Method for purifying plastic and / or elastomer oil compositions by liquid-liquid extraction

Abstract

The invention relates to a method for purifying a composition of hydrocarbon compounds comprising a plastic and / or elastomer liquefaction oil optionally mixed with biomass, comprising the following steps: (a) providing a composition of hydrocarbon compounds comprising a plastic and / or elastomer liquefaction oil optionally mixed with biomass, said composition containing at least 1% by mass of heteroatoms, (b) a step of liquid-liquid extraction by bringing the composition provided in step (a) into contact with a solvent consisting of at least one heteroatom-free hydrocarbon compound, (c) a step of recovering a first phase and a second phase which are immiscible, the first phase containing the composition depleted in heteroatoms and the solvent, while the second phase is enriched in heteroatoms, (d) a separation step during which the solvent is separated from the rest of the first phase, forming a purified composition.

Description

PROCESS FOR PURIFYING OIL, PLASTIC AND / OR ELASTOMER COMPOSITIONS BY LIQUID-LIQUID EXTRACTION Technical field of the invention

[0001] The present invention relates to the recovery of oils obtained from the liquefaction of plastic and / or elastomer waste. The process according to the invention makes it possible, in particular, to purify the liquefaction oil obtained from plastic and / or elastomer waste of all kinds, regardless of its origin, especially when this plastic and / or elastomer waste contains, in varying proportions, other types of waste such as lignocellulosic biomass. Technological background

[0002] Plastic and / or elastomeric waste is most often sent to landfills or incinerated, with a smaller portion being recycled. However, there is a significant need, encouraged by regulations, to limit the amount of plastic and / or elastomeric waste in landfills. Furthermore, disposing of plastic waste in landfills is becoming increasingly difficult. Therefore, recycling is essential.

[0003] One possible method for recycling this waste is liquefaction by pyrolysis or hydrothermal liquefaction. However, the resulting oil typically 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 commonly used to recycle plastics. Furthermore, dienes readily react to form gums. Dienes are also coke precursors in high-temperature processes such as steam cracking. Advanced waste sorting can be performed prior to liquefaction to maximize the presence of polyolefins and to exclude plastics such as PET, PA, PVC, PS, and biomass. Nevertheless, this sorting is not optimal, and these plastics still end up in the waste to be liquefied, leading to the presence of heteroatoms in the oil.It is therefore necessary to treat the liquefaction oils of plastics and / or elastomers in order to be able to recycle them.

[0004] Numerous treatment processes exist for reducing the heteroatom content of plastic liquefaction oils. One such process is liquid-liquid extraction, in which the oil is washed with water or a polar solvent such as DMSO, ethylene glycol, or propylene carbonate to extract heteroatom-rich molecules (Si, N, O, S) that are released into the water or polar solvent. Another method is hydrotreating the oil (possibly mixed with a fossil-based filler) to remove S, N, O, and Si heteroatoms, as well as transition metals if present. These processes can be carried out sequentially.

[0005] Most existing purification treatments are carried out at relatively high temperatures, primarily to enable the efficient removal of heteroatoms, particularly silicon. While treatments in a basic medium effectively remove silicon, chlorine, and other heteroatoms such as oxygen and nitrogen, the high temperatures involved can lead to secondary reactions such as gum formation through diene polymerization. Furthermore, when there is a high proportion of biomass in the feedstock, the high temperature also results in significant fouling through polyol polymerization.

[0006] Furthermore, the difficulty of sorting waste and separating biomass leads to the incineration of a large proportion of plastic along with biomass. Processes are generally geared towards upstream sorting, and less towards molecular separation to recover the components or fractions useful to each industry. The presence of high concentrations of heteroatoms in these oils thus limits their suitability for the chemical recycling of plastic.

[0007] There is therefore a need to improve existing purification processes, and in particular to remove heteroatoms, and especially oxygen, nitrogen, sulfur, metals, in particular transition metals, and halides initially contained in a plastic liquefaction oil.

[0008] The invention aims to overcome all or part of the disadvantages of the prior art.

