Process for purifying a plastic and / or elastomer liquefaction oil composition comprising a Diels-Alder cycloaddition step

Abstract

The invention relates to a method for purifying a composition comprising a plastic and / or elastomer liquefaction oil, including a step of contacting it with a dienophile compound under Diels-Alder cycloaddition conditions, followed by a step of removing or transforming the cycloaddition products. The purified composition thus obtained can then optionally be further purified before being sent for subsequent treatments such as hydrotreating, cracking, hydrocracking, or steam cracking. (Short figure: Fig. 1)

Description

Title of the invention: Process for purifying a plastic and / or elastomer liquefaction oil composition comprising a Diels-Alder cycloaddition step. Technical field of the invention

[0001] The present invention relates to a purification process by treatment in the presence of a dienophile under Diels-Alder cycloaddition conditions of a composition comprising a plastic and / or elastomer liquefaction oil and its subsequent use in refining and petrochemical processes. The process according to the invention makes it possible, in particular, to reduce the diene concentration of feedstocks from plastic and / or elastomer waste, notably for their use in a steam cracking process or in any other refining process for the production of fuels, solvents, or monomers. Technological background

[0002] Plastic waste is most often sent to landfills or incinerated, and a smaller portion is sent for recycling. However, there is a significant need, encouraged by regulations, to limit plastic waste in landfills. On the other hand, disposing of plastic waste in landfills is becoming increasingly difficult. It is therefore necessary to recycle plastic waste.

[0003] One possible method for recycling plastic is plastic liquefaction by pyrolysis or hydrothermal liquefaction. However, the resulting plastic oil generally contains large quantities of dienes and heteroatoms, including silicon and metals. These numerous heteroatoms, including silicon and metals, are contaminants for the catalysts in the hydrotreating processes typically used to recycle plastics. Furthermore, dienes readily react to form gums. Dienes are also precursors to coke in a steam cracker. Therefore, it is necessary to treat the plastic liquefaction oils in order to recycle them.

[0004] There are many treatment processes that allow the content of heteroatoms, and in particular silicon, in plastic liquefaction oils to be reduced.

[0005] Some of them consist of heating the plastic oil in the presence of a basic compound, generally in aqueous solution.

[0006] Thus, patent application WO2021 / 105326 claims a process for the recovery of liquefied plastic waste comprising a pretreatment step of the liquefied plastic waste by contacting it with an aqueous medium having a pH of at least 7 at a temperature of 200 °C or more, followed by liquid-liquid separation in in which the aqueous phase is separated from the organic phase to produce a pre-treated liquefied waste plastic. The proposed solution involves using a NaOH solution in water. The separation of the aqueous and organic phases is achieved by physical methods (centrifugation) or chemical methods (addition of separation aids, for example, non-aqueous solvents, addition of extra aqueous medium used for contacting, or of an aqueous medium with a different alkaline concentration), or by gravity.

[0007] It is also possible to reduce gum formation by adding an additive such as that proposed in patent application WO 2023 / 134977 A1 filed by the applicant, in which gum-reducing additives (in particular antioxidants and / or antipolymers), possibly in combination with dispersing agents and / or metal passivating agents and / or chelating agents, are added to a plastics oil. These additives nevertheless remain in the plastics oil and are likely to interfere with certain subsequent treatments.

[0008] Patent application WO2023 / 064375 also describes a method for reducing and preventing fouling of a synthetic feedstock composition comprising pyrolysis oil. The proposed solution includes the addition of an antifouling agent comprising a carboxylic acid anhydride or a copolymer of a dicarboxylic acid anhydride and an alpha olefin. This antifouling agent can be added to the inlet of a quenching tower or condenser in which pyrolysis vapors are cooled to a temperature of 100 °C to 200 °C, or to the stored pyrolysis oil. Filtration can be provided to remove solid products formed as a result of interaction with the antifouling agent. The presence of liquid products resulting from this interaction is mentioned in paragraph

[0056] . The nature of these products is not specified, and their removal is not intended. Furthermore, the added additives remain present in the pyrolysis oil..

[0009] There is therefore a need to improve existing purification processes, in particular to reduce the diene content. Summary of the invention

[0010] To this end, the invention proposes a method for purifying a composition comprising a plastic and / or elastomer liquefaction oil comprising the following steps: (a) provide a composition comprising a plastic and / or elastomer liquefaction oil, said composition containing conjugated dienes and having a diene index of at least 1 gI2 / 100g, in particular measured according to method UOP326, (b) treat the composition of step (a) under conditions of a Diels-Alder cycloaddition in the presence of at least one dienophile compound having at a C=C double bond, and optionally at least one electron-withdrawing group, during which at least a portion of the conjugated dienes contained in the composition react with at least one dienophile compound via a Diels-Alder cycloaddition reaction, to produce an effluent containing a modified composition exhibiting a reduced content of conjugated dienes and comprising products of the Diels-Alder reaction, (c) subject the effluent from step (b) to at least one step selected from (c1) a step of removing the products of the Diels-Alder reaction by washing in the presence of water or an immiscible organic solvent, (c2) a treatment step in the presence of a basic compound at a temperature of not more than 450°C, or (c3) a hydrogenation step at a temperature of not more than 400°C of the products of the Diels-Alder reaction.

[0011] The sequence of steps in the process according to the invention makes it possible to reduce the quantity of conjugated dienes present in the oil, and consequently the diene index of the oil, but also to prevent a retro-Diels-Alder reaction either by eliminating the Diels-Alder products, by washing with water (step c1) or by basic treatment (step c2), or by transforming the Diels-Alder products (step c3). Thus, there is no risk of reformation of conjugated dienes.

[0012] The electron-withdrawing group of the dienophile compound used in step (b) can be selected from a nitro group (-NO2), a sulfonyl group (-SO2R), a nitrile group (-CN), a sulfo group (-SO3H), an aldehyde group (-CHO), a ketone group (-COR), a carboxyl group (-COOH), a carboxylate group (-COO), an ester group (COOR), an acyl chloride group (-COC1), an amide group (-CONH2), a hydroxyl group (-OH), an ether group (-OR), a tertiary amine group (-NR3), a primary amine group (-NH2), a phenyl group (-C6H5), a vinyl group (-CH=CH2), a hydrogen, and a halogen selected from fluorine, chlorine, bromine or iodine.

[0013] For example, the dienophile compound can be chosen from an unsaturated carboxylic acid, an unsaturated dicarboxylic acid, an unsaturated carboxylic acid anhydride, an unsaturated dicarboxylic acid anhydride, an unsaturated dicarboxylic acid ester, an unsaturated ketone, an unsaturated aldehyde, an alkene, alone or in mixture.

[0014] Step (b) according to the invention may include one or more of the following features: - prior to step (b), the composition is subjected to (i) filtration, (ii) washing with water or a polar solvent immiscible with the composition, (iii) distillation, (iv) decantation, or (v) a combination of two, three or four of steps (i) to (iv), - prior to or during step (b), said dienophile compound is introduced into the composition (i) in solid form, (ii) previously solubilized in an aqueous medium, preferably water, (iii) previously solubilized in an organic solvent, (iv) in liquid form, or (v) in gaseous form, - the number of moles of said dienophile compound is at least equal to the number of moles of conjugated dienes present in the composition, in particular measured via the diene index, for example by the UOP326 method, - step b) is carried out at a temperature of 10 to 150 °C, preferably 20 to 120 °C, more preferably 20 to 50 °C, - step b) is carried out for a period of 1 minute to 72 hours, preferably 10 minutes to 72 hours, more preferably 20 minutes to 72 hours, 30 minutes to 48 hours, or 60 minutes to 36 hours.

[0015] The method according to the invention may include one or more of the following features: - step (c) is preceded or followed by a solids separation step by (i) filtration, (ii) centrifugation, (iii) hydrocyclone or (iv) a combination of two or more of these steps, - step (c) is followed by an additional purification step (d) in which the purified composition is further purified by passing over a solid adsorbent in order to reduce the content of at least one element among F, Cl, Br, I, O, N, S, Se, Si, P, As, Fe, Ca, Na, K, Mg and Hg and / or the water content,

[0016] Step (c) according to the invention may include one or more of the following features:

[0017] - step (cl) is carried out in the presence of water at neutral, basic or acidic pH, or in presence of an organic solvent that is immiscible with the modified composition,

[0018] - step (c2) includes at least one of the following features: - step (c2) is carried out in the presence of (i) a solid basic compound, (ii) a basic compound previously solubilized in an aqueous medium, preferably water, or (iii) a basic compound previously solubilized in a solvent; - step c2) is implemented in the presence of 0.1 to 50% by mass of basic compound relative to the total mass of the treated organic phase, - step (c2) is carried out at a temperature of 50 to 250 °C, preferably 50 to 225 °C, more preferably 50 to 200 °C, - step (c2) is carried out for a duration of 0.1 seconds to 3 hours, preferably from 0.1 seconds to 2 hours, more preferably from 1 minute to 1 hour, even more preferably from 1 minute to 20 minutes or from 1 minute to 16 minutes, - the basic compound comprises an oxide, hydroxide, bicarbonate or alkoxide of an alkali metal cation or an alkaline earth metal cation, or a hydroxide or bicarbonate of a quaternary ammonium cation, alone or in mixture, - the basic compound is chosen from LiOH, NaOH, CsOH, Ba(OH)2, Na2O, KOH, K2O, CaO, Ca(OH)2, MgO, Mg(OH)2, NH4OH, TMAOH, TEAOH, TBAOH, EtONa, MeONa and their mixtures,

[0019] - step (c3) includes at least one of the following features: - Step (c3) is carried out at a temperature of 100 °C to 400 °C, - Step (c3) is carried out at an absolute pressure of 20 to 250 bars, - Step (c3) is carried out at an hourly volumetric rate of 0.1 to 10 h1, - Step (c3) is carried out in a mixture with a fossil hydrocarbon feedstock.

[0020] Advantageously, the composition from step (c) or (d) can undergo (e) a catalytic hydrotreatment in one or two steps to provide a purified hydrotreated composition.

[0021] The hydrotreatment of step (e):

[0022] - can be carried out in a single step in which the purified composition of the step (c) or (d) is hydrotreated at a temperature of 200 to 450°C, preferably 200 to 340°C in the presence of hydrogen at an absolute pressure of 20 to 160 bar, preferably 30 to 100 bar and in the presence of at least one hydrotreating catalyst, or

[0023] - can be carried out in a first step (e-1) in which the purified composition of step (c) or (d) is hydrotreated at a temperature of 80 to 250°C, preferably 130 to 250°C in the presence of hydrogen at an absolute pressure of 5 to 60 bar, preferably 20 to 50 bar and in the presence of at least one first hydrotreating catalyst, and in a second step (e-2) in which the effluent from step (e-1) is hydrotreated at a temperature of 200 to 450°C, preferably 250 to 340°C in the presence of hydrogen at an absolute pressure of 20 to 160 bar, preferably 30 to 100 bar and in the presence of at least one second hydrotreating catalyst.

[0024] Advantageously, the purified hydrotreated composition exiting step (e) can be washed with water to remove inorganic compounds such as hydrosulfide, hydrogen chloride, ammonia.

[0025] Advantageously, the purified composition of step (c) or (d), or the hydrotreated purified composition of step (e) optionally washed with water, can be used as is or separated into usable streams for the preparation of fuels and combustibles such as LPG, gasoline, diesel, heavy fuel oil, kerosene and / or for the preparation of lubricants and / or base oils.

[0026] Advantageously, the purified composition of step (c) or (d), or the hydrotreated purified composition of step (e), can be subjected, pure or diluted, optionally after separation into usable streams, to a steam cracking step to produce olefins such as ethylene and propylene, which can then be used to manufacture new polymers by polymerization.

