the American Chemical Society, 6Q, 309 (1938).

[0065] Advantageously, the adsorbent contains less than 1% by weight of metallic elements, preferably no metallic elements. The term "metallic elements of the adsorbent" should be understood to refer to elements of groups 6 to 10 of the Periodic Table of the Elements (new IUPAC classification). The residence time of the feedstock in the adsorbent section is generally between 1 and 180 minutes.

[0066] The adsorption section of optional step a0) comprises at least one adsorption tower, preferably at least two adsorption towers, and preferentially two to four adsorption towers, containing the adsorbent. When the adsorption section comprises two adsorption towers, one operating mode may be referred to in technical terms as "swing" operation, in which one tower is online, i.e., in service, while the other tower is in reserve. When the adsorbent in the online tower is exhausted, it is isolated, while the in-reserve tower is placed online, i.e., in service. The spent adsorbent is subsequently regenerated in situ and / or replaced with fresh adsorbent so that the tower containing it can again be placed online where the other tower is isolated.

[0067] Another mode of operation is to have at least two columns operated in series. When the adsorbent in the first column is exhausted, the first column is isolated and the spent adsorbent is either regenerated in-situ or replaced with fresh adsorbent. The column is then brought back online with the last column in place, and so on. This mode of operation is known as permutable mode, or PRS for Permutable Reactor System, or by other technical terms, "lead and lag." The combination of at least two adsorption columns makes it possible to overcome the possible and potentially rapid poisoning and / or plugging of the adsorbent due to the combined effects of metallic contaminants, diolefins, gums derived from diolefins, phosphorus, sodium, calcium, and insolubles that may be present in the feedstock being treated. The reason for this is that the presence of at least two adsorption columns advantageously facilitates replacement and / or regeneration of the adsorbent without shutting down the pretreatment unit and thus the process, reducing the risk of clogging and thus making it possible to avoid shutting down the unit due to clogging, control costs and limit adsorbent consumption.

[0068] According to another variant, the optional pretreatment step a0) is carried out in a washing section by contacting the feedstock with at least one washing liquid. This washing liquid may be an organic solvent or an aqueous solution or an aqueous solution containing organic compounds. Preferably, the washing liquid is an aqueous solution, which may be, for example, water, preferably demineralized and aerated water, or an acidic or basic solution. This washing section may comprise a device for contacting the feedstock with the washing liquid and separating the phases to obtain, on the one hand, a pretreated feedstock and, on the other hand, an aqueous solution containing impurities. Among these devices, for example, stirred reactors, decanters, mixer-decanters, cocurrent or countercurrent washing columns may be used. Advantageously, the washing column is a packed column, a plate column, a stirred column or a pulse column; the ratio between the amount of washing liquid and the amount of feedstock is between 0.01 and 100, preferably between 0.1 and 10, preferably between 0.15 and 2.

[0069] Said optional pretreatment step a0) may optionally be fed with a recycle stream, advantageously at least a portion of the recycle stream obtained from step d) or optional step e) of the process, either in a mixture with or separately from the feedstock comprising pyrolysis oil and / or the feedstock derived from renewable resources.

[0070] Said optional pretreatment step a0) thus makes it possible to obtain a pretreated feedstock, which is then fed to the selective hydrogenation step a) or to the hydroconversion step b).

[0071] (Selective Hydrogenation Step a) (Optional)) According to the present invention, the method may comprise a step a) of selective hydrogenation of a feedstock containing plastic pyrolysis oil, and optionally a feedstock derived from renewable resources, if such a feedstock is introduced into step a), which step a) is carried out in the presence of hydrogen under conditions of hydrogen pressure and temperature that allow the feedstock to be maintained in the liquid phase, and with an amount of soluble hydrogen just required for the selective hydrogenation of the diolefins present in the feedstock. Selective hydrogenation of at least a portion of the diolefins in the liquid phase thus makes it possible to avoid or at least limit the formation of "gums," i.e., polymerization of diolefins and thus the formation of oligomers and polymers, which can clog the reaction sections of hydrodemetallization step b) and / or hydrotreating step c). Styrenic compounds optionally present in the feedstock, especially styrene, may also behave similarly to diolefins with respect to the formation of gums due to the fact that the double bond of the vinyl group is conjugated with the aromatic nucleus. Said selective hydrogenation step a) makes it possible to obtain a selectively hydrogenated effluent, ie an effluent having a reduced content of olefins, in particular diolefins, and optionally styrene.

[0072] According to the invention, the selective hydrogenation step a) is carried out in a reaction section, which is fed at least with the feedstock (optionally pretreated) comprising plastic pyrolysis oil and with a gas stream comprising hydrogen (H).

[0073] Optionally, the reaction section of step a) may also be fed at least in part with a feedstock (optionally pretreated) derived from renewable resources.

[0074] Optionally, the reaction section of said step a) may also be fed with a recycle stream, advantageously at least part of a recycle stream obtained from step d) or optional step e) of the present process.

[0075] The feeding of the feedstock and / or recycle stream derived from renewable resources can be advantageously carried out directly at the inlet of the reaction section of step a), either in admixture with said feedstock comprising plastic pyrolysis oil or separately from said feedstock.

[0076] The reaction section comprises a selective hydrogenation in the presence of at least one selective hydrogenation catalyst, preferably in a fixed bed, advantageously at an average temperature (or WABT as defined below) of 80 to 280°C, preferably 120 to 260°C, preferably 130 to 250°C, and at a hydrogen partial pressure of 1.0 to 20.0 MPa (absolute), preferably 5.0 to 15.0 MPa (absolute), and at an hourly space velocity (HSV) of 0.3 to 10.0 h -1 , preferably 0.5 to 5.0 hours -1 is.

[0077] According to the present invention, the "temperature" of the reaction section containing at least one fixed bed reactor is the average temperature of the reaction section containing at least one fixed bed reactor and corresponds to the weight-average bed temperature (WABT) in the terminology well known to those skilled in the art. The average temperature is advantageously determined depending on the catalyst system used, the devices and their configuration. The average temperature (i.e., WABT) is calculated as follows:

[0078]

number

[0079] In the formula, T inlet : temperature of the effluent at the inlet of the reaction section, T outlet : the temperature of the effluent at the outlet of the reaction section.

[0080] The hourly space velocity (HSV) is defined here as the ratio of the hourly volumetric flow rate of the feedstock entering the reaction section to the volume of the catalyst(s). The expression "feedstock entering the reaction section of step a)" is intended to mean all of the "fresh" feedstock (optionally pretreated), i.e., comprising at least pyrolysis oil, and optionally comprising part or all of the feedstock derived from renewable resources, optionally supplemented with recycle streams obtained from steps d) and / or e).

[0081] The amount of gas stream containing hydrogen (H2) fed to the reaction section of step a) is advantageously determined so that the hydrogen coverage is proportional to the volume (m2) of the feedstock entering the reaction section. 3 ) per 1-200Nm of hydrogen 3 (Nm 3 / m 3 ), preferably the volume of the feedstock (m 3 ) 1 to 50 Nm of hydrogen per 3 (Nm 3 / m 3 ), preferably the volume of the feedstock (m 3 ) 5 to 20 Nm of hydrogen per 3 (Nm 3 / m 3 ) is the amount.

[0082] The hydrogen coverage is defined as the ratio of the volumetric flow rate of hydrogen measured under standard temperature and pressure conditions relative to the volumetric flow rate of the feedstock (not taking into account any recycle fraction) as it may be pretreated entering the reaction section at 15°C (volume of feedstock (m 3 ) per standard m of H2 3 (Nm 3 is shown).

[0083] The hydrogen-containing gas stream fed to the reaction section of step a) may consist of hydrogen feed and / or recycled hydrogen, advantageously obtained from step d) or optional step e).

[0084] The selective hydrogenation step a) is preferably carried out in a fixed bed. It may also be carried out in an ebullated or moving bed.

[0085] Advantageously, the reaction section of step a) comprises 1 to 5 reactors. According to a particular embodiment of the invention, the reaction section comprises 2 to 5 reactors, which are operated in a variable sequence mode, referred to by the term PRS for Permutable Reactor System or alternatively by the term "lead and lag". The combination of at least two reactors in PRS mode makes it possible to isolate one reactor, discharge the spent catalyst, recharge it with fresh catalyst and return said reactor to operation without shutting down the process. PRS technology is particularly described in patent FR 2 681 871.

[0086] According to one particularly preferred variant, the selective hydrogenation reaction section of step a) comprises two fixed-bed reactors operated in variable sequence mode.

[0087] Advantageously, reactor internals, for example of the filter plate type, may be used to prevent clogging of the reactor(s). Examples of filter plates are described in patent FR 3 051 375.

[0088] Advantageously, said selective hydrogenation catalyst comprises a support, preferably a mineral support, and a hydrodehydrogenation functional group.

[0089] According to one variant, the hydrodehydrogenation functional group comprises in particular at least one group VIII element and at least one group VIB element, the at least one group VIII element being preferably selected from nickel and cobalt, and the at least one group VIB element being preferably selected from molybdenum and tungsten. According to this variant, the total content, expressed as oxides of metallic elements from groups VIB and VIII, relative to the total weight of the catalyst, is preferably between 1% and 40% by weight, preferentially between 5% and 30% by weight. 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.

[0090] The weight ratio of Group VIB metal(s) to Group VIII metal(s), expressed as metal oxides, is preferably 1-20, preferably 2-10.

[0091] According to this variant, the reaction section of step a) for example comprises a hydrogenation catalyst comprising 0.5% to 12% by weight of nickel, preferably 1% to 10% by weight of nickel (expressed as nickel oxide NiO relative to the weight of the catalyst), and 1% to 30% by weight of molybdenum, preferably 3% to 20% by weight of molybdenum (expressed as molybdenum oxide MoO3 relative to the weight of the catalyst), on a support, preferably an inorganic support, preferably an alumina support.

[0092] According to another variant, the hydrodehydrogenation functional group comprises, and preferably consists of, at least one group VIII element, preferably nickel. According to this variant, the nickel content, expressed as NiO, is preferably between 1% and 50% by weight, preferably between 10% and 30% by weight, relative to the weight of the catalyst. This type of catalyst is preferably used in its reduced form on a support (preferably a mineral support), preferably on an inorganic support, preferably on an alumina support.

[0093] The support for the at least one selective hydrogenation catalyst is preferably selected from alumina, silica, silica-alumina, magnesia, clay, and mixtures thereof. The support may contain a dopant compound, in particular an oxide selected from boron oxide, especially boron trioxide, zirconia, ceria, titanium oxide, phosphorus pentoxide, and mixtures of these oxides. Preferably, the at least one selective hydrogenation catalyst comprises an alumina support, optionally doped with phosphorus and optionally boron. If phosphorus pentoxide 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. If boron trioxide B2O3 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. The alumina used may be, for example, γ (gamma) or η (eta) alumina.