[0009] The invention aims to provide a purification process for a composition of hydrocarbon compounds comprising a plastic and / or elastomer liquefaction oil optionally mixed with biomass, comprising the following steps:

[0010] (a) a step of supplying a composition of hydrocarbon compounds comprising a plastic and / or elastomer liquefaction oil optionally mixed with biomass, said composition containing at least 1% by mass of heteroatoms,

[0011] (b) a liquid-liquid extraction step by contacting the hydrocarbon compound composition provided in step (a) with a solvent consisting of at least one heteroatom-free hydrocarbon compound,

[0012] (c) a step of recovering a first phase and a second immiscible phase, the first phase containing the composition of hydrocarbon compounds depleted in heteroatoms and the solvent, while the second phase is enriched in heteroatoms,

[0013] (d) a separation step in which the solvent is separated from the remainder of the first phase forming a purified composition.

[0014] The hydrocarbon compound composition comprising a plastic and / or elastomer liquefaction oil optionally mixed with treated biomass in the present invention thus includes hydrocarbon compounds free of heteroatoms, namely paraffins, isoparaffins, olefins, diolefins, naphthenes, aromatics, etc., which it is desirable to recover, and hydrocarbon compounds comprising heteroatoms, in particular N, S, O, Si, or even transition metals, which are considered impurities that it is preferable to remove. These compounds considered impurities are essentially polar compounds containing heteroatoms (N, S, O) or salts that may include a cation, such as the ammonium cation, an alkali metal cation, an alkaline earth element cation, a transition metal cation, and an anion, such as a carboxylate, sulfate, phosphate, nitrate, or halide ion.

[0015] The liquid-liquid extraction step of the process of the present invention allows the extraction of heteroatom-free hydrocarbon compounds from the composition using the chosen specific solvent. The impurities are found in a phase immiscible with the phase containing the solvent and the heteroatom-free hydrocarbon compounds. The solvent is then simply removed to recover these heteroatom-free hydrocarbon compounds. These compounds can then be sent to subsequent catalytic treatments with a reduced risk of catalyst deactivation. The process according to the invention also has the advantage of a higher yield compared to processes in which the impurities are found in water or a polar solvent.When the composition contains biomass liquefaction oil, rich in heteroatoms, the process according to the invention makes it possible to efficiently separate the compounds containing heteroatoms from the biomass, while the other hydrocarbon compounds from the biomass remain in the composition. The implementation of the invention is therefore particularly advantageous when biomass has been liquefied in a mixture with plastic and / or elastomers, and / or when biomass liquefaction oil is present in the composition of hydrocarbon compounds.

[0016] The composition used in the present invention may comprise at least one of the following characteristics: - said composition contains at least 10% by weight of plastic and / or elastomer liquefaction oil optionally mixed with biomass, the other part of said composition being a diluent, or said composition contains only plastic and / or elastomer liquefaction oil optionally mixed with biomass, - said composition comprises biomass liquefaction oil, - said plastic and / or elastomer liquefaction oil optionally mixed with biomass in said composition 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, more preferably at most 560°C, more preferably at most 450°C, more preferably at most 350°C, Preferably 250°C,- said plastic and / or elastomer liquefaction oil, optionally mixed with biomass, contains from 0 to 60% by weight of oxygen relative to the total weight of said liquefaction oil; - said plastic and / or elastomer liquefaction oil, optionally mixed with biomass, contains at least 1 ppm by weight of nitrogen, preferably at most 6% by weight of nitrogen, relative to the total weight of said liquefaction oil; - said plastic and / or elastomer liquefaction oil, optionally mixed with biomass, contains at least 2 ppm of sulfur, preferably at most 30,000 ppm of sulfur, relative to the total weight of said liquefaction oil; - said plastic and / or elastomer liquefaction oil, optionally mixed with biomass, contains at least 1 ppm by weight of silicon, preferably at most 5,000 ppm by weight of silicon. and / or at least 1 ppm by weight of Si, preferably at most 1000 ppm by weight of Si,relative to the total weight of said liquefaction oil, - said plastic liquefaction oil contains at least 1 ppm by weight of Cl, preferably not more than 6000 ppm by weight, and / or at least 1 ppm by weight of P, preferably not more than 5000 ppm by weight relative to the total weight of said liquefaction oil, - prior to step (b), said composition is subjected to (i) filtration, (ii) washing with a polar solvent, (iii) distillation, (iv) decantation, or (v) a combination of two, three, or four of steps (i) to (iv).