[0027] Advantageously, the purified composition of step (c) or (d), or the hydrotreated purified composition of step (e), can be treated, pure or diluted, optionally after separation into usable streams, in a steam cracker to produce olefins, and / or a catalytic fluidized bed cracker, and / or a hydrocracker, and then optionally in a steam cracker, and / or a hydrotreating reactor, in particular a catalytic hydrogenation reactor.

[0028] Advantageously, step a) may include the preliminary step a1) of providing a stream of plastic and / or elastomer waste; a2) liquefying said plastic and / or elastomer waste stream by pyrolysis or hydrothermal liquefaction at a temperature of at least 200°C; a3) recovering a liquefaction effluent and separating said liquefaction effluent into a hydrocarbon fraction Cl to C4, and optionally into an aqueous fraction, the remaining fraction being said plastic and / or elastomer liquefaction oil; a4) optionally mixing said remaining fraction with a solvent or a diluent.

[0029] The previously described steps of the process according to the invention can be carried out one after the other without intermediate steps except for the optional additional steps described.

[0030] In particular, in one embodiment, the process according to the invention comprises only steps (a) to (c), and optionally the other steps described. Definitions

[0031] Unless explicitly stated otherwise, the standards mentioned in the rest of the description correspond to the standard in force on July 12, 2024.

[0032] For the purposes of this description, the following definitions are given:

[0033] The terms "including" and "includes" as used herein are synonymous with "including", "includes" or "contains", "containing", and are inclusive or boundless and do not exclude additional features, elements or unspecified method steps.

[0034] The specification of a decimal-free numeric domain includes all integers and, where appropriate, fractions of them (for example, 1 to 5 may include 1, 2, 3, 4 and 5 when reference is made to a number of elements, and may also include 1.5, 2, 2.75 and 3.80, when reference is made to, for example, a measure.).

[0035] The specification of a decimal also includes the decimal itself (for example, "from 1.0 to 5.0" includes 1.0 and 5.0). Any range of numeric values ​​recited herein also includes any subrange of numeric values ​​mentioned above.

[0036] The expressions % by weight and % by weight have an equivalent meaning and refer to the proportion of the mass of a product relative to 100g of a composition comprising it.

[0037] Unless otherwise indicated, measurements given in parts per million (ppm) are expressed by weight.

[0038] The terms "alkane" or "alkanes" used herein describe branched or unbranched acyclic hydrocarbons having the general formula CnH2n+2, and thus consisting entirely of saturated hydrogen and carbon atoms; see, for example, IUP AC. Compendium of Chemical Terminology, 2nd edition (1997). The term "alkanes" therefore refers to unbranched alkanes ("normal paraffins" or "n-paraffins" or "n-alkanes" or "paraffins") and branched alkanes ("iso-paraffins" or "iso-alkanes"), but excludes naphthenes (cycloalkanes). They are sometimes designated by the symbol "HC-".

[0039] The terms "olefin" or "alkene" used here refer to an unsaturated hydrocarbon compound containing at least one carbon-carbon double bond. They are sometimes designated by the symbol "HC=".

[0040] The term "alkyne" used here refers to an unsaturated hydrocarbon compound containing at least one carbon-carbon triple bond.

[0041] The term “diene” designates a non-aromatic compound comprising at least two C=C double bonds. By “conjugated diene” is meant a non-aromatic compound comprising at least two C=C double bonds separated by a single C=C single bond.

[0042] The term "hydrocarbon" refers to both alkanes (saturated hydrocarbons), cycloalkanes, aromatics and unsaturated hydrocarbons.

[0043] The Hourly Volumetric Velocity (WH) is defined as the hourly volume of charge flux per unit catalytic volume and is expressed here in h*.

[0044] By "heteroatom" is meant any element of an organic compound other than carbon and hydrogen.

[0045] The concentration of heteroatoms in the hydrocarbon matrix can be determined by any method known in the art. In particular, relevant characterization methods include X-ray fluorescence (XRF), inductively coupled plasma mass spectrometry (ICP-MS), and inductively coupled plasma atomic emission spectrometry (ICP-AES). Analytical scientists are able to identify the most suitable method for measuring each metal and, more generally, each heteroatom, depending on the hydrocarbon matrix considered. The oxygen content can be measured according to ASTM D5622 / D2504. The nitrogen content can be measured according to ASTM D4629. The sulfur content can be measured according to ISO 20846. The content of halogens, including chlorine, bromine, fluorine, can be measured according to the standard: ASTM D7359.

[0046] The aromatic content can be measured by gas chromatography, for example by a GCxGC or GC method, or by liquid chromatography, or by proton NMR and / or carbon NMR.

[0047] The maleic anhydride value (MAV) corresponds to the amount of maleic anhydride that reacts with 100 parts of oil under specific conditions. It is a measure of the conjugated double bonds in the oil. One mole of maleic anhydride corresponds to one conjugated double bond. The term maleic anhydride value (MAV) refers to the analytical method by titration, expressed in mg of maleic acid per g of sample.

[0048] The diene index (DV) or "diene index" is also a measure of conjugated double bonds and refers to the analytical method by titration expressed in g of diiodine per 100 g of sample, also measured by the UOP 326 method. There is a correlation between MAV = DV *3.863 since 2 moles of iodine correspond to 1 mole of maleic anhydride.

[0049] The term "Bramine number" refers to the quantity of bromine in grams that has reacted with 100 g of sample. This number indicates the quantity of olefins in a sample. It is determined in grams of Br2 per 100 grams of solution (gBr2 / 100g) and can be measured according to ASTM DI 159.

[0050] The term "Bramine Index" is the number of milligrams of bromine that react with 100 g of sample. It is determined in milligrams of Br2 per 100 g of solution (mg Br2 / 100g) and can be measured according to ASTM D2710 or ASTM D5776 methods.

[0051] Boiling points as mentioned herein are measured at atmospheric pressure, unless otherwise specified. An initial boiling point is defined as the temperature at which the first vapor bubble forms. A final boiling point is the highest temperature attainable during distillation. At this temperature, no more vapor can be transported to a condenser. The determination of the initial and final boiling points relies on techniques known in the trade, and several methods adapted according to the distillation temperature range are applicable, for example, NF EN 15199-1 or ASTM D2887 for measuring the boiling points of petroleum fractions by gas chromatography, ASTM D7169 for heavy hydrocarbons, and ASTM D7500, D86, or DI 160 for distillates.

[0052] The term “polar solvent” as used in this patent application covers all chemical species, alone or in mixtures, comprising at least one carbon-hydrogen, carbon-halogen, carbon-chalcogen or carbon- nitrogen and having a non-zero dipole moment. It is understood that the term "polar solvent" in the context of this definition specifically excludes water.

[0053] The term "solvent" includes the aforementioned "polar solvents" and nonpolar solvents, which include, for example, any type of linear, branched, cyclic and / or aromatic saturated or unsaturated hydrocarbon such as pentane, cyclohexane, olefins, toluene or xylene or certain other solvents with zero or almost zero dipole moment such as tetrachloromethane or carbon disulfide.

[0054] The term "naphtha" or "naphtha fraction" refers to the general definition used in the oil and gas industry. In particular, it is a hydrocarbon obtained from the distillation of crude oil and whose boiling point is between 15 and 160 °C, according to standard NF EN 15199-1. Naphtha contains practically no olefins because the hydrocarbons are derived from crude oil. Naphtha is generally considered to have a carbon number between C5 and Cl1, although the carbon number can reach C15 in some cases. It is also generally accepted that the density of naphtha is between 0.65 and 0.77 g / mL.

[0055] A kerosene cut or fraction typically has boiling points ranging from 130 °C to 300 °C. It typically has an initial boiling point according to ASTM D86 of 130 to 160 °C and a final boiling point according to ASTM D86 of 220 °C to 300 °C.

[0056] A diesel or gasoil fraction may typically have an initial boiling point of 220 to 270 °C and a final boiling point of less than or equal to 400 °C, preferably less than or equal to 375 °C according to ASTM D86.

[0057] A vacuum-type diesel fraction can typically have an initial boiling point of 350 to 400 °C and a final boiling point of less than or equal to 550 °C, for example 490 to 550 °C according to ASTM D86.

[0058] The term "liquefaction oil" means an oil obtained from a pyrolysis process and / or a hydrothermal liquefaction process of a hydrocarbon feedstock. This hydrocarbon feedstock may include plastics, biomass, and / or elastomers, alone or in mixtures, including waste materials. A liquefaction oil may be formed from a mixture of two or more liquefaction oils obtained from the liquefaction of different hydrocarbon feedstocks.

[0059] The pyrolysis process should be understood as a thermal cracking process, typically carried out at a temperature of 300 to 1000 °C or 400 to 700 °C, implemented in the presence or without a catalyst and / or a gas (rapid pyrolysis, slow pyrolysis, flash pyrolysis, catalytic pyrolysis, hydropyrolysis, steam pyrolysis, ...).

[0060] The hydrothermal liquefaction (or HTL) process is a thermochemical conversion process using water as a solvent, reactant, and catalyst for the degradation reactions of a feedstock hydrocarbon, with water typically in a subcritical or supercritical state. The hydrothermal liquefaction process is typically carried out at a temperature of 250 to 500 °C and at pressures of 10 to 25-40 MPa in the presence of water.

[0061] The expression "plastic and / or elastomer liquefaction oil" or "oil resulting from the liquefaction of plastic and / or elastomers" or "liquefaction oil of plastic and / or elastomer waste" or "plastic and / or elastomer oil" refers to hydrocarbon liquid products obtained from pyrolysis or hydrothermal liquefaction of plastics, namely thermoplastic and / or thermosetting polymers, and / or elastomers (for example, latex possibly vulcanized or tires), alone or in mixture, and generally in the form of waste, optionally in mixture with at least one other feedstock, in particular in the form of waste, such as biomass, for example selected from lignocellulosic biomass, paper and cardboard.

[0062] The plastic can be of any type, including any type of new or used plastic, included in household (post-consumer) or industrial waste. Plastics are defined as materials made up of polymers and optionally of auxiliary components such as plasticizers, fillers, colorants, catalysts, flame retardants, stabilizers, etc. For example, these polymers can be polyethylene, halogenated polyethylene (Cl, F), polypropylene, polystyrene, polybutadiene, polyisoprene, poly(ethylene terephthalate) (PET), acrylonitrile-butadiene-styrene (ABS), polybutylene, poly(butylene terephthalate) (PBT), polyvinyl chloride (PVC), polyvinylidene chloride, polyester, polyamide, polycarbonate, polyether, epoxy polymer, polyacetal, polyimide, polyesteramide, silicone, etc.In general, any polymer or mixture of polymers capable of producing hydrocarbons by liquefaction can be used.

[0063] Biomass can be defined as an organic product of plant or animal origin. Biomass thus includes (i) biomass produced from surplus agricultural land not used for human or animal consumption: dedicated crops, known as energy crops; (ii) biomass produced by deforestation (forest maintenance) or the clearing of agricultural land; (iii) agricultural residues from cereal crops, vines, orchards, olive trees, fruits and vegetables, agri-food residues, etc.; (iv) forestry residues from silviculture and wood processing; (v) agricultural residues from livestock farming (manure, slurry, bedding, droppings, etc.); (vi) household organic waste (paper, cardboard, green waste, etc.); (vii) ordinary industrial organic waste (paper, cardboard, wood, putrescible waste, etc.).The plastic liquefaction oil treated by the invention can be obtained from the liquefaction of waste containing at least 1% by mass, optionally from 1 to 50% by mass, from 2 to 30% by mass or in a range. defined by any two of these limits, one or more of the aforementioned biomasses, residues and organic waste, and the remainder consisting of plastic waste, optionally mixed with elastomers, particularly in waste form.