[0094] The selective hydrogenation catalyst is, for example, in the form of extrudates.

[0095] Highly preferably, in order to hydrogenate diolefins as selectively as possible, step a) may employ, in addition to the selective hydrogenation catalyst described above, at least one selective hydrogenation catalyst used in step a) which comprises, on an alumina support, less than 1% by weight of nickel, expressed as nickel oxide NiO, and at least 0.1% by weight of nickel, preferably 0.5% by weight of nickel, relative to the weight of the catalyst, and less than 5% by weight of molybdenum, expressed as molybdenum oxide MoO, and at least 0.1% by weight of molybdenum, preferably 0.5% by weight of molybdenum, relative to the weight of the catalyst. This catalyst, with a moderate metal loading, is preferably placed upstream of the selective hydrogenation catalyst described above.

[0096] The hydrogenated effluent obtained at the end of step a) has a reduced content of impurities, in particular diolefins, relative to the content of the same impurities, in particular diolefins, contained in the feedstock of the process. The selective hydrogenation step a) generally makes it possible to convert at least 30%, preferably at least 40%, of the diolefins contained in the initial feedstock. The hydrogenated effluent obtained at the end of the selective hydrogenation step a) is preferably sent directly to the hydrodemetallization step b).

[0097] (Hydrodemetallization step b) According to the present invention, the method comprises a hydrodemetallization step b), which is carried out in a hydrodemetallization reaction section comprising at least one hydrodemetallization catalyst, to which is fed at least the feedstock (optionally pretreated) comprising plastic pyrolysis oil and / or the hydrogenated effluent obtained from step a), and a gas stream comprising hydrogen, the hydrodemetallization reaction section being carried out at an average temperature of 140 to 400°C, a hydrogen partial pressure of 1.0 to 20.0 MPa (absolute), and an hourly space velocity of 0.1 to 10.0 h -1 to obtain a demetallized effluent.

[0098] Optionally, the reaction section of step b) may also be fed at least in part with a feedstock (optionally pretreated) derived from renewable resources.

[0099] Optionally, the reaction section of said step b) may also be fed with a recycle stream, advantageously at least part of a recycle stream obtained from step d) or optional step e) of the present process.

[0100] Depending on the composition of the feedstock, the conditions of the hydrodemetallization step make it possible to carry out hydrodemetallization reactions, in particular silicon retention, hydrogenation reactions, in particular diolefin and olefin hydrogenation reactions, hydrotreating reactions, in particular chlorine, nitrogen and sulfur conversion, hydrocracking and / or decarboxylation of ester groups.

[0101] The hydrodemetallization step b) may be carried out in a hydrodemetallization reaction section, which comprises at least one hydrodemetallization catalyst and employs at least one ebullated bed, entrained bed, moving bed and / or fixed bed reactor.

[0102] According to one preferred mode, step b) is carried out in a fixed bed. Step b) carried out in a fixed bed is carried out under conditions of hydrogen pressure and temperature that allow, in particular, at least partial hydrogenation of diolefins and olefins to be carried out, in particular in the absence of optional selective hydrogenation step a), at the beginning of the hydrodemetallization reaction section, while allowing an elevated temperature profile in which the outlet temperature of the reaction section of step b) is preferably at least 15°C higher than the inlet temperature of the reaction section of b). In practice, the required amount of hydrogen is injected to allow at least partial hydrogenation of diolefins and olefins present in the feedstock, at least partial hydrodemetallization of metals and / or metalloids, in particular retention of silicon, and also at least partial conversion of chlorine (to HCl by hydrodechlorination mechanism). Hydrogenation of diolefins and olefins thus makes it possible to avoid or at least limit the formation of "gums" that could clog the reaction section of hydrotreating step c), i.e., polymerization of diolefins and olefins, and thus the formation of oligomers and polymers. In parallel with the hydrogenation, the hydrodemetallization, in particular the retention of silicon during step b), makes it possible to limit the catalyst deactivation in the reaction section of the hydrotreating step c).Furthermore, the conditions of step b), in particular the temperature and the increasing temperature profile, make it possible to convert at least a portion of the chlorine, to carry out a portion of the hydrotreating and thus a portion of the nitrogen and sulfur removal, and to carry out a portion of the conversion of triglycerides and / or free fatty acids into hydrocarbon-based molecules via decarboxylation and / or hydrogenolysis mechanisms of the ester groups.

[0103] When step b) is carried out in a fixed bed, temperature control in this step is thus crucial and must satisfy conflicting constraints. On the one hand, the temperature at the inlet and throughout the hydrodemetallization section must be low enough to allow the hydrogenation of diolefins and olefins at the start of the hydrodemetallization section, especially in the absence of optional step a). On the other hand, the temperature at the inlet of the hydrodemetallization section must be high enough to avoid catalyst deactivation caused by the deposition of impurities, which is promoted at low temperatures. Since the hydrogenation reactions, especially those for the hydrogenation of part of the olefins and diolefins, and also the decarboxylation and / or hydrocracking of ester groups, are highly exothermic, an increasing temperature profile is therefore observed in the hydrodemetallization section. This higher temperature at the end of said section makes it possible to carry out the hydrodemetallization and hydrodechlorination reactions. Therefore, the temperature at the outlet of the reaction section of step b) is more preferably at least 15°C higher, preferably at least 25°C higher, particularly preferably at least 30°C higher than the temperature at the inlet of the reaction section of step b).

[0104] The temperature difference between the inlet and the outlet of the reaction section of step b) can be adapted to the optional injection of any gas (hydrogen) or liquid quench stream (e.g., recycling of streams originating from step d) and / or step e)).

[0105] The temperature difference between the inlet and the outlet of the reaction section of step b) is solely due to the exothermic nature of the chemical reaction carried out in the reaction section and can therefore be accommodated without the use of heating means (oven, heat exchanger, etc.).

[0106] The inlet temperature of the reaction section in step b) is 135 to 385°C, preferably 210 to 335°C.

[0107] The outlet temperature of the reaction section in step b) is 150 to 400°C, preferably 225 to 350°C.

[0108] According to the invention, it is advantageous to carry out the hydrogenation of diolefins and olefins, the hydrodemetallization reaction, in particular the retention of silicon, and part of the hydrotreating reaction at least partially in one and the same step and at a temperature sufficient to limit the deactivation of the catalyst in step c), which also makes it possible to benefit from the heat of the reaction and have an increasing temperature profile in this step, thus eliminating the need for a heating device between the catalytic section for hydrodemetallization and the catalytic section for hydrotreating.

[0109] In the reaction section, hydrodemetallization is carried out in the presence of at least one hydrodemetallization catalyst, advantageously at an (average) temperature (i.e., WABT as defined above in step a)) of 140 to 400°C, preferably 220 to 350°C, particularly preferably 260 to 330°C, at a hydrogen partial pressure of 1.0 to 20.0 MPa (absolute), preferably 1.5 to 15.0 MPa (absolute), and at an hourly space velocity (HSV) of 0.1 to 10.0 h -1 , preferably 0.2 to 5.0 h -1 , highly preferably 0.3~3.0h -1 is.

[0110] The amount of gas stream containing hydrogen (H2) fed to said reaction section of step b) is advantageously determined by the hydrogen coverage of the volume (m2) of the feedstock. 3 ) 50-1000Nm of hydrogen per 3 (Nm 3 / m 3 ), preferably the volume of the feedstock (m 3 ) 50-500Nm of hydrogen per 3 (Nm 3 / m 3 ), preferably the volume of the feedstock (m 3 ) 200-300Nm of hydrogen per 3 (Nm 3 / m 3In fact, the amount of hydrogen required to enable at least partial hydrogenation of diolefins and olefins, as well as at least partial hydrodemetallization of metals, in particular retention of silicon, and also at least partial conversion of chlorine (to HCl) and, optionally, at least partial conversion of esters of renewable resources, is greater than the amount of hydrogen required to enable only the hydrogenation of diolefins to be carried out as described in FR 20 / 01.758.

[0111] The hourly space velocity (HSV) and hydrogen coverage are defined as described in step a), and as "feedstock entering the reaction section", all of the "fresh" feedstock is optionally pretreated (step a0)), optionally selectively hydrogenated (step a)), i.e. comprises at least pyrolysis oil, optionally comprises part or all of the feedstock derived from renewable resources, and optionally supplemented with recycle streams obtained from steps d) and / or e).

[0112] Advantageously, the reaction section of step b) comprises from 1 to 5 reactors, preferably from 2 to 5 reactors, particularly preferably it comprises 2 reactors.

[0113] The reactor(s) of the reaction section of step b) may be of the fixed bed, ebullated bed, entrained bed and / or moving bed reactor type.

[0114] According to one variant, the reaction section comprises an ebullated bed reactor or a moving bed reactor, which allows catalyst introduction and withdrawal operations to compensate for deactivation.

[0115] According to another preferred variant, the reaction section comprises one fixed bed reactor, preferably two fixed bed reactors, said reactors having n catalyst beds, n being an integer greater than or equal to 1, each containing at least one hydrodemetallization catalyst.

[0116] According to one particular embodiment, as described in FR 2969642, all or part of the feedstock can be injected in stages at the inlet of each catalyst bed to manage the exotherm, where the total feedstock flow is divided into a predetermined number of different partial flows equal to the number of catalyst beds in the reactor, and the different partial flows are injected at increasing rates at the inlet of successive catalyst beds.

[0117] According to one variant, the catalyst bed reactors are operated in a fixed-bed, variable-configuration mode, also known as a "PRS" (Permutable Reactor System) or alternatively as "lead and lag". The combination of at least two reactors in a PRS mode makes it possible to isolate one reactor, discharge the spent catalyst, recharge it with fresh catalyst and return said reactor to service without shutting down the process. The PRS technology is particularly described in FR 2681871. The advantage of a hydrodemetalization reaction section comprising several reactors in a variable-configuration mode is that it makes it possible to optimally treat the feedstock while at the same time reducing the risk of clogging and / or deactivation of the catalyst bed(s), thus avoiding unit shutdowns due to clogging and / or deactivation.

[0118] According to one particularly preferred variant, the hydrodemetallation reaction section of step b) comprises two reactors operated in variable sequence mode.

[0119] Advantageously, reactor internals, for example of the filter plate type, may be used to prevent clogging of the reactor(s). Examples of filter plates are described in FR 3051375.

[0120] Advantageously, said hydrodemetallization catalyst comprises a support, preferably a mineral support, and hydrodehydrogenation functional groups.