[0017] Step (a) may include a liquefaction step of plastics and / or elastomers, optionally in mixture with biomass.

[0018] In particular, the supply step (a) may include: (a1) a step of supplying a stream of plastic and / or elastomer waste, optionally mixed with biomass, (a2) a step of liquefying waste containing plastics and / or elastomers, optionally mixed with biomass, and obtaining a hydrocarbon product comprising a gaseous phase, a liquid phase and a solid phase, (a3) ​​a step of recovering the liquefaction effluent and separating said effluent into a hydrocarbon fraction C1 to C4, and optionally into an aqueous fraction, said remaining fraction forming a composition comprising, or consisting of, a plastic and / or elastomer liquefaction oil optionally mixed with biomass, (a4) an optional step of mixing the composition with a diluent and / or a biomass liquefaction oil.

[0019] The solvent used in step (b) of the process may have one or more of the following characteristics: - the solvent consists of C3-Cn hydrocarbon compounds, where n is an integer greater than three, and the Cn hydrocarbon compound has a final boiling point less than or equal to a predetermined boiling point corresponding to an initial boiling point of the composition or to an initial boiling point of hydrocarbon compounds of interest to be extracted present in said composition; - the solvent consists of C3-C10 hydrocarbon compounds; - the solvent consists predominantly (more than 50% by mass) of alkanes, for example, 90 to 100% by mass of alkanes, preferably 95 to 100% by mass, more preferably 96 to 100% by mass, even more preferably 97 to 100% by mass; - the solvent has an olefin and / or aromatic content of less than 4% by mass, preferably less than 3% by mass.

[0020] Step (b) may include at least one of the following features: - a solvent / composition ratio of 5 to 95% by mass, preferably 20 to 80% by mass, - a contact time ranging from a few seconds to 1 hour, - temperature and pressure conditions in which the solvent is in the liquid phase, - temperature and pressure conditions below the critical point of each constituent of the solvent, - the addition of water and / or a polar solvent with the solvent, in an amount such that the mass ratio of water and / or polar solvent to heteroatoms present in the composition is 0.7 to 1.3, preferably 0.9 to 1.1.

[0021] The second separation step may include at least one of the following features: - step (d) is a separation step by distillation, evaporation or compression, - the separated solvent is returned to step (b), - the purified composition from step (d) contains at most 4% by mass of heteroatoms, preferably at most 3% by mass of heteroatoms, more preferably at most 1% by mass.

[0022] The process according to the invention may further include: - a step separating the oxygenated compounds present in the second phase from step (c), optionally preceded by a step removing the solids.

[0023] Advantageously, the purified composition from step (d) can undergo a purification step (e) 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.

[0024] Advantageously, (f) the purified composition from step (d), optionally further purified in step (e), can undergo catalytic hydrotreating in one or two steps to provide a purified hydrotreated composition. Since the composition treated in step (f) has a reduced heteroatom content, it is possible to reduce the hydrogen consumption of step (f) and extend the catalyst lifetime by reducing fouling due to the highly exothermic reaction that occurs during the hydrotreating of hydrocarbon compounds containing heteroatoms.

[0025] The hydrotreated composition exiting step (f) can then be washed with water to remove inorganic compounds such as hydrosulfide, hydrogen chloride, ammonia.