[0064] Elastomers are linear or branched polymers transformed by vulcanization into a weakly cross-linked, infusible and insoluble three-dimensional network. These include natural or synthetic rubbers. They can be found in tire-type waste or any other household or industrial waste containing elastomers, natural and / or synthetic rubber, mixed or not with other components such as plasticizers, fillers, vulcanizing agents, vulcanization accelerators, additives, etc. Examples of elastomeric polymers include ethylene-propylene copolymers, ethylene-propylene-diene terpolymer (EPDM), polyisoprene (natural or synthetic), polybutadiene, styrene-butadiene copolymers, isobutene-based polymers, isobutylene-isoprene copolymers (chlorinated or brominated), acrylonitrile butadiene copolymers (NBR), polychloroprenes (CR), polyurethanes, silicone elastomers, etc.The plastic and / or elastomer liquefaction oil treated by the invention can be derived from the liquefaction of waste containing at least 1% by mass, optionally from 1 to 50% by mass, from 2 to 30% by mass or within a range defined by any two of these limits, of one or more of the aforementioned elastomers, in particular in the form of waste, the remainder being made up of plastic waste, optionally mixed with biomass, residues and organic waste.

[0065] By "hydrotreating" is meant any process in which hydrocarbons react with dihydrogen, typically under pressure, in the presence or not of a catalyst. Hydrotreating may thus include one or more reactions selected from hydrodesulfurization (HDS), hydrodeazotation (HDN), hydrodeoxygenation (HDO), hydrodemetallation (HCM), hydrocracking, hydroisomerization and hydrogenation (hydrogenation of unsaturated compounds into saturated compounds).

[0066] By "hydrotreating catalyst" is meant a catalyst that promotes the incorporation of hydrogen into the products. This type of catalyst is typically a metallic catalyst comprising one or more metals from groups 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13 and 14 of the periodic table.

[0067] The particular features, structures, properties, embodiments of the invention can be freely combined into one or more embodiments not specifically described here, as may be apparent to specialists in the processing of plastic liquefaction oils implementing their general knowledge. Detailed description of the invention

[0068] Description of the composition comprising a plastic and / or elastomer liquefaction oil

[0069] The composition provided in step (a) includes a plastic and / or elastomer liquefaction oil.

[0070] In one embodiment, the composition may comprise only a plastic and / or elastomer liquefaction oil, in particular only a plastic and / or elastomer pyrolysis oil or only a plastic and / or elastomer hydrothermal liquefaction oil.

[0071] Alternatively, the composition may comprise at least 1% by mass of plastic and / or elastomer liquefaction oil. The remainder may then consist of up to 99% by mass of a diluent or solvent such as a hydrocarbon, and / or one or more of the components listed below, preferably a component derived from biomass or biomass waste.

[0072] In one embodiment, the composition may comprise at least 5% by mass, preferably 10% by mass, more preferably at least 25% by mass, even more preferably at least 50% by mass, more preferably 75% by mass, and even more preferably at least 90% by mass of plastic and / or elastomer liquefaction oil. The composition may comprise at most 80% by mass, 90% by mass, 95% by mass, or 100% by mass of plastic and / or elastomer liquefaction oil. The mass content of plastic and / or elastomer liquefaction oil(s) in the composition may fall within any range defined by two of the aforementioned limits.

[0073] In a particular embodiment, the composition may comprise only an elastomer liquefaction oil, in particular only an elastomer pyrolysis oil or only an elastomer hydrothermal liquefaction oil. Typically, these elastomers are waste products, such as used tires.

[0074] In another particular embodiment, the composition may comprise only a plastics liquefaction oil, in particular only a plastics pyrolysis oil or only a plastics hydrothermal liquefaction oil, in particular obtained from waste made of plastic, optionally mixed with biomass.

[0075] The composition may further include a component derived from biomass or biomass waste, such as tall oil, used cooking oil, animal fat, vegetable oil such as rapeseed, canola, castor, palm, or soybean oil, oil extracted from algae, oil extracted from the fermentation of oil-producing microorganisms such as oleaginous yeasts, or oil of liquefaction of biomass, in particular a biomass liquefaction oil such as from Panicum virgatum or a lignocellulosic biomass liquefaction oil, for example a liquefaction oil of wood, paper and / or cardboard, an oil obtained by liquefaction of ground-up used furniture, as well as mixtures thereof.

[0076] The composition may further include a diluent miscible with the liquefaction oil of plastic and / or elastomers. This diluent preferably has a diene value of not more than 0.5 g I₂ / 100 g, measured according to UOP 326, and a bromine value of not more than 5 g Br₂ / 100 g, measured according to ASTM DI 159. The diluent is preferably selected from a naphtha and / or a paraffinic solvent and / or a direct-distillation diesel or gas oil, containing not more than 1 wt% of sulfur, preferably not more than 0.1 wt% of sulfur, and / or a hydrocarbon stream having a boiling range between 50 °C and 150 °C or between 150 °C and 250 °C or between 200 °C and 350 °C, preferably having a bromine value of not more than 5 g Br₂ / 100 g, and / or a diene value of not more than 0.5 g I₂ / 100 g. gI2 / 100g, and / or the effluent from the optional hydrotreatment step of the process according to the invention, or any combination thereof.

[0077] The diluent can be added at a concentration of up to 80% by weight, preferably up to 50% by weight, for example from 5 to 50% by weight. Optionally, the diluent can be separated at the outlet of the optional hydrotreating step by flash or distillation and, preferably, recycled at the inlet of this hydrotreating step.

[0078] The composition supplied in step (a) may have a bromine value of at most 150 g Br2 / 100g, preferably at most 100 g Br2 / 100g, even more preferably at most 80 g Br2 / 100g, the most preferred being at most 50 g Br2 / 100g, as measured according to ASTM DI 159. In general, the composition supplied in step (a) has a bromine value of at least 1 g Br2 / 100g.

[0079] The composition supplied in step (a) may have a diene index of at least 1 gI2 / 100g, preferably of no more than 50 gI2 / 100g, in particular measured according to the UOP 326 method.

[0080] The composition may also have a heteroatom content of at least 20 ppm and generally of no more than 30% by mass.

[0081] Step (a) of supplying the composition may include:

[0082] (al) a step of supplying a stream of plastic and / or elastomer waste,

[0083] (a2) a step of liquefying waste containing plastics and / or elastomers, and the production of a hydrocarbon product comprising a gaseous phase, a liquid phase and a solid phase,

[0084] (a3) ​​a step of recovering the liquefaction effluent and separating said effluent in a fraction of hydrocarbons Cl to C4, and optionally in a fraction aqueous, the remaining fraction forming a liquefaction oil for plastics and / or elastomers,

[0085] (a4) an optional step of mixing the plastic liquefaction oil and / or of elastomers with a diluent or solvent.

[0086] The liquefaction step (a2) may include a pyrolysis step, typically carried out at a temperature of 300 to 1000°C or 400 to 700°C, this pyrolysis being for example a rapid pyrolysis or a flash pyrolysis or a catalytic pyrolysis or a hydropyrolysis.

[0087] Alternatively or in combination, the liquefaction step (a2) may include a hydrothermal liquefaction step, typically carried out at a temperature of 250 to 500 °C and at pressures of 10 to 25-40 MPa.

[0088] The waste supplied at step (al) may be plastic waste and / or elastomer waste, including tires, possibly mixed with biomass, as previously described.

[0089] The recovery and separation step (a3) ​​eliminates the gaseous phase, essentially C1-C4 hydrocarbons, the aqueous fraction when present, and the solid phase (typically char) to recover only the liquid organic phase (also called "remaining fraction" in this application) forming a liquefaction oil.

[0090] Plastic and / or elastomer liquefaction oils contain, in particular, paraffins, i-paraffins (isoparaffins), dienes, alkynes, olefins, naphthenes, and aromatics. Plastic and / or elastomer liquefaction oils also contain impurities containing heteroatoms, such as chlorinated, oxygenated, sulfurous, nitrogenous, and / or silylated organic compounds, metals, salts, and phosphorus compounds.

[0091] The composition of the plastic and / or elastomer liquefaction oil depends on the nature of the plastic and / or elastomers liquefied, and optionally on any other waste (biomass) liquefied with the plastic and / or elastomers, and is essentially (in particular more than 80% by mass, most often more than 90% by mass) made up of hydrocarbons having from 1 to 150 carbon atoms and impurities.

[0092] A plastic and / or elastomer liquefaction oil typically comprises 5 to 80% by mass of paraffins (including cycloparaffins), 10 to 95% by mass of unsaturated compounds (including olefins, dienes, and acetylenes), and 5 to 70% by mass of aromatics. These contents can be determined by gas chromatography.

[0093] In particular, a plastic and / or elastomer liquefaction oil may comprise a bromine content of 10 to 130 g Br / 100 g, as measured according to the ASTM DI 159 standard, and / or a maleic anhydride index (UOP 326) of 1 to 55 mg maleic anhydride / lg.

[0094] A plastic liquefaction oil may have a diene index of at most 50 gI2 / 100 g, preferably of at most 25 gI2 / 100 g, preferably even more of at most 10 gI2 / 100 g, in particular measured according to UOP 326 standard.

[0095] In a preferred embodiment, said plastic and / or elastomer liquefaction oil has an initial boiling point of at least 15°C, and a final boiling point of at most 700°C, preferably at most 600°C, (measured according to standard NF EN 15199-1).

[0096] A plastic and / or elastomer liquefaction oil typically comprises at least 20 ppm of heteroatoms, or even at least 30 ppm of heteroatoms, including silicon, and typically at most 30% by mass of heteroatoms.

[0097] A plastic and / or elastomer liquefaction oil may, in particular, further comprise one or more of the following heteroatom contents: 0 to 8% by mass of oxygen (e.g., measured according to ASTM D5622), 1 to 20,000 ppm of nitrogen (e.g., measured according to ASTM D4629), 2 to 20,000 ppm of sulfur (e.g., measured according to ISO 20846), 1 to 10,000 ppm of metals, in particular more than 2 ppm (e.g., measured by ICP), 5 to 6,000 ppm of chlorine, preferably not more than 5,000 ppm (e.g., measured according to ASTM D7359), 0 to 200 ppm of bromine (e.g., measured according to ASTM D7359), 1 to 40 ppm of fluorine (e.g., measured according to the standard ASTM D7359), 1 to 2000 ppm of silicon, preferably at most 1000 ppm (e.g. measured by XRF), at least 1 ppm of P, preferably at most 5000 ppm of P.

[0098] A liquefaction oil for elastomers, and in particular for tires, may comprise one or more of the following characteristics:

[0099] A diene index of 1 to 50 gl2 / 100,

[0100] An aromatic compound content of 5 to 80% by mass, most often 20 to 80% by mass, or even 30 to 80% by mass,

[0101] Heteroatom contents of 0 to 10% by mass.

[0102] Tires have the advantage of possessing a non-negligible biogenic fraction (rubber from the Hevea tree), which allows them to be recycled into hydrocarbon products that are partly bio-based.

[0103] Generally, the bio-based carbon content of a tire oil, measured according to ASTM D6866-24, DIN 51637 (2014) or ASTM D7026, is at least 30% by mass, preferably at least 40% by mass, and can reach 100% by mass, particularly for tires made from synthetic rubber of renewable origin (for example, from butadiene produced from ethanol derived from of biomass). "Bio-based carbon" means carbon derived from biomass. Bio-based carbon does not include carbon derived from fossil materials.

[0104]

[0105] Detailed description of the optional step of processing the composition provided in step (a)

[0106] Between steps (a) and (b), the invention may also include an optional pretreatment step, in which the composition is subjected, in particular immediately before step (v), to (i) filtration, (ii) washing with water or a polar solvent immiscible with the composition, (iii) distillation, (iv) decantation, or (v) a combination of two, three, or four of steps (i) to (iv). This additional step may remove some of the impurities contained in the composition, such as oxygen, nitrogen, chlorine, sulfur, or other heteroatoms. In particular, reducing the amount of oxygen may prevent the formation of solids and / or gels during a subsequent hydrotreatment step.