[0121] According to one variant, the hydrodehydrogenation functional group comprises, in particular, at least one group VIII element and at least one group VIB element, the group VIII element being preferably selected from nickel and cobalt, and the group VIB element being preferably selected from molybdenum and tungsten. According to this variant, the total content, expressed as oxides of metallic elements from groups VIB and VIII, relative to the total weight of the catalyst, is preferably between 1% and 40% by weight, preferentially between 5% and 30% by weight. If the metal is cobalt or nickel, the metal content is expressed as CoO and NiO, respectively. If the metal is molybdenum or tungsten, the metal content is expressed as MoO3 and WO3, respectively.

[0122] The weight ratio between the group VIB metal(s) and the group VIII metal(s), expressed as metal oxides, is preferably 1-20, preferably 2-10.

[0123] According to this variant, the reaction section of step b) for example comprises a hydrodemetallization catalyst comprising 0.5% to 12% by weight of nickel, preferably 1% to 10% by weight of nickel (expressed as nickel oxide NiO relative to the weight of the catalyst), and 1% to 30% by weight of molybdenum, preferably 3% to 20% by weight of molybdenum (expressed as molybdenum oxide MoO3 relative to the weight of the catalyst), on a support, preferably a mineral support, preferably an alumina support.

[0124] According to another variant, the hydrodehydrogenation functional group comprises, and preferably consists of, at least one element of group VIII, preferably nickel. According to this variant, the content of nickel oxide is preferably between 1% and 50% by weight, preferably between 10% and 30% by weight, relative to the weight of the catalyst. This type of catalyst is preferably used in its reduced form on a support, preferably a mineral support, preferably an alumina support.

[0125] The support for the hydrodemetalization catalyst is preferably selected from alumina, silica, silica-alumina, magnesia, clay, and mixtures thereof. The support may contain a dopant compound, particularly an oxide selected from boron oxide, especially boron trioxide, zirconia, ceria, titanium oxide, phosphorus pentoxide, and mixtures of these oxides. Preferably, the hydrodemetalization catalyst comprises an alumina support, optionally doped with phosphorus and optionally boron. When phosphorus pentoxide 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 the alumina, and advantageously at least 0.001% by weight relative to the total weight of the alumina. The alumina used may be, for example, γ (gamma) or η (eta) alumina.

[0126] The hydrodemetallization catalyst is, for example, in the form of extrudates.

[0127] Highly preferably, step b) may employ at least one hydrodemetallization catalyst used in step b) which, in addition to the hydrodemetallization catalyst(s) described above, comprises, on an alumina support, less than 1% by weight of nickel and at least 0.1% by weight of nickel, preferably 0.5% by weight, expressed as nickel oxide NiO relative to the weight of the catalyst, and less than 5% by weight of molybdenum and at least 0.1% by weight of molybdenum, preferably 0.5% by weight, expressed as molybdenum oxide MoO relative to the weight of the catalyst. This catalyst is not highly loaded with metal and may preferably be placed upstream or downstream, preferably downstream, of the hydrodemetallization catalyst(s) described above.

[0128] Advantageously, the catalyst used in step b) can be selected from known hydrodemetallization, hydrotreating or silicon capture catalysts, and combinations thereof, that are particularly used for the treatment of petroleum fractions. Known hydrodemetallization catalysts are, for example, those described in patents EP 0113297, EP 0113284, US 5221656, US 5827421, US 7119045, US 5622616 and US 5089463. Known silicon capture catalysts are, for example, those described in patent applications CN 102051202 and US 2007 / 080099.

[0129] Said hydrodemetallization step b) makes it possible to obtain a demetallized effluent having a reduced content of silicon and, in some cases, a reduced content of olefins, in particular diolefins, metals and chlorine. Preferably, at least 50%, more preferentially at least 75%, of the chlorine and silicon of the initial feedstock is removed during step b). The demetallized effluent obtained at the end of hydrodemetallization step b) is preferably sent directly to hydrotreating step c).

[0130] (Hydrotreatment step c) According to the invention, the process comprises a hydrotreating step c), which is carried out in a hydrotreating reaction section comprising at least one hydrotreating catalyst, which is fed at least with the demetallized effluent from step b) and with a gas stream containing hydrogen, the temperature used in the hydrotreating reaction section being between 250 and 450°C, the partial pressure of hydrogen being between 1.0 and 20.0 MPa (absolute), and the hourly space velocity being between 0.1 and 10.0 h -1 to obtain a hydrotreated effluent.

[0131] Optionally, the reaction section of step c) may also be fed at least in part with a feedstock (optionally pretreated) derived from renewable resources.

[0132] According to one variant, at least part, preferably all, of the feedstock derived from renewable resources is introduced into step c).

[0133] Optionally, the reaction section of said step c) may likewise be fed with a recycle stream, advantageously at least a portion of a recycle stream advantageously obtained from step d) or optional step e) of the present process.

[0134] Advantageously, step c) carries out hydrotreating reactions well known to those skilled in the art, more particularly hydrotreating reactions such as hydrogenation of aromatic compounds, hydrodesulfurization and hydrodenitrification. Furthermore, hydrodemetallization is continued with the hydrogenation of olefins and remaining halogenated compounds. Step c) also carries out reactions of hydrogenolysis and / or decarboxylation of ester functional groups derived from triglycerides and / or free fatty acids from renewable resources.

[0135] The hydrotreating reaction section is advantageously carried out at a pressure equivalent to that used in the reaction section of hydrodemetallization step b), but at a temperature higher than that of the reaction section of hydrodemetallization step b). Thus, the hydrotreating reaction section is advantageously carried out at an (average) hydrotreating temperature of 250 to 450°C, preferably 280 to 380°C, a hydrogen partial pressure of 1.0 to 20.0 MPa (absolute), and an hourly space velocity (HSV) of 0.1 to 10.0 h -1 , preferably 0.1 to 5.0 h -1 , preferentially 0.2 to 2.0 hours -1 , preferably 0.2 to 1 hour -1 The hydrogen coverage in step c) is advantageously determined by the volume (m ) of the feedstock fed to step c). 3 ) 50-1000Nm of hydrogen per 3 , preferably the volume (m ) of feedstock fed to step c) 3 ) 50-500Nm of hydrogen per 3 , preferably the volume (m) of feedstock fed to step c) 3 ) 100-300Nm of hydrogen per 3The definitions of temperature (WABT), HSV and hydrogen coverage correspond to those above, and the "feedstock entering the reaction section of step c)" is the demetallized effluent obtained from step b), optionally partly or entirely from a feedstock derived from renewable sources, optionally supplemented with recycle streams obtained from steps d) and / or e).

[0136] The (average) temperature in the reaction section of step c) is preferably higher than the (average) temperature in the hydrodemetallization reaction section of step b), preferably by at least 10°C higher, preferably by at least 15°C higher.

[0137] The hydrogen-containing gas stream fed to the reaction section of step c) may consist of hydrogen feed and / or recycled hydrogen, advantageously recycled hydrogen obtained from step d) or optional step e).

[0138] Advantageously, the reaction section of said step c) comprises from 1 to 5 reactors, preferably from 2 to 5 reactors, particularly preferably it comprises 2 reactors.

[0139] The reactor(s) of the reaction section of step c) may be of the fixed bed, ebullated bed, entrained bed and / or moving bed reactor type.

[0140] According to one variant, the reaction section comprises an ebullated bed reactor or a moving bed reactor, which allows catalyst introduction and withdrawal operations to compensate for deactivation.

[0141] Advantageously, said step c) is carried out in a hydrotreating reaction section comprising at least one, preferably 1 to 5, fixed bed reactors, said reactors comprising n catalyst beds, n being an integer greater than or equal to 1, preferably between 1 and 10, preferably between 2 and 5, said bed(s) each comprising at least one and preferably not more than 10 hydrotreating catalysts. When a reactor comprises several catalyst beds, i.e. at least 2, preferably between 2 and 10, preferably between 2 and 5, said catalyst beds are preferably arranged in series within said reactor.

[0142] In one preferred embodiment of the present invention, the hydrotreating reaction section comprises a single fixed bed reactor containing n catalyst beds, where n is an integer greater than or equal to 1, preferably between 1 and 10, preferably between 2 and 5.

[0143] According to one embodiment, as described above, all or part of the feedstock can be injected in stages at the inlet of each catalyst bed to manage the heat generation. According to one variant, in particular when a feedstock derived from renewable resources is injected in step c), the feedstock (pyrolysis oil) obtained from step b) is introduced at the top of the hydrotreating reaction section c), while the feedstock derived from renewable resources is injected in increasing proportions at the inlet of each catalyst bed in stages, which allows for better management of the heat generation.

[0144] If step c) is carried out in a hydrotreating reaction section comprising several reactors, preferably two reactors, these reactors can be operated in series and / or in parallel and / or in variable sequence (i.e. PRS) mode and / or in swing mode. The various optional operating modes, PRS mode (or lead and lag) and swing mode, are well known to those skilled in the art and are advantageously defined above.

[0145] The hydrotreating catalyst comprises a support, preferably a mineral support, and at least one metallic element having hydrodehydrogenation function. The metallic element having hydrodehydrogenation function advantageously comprises at least one element from group VIII and / or at least one element from group VIB, the at least one element from group VIII being preferably selected from the group consisting of nickel and cobalt, and the at least one element from group VIB being preferably selected from the group consisting of molybdenum and tungsten. The total content of oxides of metallic elements from groups VIB and VIII is preferably between 0.1% and 40% by weight, and preferentially between 5% and 35% 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. The weight ratio of the Group VIB metal(s) to the Group VIII metal(s), expressed as metal oxides, is preferably 1.0 to 20, preferably 2.0 to 10. For example, the hydrotreating reaction section of step b) of the method comprises a hydrotreating catalyst comprising 0.5% to 10% by weight of nickel, expressed as nickel oxide NiO, preferably 1% to 8% by weight of nickel, relative to the total weight of the hydrotreating catalyst, and 1.0% to 30% by weight of molybdenum, preferably 3.0% to 29% by weight of molybdenum, expressed as molybdenum oxide MoO3, relative to the total weight of the hydrotreating catalyst, on a mineral support, preferably an alumina support.

[0146] The support for the hydrotreating catalyst is advantageously selected from alumina, silica, silica-alumina, magnesia, clay, and mixtures thereof. The support may contain a dopant compound, in particular an oxide selected from boron oxide, especially boron trioxide, zirconia, ceria, titanium oxide, phosphorus pentoxide, and mixtures of these oxides. Preferably, the hydrotreating catalyst comprises an alumina support, preferably an alumina support doped with phosphorus and optionally boron. If phosphorus pentoxide 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. If boron trioxide B2O5 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. The alumina used may be, for example, γ (gamma) or η (eta) alumina.