[0026] Advantageously, the purified composition separated in step (d), optionally further purified in step (e), or the hydrotreated composition of step (f), optionally washed with water, may be: (g) subjected, pure or diluted, optionally after separation into usable streams, to a steam cracking step, and / or (h) subjected, pure or diluted, optionally after separation into usable streams, to a fluidized bed catalytic cracking step, and / or (i) subjected, pure or diluted, optionally after separation into usable streams, to a hydrocracking step, and / or (j) subjected, pure or diluted, optionally after separation into usable streams, to a catalytic hydrogenation step, and / or (k) used as is or separated into usable streams for the preparation of fuels and combustibles such as LPG, gasoline, diesel, heavy fuel oil and / or for the preparation of lubricants and / or base oils.

[0027] The process according to the invention may in particular include only the steps (a) to (d) previously described, and optionally the steps (e) to (k). Definitions

[0028] For the purposes of this description, the following definitions are given:

[0029] The terms "including" and "comprises" 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.

[0030] The specification of a numeric domain without decimals includes all whole numbers 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.).

[0031] The specification of a decimal also includes the decimal itself (for example, "from 1.0 to 5.0" includes both 1.0 and 5.0). Any range of numeric values ​​stated here also includes any subrange of numeric values ​​mentioned above.

[0032] The expressions % by weight and % by mass have an equivalent meaning and refer to the proportion of the mass of a product relative to 100g of a composition comprising it.

[0033] Unless otherwise stated, measurements given in parts per million (ppm) are expressed by weight.

[0034] The terms "alkane" or "alkanes" used here describe branched or unbranched acyclic hydrocarbons with the general formula CnH2n+2, and therefore composed entirely of saturated hydrogen and carbon atoms; see, for example, IUPAC. Compendium of Chemical Terminology, 2nd edition (1997). The term "alkanes" thus 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-".

[0035] 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=".

[0036] The term "hydrocarbon" or "hydrocarbon compound" refers to alkanes (saturated hydrocarbons), cycloalkanes, aromatics and unsaturated hydrocarbons.

[0037] By "heteroatom" we mean any element of an organic compound other than carbon and hydrogen.

[0038] 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 can identify the most suitable method for measuring each metal and, more generally, each heteroatom, depending on the hydrocarbon matrix under consideration. Oxygen content can be measured according to ASTM D5622-17 / D2504-88 (2015). Nitrogen content can be measured according to ASTM D4629-17. Sulfur content can be measured according to ISO 20846:2011. Halogen content, including chlorine, bromine, and fluorine, can be measured according to ASTM D7359-18.

[0039] Boiling points as mentioned here 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. Determining the initial and final boiling points involves established techniques, and several methods adapted to the distillation temperature range are applicable, for example, NF EN 15199-1 (2020 version) or ASTM D2887 for measuring the boiling points of petroleum fractions by gas chromatography, ASTM D7169 for heavy hydrocarbons, and ASTM D7500, D86, or D1160 for distillates.

[0040] The term "Bramine Index" refers to 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.

[0041] Liquefaction oil is defined as an oil produced by a pyrolysis and / or 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.

[0042] The expression "plastic and / or elastomer liquefaction oil optionally mixed with biomass" or "oil resulting from the liquefaction of plastic and / or elastomers optionally mixed with biomass" or "plastic and / or elastomer waste liquefaction oil optionally mixed with biomass" 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 (e.g. latex possibly vulcanized or tires), the plastics and / or elastomers being optionally mixed with biomass.

[0043] Plastic can be of any type, including any type of new or used plastic found in household (post-consumer) or industrial waste. Plastics are defined as materials composed of polymers and optionally 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.

[0044] 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, vineyards, orchards, olive groves, fruits and vegetables, and food processing residues; (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.); and (vii) ordinary industrial organic waste (paper, cardboard, wood, putrescible waste, etc.).

[0045] Elastomers are linear or branched polymers transformed by vulcanization into a weakly cross-linked, infusible, and insoluble three-dimensional network. They include natural and 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 plastics, 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), and polychloroprenes (CR), polyurethanes, silicone elastomers, etc.