[0107] During the additional washing step (ii), the volume ratio of polar solvent or water / composition can be from 1 / 99 to 90 / 10, from 10 / 90 to 90 / 10, from 20 / 80 to 80 / 20, from 30 / 70 to 70 / 30, from 35 / 65 to 65 / 35, from 35 / 65 to 60 / 40, or from 40 / 60 to 60 / 40.

[0108] When water is used for washing (ii), it may have an acidic, basic, or neutral pH. An acidic pH can be obtained by adding one or more organic or inorganic acids. Examples of usable organic acids include citric acid (C6H8O7), formic acid (CH2O2), and acetic acid (CH3COOH). Examples of inorganic acids are sulfamic acid (H3NSO3), hydrochloric acid (HCl), nitric acid (HNO3), sulfuric acid (H2SO4), and phosphoric acid (H3PO4). A basic pH can be obtained by adding oxides of alkali and alkaline earth metals, hydroxides of alkali and alkaline earth metals (e.g. NaOH, KOH, Ca(OH)2), bicarbonates of alkali and alkaline earth metals and amines (e.g. triethylamine, ethylenediamine, ammonia).

[0109] The polar solvent may have a density greater or less than the density of the composition comprising a plastic and / or elastomer liquefaction oil.

[0110] In particular, the density of the polar solvent may be 3 to 50% higher or lower than that of the composition.

[0111] The polar solvent is a solvent that is not miscible with the composition comprising a liquefaction oil of plastic and / or elastomers to be purified.

[0112] By way of example, a polar solvent (or a mixture of polar solvents, as the case may be) may be considered immiscible when its recovery rate is greater than or equal to 0.95. This recovery rate is defined as the ratio of volume of extract on the initial volume of solvent, this extract being a phase containing the solvent, not miscible with the composition containing a liquefaction oil, recovered after stirring and decanting a mixture of one part by volume of solvent with twenty-five parts by volume of the composition containing a liquefaction oil to be purified, at atmospheric pressure and at a temperature of 20°C.

[0113] This recovery rate can be determined in particular by following the following procedure: - Introduction of 50 mL of a composition containing a liquefaction oil into a flat-bottomed flask with a volume of 100 mL, using a precision pipette of + / -0.5 mL, - Introduce 2 mL of solvent into the flask, using a precision pipette of + / -0.1 mL, - Insert a magnetic rod, close the balloon with a polypropylene stopper, - Stir the mixture on a mechanical stirrer at a speed of 500 rpm for 5 minutes. - At the end of the 5 minutes, stop the stirring, remove the magnetic bar using a magnetic rod, - Transfer the contents of the balloon into a graduated tube with an accuracy of + / -0.05 mL for a volume less than or equal to 2 mL and an accuracy of + / -0.1 mL for a volume greater than 2 mL. - Wait for complete separation by decantation and measure the volume of the 2 phases using the graduations. Complete separation is considered to have been achieved when the volumes of the two phases no longer change.

[0114] Acceptable immiscible polar solvents include (i) sulfur compounds, for example dimethyl sulfoxide, (ii) nitrogen compounds, for example A,A-dimethylformamide, (iii) halogenated compounds, for example dichloromethane or chloroform, (iv) ethylene glycol, or: - glycol ethers, including in particular polyethylene glycol with chemical formula HO-(CH2-CH2-O)nH and average mass molar mass of 90 to 800g / mol, for example diethylene glycol and tetraethylene glycol, polypropylene glycol with chemical formula H[OCH(CH3)CH2]nOH and average mass molar mass of 130 to 800g / mol, for example dipropylene glycol and tetrapropylene glycol, - dialkyl formamides, in which the alkyl group can comprise from 1 to 8 or from 1 to 3 carbon atoms, notably dimethyl formamide (DMF), - dialkyl sulfoxides, in which the alkyl group may comprise from 1 to 8 or from 1 to 3 carbon atoms, notably dimethyl sulfoxide (DMSO) and sulfolane, - compounds comprising a furan ring, - cyclic carbonate esters, including those with 3 to 8 or 3 to 4 carbon atoms, notably propylene carbonate and ethylene carbonate.

[0115] One or more of the aforementioned solvents may be used. However, advantageously, only one of the aforementioned solvents may be used provided that it is immiscible with the composition containing a liquefaction oil to be purified.

[0116] Preferably, the polar solvent may be ethylene glycol or a glycol ether, in particular polyethylene glycol of chemical formula HO-(CH2-CH2-O)nH of average mass molar mass of 90 to 800g / mol or polypropylene glycol of chemical formula H[OCH(CH3)CH2]nOH of average mass molar mass of 130 to 800g / mol, or a compound comprising a furan ring, or a cyclic carbonate ester, in particular propylene or ethylene carbonate, alone or in mixture, preferably alone.

[0117] In a preferred embodiment, the polar solvent is chosen from propylene carbonate, ethylene carbonate, ethylene glycol and polyethylene glycol of chemical formula HO-(CH2-CH2-O)nH of average molar mass of 90 to 800g / mol, alone or in mixture, preferably alone.

[0118] Description of step (b) of treatment with a dienophile compound

[0119] Step (b) is a treatment step of the composition provided in step (a) in the presence of at least one dienophile compound under Diels-Alder cycloaddition conditions to produce an effluent containing a modified composition having a reduced content of conjugated dienes and comprising products of the Diels-Alder reaction.

[0120] This treatment makes it possible in particular to reduce the content of conjugated dienes by making them react with a dienophile by Diels-Alder cycloaddition.

[0121] The Diels-Alder reaction is a cycloaddition reaction between an alkene, also called a dienophile, and a conjugated diene to form a cyclohexene derivative. This reaction is reversible via a reaction called the retro-Diels-Alder reaction; thus, above a certain temperature, the ring will break down to regenerate a conjugated diene and a dienophile.

[0122] The dienophile can be added to the composition provided in step (a) either prior to step (b) or during step (b).

[0123] The dienophile may be added to the composition in solid form or previously dissolved in an aqueous medium, preferably water, or previously dissolved in an organic solvent, miscible or immiscible with the composition. The amount of solvent or water used may be just sufficient to dissolve the dienophile. Preferably, the solvent used is a solvent of the dienophile and is miscible with the composition to be treated. For example, toluene or acetone may be used as a solvent.

[0124] The dienophile can also be introduced into the composition in liquid or gaseous form.

[0125] In a preferred embodiment, the dienophile is added without solubilization in an organic solvent or in an aqueous medium such as water.

[0126] The amount of dienophile used can advantageously be chosen so that the number of moles of dienophile compound is at least equal to the number of moles of conjugated dienes present in the composition, this number of moles being determined by measuring the diene index, for example according to the UOP 326 method. In particular, step b) can advantageously be carried out by adding a number of moles of dienophile compound equal to the number of moles of conjugated dienes present in the composition.

[0127] In general, 1% or more by mass of dienophile compound may be added relative to the total mass of the composition being treated, and up to 10% by mass.

[0128] The dienophile compound used typically has at least one C=C double bond, generally at least one or two double bonds, and optionally an electron-withdrawing group. An electron-withdrawing group is understood to be an atom or group of atoms with an electron-withdrawing inductive effect and / or an electron-withdrawing mesomeric effect. Preferably, groups whose electron-withdrawing effect (whether inductive or mesomeric) outweighs any electron-donating effect are preferred.

[0129] The electron-withdrawing group can be selected from a nitro group (-NO2), a sulfonyl group (-SO2R), a nitrile group (-CN), a sulfo group (-SO3H), an aldehyde group (-CHO), a ketone group (-CO), a carboxyl group (-COOH), a carboxylate group (-COO), an ester group (COOR), an acyl chloride group (-COQ), an amide group (-CONH2), a hydroxyl group (-OH), an ether group (-OR), a tertiary amine group (-NR3), a primary amine group (-NH2), a phenyl group (-C6H5), a vinyl group (-CH=CH2), a hydrogen, and a halogen selected from fluorine, chlorine, bromine or iodine.

[0130] In a preferred embodiment, the dienophile compound comprises at least one or two double bonds, and optionally at least one group selected from a carboxyl group (-COOH), a carboxylate group (-COO), an aldehyde group (-CHO), a ketone group (-CO) and an ester group (COOR).

[0131] The dienophile compound may be selected from an unsaturated carboxylic acid, an unsaturated dicarboxylic acid, an unsaturated carboxylic acid anhydride, an unsaturated dicarboxylic acid anhydride (e.g. maleic anhydride), an unsaturated dicarboxylic acid ester, an unsaturated ketone, an unsaturated aldehyde, an alkene (e.g. ethylene, propylene, butylene), alone or in mixture.

[0132] In a preferred embodiment, the dienophile compound may be selected from the group consisting of: an unsaturated carboxylic acid, in particular a C3-C5 acid comprising at least one or two double bonds, an unsaturated dicarboxylic acid, in particular a C4-C8 acid comprising at least one or two double bonds, an anhydride of these acids, an ester of an unsaturated dicarboxylic acid, in particular a C3-C15 ester comprising at least one or two double bonds, an ester of an unsaturated dicarboxylic acid, in particular a C3-C15 ester comprising at least one or two double bonds, an alkene, in particular a C2-C8 alkene, an unsaturated ketone, in particular a C3-C8, an unsaturated aldehyde, in particular a C2-C8, alone or in mixture.

[0133] By way of example, the dienophile compound may be selected from acrylic acid, maleic acid, maleic anhydride, an alkyl acrylate or methacrylate, in particular a C1-C4 alkyl acrylate or methacrylate, for example a methyl or ethyl acrylate or methacrylate, a dialkyl maleate, in particular a dialkyl maleate having the alkyl group in C1-C4, for example a dimethyl or diethyl maleate, an alkene, in particular ethylene, propylene, butylene, 1-hexene.

[0134] In a particular embodiment, the dienophile compound is not a carboxylic or dicarboxylic acid anhydride, and in particular is not maleic anhydride.

[0135] Step (b) is typically carried out at a temperature of 10 to 150 °C, preferably 20 to 120 °C, and more preferably 20 to 50 °C, for example at room temperature, in particular without external heating. When the dienophile compound is solubilized in a solvent, a temperature lower than the boiling point of the solvent at the pressure considered may be chosen.

[0136] The duration of contact of the salt with the composition can be from 1 minute to 72 hours, preferably from 10 minutes to 72 hours, more preferably from 20 minutes to 72 hours, from 30 minutes to 48 hours, or from 60 minutes to 36 hours or in any interval defined by two of these limits.

[0137] Step (b) of the treatment can be carried out at atmospheric pressure.

[0138] The treatment in step (b) can be carried out in any device that allows contact between the dienophile compound and the composition. This can be at least one reactor, preferably equipped with a mixing device, for example, an Archimedes screw, a mixer, or a static mixer.

[0139] Detailed description of the optional additional solids separation step

[0140] Step (c) may be preceded or followed by a solids separation step by (i) filtration, (ii) centrifugation, (iii) hydrocyclone, or (iv) a combination of two or three of these steps. This solids separation step may facilitate the implementation of step (c) by removing all or part of the solids present in the effluent from step (b).

[0141] Detailed description of step (c)

[0142] During step (c), the effluent from step (b) is subjected to at least one step selected from:

[0143] (cl) a step for removing the products of the Diels-Alder reaction by washing,

[0144] (c2) a treatment step in the presence of a basic compound at a temperature of up to 450°C, and

[0145] (c3) a hydrogenation step at a temperature of at most 350 °C of the products of the Diels-Alder's reaction.

[0146] The decrease in diene index observed between the entry and exit of this step is typically at least 10%, preferably at least 25%, measured according to UOP 326.

[0147] Only one of the steps cl to c3 can be implemented.