[0147] The hydrotreating catalyst is, for example, in the form of extrudates.

[0148] Known hydrotreating catalysts are, for example, those described in patents EP 0113297, EP 0113284, US Pat. No. 6,589,908, US Pat. No. 4,818,743 or US Pat. No. 6,332,976.

[0149] Advantageously, the hydrotreating catalyst used in step c) of the process has a specific surface area of ​​250 m 2 / g or more, preferably 300m 2 The specific surface area of ​​the hydrotreating catalyst is advantageously 800 m 2 / g or less, preferably 600m 2 / g or less, especially 400m 2 / g or less. The specific surface area of ​​the hydrotreating catalyst is measured by the BET method, i.e., the specific surface area is determined by nitrogen adsorption according to standard ASTM D 3663-78, which was established from the Brunauer-Emmett-Teller method described in The Journal of the American Chemical Society, 6Q, 309 (1938). Such a specific surface area makes it possible to further improve the removal of contaminants, in particular metals such as silicon.

[0150] According to another aspect of the present invention, the hydrotreating catalyst also contains one or more organic compounds containing oxygen and / or nitrogen and / or sulfur. Such catalysts are often referred to by the term "additivated catalyst." Generally, the organic compounds are selected from compounds containing one or more chemical functional groups selected from carboxylic acid, alcohol, thiol, thioether, sulfone, sulfoxide, ether, aldehyde, ketone, ester, carbonate, amine, nitrile, imide, oxime, urea, and amide groups, or compounds containing a furan ring, or sugars.

[0151] Since renewable resource feedstocks contain little or no sulfur, depending on the sulfur content of the plastic pyrolysis-derived feedstock, it may be advantageous to inject a sulfur-containing compound, such as DMDS, to maintain the active phase of the catalyst in the sulfide form. The addition of sulfur-containing compounds may also be made to the catalysts of the other steps (steps a), b) and / or c').

[0152] Advantageously, the hydrotreating step c) not only allows for the hydrotreating of at least 80% of the nitrogen remaining after the hydrodemetallization step b), but also allows for a conversion of at least 80% of the triglycerides. Step c) also allows for the partial removal of other impurities present in the feedstock, such as aromatic compounds, metallic compounds, sulfur-containing compounds, nitrogen-containing compounds, halogenated compounds (especially chlorinated compounds) or oxygen-containing compounds. Preferably, the nitrogen content at the output of step c) is less than 10 ppm by weight. Step c) may also allow for an even further reduction in the content of contaminants, such as the content of metals, in particular the silicon content. Preferably, the metal content at the output of step c) is less than 10 ppm by weight, and the silicon content is less than 5 ppm by weight.

[0153] (Hydrocracking step c') (optional) According to one variant, the process of the invention may comprise a hydrocracking step c') carried out on the hydrocarbon fraction comprising compounds with a boiling point above 175°C, either immediately after the hydrotreating step c) or after the fractionation step e).

[0154] Advantageously, step c') carries out a hydrocracking reaction well known to those skilled in the art, making it possible more particularly to convert heavy compounds, such as compounds with a boiling point above 175° C., into compounds with a boiling point below 175° C., contained in the hydrotreated effluent obtained from step c) or separated during the optional fractionation step e). Other reactions may follow, such as hydrogenation of olefins or aromatics, hydrodemetallization, hydrodesulfurization, hydrodenitrification, etc.

[0155] Compounds with boiling points above 175°C have a high BMCI and contain more naphthenics, naphthenic aromatics, and aromatics relative to the lighter compounds, resulting in a higher C / H ratio. This high ratio causes coking in the steam cracker, necessitating a dedicated steam cracking furnace for this fraction. If it is desired to minimize the yield of these heavy compounds (diesel fraction) and maximize the yield of light compounds (naphtha fraction), these compounds can be at least partially converted to light compounds by hydrocracking and are generally the favored fractions for a steam cracking unit.

[0156] The process of the present invention may therefore comprise a hydrocracking step c'), which is carried out in a hydrocracking reaction section comprising at least one hydrocracking catalyst, which hydrocracking reaction section is fed with the hydrotreated effluent obtained from step c) and / or the fraction obtained from step e) comprising compounds with a boiling point above 175°C, and a gas stream comprising hydrogen, the (average) temperature used in the hydrocracking reaction section being between 250 and 450°C, the partial pressure of hydrogen being between 1.5 and 20.0 MPa (absolute) and the hourly space velocity being between 0.1 and 10.0 h -1 to obtain a hydrocracked effluent, which is sent to the separation step d).

[0157] Therefore, the hydrocracking reaction section is advantageously carried out at a hydrocracking temperature of 250 to 450°C, preferably 320 to 440°C, a hydrogen partial pressure of 1.5 to 20.0 MPa (absolute), preferably 2 to 18.0 MPa (absolute), and an hourly space velocity (HSV) of 0.1 to 10.0 h -1 , preferably 0.1 to 5.0 h -1 , preferably 0.2 to 4 hours -1 The hydrogen coverage in step c') is advantageously determined by the volume (m ) of the feedstock fed to step c'). 3 ) 80-2000Nm of hydrogen per 3 , preferably step c') 3) Hydrogen 200~1800Nm 3 The definitions of temperature (WABT), HSV and hydrogen coverage correspond to those described above, and the hydrotreated effluent obtained from step c) and / or the hydrocarbon fraction containing compounds with a boiling point above 175° C. obtained from step e) are used as the “feedstock entering the reaction section of step c′”).

[0158] Advantageously, the hydrocracking reaction section is carried out at a pressure equivalent to that used in the reaction section of hydrodemetallization step b) or hydrotreating step c). According to another variant, the hydrocracking reaction section is carried out at a pressure exceeding that used in the reaction section of hydrodemetallization step b) or hydrotreating step c).

[0159] The reactor(s) of the reaction section of step c') may be of the fixed-bed, ebullated-bed, entrained-bed and / or moving-bed reactor type, preferably of the fixed-bed reactor type.

[0160] Advantageously, said step c') is carried out in a hydrocracking reaction section comprising at least one, preferably 1 to 5, fixed bed reactors having n catalyst beds, n being an integer greater than or equal to 1, preferably between 1 and 10, preferably between 2 and 5, said bed(s) each comprising at least one and preferably not more than 10 hydrocracking catalysts. When the reactor comprises several catalyst beds, i.e. at least 2, preferably between 2 and 10, preferably between 2 and 5, said catalyst beds are preferably arranged in series within said reactor.

[0161] The hydrotreating step c) and the hydrocracking step c') may advantageously be carried out in the same reactor or in different reactors, where, if they are carried out in the same reactor, the reactor comprises several catalyst beds, the first of which comprises the hydrotreating catalyst(s) and the subsequent catalyst beds comprising the hydrocracking catalyst(s).

[0162] The hydrocracking step can be carried out in one step (step c') or in two steps (steps c') and c''). When it is carried out in two steps, fractionation of the effluent obtained from the first hydrocracking step c') is carried out, which makes it possible to obtain, during steps d) and e), a fraction containing compounds with a boiling point above 175°C (diesel fraction), which fraction is introduced into a second hydrocracking step c''), which comprises a dedicated second hydrocracking reaction section different from the first hydrocracking reaction section c'). This configuration is particularly suitable when it is desired to maximize the naphtha fraction.

[0163] The second hydrocracking step c'') is carried out in a hydrocracking reaction section using at least one fixed bed, which contains n catalyst beds, n being an integer greater than or equal to 1, each containing at least one hydrocracking catalyst, and the hydrocracking reaction section is fed with at least the fraction containing compounds having a boiling point above 175°C obtained from step e) and a gas stream containing hydrogen, the average temperature used in the hydrocracking reaction section being 250 to 450°C, the partial pressure of hydrogen being 1.5 to 20.0 MPa (absolute), and the hourly space velocity being 0.1 to 10.0 h -1 to obtain a hydrocracked effluent, which is sent to separation step d). Suitable operating conditions and catalysts used in the second hydrocracking step are those described for the first hydrocracking step. The operating conditions and catalysts used in the two hydrocracking steps may be the same or different.

[0164] The second hydrocracking step is preferably carried out in a hydrocracking reaction section comprising at least one, preferably from 1 to 5, fixed bed reactors, the fixed bed reactors comprising n catalyst beds, n being an integer greater than or equal to 1, preferably from 1 to 10, preferably from 2 to 5, and the bed(s) each comprising at least one, and preferably not more than 10, types of hydrocracking catalysts.

[0165] These operating conditions used in the hydrocracking step(s) generally make it possible to obtain a conversion per pass of more than 15 wt. %, and even more preferably 20 to 95 wt. %, to a product having at least 80 vol. % of compounds with a boiling point of 175° C. or less, preferably less than 160° C., preferably less than 150° C. If the process is carried out in two hydrocracking steps, the conversion per pass in the second step is kept moderate so as to maximize the selectivity for compounds of the naphtha fraction (with a boiling point of 175° C. or less, in particular between 80° C. and 175° C. or less). The recycle ratio is defined as the ratio between the flow rate of compounds with a boiling point above 175° C. obtained from step e) and the flow rate of the feedstock of step c); preferentially, this ratio is between 0.2 and 4, preferably between 0.5 and 2.5.

[0166] The hydrocracking step(s) thus do not necessarily make it possible to convert all compounds with a boiling point above 175°C (diesel fraction) into compounds with a boiling point below 175°C (naphtha fraction). Therefore, after fractionation step e), a more or less significant proportion of compounds with a boiling point above 175°C may remain. To increase the conversion, at least a portion of this unconverted fraction can be recycled to step c') as described below or alternatively sent to a second hydrocracking step c''). Another portion can be purged. Depending on the operating conditions of the process, said purge may amount to 0 to 10% by weight, preferably 0.5% to 5% by weight, of the fraction containing compounds with a boiling point above 175°C, relative to the incoming feedstock.

[0167] According to the present invention, the hydrocracking step(s) is / are operated in the presence of at least one hydrocracking catalyst.

[0168] The hydrocracking catalyst(s) used in the hydrocracking step(s) are conventional hydrocracking catalysts known to those skilled in the art, which are of the bifunctional type combining an acid functional group with a hydrodehydrogenation functional group and, optionally, at least one binding matrix. The acid functional group is a high surface area (typically 150-800 m) catalyst with surface acidity. 2 / g) of the support, such as halogenated (especially chlorinated or fluorinated) alumina, combinations of boron and aluminum oxides, amorphous silica-alumina and zeolites. The hydrodehydrogenation functional groups are provided by at least one metal from group VIB and / or at least one metal from group VIII of the periodic table.