[0046] Hydrotreating refers to any process in which hydrocarbons react with dihydrogen, typically under pressure, with or without a catalyst. Hydrotreating can thus include one or more reactions chosen from among hydrodesulfurization (HDS), hydrodeazotation (HDN), hydrodeoxygenation (HDO), hydrodemetallation (HCM), hydrocracking, hydroisomerization, and hydrogenation (hydrogenation of unsaturated compounds into saturated compounds).

[0047] A "hydrotreating catalyst" is a catalyst that promotes the incorporation of hydrogen into 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. Detailed description of the invention

[0048] Description of the composition including a plastic and / or elastomer liquefaction oil

[0049] The composition provided in step (a) includes a plastic and / or elastomer liquefaction oil optionally mixed with biomass.

[0050] In one embodiment, the composition may comprise only a plastic and / or elastomer liquefaction oil optionally mixed with biomass, in particular only a plastic and / or elastomer pyrolysis oil optionally mixed with biomass or only a plastic and / or elastomer hydrothermal liquefaction oil optionally mixed with biomass.

[0051] Alternatively, the composition may include at least 1% by mass of plastic liquefaction oil and / or elastomers, optionally mixed with biomass. The remainder may then consist of no more than 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 and / or biomass waste.

[0052] 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, optionally blended with biomass. 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, optionally blended with biomass. The mass content of plastic and / or elastomer liquefaction oil(s), optionally blended with biomass, in the composition may fall within any range defined by two of the aforementioned limits.

[0053] In one embodiment the composition may include, or be made up of, oil from the liquefaction of plastics and / or elastomers, generally in the form of waste, optionally mixed with at least one other filler, in particular in the form of waste, such as biomass, for example selected from lignocellulosic biomass, paper, cardboard, organic residues and waste.

[0054] The composition treated by the invention may, in particular, be derived from the liquefaction of waste containing at least 1% by mass, optionally from 1 to 95% by mass, for example, at least 1, 2, or 5% by mass and at most 90, 80, 75, 50, 30, 25, or 10% by mass, or within a range defined by any two of the aforementioned limits, of one or more of the aforementioned biomasses, residues, and organic wastes, the remainder being composed of plastic waste and / or elastomers, particularly in waste form. In a preferred embodiment, the composition treated by the invention is derived from the liquefaction of waste containing 0 to 5% by mass, preferably 0 to 1% by mass, of one or more of the aforementioned biomasses, residues, and organic wastes, the remainder being composed of plastic waste and / or elastomers, particularly in waste form.

[0055] The composition may thus comprise from 0 to 95% by mass, for example 0, 1, 2, or 5% by mass or more, and at most 90, 80, 75, 50, 30, 25, or 10% by mass, or within a range defined by any two of the aforementioned limits, of biomass oil, namely oil derived from the liquefaction of biomass, and in particular from liquefied biomass mixed with plastic and / or elastomers, or from the addition of liquefied biomass alone. In a preferred embodiment, the composition may comprise only oil derived from the liquefaction of plastic and / or elastomers mixed with biomass. Preferably, the composition comprises from 0 to 5% by mass, and more preferably from 0 to 1% by mass, of biomass oil.

[0056] Thus, for the purposes of the invention, "plastic and / or elastomer liquefaction oil optionally mixed with biomass" or "plastic and / or elastomer liquefaction oil containing a variable proportion of biomass" means (i) an oil obtained from the liquefaction of plastic and / or elastomers, the plastic and / or elastomers being optionally liquefied in a mixture with biomass, (ii) an oil obtained from the liquefaction of plastic and / or elastomers only, this oil being optionally mixed with a biomass liquefaction oil, or (iii) a mixture of oils (i) and (ii).