[0148] Different combinations of these steps may also be envisaged. In a preferred embodiment, the following combinations may be envisaged: c 1 followed by c3, c2 followed by cl, c2 followed by cl then by c3, c3 followed by c2 then cl, or step c3 only.

[0149] In particular, step (c) may have the following embodiments, going from most preferred to least preferred: only step c3, only step cl, the succession of steps c2 then cl only, the succession of steps cl then c3 only, the succession of steps c2 then cl then c3 only, the succession of steps c3 then c2 then cl only.

[0150] Without wishing to be bound by a theory, it is assumed that steps cl and c2 allow an opening of the Diels-Alder products, subsequently facilitating their elimination.

[0151] During step (cl), the effluent from step (b) is subjected to washing with water at neutral, basic or acidic pH, or with an organic solvent that is not miscible with the composition from step (b).

[0152] This step (cl) allows the products of the Diels-Alder reaction present in the effluent exiting step (b) to be eliminated.

[0153] At the outlet of step (cl), a phase containing the purified composition with a reduced content of conjugated dienes is thus recovered, as well as a phase containing water or the immiscible solvent used for washing, salt, impurities, and the products of the Diels-Alder reaction. In other words, at the outlet of the washing step, these phases are recovered separately, for example, following a liquid / liquid separation (centrifugation and / or decantation and / or other) carried out at the end of the washing step.

[0154] The water used in step (cl) may have an acidic pH (pH<7), basic pH (pH >7) or neutral pH (pH=7), preferably a neutral pH.

[0155] In one embodiment, the water used has an acidic or neutral pH. In particular, the water used does not contain any basic compound and, specifically, does not contain any basic compound comprising an alkali metal or alkaline earth metal cation. This is particularly advantageous when step (c1) follows step (c2).

[0156] An acidic pH can be obtained by adding one or more organic or inorganic acids. Examples are given with reference to washing (ii) of the optional pretreatment step. Preferably, the water can have a pH of 0.1 to 6.9.

[0157] A basic pH can be obtained by adding a basic compound, for example those mentioned above with reference to washing (ii) or those used in step (cl). Preferably, the water can have a pH of 7.1 to 14.

[0158] The immiscible solvent can be any organic solvent immiscible with the effluent from step (b), in particular one in which the products of the Diels-Alder reaction are soluble. A usable immiscible solvent is, for example, a polar solvent, in particular those described in the optional pretreatment step, and water. Such a solvent makes it possible, in particular, to solubilize the products of the Diels-Alder reaction comprising a polar functional group, for example, those obtained from a dienophile comprising a polar functional group.

[0159] Step (cl) can be carried out at a temperature from 10°C to 120°C, preferably from 15°C to 95°C, more preferably from 15°C to 80°C, or even within any range defined by any two of these limits, advantageously without external heating. Step (cl) is typically carried out at atmospheric pressure.

[0160] During step (cl), the solvent or water / effluent volume ratio can be from 1 / 99 to 90 / 10, from 20 / 80 to 80 / 20, from 30 / 70 to 70 / 30, from 35 / 65 to 65 / 35, from 35 / 65 to 60 / 40, from 40 / 60 to 60 / 40, or in any interval defined by any two of the aforementioned bounds.

[0161] Step (c1) may include, or consist of, bringing the effluent from step (b) into contact with water or an immiscible solvent by any means known in the prior art.

[0162] For example, the effluent from step (b) and the solvent or water can be introduced into tanks, reactors, or mixers commonly used in the industry, and the two components can be mixed. Contacting them may involve vigorously agitating the two components by a mixing device. For example, the two components may be mixed together by stirring or shaking. Alternatively, contacting them may be carried out in a chamber in which the two components flow in opposite directions, for example, in contact columns with suitable packing to increase contact between the phase of the treated composition and water or an immiscible solvent. Alternatively, contact can be made in a static mixer in co-current mode or in a cavitation section.

[0163] This contact may occur more than once, particularly under the conditions described above. For example, two or more washes may be carried out, for example two to four washes.

[0164] The washing step (cl) can be implemented continuously or in batch.

[0165] Step (c2) is a treatment step of the effluent from step (b) in the presence of a basic compound at a temperature of no more than 450 °C to obtain an organic effluent comprising a treated composition.

[0166] This treatment makes it possible in particular to modify the compounds containing heteroatoms and the products of the Diels-Alder reaction in order to promote their subsequent elimination and also to eliminate the heteroatoms, in particular metals, silicon, phosphorus and nitrogen.

[0167] Step (c2) is carried out in the presence of a basic compound, preferably a nucleophilic basic compound.

[0168] Advantageously, the amount of basic compound used is from 0.1 to 50% by mass, preferably from 0.1 to 40% by mass, more preferably from 0.1 to 30% by mass, preferably from 0.1 to 20% by mass, even more preferably from 0.1 to 15% by mass relative to the total mass of the composition treated (effluent from step (b)).

[0169] Preferably, the amount of basic compound used is at least 0.5% by mass, more preferably at least 1% by mass, even more preferably at least 3% by mass, even more preferably at least 5% by mass or even at least 10% by mass, and at most 50% by mass, 40% by mass, 30% by mass, 20% by mass or 15% by mass, relative to the total mass of the composition treated (effluent from step (b)).

[0170] In one embodiment, during step (c2), the effluent from step (b) can be brought into contact with 0.1 to 15% by mass of a basic compound, preferably in the presence of water, more preferably with 0.5 to 15% by mass of a basic compound, even more preferably with 1 to 15% by mass of a basic compound, in particular 3 to 15% by mass, or even 5 to 15% by mass or 10 to 15% by mass relative to the total mass of the composition treated, or within any range defined by two of the preceding limits.

[0171] The basic compound can be added to the effluent supplied by step (b) either before step (c2) or during step (c2). This addition of the basic compound may optionally be followed by a mixing step before the implementation of step (c2).

[0172] The basic compound can be added in solid form or solubilized in an aqueous medium, preferably water or a solvent. In particular, step (c2) can be carried out without the addition of any solvent other than water or a solvent that may already be present in the composition.

[0173] Advantageously, the basic compound added in step (c2) is in solution in water. Thus, during step (c2), the effluent from step (b) can be brought into contact with an aqueous solution of a basic compound, preferably a basic compound comprising an alkali metal or alkaline earth cation. A person skilled in the art will then choose a quantity of water sufficient to dissolve / solubilize the basic compound, preferably the smallest possible quantity of water, or just enough to saturate the water with the basic compound.

[0174] Alternatively, the basic compound may be added solubilized in a solvent, miscible or immiscible with said effluent.

[0175] When the basic compound is solubilized in a solvent or in water, a person skilled in the art will then choose a quantity of solvent / water sufficient to dissolve / solubilize it, preferably the smallest possible quantity of solvent / water. The volume ratio of the solvent / water containing the basic compound to the organic phase, i.e., the volume ratio of the mixture (basic compound + solvent or water) to the organic phase, may be from 0.1 / 99.9 to 80 / 20, from 1 / 99 to 80 / 20, from 1 / 99 to 70 / 30, from 1 / 99 to 65 / 35, from 1 / 99 to 60 / 40, from 1 / 99 to 50 / 50, or within any range defined by any two of the aforementioned limits.

[0176] A solution, in particular an aqueous solution, saturated with a basic compound may advantageously be used.

[0177] Advantageously, the basic compound added in step (c) is in solution in water or in a solvent, and the basic compound content of the water or solvent is from 0.1 to 50% by mass, preferably from 15 to 50% by mass, more preferably from 25% to 50% by mass, preferably from 40 to 50% by mass, even more preferably the water (or solvent) is saturated with basic compound, in particular the water (or solvent) contains just enough basic compound to obtain a saturated solution.

[0178] A usable miscible solvent may be a polar solvent comprising an alcohol function and / or an ether function, ideally chosen from alcohols in Cl to C4, preferably from methanol, ethanol, propan-l-ol, propan-2-ol, butan-l-ol, butan-2-ol, 2-methylpropan-l-ol, propylene glycol.

[0179] A usable immiscible solvent may be an immiscible polar solvent.

[0180] A polar solvent, or water, makes it possible in particular to solubilize the products of the Diels-Alder reaction comprising a polar function, for example those obtained from a dienophile comprising a polar function.

[0181] By way of example, a polar solvent (or a mixture of polar solvents, as appropriate) may be considered immiscible when its recovery rate is greater than or equal to 0.95, as previously described. Acceptable immiscible polar solvents are described with reference to the optional washing treatment step (ii) described previously.

[0182] At the outlet of step (c2), a phase containing the purified composition with a reduced content of conjugated dienes and heteroatoms can then be recovered, along with a phase containing the water or immiscible solvent used, the salt, impurities, and the products of the Diels-Alder reaction. In other words, at the outlet of this step, these phases can be recovered separately, for example, following a liquid / liquid separation (centrifugation and / or decantation and / or other) carried out at the end of step (c2) and / or by implementing step (c1).

[0183] Alternatively, at the outlet of step (c2), a single phase can be recovered containing the purified composition with a reduced content of conjugated dienes and heteroatoms, and the miscible solvent used in which the salt, impurities, and Diels-Alder reaction products are solubilized. At the outlet of this step, the purified composition can then be separated by distillation.

[0184] In one embodiment, the basic compound may comprise an oxide, hydroxide, bicarbonate, or alkoxide of an alkali metal cation or an alkaline earth metal cation, or a hydroxide or bicarbonate of a quaternary ammonium cation, for example, tetramethylammonium (TMA+), tetraethylammonium (TEA+), tetrapropylammonium (TPA+), or tetrabutylammonium (TBA+). Preferably, the basic compound may comprise one of the aforementioned oxides or hydroxides, alone or in a mixture.

[0185] In a preferred embodiment, the basic compound may be selected from LiOH, NaOH, CsOH, Ba(OH)2, Na2O, KOH, K2O, CaO, Ca(OH)2, MgO, Mg(OH)2, NH4OH, TMAOH, TEAOH, TBAOH, EtONa, MeONa, and mixtures thereof. A preferred basic compound may be selected from NaOH, KOH, and mixtures thereof, preferably in aqueous solution.

[0186] The solvent used to solubilize the basic compound may be water, an alcohol, for example methanol or ethanol, or any other organic solvent suitable for solubilizing the chosen basic compound, preferably water.

[0187] Step (c2) can be carried out at a temperature of at most 250 °C, preferably at most 225 °C. In one embodiment, step (c2) can be carried out at a temperature of 50 to 250 °C, preferably 50 to 225 °C or 50 to 200 °C, or even 90 °C to 200 °C or 150 to 200 °C or in any range defined by any two of these limits.

[0188] The treatment step (c2) can be carried out at an absolute pressure of 0.1 to 100 bar, preferably from 1 to 50 bar.

[0189] In a particularly preferred embodiment, step (c2) is carried out for a duration of 1 minute to 3 hours, preferably from 1 minute to 1 or 2 hours, more preferably from 1 minute to 20 minutes, preferably from 1 minute to 16 minutes, at a temperature of at most 250°C, more preferably at most 225°C, and even more preferably at most 200°C. In this particularly preferred embodiment, step (c2) may be carried out at a temperature of at least 50°C, preferably at least 90°C, and more preferably at least 150°C. In this particularly preferred embodiment, step (c2) may be carried out at an absolute pressure of 0.1 to 100 bar, preferably from 1 to 50 bar.

[0190] In this particularly preferred embodiment, the effluent from step (b) can advantageously be brought into contact with:

[0191] - 0.1 to 15% by mass of a basic compound, advantageously comprising a cation of alkali or alkaline earth metal, and preferably in the presence of water, preferably with 0.5 to 15% by mass of a basic compound, more preferably with 1 to 10% by mass of a basic compound (mass percentages of basic compound relative to the organic phase), and / or

[0192] - with water containing 15 to 50% by mass of basic compound, preferably 25% to 50% by mass, preferably 40% to 50% by mass (mass percentages of basic compound relative to water), even more preferably with water saturated with basic compound.