[0169] Preferably, the hydrodehydrogenation functional group contained in the hydrocracking catalyst(s) comprises at least one metal from group VIII selected from iron, cobalt, nickel, ruthenium, rhodium, palladium and platinum, preferably cobalt and nickel. Preferably, the catalyst(s) also comprise at least one metal from group VIB selected from chromium, molybdenum and tungsten, alone or in a mixture, preferably molybdenum and tungsten. Hydrodehydrogenation functional groups of the NiMo, NiMoW or NiW type are preferred.

[0170] Preferably, the content of metal from group VIII in the hydrocracking catalyst(s) is advantageously between 0.5% and 15% by weight, preferably between 1% and 10% by weight, the percentages being expressed as percentages by weight of oxide 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.

[0171] Preferably, the content of metal from group VIB in the hydrocracking catalyst(s) is advantageously between 5% and 35% by weight, preferably between 10% and 30% by weight, the percentages being expressed as percentages by weight of the oxide relative to the total weight of the catalyst. When the metal is molybdenum or tungsten, the metal content is expressed as MoO3 and WO3, respectively.

[0172] The hydrocracking catalyst(s) may optionally comprise at least one promoter element deposited on the catalyst, the promoter element being selected from the group formed by phosphorus, boron, and silicon, and the hydrocracking catalyst(s) may optionally comprise at least one element from Group VIIA (chlorine and fluorine are preferred), optionally at least one element from Group VIIB (manganese is preferred), and optionally at least one element from Group VB (niobium is preferred) deposited on the catalyst.

[0173] Preferably, the hydrocracking catalyst(s) comprise at least one amorphous or low-crystallinity porous inorganic matrix of the oxide type, chosen from alumina, silica, silica-alumina, aluminates, alumina-boron oxide, magnesia, silica-magnesia, zirconia, titanium oxide or clays, alone or in mixtures, preferably alumina or silica-alumina, alone or in mixtures.

[0174] Preferably, the silica-alumina contains more than 50% by weight alumina, preferably more than 60% by weight alumina.

[0175] Preferably, the hydrocracking catalyst(s) optionally also comprise a zeolite selected from Y zeolites, preferably USY zeolites, alone or in combination with other zeolites, alone or as mixtures, from among Beta, ZSM-12, IZM-2, ZSM-22, ZSM-23, SAPO-11, ZSM-48 or ZBM-30 zeolites. Preferably, the zeolite is USY zeolite alone.

[0176] When said catalyst comprises a zeolite, the content of zeolite in the hydrocracking catalyst(s) is advantageously between 0.1% and 80% by weight, preferably between 3% and 70% by weight, the percentages being expressed as the percentage of zeolite relative to the total weight of the catalyst.

[0177] Suitable catalysts comprise, and preferably consist of, at least one metal from Group VIB, optionally at least one non-noble metal from Group VIII, at least one promoter element, preferably phosphorus, at least one Y zeolite, and at least one alumina binder.

[0178] An even more preferred catalyst comprises, preferably consists of, nickel, molybdenum, phosphorus, USY zeolite, optionally further beta zeolite, and alumina.

[0179] Another suitable catalyst comprises, and preferably consists of, nickel, tungsten, alumina, and silica-alumina.

[0180] Another suitable catalyst comprises, preferably consists of, nickel, tungsten, USY zeolite, alumina, and silica-alumina.

[0181] The hydrocracking catalyst is, for example, in the form of extrudates.

[0182] In one variant, the hydrocracking catalyst used in step c'') comprises a hydrodehydrogenation functional group containing at least one noble metal from group VIII chosen from palladium and platinum, either alone or in a mixture. The content of noble metal from group VIII is advantageously between 0.01% and 5% by weight, preferably between 0.05% and 3% by weight, the percentages being expressed as percentages by weight of oxide (PtO or PdO) relative to the total weight of the catalyst.

[0183] According to another aspect of the present invention, the hydrogenolysis catalyst also contains one or more organic compounds containing oxygen and / or nitrogen and / or sulfur. Such catalysts are often referred to by the term "additive catalyst." Generally, the organic compounds are selected from compounds containing one or more chemical functional groups selected from carboxylic acid, alcohol, thiol, thioether, sulfone, sulfoxide, ether, aldehyde, ketone, ester, carbonate, amine, nitrile, imide, oxime, urea, and amide groups, or compounds containing a furan ring, or sugars.

[0184] The preparation of the catalysts of steps a), b), c), c') or c'') is known and generally comprises a step of impregnation of the Group VIII metal and the Group VIB metal, if present, and optionally phosphorus and / or boron on the support, followed by drying and then, optionally, calcination. In the case of doped catalysts, the preparation is generally carried out by simply drying without calcination after the introduction of the organic compound. The term "calcination" here means a heat treatment at a temperature above 200°C under air or a gas containing oxygen. Before their use in the process steps, the catalysts are generally subjected to sulfurization to form the active species. The catalyst of step a) can also be a catalyst used in its reduced form, and therefore a reduction step is included in its preparation.

[0185] The hydrogen-containing gas stream is fed to the reaction section of a), b), c), c') or c'') and may consist of the hydrogen feed and / or recycled hydrogen from step d) and / or recycled hydrogen, advantageously from step d) or optional step e). Preferably, an additional gas stream containing hydrogen is introduced at the inlet of each reactor, in particular those operating in series, and / or at the inlet of each catalyst bed, advantageously starting from the second catalyst bed of the reaction section. These additional gas streams are also called cooling streams. They make it possible to control the temperature in the reactors where the reactions involved are generally highly exothermic.

[0186] Optionally, each of steps a), b), c), c') or c'') may employ a heating section located upstream of the reaction section, in which the incoming effluent is heated to reach an appropriate temperature. Said optional heating section may therefore comprise one or more exchangers (preferably allowing heat exchange between the hydrotreated and / or hydrocracked effluent and the feedstocks feeding steps b), c) and c') and / or a preheat oven.

[0187] However, by carrying out step b) with a relatively high temperature ramp profile, it is possible in some cases to eliminate the need for a heating device or at least reduce the heat requirement between the hydrodemetallization catalyst section of step b) and the hydrotreating catalyst section of step c).

[0188] (Separation step d)) According to the invention, the treatment method comprises a separation step d), advantageously carried out in at least one washing / separation section to which is fed at least the hydrotreated effluent obtained from step c) or the hydrocracked effluent obtained from optional steps c') and c'') and an aqueous solution, to obtain at least one gaseous effluent, an aqueous effluent and a hydrocarbon-based effluent.

[0189] The gaseous effluent obtained at the end of step d) advantageously comprises hydrogen, preferably at least 80% by volume, preferably at least 85% by volume of hydrogen. Advantageously, said gaseous effluent may be at least partially recycled to the selective hydrogenation step a) and / or hydrodemetallization step b) and / or hydrotreating step c) and / or hydrocracking step c') and / or hydrocracking step c'').

[0190] The aqueous effluent obtained at the end of step d) advantageously contains ammonium salts and / or hydrochloric acid.

[0191] This separation step d) particularly allows for the removal of ammonium chloride salts. These are formed by the reaction between chloride ions and ammonium ions, the former being released in the form of HCl by the hydrogenation of chlorinated compounds during step c) and subsequently dissolved in water, and the latter being generated in the form of NH3 by the hydrogenation of nitrogenous compounds during step c) and / or provided by the injection of amines and subsequently dissolved in water. This therefore limits the risk of clogging due to precipitation of ammonium chloride salts, particularly in the transfer lines and / or in the sections of the method of the invention and / or in the transfer lines to the steam cracker. This also allows for the removal of hydrochloric acid formed by the reaction of hydrogen ions with chloride ions.

[0192] Depending on the content of chlorinated compounds in the initial feedstock to be treated, a stream containing amines, such as monoethanolamine, diethanolamine and / or monodiethanolamine, may be injected upstream of or midway between the selective hydrogenation step a) and / or the hydrodemetallization step b) and / or the hydrotreating step c) and / or the hydrocracking step c′) and / or the separation step d), preferably upstream of the hydrotreating step c), to ensure a sufficient amount of ammonium ions to combine with the chloride ions formed during the hydrotreating step c) and thus limit the formation of hydrochloric acid and therefore corrosion downstream of the separation section.

[0193] Advantageously, separation step d) comprises the injection of an aqueous solution, preferably water, into the hydrotreated effluent obtained from step c) or the hydrocracked effluent obtained from optional steps c') and c''), upstream of the washing / separation section, to at least partially dissolve the ammonium chloride salts and / or hydrochloric acid, thus improving the removal of chlorinated impurities and reducing the risk of clogging caused by the accumulation of ammonium chloride salts.

[0194] The temperature at which separation step d) is advantageously carried out is between 50 and 450°C, preferentially between 100 and 440°C, preferably between 200 and 420°C. It is important to carry out said step within this temperature range (and therefore not to cool the effluent of step c) too much), knowing that clogging of the lines may occur due to precipitation of ammonium chloride salts. Advantageously, separation step d) is carried out at a pressure close to that used in steps a), b) and / or c), preferably between 1.0 and 20.0 MPa, to facilitate the recycling of hydrogen.

[0195] The washing / separation section of step d) may be carried out at least in part in common or separate washing and separation equipment, which is well known (separation vessels, pumps, heat exchangers, washing columns, etc. which may be operated at various pressures and temperatures).

[0196] In one optional embodiment of the present invention, separation step d) comprises the injection of an aqueous solution into the hydrotreated effluent obtained from step c), followed by a scrubbing / separation section, advantageously comprising separate phases for obtaining at least one aqueous effluent loaded with ammonium salts, a washed liquid hydrocarbon-based effluent and a partially washed gaseous effluent. The aqueous effluent loaded with ammonium salts and the washed liquid hydrocarbon-based effluent may then be separated in a decanting vessel to obtain said hydrocarbon-based effluent and said aqueous effluent. The partially washed gaseous effluent is introduced in parallel into a scrubbing column, where it flows countercurrently relative to an aqueous stream, preferably of the same nature as the aqueous solution injected into the hydrotreated effluent, thereby making it possible to at least partially, preferably completely, remove the hydrochloric acid and CO contained in the partially washed gaseous effluent and thus obtain said gaseous effluent, preferably essentially comprising hydrogen, and an acidic aqueous stream. The aqueous effluent obtained from the decanting vessel may optionally be mixed with the acidic aqueous stream and optionally used as a mixture with the acidic aqueous stream to feed the aqueous stream to step d) of separation into the aqueous solution upstream of the washing / separation section and / or into the aqueous stream in a wash column in a water recycle circuit, which may include a supply of water and / or a basic solution and / or a purge to remove dissolved salts.