[0057] The composition may further include a diluent miscible with the plastic and / or elastomer liquefaction oil, optionally mixed with biomass. This diluent preferably has a diene value of no more than 0.5 g I2 / 100 g, measured according to UOP 326, and a bromine value of no more than 5 g Br2 / 100 g, measured according to ASTM D1159. The diluent is preferably selected from a naphtha and / or a paraffinic solvent and / or a direct distillation diesel or gas oil, containing at most 1% by weight of sulfur, preferably at most 0.1% by weight of sulfur, and / or a hydrocarbon stream having a boiling range between 50°C and 150°C or a boiling range between 150°C and 250°C or a boiling range between 200°C and 350°C, preferably having a bromine value of at most 5 gBr2 / 100g, and / or a diene value of at most 0.5 gI2 / 100g, and / or the effluent from the optional hydrotreating step of the process according to the invention, or any combination thereof.

[0058] The diluent may 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 may be separated at the outlet of the optional hydrotreating step by flash or distillation and, preferably, recycled at the inlet of this hydrotreating step.

[0059] The compositions provided in step (a) comprising the aforementioned variable proportions of biomass or biomass oils typically exhibit one or more of the properties described below.

[0060] The composition supplied in step (a) may have a bromine value of not more than 150 g Br2 / 100 g, preferably not more than 100 g Br2 / 100 g, even more preferably not more than 80 g Br2 / 100 g, the most preferred being not more than 50 g Br2 / 100 g, as measured according to ASTM D1159. In general, the composition supplied in step (a) has a bromine value of at least 1 g Br2 / 100 g.

[0061] 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 method UOP 326-17.

[0062] The composition may also have a heteroatom content of at least 1% by mass and generally of no more than 60% by mass.

[0063] Step (a) of providing the composition may include:

[0064] (a1) a step of supplying a stream of plastic and / or elastomer waste, optionally mixed with biomass,

[0065] (a2) a step of liquefying waste containing plastics and / or elastomers, and optionally mixed with biomass, and obtaining a hydrocarbon product comprising a gaseous phase, a liquid phase and a solid phase,

[0066] (a3) a step of recovering the liquefaction effluent and separating said effluent into a hydrocarbon fraction C1 to C4, and optionally into an aqueous fraction, said remaining fraction forming a composition comprising, or consisting of, a plastic and / or elastomer liquefaction oil, optionally mixed with biomass,

[0067] (a4) an optional step of mixing the composition, namely plastic and / or elastomer liquefaction oil, optionally mixed with biomass, with a diluent and / or biomass liquefaction oil.

[0068] The diluent can be as previously defined.

[0069] The liquefaction step (a2) may include a pyrolysis step, typically carried out at a temperature of 200 °C to 1000 °C or 400 to 700 °C. This pyrolysis may be, for example, rapid pyrolysis, flash pyrolysis, catalytic pyrolysis, hydropyrolysis, or steam pyrolysis. The pyrolysis process should be understood as a thermal cracking process, carried out with or without a catalyst and / or a gas.

[0070] 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 pressures of 10 to 25-40 MPa in the presence of water. 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 hydrocarbon feedstock, with the water typically in a subcritical or supercritical state.

[0071] The waste supplied at step (a1) may be plastic waste and / or elastomer waste, including tires, possibly mixed with biomass as previously described.

[0072] The recovery and separation step (a3) ​​allows 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.

[0073] Plastic and / or elastomer liquefaction oils, optionally blended with biomass, contain paraffins, i-paraffins (isoparaffins), dienes, alkynes, olefins, naphthenes, and aromatics. These oils also contain impurities containing heteroatoms, the proportion of which depends on the ratio of polymers containing these heteroatoms to the proportion of biomass. These impurities may include chlorinated, oxygenated, sulfurous, nitrogenous, and / or silylated organic compounds, metals, salts, and phosphorus compounds.

[0074] The composition of the plastic and / or elastomer liquefaction oil optionally mixed with biomass 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 or separately, 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.

[0075] A plastic and / or elastomer liquefaction oil, optionally blended with biomass, 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 or NMR.

[0076] In particular, a plastic and / or elastomer liquefaction oil optionally blended with biomass may have a Bromine number of 10 to 130 g Br / 100g, as measured according to ASTM D1159 based on its olefin content, and / or a Maleic Anhydride Number (UOP 326) of 1 to 55 mg Maleic Anhydride / 1g.