[0193] A preferred strong base may be selected from LiOH, NaOH, CsOH, Ba(OH)2, Na2O, KOH, K2O, CaO, Ca(OH)2, MgO, Mg(OH)2, TMAOH, TEAOH, TBAOH, EtONa, MeONa and mixtures thereof. A further preferred strong base may be selected from NaOH, KOH and mixtures thereof, particularly for the implementation of the particularly preferred embodiment.

[0194] Step (c3) is a hydrogenation step of the products of the Diels-Alder reaction, more precisely of the C=C double bonds present in the composition.

[0195] Step (c3) is specifically designed to hydrogenate the C=C double bonds present on the products of the Diels-Alder reaction, so that the reverse Diels-Alder reaction can no longer occur. This step has the advantage of a higher yield of treated oil since the products of the Diels-Alder reaction are not eliminated, but transformed.

[0196] Step (c3) is typically carried out at a temperature of 100 °C to 400 °C.

[0197] Step (c3) can, moreover, be implemented at an absolute pressure of 20 to 200 bars.

[0198] Step (c3) can be implemented at an hourly volumetric rate (WH) of 0.1 to 10 h1.

[0199] This step can be implemented with an H2 flow rate ranging from 10NL / L to 1000NL / L (NL of H2 per L of material to be hydrogenated).

[0200] Step (c3) is typically carried out in the presence of at least one hydrotreating catalyst. Conventional hydrotreating and / or hydrogenation catalysts may be used.

[0201] This may be a catalyst comprising at least one metal from groups 8-10, preferably chosen from the Pt, Pd, Ni group and / or mixtures thereof, on a support such as alumina, titanium, silica, zirconia, magnesia, carbon and / or mixtures thereof. For example, a Ni-based catalyst passivated after its reduction, preferably using a dialkyl sulfide such as dimethyl sulfide (DMS) or diethyl sulfide (DES), or thiophenic compounds, may be used. It may also be a catalyst comprising at least one metal from group 6, such as Mo, W, in combination or not with a promoter chosen from at least one metal from groups 8-10, such as Ni and / or Co, and / or a mixture thereof, these metals being used in sulfide form and preferably supported on alumina, titanium, zirconia, silica, carbon and / or mixtures thereof. As an example, a NiMo (0.1-60% by mass) and / or CoMo (0.1-60% by mass) generally on a support, or a hydrogenation catalyst comprising Pd (0.1-10% by weight) and / or Ni (0.1-60% by weight) and / or NiMo (0.1-60% by weight).

[0202] Step (c3) can be carried out in a single reactor with several catalytic beds connected in series with possibly dihydrogen additions between the beds or in several reactors in series depending on the objective sought.

[0203] Guard reactors may also be provided to remove any chlorine, metals, and silicon that may still be present. For example, a silicon trap (for instance, at the inlet of step (c3)) may be provided, which may be in a separate reactor or form the upper bed of a reactor. This trap may operate at a temperature of at least 200°C, and / or at a WH of 1 to 10 h-l, and / or at an absolute pressure of 10 to 160 bar in the presence of H2; optionally with a metal trap operating at a temperature of at least 200°C, at a WH of 1 to 10 h-l, and at an absolute pressure of 10 to 160 bar in the presence of H2.

[0204] When this step (c3) is carried out on the effluent directly from step b) (without prior step cl or c2), it can advantageously be carried out at a temperature of 80 to 250°C, preferably 130 to 250°C in the presence of hydrogen at an absolute pressure of 5 to 60 bars, preferably 20 to 50 bars.

[0205] In this step, the effluent from step b) or from one of steps (c2) or (c1) can be treated by mixing it with a fossil hydrocarbon feedstock. This allows the effluent from step b) or from one of steps (c2) or (c1) to be sent to an existing hydrotreating unit normally used to treat a fossil hydrocarbon feedstock.

[0206] This fossil hydrocarbon charge can be a naphtha fraction, a diesel fraction or a kerosene fraction or a vacuum diesel type fraction.

[0207] The effluent from step b) or from one of steps (c2) or (cl) can then represent from 5 to 50% by mass of the total load entering step (c3), preferably from 5 to 30% by mass, more preferably from 5 to 25% by mass, in particular from 5 to 10% by mass.

[0208] Optional trapping step (d)

[0209] The composition from step (c) can be further purified by passing over a solid adsorbent in order to reduce the content of at least one element among F, Cl, Br, I, O, N, S, Se, Si, P, As, Fe, Ca, Na, K, Mg and Hg and / or the water content.

[0210] Typically, the composition from step (c) can be contacted with silica gel, clays, alkali or alkaline earth metal oxide, iron oxide, ion exchange resins, activated carbon, activated aluminum oxide, molecular sieves, alkali oxide and / or porous supports containing modified or unmodified double lamellar hydroxide and silica gel, or any mixture thereof, to trap silicon and / or metals and / or phosphorus and / or halogenates.

[0211] The adsorbent can be operated in regenerative or non-regenerative mode, at a temperature below 400°C, preferably below 100°C, more preferably below 60°C, selected from: (i) a silica gel, (ii) a clay, (iii) crushed clay, (iv) apatite, (v) hydroxyapatite and combinations thereof, (vi) an alumina, for example, alumina obtained by boehmite precipitation, calcined alumina such as Sasol's Ceralox®, (vii) boehmite, (viii) bayerite, (ix) hydrotalcite, (x) a spinel such as Sasol's Pural® or Puralox®, (xi) a promoted alumina, for example, BASF's Selexsorb®, acid-promoted alumina, or zeolite-promoted alumina and / or by a metal such as Ni, Co, Mo or a combination of at least two of them, (xii) an acid-treated clay such as Clariant's Tonsil®, (xiii) a molecular sieve in the form of an aluminosilicate containing an alkali or alkaline earth cation, for example 3A sieves,4A, 5A, 13X, for example marketed under the brand name Siliporite ® of Ceca, (xiv) a zeolite, (xv) an activated carbon, or a combination of at least two adsorbents, the adsorbent or at least two adsorbents retaining at least 20% by weight, preferably at least , 50% by weight of at least one element among F, Cl, Br, I, O, N, S, Se, Si, P, As, Fe, Ca, Na, K, Mg and Hg and / or water.

[0212] According to a preferred embodiment, the adsorbent is regenerable, has a specific surface area of ​​at least 200 m2 / g and is operated, for example in a fixed bed reactor, at a temperature below 100°C and / or a WH of 0.1 to 10 h 1 and / or at a pressure of 1 to 90 bar in the presence of H2 or in the absence of H2.

[0213] Detailed description of the optional catalytic hydrotreating step (e)

[0214] The hydrotreating of step (e) can be carried out in one step or in two steps.

[0215] When step (c) ends with a step (c3), step (e) may possibly be implemented in the same reactor as step (c3).

[0216] When step (c) ends with a step (c3), step (e) may advantageously be carried out in a single step, as described below.

[0217] When step (c) ends with a step (c3), the hydrotreating step (e) may be carried out on the effluent from step (c3) alone or diluted with a fossil hydrocarbon feedstock, in order to obtain an effluent concentration ranging from 0.01% by weight to a maximum of 50% by weight; preferably from 0.1% by weight to 25% by weight, even more preferably from 1% by weight to 20% by weight.

[0218] When carried out in a single step, the composition from step (c) or (d) is hydrotreated at a temperature of 200 to 450°C, preferably 200 to 340°C in the presence of hydrogen at an absolute pressure of 20 to 160 bar, preferably 30 to 100 bar and in the presence of at least one hydrotreating catalyst, for example a NiMo (0.1-60% by mass) and / or CoMo (0.1-60% by mass) type catalyst, generally on a support.

[0219] Alternatively, the hydrotreating of step (e) can be carried out in a first step (e-1) in which the composition from step (c) or (d) is hydrotreated, preferably selectively hydrogenated, at a temperature of 80 to 250°C, preferably 130 to 250°C in the presence of hydrogen at an absolute pressure of 5 to 60 bar, preferably 20 to 50 bar, and in the presence of at least one first hydrotreating catalyst, preferably a hydrogenation catalyst, for example a hydrogenation catalyst comprising Pd (0.1-10 wt.%) and / or Ni (0.1-60 wt.%) and / or NiMo (0.1-60 wt.%), and in a second step (e-2) in which the effluent from step (e-1) is hydrotreated at a temperature of 200 to 450°C, preferably from 250 to 340°C in the presence of hydrogen at an absolute pressure of 20 to 160 bar, preferably from 30 to 100 bar and in the presence of at least one second hydrotreating catalyst, for example a NiMo (0.1-60% by weight) and / or CoMo (0.1-60% by weight).

[0220] When carried out in two steps, the first hydrotreating step (e-1) can hydrogenate the remaining dienes, and in particular the conjugated dienes, and the acetylenic bonds. The decrease in diene value observed between the inlet and outlet of the first hydrotreating step is typically at least 10%, preferably at least 25%, measured according to UOP 326. In the second step (e-2), a catalyst known to hydrogenate the olefins and convert the sulfur and nitrogen components to H2S and NH3, respectively, may advantageously be used.

[0221] During the first step (e-1), the composition may pass through one or more catalytic beds, preferably with an overall temperature increase of at most 150°C, preferably at most 100°C, and / or a temperature increase of at most 100°C, preferably at most 50°C, for each catalytic bed. Advantageously, an intermediate quenching between the catalytic beds may be provided, preferably carried out with H2 or with the hydrotreated composition recovered in step (e). This first step may be carried out in a fixed-bed reactor, preferably in the presence of at least one catalyst, typically a hydrogenation catalyst. It may be a catalyst comprising at least one metal from groups 8-10, preferably chosen from the Pt, Pd, Ni group and / or mixtures thereof on a support such as alumina, titanium, silica, zirconia, magnesia, carbon and / or mixtures thereof.For example, a passivated Ni-based catalyst will be used after its reduction, preferably using a di-alkyl sulfide such as Dimethyl Sulfide (DMS) or Diethyl Sulfide (DES), or thiophenic compounds. It may also be a catalyst comprising at least one metal from group 6, such as Mo, W, in combination or not with a promoter chosen from at least one metal from groups 8-10, such as Ni and / or Co, and / or a mixture thereof, these metals being used in sulfide form and preferably supported on alumina, titanium, zirconia, silica, carbon and / or mixtures thereof.

[0222] During the second step (e-2), the effluent from step (e-1) may pass through one or more catalytic beds, preferably with an overall temperature increase of at most 100°C, and / or a temperature increase of at most 50°C on each catalytic bed. Advantageously, an intermediate quenching step may be provided between the catalytic beds, this quenching being preferably carried out with H2 or with the hydrotreated composition recovered in step e). This second step may be carried out in a fixed-bed reactor, preferably in the presence of at least one catalyst, typically a hydrogenation catalyst. This may be a catalyst comprising a hydrogenating function, namely at least one metal from group 6 such as, for example, Mo, W, in combination or not with a promoter selected from at least one metal from groups 8-10 such as, for example, Ni and / or Co, and / or or a mixture thereof, these metals preferably being used in sulfide form and supported on alumina, titanium, zirconia, silica, carbon and / or mixtures thereof. The catalyst may also have a trapping function and for this purpose have a BET surface area of ​​150 m² / g to 400 m² / g.

[0223] Guard reactors may also be provided to remove any chlorine, metals, and silicon that may still be present. A silicon trap may be provided (for example, at the inlet of the hydrotreating stage or at the inlet of the second hydrotreating stage when there are two stages), which may be in a separate reactor or form the upper bed of a reactor. This trap may operate at a temperature of at least 200°C, and / or at a water activity (Wh) of 1 to 10 h-l, and / or at an absolute pressure of 10 to 160 bar in the presence of H2; optionally with a metal trap operating at a temperature of at least 200°C, at a water activity (Wh) of 1 to 10 h-l, and at an absolute pressure of 10 to 160 bar in the presence of H2.