[0197] The purification of the gaseous effluent containing hydrogen can be carried out by known techniques (purging, amine scrubbing, pressure swing adsorption or PSA, etc.). Preferably, the purification of the gaseous effluent containing hydrogen is carried out at least by an amine scrubbing column, which makes it possible to at least partially remove the carbon dioxide formed during the decarboxylation of the ester groups of the renewable resource. Monoethanolamine, diethanolamine and / or monodiethanolamine are examples of amines that may be used in the column for scrubbing the gas.

[0198] In another optional embodiment of the invention, separation step d) may advantageously comprise a "high pressure" washing / separation section, which operates at a pressure close to that of the selective hydrogenation step a) and / or hydrodemetallization step b) and / or hydrotreating step c) and / or optional hydrocracking step c'), preferably at a pressure of 1.0 to 20.0 MPa, to facilitate the recycling of hydrogen. This optional "high pressure" section of step d) may be completed with a "low pressure" section to obtain a hydrocarbon-based liquid fraction free of gaseous parts dissolved at high pressure and intended to be processed directly in a steam cracking process or optionally sent to fractionation step e).

[0199] The gas fraction(s) obtained from separation step d) may undergo further purification(s) and separation(s) with the aim of recovering at least one hydrogen-rich gas and / or light hydrocarbons. The hydrogen-rich gas may be recycled upstream of steps a) and / or b) and / or c) and / or c') and / or c''), and the liquid hydrocarbons, in particular ethane, propane and butane, may advantageously be sent, separately or as a mixture, to one or more furnaces of steam cracking step f) in order to increase the overall yield of olefins.

[0200] The hydrocarbon-based effluent obtained from separation step d) is sent either partially or totally directly to the inlet of the steam cracking unit or to an optional fractionation step e), preferably the hydrocarbon-based liquid effluent is sent partially or totally, preferably totally, to fractionation step e).

[0201] (Fractionation step e) (optional) The process according to the invention may comprise a step of fractionating all or part, preferably all, of the hydrocarbon-based effluent obtained from step d) to obtain at least one gas stream and at least two liquid hydrocarbon-based streams, said two fluid hydrocarbon-based streams being at least one naphtha fraction comprising compounds having a boiling point below 175°C, in particular between 80 and 175°C, and at least one hydrocarbon fraction comprising compounds having a boiling point above 175°C.

[0202] Step e) makes it possible in particular to remove gases dissolved in the liquid hydrocarbon-based effluent, such as ammonia, hydrogen sulfide and light hydrocarbons containing 1 to 4 carbon atoms.

[0203] The optional fractionation step e) is advantageously carried out at a pressure of up to 1.0 MPa (absolute), preferably between 0.1 and 1.0 MPa (absolute).

[0204] According to one embodiment, step e) may be carried out in a section advantageously comprising at least one stripping tower, the stripping tower being equipped with a reflux circuit, the reflux circuit comprising a reflux vessel. Said stripping tower is fed with the hydrocarbon-based liquid effluent obtained from step d) and a steam stream. The hydrocarbon-based liquid effluent obtained from step d) may optionally be heated before entering the stripping tower. Thus, the lightest compounds are entrained at the top of the tower and conveyed to a reflux circuit comprising a reflux vessel, where gas / liquid separation takes place. The gas phase comprising light hydrocarbons is withdrawn as a gas stream from the reflux vessel. A naphtha fraction comprising compounds with a boiling point of 175° C. or less is advantageously withdrawn from the reflux vessel. A hydrocarbon fraction comprising compounds with a boiling point above 175° C. is advantageously withdrawn at the bottom of the stripping tower.

[0205] According to other embodiments, fractionation step e) may use a stripping column followed by a distillation column or may comprise only a distillation column.

[0206] The naphtha fraction containing compounds with a boiling point of ≦175° C. and the fraction containing compounds with a boiling point of above 175° C. may optionally be mixed and sent in whole or in part to a steam cracking unit, at the outlet of which olefins may be (re)formed and participate in the formation of polymers. Preferably, only a portion of said fractions is sent to the steam cracking unit; at least a portion of the remaining portion is optionally recycled to at least one of the process steps and / or sent to a storage unit for fuels obtained from conventional petroleum-based feedstocks, such as a naphtha storage unit, a diesel storage unit or a kerosene storage unit.

[0207] According to a preferred embodiment, the naphtha fraction containing compounds with a boiling point of less than or equal to 175° C. is sent in whole or in part to a steam cracking unit, while the fraction containing compounds with a boiling point of more than 175° C. is recycled to steps a) and / or b) and / or c) and / or c′) and / or sent to a fuel storage unit.

[0208] In certain embodiments, the optional fractionation step e) may make it possible to obtain, in addition to the gas stream, a naphtha fraction comprising compounds having a boiling point of less than or equal to 175° C., preferably between 80 and 175° C., a diesel fraction comprising compounds having a boiling point above 175° C. and less than 385° C., and a hydrocarbon fraction comprising compounds having a boiling point of more than or equal to 385° C., known as the heavy hydrocarbon fraction. The naphtha fraction may be sent, in whole or in part, to a steam cracking unit and / or to a naphtha pool obtained from conventional petroleum-based feedstocks; it may be recycled; the diesel fraction may be sent, in whole or in part, either to a steam cracking unit or to a diesel pool obtained from conventional petroleum-based feedstocks or may be recycled elsewhere; the heavy fraction may, for its part, at least in part, be sent to a steam cracking unit or recycled, in particular recycled to step c') or step c'').

[0209] In another specific embodiment, the naphtha fraction obtained from step e) containing compounds having a boiling point of 175° C. or less is fractionated into a heavy naphtha fraction containing compounds having a boiling point of 80 to 175° C. and a light naphtha fraction containing compounds having a boiling point of less than 80° C., and at least a portion of the heavy naphtha fraction is sent to an aromatics complex containing at least one naphtha reforming step for the purpose of producing aromatic compounds. According to this embodiment, at least a portion of the light naphtha fraction is sent to the steam cracking step f) described below.

[0210] The gas fraction(s) obtained from fractionation step e) may undergo further purification(s) and separation(s) with the aim of recovering at least light hydrocarbons, in particular ethane, propane and butane, which may advantageously be sent separately or as a mixture to one or more of the furnaces of steam cracking step f), increasing the overall yield of olefins.

[0211] (Recycling of fractions containing compounds with boiling points above 175°C) At least one fraction of the cut comprising compounds having a boiling point above 175° C. obtained from fractionation step e) can be recovered and constitute a recycle stream, which is sent upstream of or directly to at least one of the reaction steps of the process according to the invention, in particular to the selective hydrogenation step a) and / or hydrodemetallization step b) and / or hydrotreating step c) and / or hydrocracking step c′) and / or hydrocracking step c″). Optionally, part of the recycle stream may be sent to optional step a0).

[0212] The recycle stream may be fed to said reaction steps a) and / or b) and / or c) and / or c') and / or c'') in a single injection or may be divided into several portions and fed to the reaction steps in several injections, i.e. to different catalyst beds.

[0213] Advantageously, the amount of the recycle stream of the fraction comprising compounds with a boiling point above 175° C. is adjusted so that the weight ratio between the recycle stream and the feedstock comprising plastic pyrolysis oil and the feedstock derived from renewable resources, i.e. the feedstock to be treated and fed to the overall process, is less than or equal to 10, preferably less than or equal to 5, and preferentially greater than or equal to 0.001, preferably greater than or equal to 0.01, preferably greater than or equal to 0.1. Highly preferably, the amount of the recycle stream is adjusted so that the weight ratio between the recycle stream and the feedstock comprising plastic pyrolysis oil and the feedstock derived from renewable resources is between 0.2 and 5.

[0214] According to one preferred variant, at least part of the fraction comprising compounds with a boiling point above 175° C. obtained from fractionation step e) is sent to hydrocracking step c′), if present.

[0215] According to another preferred variant, at least part of the fraction comprising compounds with a boiling point above 175° C. obtained from fractionation step e) is sent to a second hydrocracking step c″), if present.

[0216] Recycling part of the fraction comprising compounds with a boiling point above 175° C. to at least one of the reaction steps of the process according to the invention or upstream thereof, in particular to the hydrocracking steps c′) and / or c″), advantageously makes it possible to increase the yield of naphtha fractions with a boiling point below 175° C. Recycling also makes it possible to dilute impurities and to control the temperature in the reaction step(s) involved, in which the reactions may be highly exothermic.

[0217] A purge may be provided for the recycle of the fraction containing compounds with a boiling point above 175° C. Depending on the operating conditions of the process, said purge may be 0-10% by weight, preferably 0.5% to 5% by weight, of the fraction containing compounds with a boiling point above 175° C. relative to the incoming feedstock.

[0218] (Recycling of the hydrocarbon-based effluent obtained from step d) and / or the naphtha fraction having a boiling point of 175°C or less obtained from step e) A portion of the hydrocarbon-based effluent obtained from separation step d) or a portion of the naphtha cut having a boiling point below 175°C obtained from optional fractionation step e) may be recovered and constitute a recycle stream, which is sent upstream of or directly to at least one of the reaction steps of the process according to the invention, in particular to the selective hydrogenation step a) and / or the hydrodemetallization step b) and / or the hydrotreating step c). Optionally, a portion of the recycle stream may be sent to the optional pretreatment step a0).

[0219] Preferably, at least a portion of the hydrocarbon-based effluent obtained from the separation step d) or at least a portion of the naphtha fraction having a boiling point below 175°C obtained from the optional fractionation step e) is fed to the hydrotreatment step c).

[0220] Advantageously, the amount of the recycle stream, i.e. the portion of the recycled product obtained, is adjusted so that the weight ratio between the recycle stream and the feedstock comprising plastic pyrolysis oil and the feedstock derived from renewable resources, i.e. the feedstock to be treated and fed to the overall process, is less than or equal to 10, preferably less than or equal to 5, and preferentially greater than or equal to 0.001, preferably greater than or equal to 0.01, preferably greater than or equal to 0.1. Highly preferably, the amount of the recycle stream is adjusted so that the weight ratio between the recycle stream and the feedstock comprising plastic pyrolysis oil and the feedstock derived from renewable resources is between 0.2 and 5.

[0221] Advantageously, at the start of the process, a hydrocarbon fraction external to the process may be used as a recycle stream. Those skilled in the art will know how to choose said hydrocarbon fraction.

[0222] Recycling of part of the product obtained into at least one of the reaction steps of the process according to the invention or upstream thereof advantageously makes it possible, firstly, to dilute impurities and, secondly, to control the temperature in the reaction step(s) involved, where the reactions may be highly exothermic.