[0077] A plastic and / or elastomer liquefaction oil optionally mixed with biomass may have a diene index of no more than 50 gI2 / 100 g, preferably no more than 25 gI2 / 100 g, preferably even more than no more than 10 gI2 / 100 g, in particular measured according to UOP 326.

[0078] In a preferred embodiment, said plastic and / or elastomer liquefaction oil optionally mixed with biomass 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 / 2).

[0079] A plastic and / or elastomer liquefaction oil optionally mixed with biomass typically comprises at least 1% by mass of heteroatoms, including silicon, and typically at most 60% by mass.

[0080] A liquefaction oil for plastics and / or elastomers, optionally blended with biomass, may include one or more of the following heteroatom contents: 0 to 60% by mass of oxygen, including 0.1 to 50% by mass (e.g., measured according to ASTM D5622); 1 ppm to 6% of nitrogen, including 5 ppm to 4% of nitrogen (e.g., measured according to ASTM D4629); 2 to 30,000 ppm of sulfur, including 50 to 30,000 ppm of sulfur, preferably not exceeding 20,000 ppm (e.g., measured according to ISO 20846); 1 to 10,000 ppm of metals, including more than 2 ppm (e.g., measured by ICP); 1 to 6,000 ppm of chlorine, preferably not exceeding 5,000 ppm, including 5 to 3,000 ppm. (e.g., measured according to ASTM D7359-18), 0 to 200 ppm of bromine (e.g., measured according to ASTM D7359-18), 1 to 40 ppm of fluorine (e.g., measured according to ASTM D7359-18), 1 to 5000 ppm of silicon, including 2 to 3000 ppm, preferably not more than 1000 ppm (e.g.measured by XRF), at least 1 ppm of P, preferably at most 5000 ppm of P.

[0081] Detailed description of the optional pre-processing step of the composition provided in step (a)

[0082] 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 a polar solvent, (iii) distillation, (iv) decantation, or (v) a combination of two or three of steps (i) to (iv). This additional step may remove some of the impurities in the composition, such as oxygen, nitrogen, chlorine, sulfur, or other heteroatoms and suspended solids. In particular, reducing the amount of oxygen may prevent the formation of solids and / or gels during a subsequent hydrotreatment step.

[0083] The polar solvent used for washing may be chosen from (i) water, (ii) C1 to C4 alcohols, preferably methanol, ethanol, propan-1-ol, propan-2-ol, butan-1-ol, butan-2-ol, 2-methylpropan-1-ol, ethylene glycol, propylene glycol, (iii) alcohols comprising an ether function, preferably glycol ethers such as polyethylene glycol, polypropylene glycol, tetraethylene glycol, diethylene glycol, triethylene glycol, and mixtures thereof.

[0084] The use of a washing step with a polar solvent can help to promote step b) of liquid-liquid extraction.

[0085] Detailed description of the steps (b) liquid-liquid extraction and (c) recovery

[0086] Step (b) is a liquid-liquid extraction step by contacting the hydrocarbon compound composition provided in step (a), optionally pretreated, with a solvent consisting of at least one hydrocarbon compound free of heteroatoms.

[0087] During this step, the hydrocarbon compounds containing heteroatoms separate, and two immiscible phases are observed: a first phase containing the solvent and the heteroatom-depleted composition, and a second phase consisting primarily of hydrocarbon compounds containing heteroatoms. This second phase may also include some of the heavy fraction of the hydrocarbon compounds initially present in the composition, as well as water if the composition contains it.

[0088] In general, the first phase is lighter than the second phase.

[0089] In order to improve the separation of hydrocarbon compounds lacking heteroatoms initially contained in the composition, the solvent may advantageously consist of C3-Cn hydrocarbon compounds, where n is an integer greater than three, and the Cn hydrocarbon compound has a final boiling point less than or equal to a predetermined boiling point corresponding to an initial boiling point of the composition or to an initial boiling point of hydrocarbon compounds of interest to be extracted present in said composition.