[0224] Thus, in general, step (e) can be carried out in a single reactor with several catalytic beds connected in series with possibly additional hydrogen between the beds or in several reactors in series depending on the objective sought.

[0225] This hydrotreating step can also have a demetallization, cracking, dearomatization function depending on the characteristics of the catalyst and the hydrotreating conditions.

[0226] The feed for hydrotreating, containing at least a portion of the composition from step (c) or (d), can advantageously be heated by a heat exchanger which is supplied by the effluent from the hydrotreatment (since hydrotreatment is exothermic, the effluent from the hydrotreatment will have a higher temperature than the feed entering the hydrotreatment).

[0227] Preferably, the feed for hydrotreatment, containing at least a portion of the composition from step (c) or (d), can be diluted with a portion of the hydrotreatment effluent, which still has a temperature higher than the desired temperature at the hydrotreatment inlet. This at least partial recycling of the hydrotreatment effluent allows for the dilution of unsaturated solids present in the purified composition and preheats the feed.

[0228] At the outlet of the hydrotreating step, the concentration of olefins, measured by the bromine index in the purified composition, is typically at most 5.0, preferably at most 2.0 gBr2 / 100g, preferably at most 1.5 gBr2 / 100g, preferably even at most 0.5 gBr2 / 100g, or even undetectable, measured according to the ASTM D1159 standard.

[0229] Optional washing step

[0230] The effluent exiting the hydrotreating step (c3) or (e), namely the hydrotreated purified composition, can be washed with water to remove inorganic compounds such as hydrosulfide, hydrogen chloride and ammonia before being subjected to further treatments.

[0231] Use of the composition from step (c) or (d) or the purified composition hydrotreated

[0232] The composition from step (c) or (d), or the purified hydrotreated composition from step (e), optionally washed with water, can be fractionated into usable streams, the cut points of which are typically chosen according to the subsequent processing. This fractionation is carried out according to distillation temperature ranges, for example, to separate streams such as LPG, gasoline, diesel, heavy fuel oil, kerosene, which can then be processed in a steam cracker and / or a catalytic cracker and / or a hydrocracker (and then possibly in a steam cracker) and / or a hydrotreating reactor and / or used as is for the preparation of fuels, lubricants, or base oils. Those skilled in the art know how to select the cuts best suited to the subsequent processing units according to the desired objective.

[0233] The composition from step (c) or (d), or the purified hydrotreated composition from step (e), optionally washed with water, can also be used diluted, for example mixed with naphtha, diesel or crude oil to obtain a concentration of purified plastic and / or elastomer liquefaction oil ranging from 0.01% by weight to a maximum of 50% by weight; preferably from 0.1% by weight to 25% by weight, even more preferably from 1% by weight to 20% by weight at the inlet of the next treatment.

[0234] Detailed description of the optional steam cracking step

[0235] The steam cracking step can be carried out on the composition from step (c) or (d), or on the purified, hydrotreated composition from step (e), optionally washed with water, with or without dilution with a conventional steam cracking feedstock. Prior to this steam cracking step, a separation step by distillation can be carried out, depending on the steam cracking furnace technology.

[0236] This steam cracking step makes it possible to produce olefins such as ethylene and propylene and aromatics. The ethylene and propylene can then advantageously be converted into polyethylene and polypropylene respectively in a polymerization section.

[0237] The steam cracking step consists of thermally cracking a mixture of the purified composition and steam in one or more furnaces at high temperatures of approximately 650 to 1000°C, preferably 700 to 900°C, typically 750 to 850°C, under low pressures (1 to 3 bar). The cracking reaction is carried out in The absence of oxygen is a key factor. The reaction time is usually very short, on the order of a few hundred milliseconds. These conditions allow the carbon-carbon bonds to break and produce unsaturated hydrocarbons with molecules smaller than the feedstock introduced into the reactor(s). The effluent from the reactor(s) is then rapidly cooled to temperatures of 400 to 550°C to limit secondary reactions such as the polymerization of olefins, dienes, and acetylenes. The cooled effluent is then fractionated to recover the light C2-C5 olefins, such as ethylene, propylene, butadiene, isobutene, n-butene, and isoprene.

[0238] The composition from step (c) or (d), or the purified hydrotreated composition from step (e), optionally washed with water, can be sent to the steam cracker undiluted or can be mixed with naphtha, diesel fuel, or crude oil to obtain a purified plastic liquefaction oil concentration ranging from 0.01 wt% to a maximum of 50 wt%; preferably from 0.1 wt% to 25 wt%, and even more preferably from 1 wt% to 20 wt% at the steam cracker inlet. The diluted purified composition is then converted into olefins, such as ethylene and propylene, and aromatics.

[0239] In a preferred embodiment, the composition from step (c) or (d), or the purified hydrotreated composition from step (e) optionally washed with water, can be sent at least partially directly into a steam cracker without further dilution than the steam used for steam cracking, and preferably as the only stream sent at least partially into the steam cracker, to produce olefins, such as ethylene and propylene, and aromatics.

[0240] The steam cracker is known per se in the art. The feedstock of the steam cracker, in addition to the stream obtained by the inventive process, may be ethane, liquefied petroleum gas, naphtha, or diesel fuels. Liquefied petroleum gas (LPG) is essentially composed of propane and butanes. Diesel fuels have a boiling range of approximately 200 to 350°C and consist of hydrocarbons from C10 to C22, including essentially linear and branched paraffins, cyclic paraffins, and aromatics (including mono-, naphtha-, and poly-aromatics).

[0241] In particular, the cracking products obtained at the outlet of the steam cracker may include ethylene, propylene and benzene, and possibly hydrogen, toluene, xylenes and 1,3-butadiene.

[0242] In a preferred embodiment, the outlet temperature of the steam cracker can be between 800 and 1200°C, preferably between 820 and 1100°C, more preferably between 830 and 950°C, more preferably between 840 and 920°C. The outlet temperature can influence the content of high-value chemicals in the cracking products obtained by this process.

[0243] In a preferred embodiment, the residence time in the steam cracker, through the radiation section of the reactor where the temperature is between 650 and 1200°C, can be between 0.005 and 0.5 seconds, preferably between 0.01 and 0.4 seconds.

[0244] In a preferred embodiment, steam cracking is carried out in the presence of steam in a ratio of 0.1 to 1.0 kg of steam per kg of hydrocarbon feed, preferably 0.25 to 0.7 kg of steam per kg of hydrocarbon feed in the steam cracker, preferably in a ratio of 0.35 kg of steam per kg of feed mixture, to obtain cracking products as defined above.

[0245] In a preferred embodiment, the reactor outlet pressure can be between 500 and 1500 mbar, preferably between 700 and 1000 mbar, and more preferably around 850 mbar. The residence time of the feedstock in the reactor and the temperature must be considered together. A lower operating pressure facilitates the formation of light olefins and reduces coke formation. The lowest possible pressure is achieved (i) by maintaining the reactor outlet pressure as close as possible to atmospheric pressure at the intake of the cracking gas compressor, and (ii) by reducing the hydrocarbon pressure through dilution with steam (which has a substantial influence on slowing down coke formation). The steam / feedstock ratio can be maintained at a level sufficient to limit coke formation.

[0246] Since the purified composition has a wide carbon number distribution (or boiling points), vaporization of such a feedstock may be incomplete at the reactor inlet temperature, at which point some hydrocarbon molecules begin to decompose. The purified composition can then be preheated to a temperature at least 10°C below the decomposition temperature and subsequently separated from the hydrocarbon vapors produced by the residual hydrocarbon liquid in a flash tank. In this flash tank, the liquid exits by gravity from the bottom and the hydrocarbon vapors from the top. Optionally, the hydrocarbon liquid can be returned to the plastics liquefaction unit or to the optional hydrocracking step.

[0247] Detailed description of the optional hydrocracking step

[0248] Prior to the steam cracking step, the composition from step (c) or (d), or the purified hydrotreated composition from step (e) optionally washed with water, may be subjected to a cracking reaction in order to reduce the length of the carbon chains of the paraffins present.

[0249] Preferably, this hydrocracking step is carried out after a hydrotreating step (c3) or (e), and before the steam cracking step or before being sent to the fuel pool.

[0250] Typically, this cracking reaction is a hydrocracking reaction carried out at a temperature of 250 to 480°C, a partial pressure of hydrogen of 1.5 to 25 MPa abs. and an hourly volumetric rate of 0.1 to 10 h*.

[0251] A usable hydrocracking catalyst includes, for example, a support selected from halogenated aluminas, combinations of boron and aluminum oxides, amorphous silica-aluminas and zeolites and a hydro-dehydrogenating function comprising at least one metal from group 6 selected from chromium, molybdenum and tungsten, alone or in mixture, and / or at least one metal from groups 8-10 selected from iron, cobalt, nickel, ruthenium, rhodium, palladium and platinum.

[0252] In one embodiment, the hydrocracking step can be carried out by adding a hydrocracking catalyst bed downstream of the last catalytic bed of the hydrotreating section. Description of the figures

[0253] [Fig-1] [Fig.1] describes one possible embodiment of the invention. In this In one possible embodiment, the plastic and / or elastomer liquefaction oil composition (1) is optionally first pretreated in a pretreatment section (A) by (i) filtration, (ii) washing with water or a polar solvent, (iii) distillation, (iv) decantation, or (v) a combination of two, three, or four of steps (i) to (iv). The pretreated composition (2) is then sent to a treatment section (B) for carrying out the Diels-Alder (DA) reaction according to step (b) of the invention. The effluent (3) which exits this treatment section (B) can then be sent to a solids separation section (SI), or be sent directly to a section (C) to carry out one or more steps selected from the step (c1) of washing, (c2) of treatment and (c3) of hydrogenation according to step (c) of the invention.The effluent (5) from step (c) is then sent, optionally after a solids separation section (S2), to an optional purification section (D) for the implementation of the adsorbent treatment step (d). The effluent (6) exiting the optional purification section (D) or the effluent (5) can then be sent to an optional hydrotreatment section (E) for the implementation of an HDT hydrotreatment step corresponding to step (e) of the invention.

[0254] The effluent (7) exiting the hydrotreatment section (E), possibly after fractionation and / or dilution, can be sent to one or more of the following optional sections: an optional hydrotreatment section (S-HDT), a An optional treatment section (S-VAPO) in a steam cracker, an optional treatment section (S-HC) in a hydrocracker, an optional treatment section (S-FCC) in a fluidized bed catalytic cracker, and an optional preparation section (S-Pool) for a fuel, lubricant, or base oil. Preferably, the effluent (7) exiting the hydrotreatment section (E) is then steam cracked to obtain olefins, which can then be polymerized. Preferably, the effluent (7) exiting the hydrocracking section (S-HC) or the section (S-FCC) is then steam cracked to obtain olefins, which can then be polymerized.

[0255] The effluent (5) exiting step (c) may optionally be sent directly to the hydrotreating step (e) (HDT) before being sent to the hydrocracking step (S-HC), advantageously followed by the fuel pool (S-Pool) or the steam cracking step (S-VAPO). When step (c) implements step (c3), the effluent from step (c) (which may have undergone one or more of steps (c1) and (c2)) may then be sent directly to the hydrocracking step (S-HC), advantageously followed by the fuel pool (S-Pool) or the steam cracking step (S-VAPO).

[0256] The effluent from step (c) can be sent to hydrocracking, hydrotreating, the fuel pool or steam cracking alone or mixed with a feedstock of fossil hydrocarbons.

[0257] The invention is illustrated by the following examples given by way of non-limiting example. Examples

[0258] Example 1: Treatment of a pyrolysis oil with maleic anhydride following a basic treatment

[0259] An HP plastic oil was subjected to the following treatments described below.