[0223] The hydrocarbon-based effluent or the hydrocarbon-based stream(s) thus obtained by treating plastic pyrolysis oil according to the method of the present invention and the feedstock from renewable resources have a composition that meets the specifications of the feedstock entering the steam cracking unit. In particular, the composition of the hydrocarbon-based effluent or the hydrocarbon-based stream(s) is preferably such that: the total content of metallic elements is less than or equal to 5.0 ppm by weight, preferably less than or equal to 2.0 ppm by weight, preferentially less than or equal to 1.0 ppm by weight, preferably less than or equal to 0.5 ppm by weight, The content of silicon (Si) element is 1.0 ppm by weight or less, preferably 0.6 ppm by weight or less, and The iron (Fe) element content is 100 ppb by weight or less, the sulfur content is less than or equal to 500 ppm by weight, preferably less than or equal to 200 ppm by weight; the oxygen content is equal to or less than 0.5% by weight, preferably less than 0.1% by weight, the nitrogen content is less than or equal to 100 ppm by weight, preferably less than or equal to 50 ppm by weight, preferably less than or equal to 5 ppm by weight; - the asphaltene content is 5.0 ppm by weight or less; the total content of elemental chlorine is equal to or less than 10 ppm by weight, preferably less than 1.0 ppm by weight; The content of olefinic compounds (monoolefins and diolefins) is less than or equal to 5.0% by weight, preferably less than or equal to 2.0% by weight, preferably less than or equal to 0.1% by weight.

[0224] The content is given as weight percentage (%), parts per million (ppm), or parts per billion (ppb), which is the relative weight concentration relative to the total weight of the stream under consideration.

[0225] The method according to the invention thus makes it possible to process plastic pyrolysis oil and a feedstock derived from renewable resources together to obtain an effluent that can be injected in whole or in part into a steam cracking unit.

[0226] (Steam cracking step f) (optional) The hydrocarbon-based effluent obtained from the separation step d) or at least one of the two liquid hydrocarbon-based streams obtained from the optional step e) may be sent in whole or in part to a steam cracking step f).

[0227] Advantageously, the gas fraction(s) obtained from the separation step d) and / or the fractionation step e) and containing ethane, propane and butane may be sent in whole or in part to a steam cracking step f).

[0228] The steam cracking step f) is advantageously carried out in at least one pyrolysis furnace, the temperature being between 700 and 900°C, preferably between 750 and 850°C, and the pressure being between 0.05 and 0.3 MPa (relative). The residence time of the hydrocarbon-based compounds is generally less than 1.0 second (denoted as s), preferably between 0.1 and 0.5 s. Steam is advantageously introduced upstream of the optional steam cracking step e), after separation (or fractionation). The amount of water introduced, advantageously in the form of steam, is advantageously between 0.3 and 3.0 kg of water per kg of hydrocarbon-based compounds by weight entering step f). Optional step f) is preferably carried out in several parallel pyrolysis furnaces, in order to adapt the operating conditions to the various streams feeding step f), in particular those obtained from step e), and to manage the decoking times of the tubes. The furnace comprises one or several tubes arranged in parallel. Furnace may refer to a group of furnaces operating in parallel. For example, a furnace may be dedicated to cracking a naphtha fraction containing compounds with a boiling point below 175°C.

[0229] The effluents from the various steam cracking furnaces are generally recombined before separation to form the effluent. It is understood that steam cracking step f) not only includes the steam cracking furnace, but also sub-steps related to steam cracking that are well known to those skilled in the art. These sub-steps may include, inter alia, heat exchangers, columns, and catalytic reactors, as well as recycle to the furnace. The columns generally allow the effluent to be fractionated with the aim of recovering at least one light fraction containing hydrogen and compounds containing 2 to 5 carbon atoms, a fraction containing pyrolysis gasoline, and optionally a fraction containing pyrolysis oil. The columns allow the various components of the fractionated light fraction to be separated to recover at least one fraction rich in ethylene (C2 fraction), a fraction rich in propylene (C3 fraction), and optionally a fraction rich in butenes (C4 fraction). The catalytic reactors make it possible, inter alia, to carry out the hydrogenation of C2, C3, and even C4 fractions and the hydrogenation of pyrolysis gasoline. Saturates, especially those containing 2 to 4 carbon atoms, are advantageously recycled to the steam cracking furnace to increase the overall yield of olefins.

[0230] This steam cracking step f) makes it possible to obtain at least one effluent containing olefins containing 2, 3 and / or 4 carbon atoms (i.e. C2, C3 and / or C4 olefins) in a satisfactory content, in particular 30% by weight or more, in particular 40% by weight or more, or even 50% by weight or more of total olefins containing 2, 3 and 4 carbon atoms, relative to the weight of the steam cracking effluent under consideration. The C2, C3 and C4 olefins can then advantageously be used as polyolefin monomers.

[0231] According to one preferred embodiment of the present invention, a method for processing feedstocks containing plastic pyrolysis oil and feedstocks derived from renewable resources comprises the following sequence of steps: b) hydrodemetallization, c) hydrotreating, d) separation or b) hydrodemetallization, c) hydrotreating, d) separation, e) fractionation or b) hydrodemetallization, c) hydrotreating, d) separation, e) fractionation and recycling of the fraction containing compounds with a boiling point below 175°C to hydrotreating step c). preferably comprising, and preferably consisting of, in the given order, to produce an effluent at least part of which is suitable for treatment in a steam cracking unit.

[0232] According to another preferred embodiment of the present invention, a method for processing a feedstock comprising pyrolysis oil comprises the following sequence of steps: b) hydrodemetallization, c) hydrotreating, c') hydrocracking, d) separation or b) hydrodemetallization, c) hydrotreating, c') hydrocracking, d) separation, e) fractionation or b) hydrodemetallization, c) hydrotreating, c') hydrocracking, d) separation, e) fractionation and recycling of the fraction containing compounds with a boiling point above 175°C to hydrocracking step c') and recycling of the fraction containing compounds with a boiling point below 175°C to hydrotreating step c). preferably comprising, and preferably consisting of, in the given order, to produce an effluent at least part of which is suitable for treatment in a steam cracking unit.

[0233] All embodiments can further comprise, and preferably consist of, a pretreatment step a0).

[0234] All embodiments can further comprise, and preferably consist of, a selective hydrogenation step a).

[0235] All embodiments may further comprise, and preferably consist of, a hydrolytic steam cracking step f).

[0236] (Analysis methods used) The analytical methods and / or standards used to determine the characteristics of the various streams, in particular the feedstocks and effluents to be treated, are known to those skilled in the art and are specifically listed below for information purposes. Other methods that are considered equivalent may also be used, in particular equivalent IP, EN or ISO methods.

[0237] [Table 1] (1) MAV method: described in the paper C. Lopez-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.

[0238] (List of drawings) The information regarding the elements referenced in Figures 1-2 is provided to enable a better understanding of the present invention, which is not limited to the specific embodiments illustrated in Figures 1-2. The various embodiments presented may be used alone or in combination with each other, with no limitations on the combinations.

[0239] FIG. 1 represents a scheme of a particular embodiment of the method of the present invention, comprising: - an optional step a) of selective hydrogenation of a hydrocarbon feedstock (1) comprising plastic pyrolysis oil in the presence of a hydrogen-rich gas (2) and an optional amine provided by a stream (3); carried out in at least one fixed-bed reactor containing at least one selective hydrogenation catalyst; obtaining an effluent (4); - step b) of hydrodemetallization of the effluent (4) obtained from step a) in the presence of hydrogen (5); carried out in at least one fixed-bed reactor, the reactor containing at least one hydrodemetallization catalyst; obtaining a demetallized effluent (6); - a step c of hydrotreating at least a portion of the effluent obtained from step b) in the presence of hydrogen (7); carried out in at least one fixed-bed reactor, this reactor containing at least one hydrotreating catalyst, to obtain a hydrotreated effluent (8); wherein a feedstock (20) derived from renewable resources is introduced into a hydrotreatment step c) (this feedstock is also introduced partly or entirely into steps a) and / or b) (not shown); - optionally a step c' of hydrocracking at least a portion of the effluent (8) obtained from step c) in the presence of hydrogen (9); carried out in at least one fixed-bed reactor containing at least one hydrocracking catalyst; obtaining a hydrocracked effluent (10); - step d of separation of the effluent (10); carrying out separation of the effluent (10) in the presence of an aqueous wash solution (11) to obtain at least one fraction (12) containing hydrogen, an aqueous fraction (13) containing dissolved salts, and a hydrocarbon-based liquid fraction (14), - an optional step e) of fractionation of the hydrocarbon-based liquid fraction (14); making it possible to obtain at least one gas fraction (15), a hydrocarbon fraction (16) comprising compounds with a boiling point below 175°C and a hydrocarbon fraction (17) comprising compounds with a boiling point above 175°C.

[0240] At the end of step d) or e), at least a portion of the hydrotreated hydrocarbon-based liquid effluent (16) is sent to a steam cracking process (not shown).

[0241] Optionally, a portion of said hydrocarbon fraction (16) comprising compounds with a boiling point below 175°C constitutes the recycle streams (16a) and / or (16b) and / or (16c) fed to steps a) and / or b) and / or c), respectively.

[0242] Optionally, a part of the fraction (17) containing compounds with a boiling point above 175° C. is fed to the hydrocracking step c′) (fraction (17a)), while another part (17b)) constitutes the purge.

[0243] Figure 2 shows the scheme of another particular embodiment of the process of the invention, based on the scheme of Figure 1. This scheme comprises, inter alia, a second hydrocracking step c''), in which the fraction (17) comprising compounds with a boiling point above 175°C obtained from step e) is fed to this second hydrocracking step c'' (fraction (17a)), which is carried out in at least one fixed-bed reactor comprising at least one hydrocracking catalyst and fed with hydrogen (18). The second hydrocracked effluent (19) is recycled to separation step d). Another part of fraction (17) constitutes the purge (17b).

[0244] Instead of injecting the amine stream (3) at the inlet of the selective hydrogenation step a), it is possible, depending on the characteristics of the feedstock, to inject it at the inlet of steps b), c), c') and d), or not at all.

[0245] Only the main steps, together with the main flows, are shown in Figures 1-2 to allow a better understanding of the invention. It is clearly understood that all equipment required for functioning (vessels, pumps, exchangers, furnaces, columns, etc.) is present, even if not shown. It is also understood that, as mentioned above, a hydrogen-rich gas stream (feed or recycle) may be injected at the inlet of each reactor or catalyst bed, or between two reactors or two catalyst beds. Means for hydrogen purification and recycling well known to those skilled in the art may be used.