[0260] For each test, 225 g of HP plastic oil was brought into contact with 7 g of maleic anhydride in the form of solid pellets. The mixture was then heated to 110°C for 3 hours. The resulting effluent was then subjected to various treatments.

[0261] In a first test, the effluent obtained was subjected to three washes with water at a volume ratio of 50 / 50. A purified HP1 oil was obtained.

[0262] In a second test, the effluent obtained was subjected to basic treatment with a 50% sodium hydroxide solution in water. 41 g of this basic solution were added to the effluent treated with maleic anhydride. The mixture was heated at 225 °C for 30 minutes. The resulting effluent was then subjected to three water washes (oil / water mass ratio of 60 / 40). A purified HP2 oil was obtained.

[0263] In a third test, the HP oil was directly subjected to basic treatment with a 50% sodium hydroxide solution in water. A purified HP3 oil was obtained.

[0264] The results are presented in Table 1.

[0265] [Tables 1] Plastic Oil HP HP1 HP2 HP3 Oxygen (% mass) 1.55 1.93 0.15 0.2 Oxygen reduction 90% 87% Nitrogen (ppm) 1701 605 89.2 157 Nitrogen reduction 64% 95% 91% Chlorine (ppm) 515 430 40 57 Chlorine reduction 17% 92% 89% Silicon (ppm) 91 -- <2 <2 Silicon reduction -- >98% >98% MAV (mg AM / g) 24.7 1.2 6.2 MAV reduction 95% 75% <5%

[0266] Example 2: Treatment of a tire oil by different dienophiles

[0267] A tire oil (noted TPO) having the characteristics set out in Table 2 was subjected to different treatments.

[0268] [Tables2] Unit Density at 15 °C kg / m3 928.2 Carbon % by mass 87.9 Hydrogen % by mass 10.8 Nitrogen PPm 6203 Sulfur PPm 8449 Biogenic carbon % by mass 50% Diene index gI2 / 100g 15

[0269] The TPO was treated with the following dienophiles: maleic anhydride, acrylic acid, methyl acrylate, methyl maleate

[0270] For each test, 1% by mass of dienophile was added to the TPO.

[0271] When the dienophile is solid, it was first ground into a powder using a mortar. Then, 0.1 g of dienophile was added to 9.9 g of TPO. The sample was then placed on a shaking table for 1 h at room temperature. An oxygen pressure analysis was then immediately performed on a 5 mL aliquot. This analysis was carried out on a Rapidoxy® instrument marketed by Anton Paar, which includes a stainless steel cell. The sample was also placed in a glass insert

[0272] The analysis is carried out under the following conditions:

[0273] - Temperature: 140 °C,

[0274] - Initial pressure: 500 kPa O2 pressure,

[0275] - Analysis time: 1 hour of analysis (3600 s).

[0276] The results are summarized in Table 3

[0277] [Tables3] Dienophile Test Maximum O2 Pressure (kPa) O2 Pressure at t=3600s (kPa) Pressure Loss (%) 1 No Dienophile (comparative) 702.5 559.4 20.4% 2 Maleic Anhydride 701.1 621.5 11.4% 3 Acrylic Acid 709.2 637.0 10.2% 4 Methyl Acrylate 711.0 625.0 12.1% 5 Dimethyl Maleate 706.3 603.2 14.6%

[0278] The greater the pressure loss in dioxygen, the more this species is consumed by chemical reactions involving in particular conjugated dienes, and therefore the more unstable the charge.

[0279] It was then observed that TPO without a dienophile tended to react much more strongly than TPO to which a dienophile had been added. It is assumed that the dienophile reacted with the conjugated dienes present in the TPO via a Diels-Aider reaction, which reduced its reactivity during the Rapidoxy® analysis.

Claims

1.

2. Demands A process for purifying a composition comprising a plastic and / or elastomer liquefaction oil, comprising the following steps: (a) provide a composition comprising a plastic and / or elastomer liquefaction oil, said composition containing conjugated dienes and having a diene index of at least 1 g² / 100 g measured according to UOP 326, (b) treat the composition of step (a) under conditions of a Diels-Alder cycloaddition in the presence of at least one dienophile compound having at least one C=C double bond, and optionally at least one electron-withdrawing group, during which at least some of the conjugated dienes contained in the composition react with the at least one dienophile compound via a Diels-Alder cycloaddition reaction, to produce an effluent containing a modified composition having a reduced content of conjugated dienes and comprising products of the Diels-Alder reaction, (c) subject the effluent from step (b) to at least one step selected from (c1) a step of removing the products of the Diels-Alder reaction by washing in the presence of water or an immiscible organic solvent, (c2) a treatment step in the presence of a basic compound at a temperature of not more than 450°C, or (c3) a hydrogenation step at a temperature of not more than 400°C of the products of the Diels-Alder reaction. A process according to claim 1, characterized in that in step (b), the electron-withdrawing group of the dienophile compound is selected from, a nitro group (-NO2), a sulfonyl group (-SO2R), a nitrile group (-CN), a sulfo group (-SO3H), an aldehyde group (-CHO), a ketone group (-CO), a carboxyl group (-COOH), a carboxylate group (-COO), an ester group (COOR), an acyl chloride group (-COC1), an amide group (-CONH2), a hydroxyl group (-OH), an ether group (-OR), a tertiary amine group (-NR3), a primary amine group (-NH2), a phenyl group (-C6H5), a vinyl group (-CH=CH2), a hydrogen, and a halogen selected from fluorine, chlorine, bromine, or iodine.

3. A process according to claim 1 or 2 characterized in that in step (b) the dienophile compound is selected from an unsaturated carboxylic acid, an unsaturated dicarboxylic acid, an unsaturated carboxylic acid anhydride, an unsaturated dicarboxylic acid anhydride, an unsaturated carboxylic acid ester, an unsaturated dicarboxylic acid ester, an unsaturated ketone, an unsaturated aldehyde, an alkene, alone or in mixture.

4. A process according to any one of claims 1 to 3, characterized in that step (b) comprises one or more of the following features: - prior to step (b), the composition is subjected to (i) filtration, (ii) washing with water or a polar solvent immiscible with the composition, (iii) distillation, (iv) decantation, or (v) a combination of two, three, or four of steps (i) to (iv), - prior to or during step (b), said dienophile compound is introduced into the composition (i) in solid form, (ii) previously dissolved in an aqueous medium, preferably water, (iii) previously dissolved in an organic solvent, (iv) in liquid form, or (v) in gaseous form, - the number of moles of said dienophile compound is at least equal to the number of moles of conjugated dienes present in the composition, - step (b) is implemented at a temperature of 10 to 150 °C, preferably 20 to 120 °C,preferably at 20 to 50 °C, - step b) is carried out for a duration of 1 minute to 72 hours, preferably 10 minutes to 72 hours, preferably 20 minutes to 72 hours, 30 minutes to 48 hours, or 60 minutes to 36 hours.

5. A process according to any one of claims 1 to 4, characterized in that it comprises at least one of the following features: - step (c) is preceded or followed by a solids separation step by (i) filtration, (ii) centrifugation, (iii) hydrocyclone or (iv) a combination of two or more of these steps, - step (c) is followed by an additional purification step (d) in which the purified composition is further purified by passing over a solid adsorbent in order to reduce the content of at least one element among F, Cl, Br, I, O, N, S, Se, Si, P, As, Fe, Ca, Na, K, Mg and Hg and / or the water content.

6. A process according to any one of claims 1 to 5, characterized in that step (cl) is carried out in the presence of water at neutral, basic or acidic pH, or in the presence of an organic solvent immiscible with the modified composition.

7. A process according to any one of claims 1 to 6, characterized in that step (c2) comprises at least one of the following: - step (c2) is carried out in the presence of (i) a solid basic compound, (ii) a basic compound previously solubilized in an aqueous medium, preferably water, or (iii) a basic compound previously solubilized in a solvent; - step (c2) is carried out in the presence of 0.1 to 50% by mass of the basic compound relative to the total mass of the treated organic phase; - step (c2) is carried out at a temperature of 50 to 250 °C, preferably 50 to 225 °C, more preferably 50 to 200 °C; - step (c2) is carried out for a duration of 0.1 seconds to 3 hours, preferably 0.1 seconds to 2 hours, more preferably from 1 minute to 1 hour, even more preferably from 1 minute to 20 minutes or from 1 minute to 16 minutes, - the basic compound comprises an oxide, a hydroxide,a bicarbonate or an alkoxide of an alkali metal cation or an alkaline earth metal cation, or a hydroxide or bicarbonate of a quaternary ammonium cation, alone or in mixtures, - the basic compound is chosen from LiOH, NaOH, CsOH, Ba(OH)2, Na2O, KOH, K2O, CaO, Ca(OH)2, MgO, Mg(OH)2, NH4OH, TMAOH, TEAOH, TBAOH, EtONa, MeONa and mixtures thereof.

8. A method according to any one of claims 1 to 7, characterized in that step (c3) comprises at least one of the following characteristics: - step (c3) is carried out at a temperature of 100 °C to 400 °C, - step (c3) is carried out at an absolute pressure of 20 to 250 bar, - step (c3) is carried out at an hourly volumetric rate of 0.1 to 10 h1, - step (c3) is implemented in mixture with a feedstock of fossil hydrocarbons.

9. A process according to any one of claims 1 to 8, wherein: (e) the composition from step (c) or (d) undergoes catalytic hydrotreatment in one or two steps to provide a purified hydrotreated composition.

10. A process according to claim 9, characterized in that the hydrotreating of step (e): - is carried out in a single step in which the purified composition of step (c) or (d) is hydrotreated at a temperature of 200 to 450°C, preferably 200 to 340°C, in the presence of hydrogen at an absolute pressure of 20 to 160 bar, preferably 30 to 100 bar, and in the presence of at least one hydrotreating catalyst, or - is carried out in a first step (e-1) in which the purified composition of step (c) or (d) is hydrotreated at a temperature of 80 to 250°C, preferably 130 to 250°C, in the presence of hydrogen at an absolute pressure of 5 to 60 bar, preferably 20 to 50 bar, and in the presence of at least one first catalyst hydrotreatment, and in a second stage (e-2) in which the effluent from stage (e-1) is hydrotreated at a temperature of 200 to 450°C,preferably at 250 to 340°C in the presence of hydrogen at an absolute pressure of 20 to 160 bar, preferably 30 to 100 bar, and in the presence of at least one second hydrotreating catalyst.

11. A process according to any one of claims 1 to 10, wherein the purified hydrotreated composition exiting step (e) is washed with water to remove inorganic compounds such as hydrosulfide, hydrogen chloride, ammonia.

12. A process according to any one of claims 1 to 11, wherein the purified composition of step (c) or (d), or the hydrotreated purified composition of step (e) optionally washed with water, is used as is or separated into usable streams for the preparation of fuels and combustibles such as LPG, gasoline, diesel, heavy fuel oil, kerosene and / or for the preparation of lubricants and / or base oils.

13. A method according to any one of claims 1 to 11, wherein the purified composition of step (c) or (d), or the composition purified hydrotreated from step (e), is treated, pure or diluted, optionally after separation into usable streams, in: - a steam cracker to produce olefins, and / or - a catalytic fluidized bed cracker, and / or - a hydrocracker, then optionally in a steam cracker, and / or - a hydrotreating reactor, in particular a catalytic hydrogenation reactor.

14. A method according to any one of the preceding claims, wherein step a) comprises the preliminary step a1) of providing a stream of plastic and / or elastomer waste; a2) liquefying said stream of plastic and / or elastomer waste by pyrolysis or hydrothermal liquefaction at a temperature of at least 200°C; a3) recovering a liquefaction effluent and separating said liquefaction effluent into a hydrocarbon fraction Cl to C4, and optionally into an aqueous fraction, the remaining fraction being said plastic and / or elastomer liquefaction oil; a4) optionally mixing said remaining fraction with a solvent or a diluent.

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