[0246] (Example) Example 1 (according to the present invention) The feedstock (1) to be treated in this process is plastic pyrolysis oil. The feedstock (2) to be treated in this process is a feedstock derived from renewable resources (rapeseed oil). The plastic pyrolysis oil is fed to a hydrodemetallization step b). The rapeseed oil is fed to a hydrotreatment step c). The characteristics of the feedstocks are shown in Table 2.

[0247] [Table 2]

[0248] The feedstock (1) is subjected to a hydrodemetallization step b), which is carried out in a fixed-bed reactor in the presence of hydrogen (5) and an alumina-supported CoMo-type hydrodemetallization catalyst under the conditions shown in Table 3.

[0249] [Table 3]

[0250] The characteristics of the effluent obtained from the hydrodemetallization step b) (corresponding to the liquid effluent (6)) are given in Table 4.

[0251] [Table 4]

[0252] The effluent (6) obtained from the hydrodemetallization step b) is subjected to the hydrotreating step c) according to the invention. A feedstock (2) derived from renewable resources (20) is also introduced into the hydrotreating step c). The feedstock fed to the hydrotreating step c) is a mixture of 50% by weight of the effluent obtained from the hydrodemetallization of plastic pyrolysis oil and 50% by weight of rapeseed oil.

[0253] The hydrotreating step c) is carried out in a fixed bed reactor in the presence of hydrogen (7) and an alumina-supported NiMo type hydrotreating catalyst under the conditions shown in Table 5.

[0254] [Table 5]

[0255] The effluent (8) obtained from the hydrotreatment step c) is subjected to a separation step d) according to the invention, in which a water stream (11) is injected into the effluent obtained from the hydrotreatment step c); this mixture is then sent to separation step d) and treated in a column for washing the acid gases. A gas fraction is obtained at the top of the acid gas washing column, while at the bottom, a two-phase separation vessel allows the separation of the aqueous and liquid phases. The gas washing column and the two-phase separator are operated at high pressure. The liquid phase is then sent to a low-pressure vessel, from which a second gas fraction is recovered, which is purged, and a liquid effluent is recovered. The yields for the various products and fractions obtained at the outlet of the hydrotreatment step c) are shown in Table 6 (these yields correspond to the ratio of the weight of the various products obtained relative to the weight of the feedstock, expressed as a percentage, and indicated as % (wt / wt)).

[0256] [Table 6]

[0257] The characteristics of the effluent obtained from separation step d) (corresponding to liquid effluent (14)) are given in Table 7.

[0258] [Table 7]

[0259] The hydrocarbon-based effluent (14) obtained from the separation step d) has a composition that is compatible with a steam cracking unit, for the following reasons: - it does not contain any olefins (monoolefins and diolefins), - it contains no chlorine (the content is undetectable and below the limit required for steam cracking feedstock); - it does not contain any iron (Fe) or metals (metal content is undetectable and below the limits required for steam cracking feedstocks, i.e., not more than 5.0 ppm by weight for metals, highly preferably not more than 1 ppm by weight; and also not more than 100 ppb by weight for Fe); Finally, it contains almost no sulfur (5.5 ppm by weight) and almost no nitrogen (1.8 ppm by weight), contents which are very significantly below the limits required for steam cracking feedstocks (less than 500 ppm by weight, preferably less than 200 ppm by weight for S and N).

[0260] The effluent (14) obtained from the separation step d) consists of approximately 11.8% naphtha-type compounds with a boiling point below 180°C.

[0261] The effluent (14) can be sent directly to the steam cracking step f).

Claims

1. 1. A method for processing a feedstock comprising plastic pyrolysis oil and a feedstock derived from renewable resources, comprising: a) an optional selective hydrogenation step, in which the feedstock containing plastic pyrolysis oil and a gas stream containing hydrogen are fed to a reaction section at least at a temperature of 80 to 280° C., a partial pressure of hydrogen of 1.0 to 20.0 MPa (absolute) and an hourly space velocity of 0.3 to 10.0 h in the presence of at least one selective hydrogenation catalyst; －１ obtaining a hydrogenated effluent; b) a hydrodemetallization step, carried out in a hydrodemetallization reaction section containing at least one hydrodemetallization catalyst, to which at least a feedstock containing plastic pyrolysis oil and / or a hydrogenated effluent obtained from step a) and a gas stream containing hydrogen are fed, the hydrodemetallization reaction section being carried out at an average temperature of 140-400° C., the partial pressure of hydrogen being 1.0-20.0 MPa (absolute), and the hourly space velocity being 0.1-10.0 h －１ obtaining a demetallized effluent; c) a hydrotreating step, carried out in a hydrotreating reaction section containing at least one hydrotreating catalyst, to which is fed at least the demetallized effluent from step b) and a gas stream containing hydrogen, the temperature during which the hydrotreating reaction section is between 250 and 450° C., the partial pressure of hydrogen is between 1.0 and 10.0 MPa (absolute) and the hourly space velocity is between 0.1 and 10.0 h －１ and wherein said feedstock derived from renewable resources is introduced in step a) and / or step b) and / or step c), optionally in a mixture with said feedstock comprising plastic pyrolysis oil, The weight ratio between the flow rate of the feedstock containing plastic pyrolysis oil and the flow rate of the introduced renewable resource derived feedstock is 0.05 to 20; c') an optional hydrocracking step, carried out in a hydrocracking reaction section comprising at least one hydrocracking catalyst, to which is fed at least the hydrotreated effluent from step c) and / or the fraction comprising compounds with a boiling point above 175°C from step e) and a gas stream comprising hydrogen, the average temperature during which the hydrocracking reaction section is used is between 250 and 450°C, the partial pressure of hydrogen is between 1.5 and 20.0 MPa (absolute) and the hourly space velocity is between 0.1 and 10.0 h －１ obtaining a hydrocracked effluent which is sent to a separation step d); d) a separation step; feeding the hydrotreated effluent from step c) and / or the hydrocracked effluent from step c') and an aqueous solution, said steps being carried out at a temperature between 50 and 450°C; obtaining at least one gaseous effluent, an aqueous effluent and a hydrocarbon-based effluent, e) optionally fractionating all or part of the hydrocarbon-based effluent obtained from step d) to obtain at least one gaseous effluent, at least one fraction comprising compounds having a boiling point less than or equal to 175° C. and at least one hydrocarbon fraction comprising compounds having a boiling point greater than 175° C.

2. The method of claim 1, comprising a fractionation step e).

3. 2. The process according to claim 1, further comprising a hydrocracking step c').

4. 2. The process of claim 1, comprising the selective hydrogenation step a).

5. 2. The method of claim 1, wherein the renewable resource derived feedstock is a feedstock containing oils and / or fats of vegetable and / or animal origin.

6. 2. The process of claim 1, wherein at least a portion of the feedstock derived from renewable resources is introduced in step c).

7. 2. The process of claim 1, wherein the temperature in the reaction section of step c) is higher than the temperature in the hydrodemetallization reaction section of step b).

8. 2. The process according to claim 1, wherein at least a portion of the hydrocarbon-based effluent obtained from the separation step d) or at least a portion of the cut comprising compounds having a boiling point below 175° C. obtained from the fractionation step e) is sent as a recycle stream to the selective hydrogenation step a) and / or the hydrodemetallization step b) and / or the hydrotreating step c).

9. 2. The process according to claim 1, wherein at least a portion of the fraction comprising compounds having a boiling point above 175° C. obtained from fractionation step e) is sent as a recycle stream to hydrodemetallization step b) and / or hydrotreating step c) and / or hydrocracking step c′).

10. 9. The method of claim 8, wherein the weight ratio between the recycle stream and the feedstock comprising plastic pyrolysis oil and the feedstock derived from renewable resources is less than or equal to 10.

11. 2. The process according to claim 1, comprising a step a0) of pretreatment of the feedstock, said pretreatment step being carried out upstream of the selective hydrogenation step a), said pretreatment step comprising a filtration step and / or an electrostatic separation step and / or a step of washing with an aqueous solution and / or an adsorption step.

12. 2. The process according to claim 1, wherein the hydrocarbon-based effluent obtained from the separation step d) or at least one of the two hydrocarbon-based liquid streams obtained from step e) is fed totally or partly to a steam cracking step f), which is carried out in at least one pyrolysis furnace, the temperature being between 700 and 900° C. and the pressure being between 0.05 and 0.3 MPa (relative).

13. 2. The method of claim 1, wherein the selective hydrogenation catalyst comprises a support selected from alumina, silica, silica-alumina, magnesia, clay, and mixtures thereof, and a hydrodehydrogenation functional element comprising either at least one Group VIII element and at least one Group VIB element, or at least one Group VIII element.

14. 2. The method of claim 1, wherein the hydrodemetallization catalyst and the hydrotreating catalyst comprise a support selected from the group consisting of alumina, silica, silica-alumina, magnesia, clay and mixtures thereof, and a hydrodehydrogenation functional element comprising at least one Group VIII element and / or at least one Group VIB element.

15. It also comprises a second hydrocracking step c''), which is carried out in a hydrocracking reaction section comprising at least one hydrocracking catalyst, to which the fraction comprising compounds having a boiling point above 175°C obtained from step e) and a gas stream comprising hydrogen are fed, the temperature in which the hydrocracking reaction section is used being between 250 and 450°C, the partial pressure of hydrogen being between 1.5 and 20.0 MPa (absolute) and the hourly space velocity being between 0.1 and 10.0 h －１ and obtaining a hydrocracked effluent which is sent to separation step d).

16. 2. The method of claim 1, wherein the hydrocracking catalyst comprises a support selected from halogenated aluminas, combinations of oxides of boron and aluminum, amorphous silica-aluminas and zeolites, and a hydrodehydrogenation functional metal comprising at least one Group VIB metal selected from chromium, molybdenum and tungsten, either alone or in admixture, and / or at least one Group VIII metal selected from iron, cobalt, nickel, ruthenium, rhodium, palladium and platinum.

17. The method of claim 1, wherein the feedstock has the following characteristics: the content of aromatic compounds is between 0 and 90% by weight, the content of halogenated compounds is between 2 and 5000 ppm by weight; the content of metallic elements is between 10 and 10,000 ppm by weight; - containing iron element, the content of which is 0 to 100 ppm by weight; The content of elemental silicon is between 0 and 1000 ppm by weight.

18. A product obtainable via the process of claim 1.

19. The product of claim 18, comprising, relative to the total weight of the product: - metallic elements with a total content of less than or equal to 5.0 ppm by weight, - containing iron element, the content of which is less than or equal to 100 ppb by weight; - elemental silicon with a content of less than or equal to 1.0 ppm by weight, - a content of sulfur not exceeding 500 ppm by weight, - nitrogen with a content of less than or equal to 100 ppm by weight, - elemental chlorine with a content of less than or equal to 10 ppm by weight.

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