[0090] Thus, the final boiling point of the solvent (i.e., the boiling point of the hydrocarbon compound Cn) is equal to, or lower than, the initial boiling point of the hydrocarbon compounds lacking heteroatoms that will be separated at the end of step (d). This extraction can notably allow the extraction of all organic compounds such as paraffins, isoparaffins, naphthenes, aromatics, (di)-olefins, etc., whose initial boiling point begins at (or is higher than) the final boiling point of the solvent and which have a final boiling point of 450 °C.

[0091] Preferably, in order to improve the extraction of hydrocarbon compounds devoid of heteroatoms initially contained in the composition, a solvent consisting mainly of alkanes, possibly containing olefins and / or aromatics, may be chosen.

[0092] A solvent may be chosen that comprises 90 to 100% by mass of alkanes, preferably 95 to 100% by mass, more preferably 96 to 100% by mass, and even more preferably 97 to 100% by mass. The remainder is then advantageously composed of olefins and / or aromatics. Preferably, the solvent has an olefin and / or aromatic content of less than 4% by mass, and preferably less than 3% by mass.

[0093] A suitable extraction solvent is one composed of C3-C10 hydrocarbon compounds, preferably C3-C6. This solvent may consist mainly of alkanes, particularly those in the ranges mentioned above. Advantageously, this solvent has a C3-C10 olefin and / or aromatic content of less than 4% by mass, preferably less than 3% by mass, or even zero.

[0094] Examples of usable alkanes include propane, butane, isobutane, pentane and its isomers, hexane and its isomers, and mixtures thereof.

[0095] The composition can be brought into contact with the solvent for a period ranging from a few seconds to 1 hour.

[0096] The contact can be made under temperature and pressure conditions in which the solvent is in liquid phase.

[0097] Advantageously, the contact can be made under temperature and pressure conditions below the critical point of each constituent of the solvent.

[0098] In general, the maximum conceivable temperature is around 350 °C and the maximum conceivable pressure is 42 bars.

[0099] Contact can be made with a solvent / composition mass ratio of 5 to 95%, preferably 20 to 80%.

[0100] The implementation conditions for step (b) can be selected to obtain a target heteroatom content in the first phase and the heteroatom-depleted composition present in the first phase. These conditions can be determined by testing. Typically, the solvent / composition mass ratio is varied to determine which ratio yields the desired target content.

[0101] Step (c) can thus allow the separate recovery of a composition depleted in heteroatoms, having a heteroatom content, in particular oxygen, of less than 4% by mass, preferably less than 3% by mass, more preferably less than 1% by mass, or even zero.

[0102] In order to improve phase separation, and in particular when the composition contains little or no water, it may be envisaged, in step b) to add water and / or a polar solvent with the solvent, in such a quantity that the mass ratio (water and / or polar solvent) / heteroatoms present in the composition is 0.7 to 1.3, preferably 0.9 to 1.1, for example 1.

[0103] Water and / or polar solvents tend to form hydrogen bonds with heteroatoms, which can increase the polarity of compounds bearing these heteroatoms and reduce their solubility in the extraction solvent. This can thus promote the separation of the compound-solvent mixture into two phases. Suitable polar solvents include alcohols, particularly C1-C3 alcohols, such as methanol and ethanol.

[0104] The composition and the extraction solvent can be brought into contact during step b) by any means known in the prior art.

[0105] For example, the composition and extraction solvent can be introduced into tanks, reactors, or mixers commonly used in the industry, and the two components can be mixed. This mixing may involve vigorous agitation of the two components using a mixing device. For example, the two components can be blended by stirring or shaking. Alternatively, the mixing can be carried out in a chamber where the composition and extraction solvent flow in opposite directions.

[0106] The contact between the two components can occur more than once. For example, after the composition and extraction solvent have been contacted for the first time, the two resulting phases can be contacted again, possibly several times. The steps of contacting and forming the two phases can be continuous. Thus, the two components can pass through a mixing device implementing step b) before entering a separation chamber in which a first and a second phase, namely respectively an extract (containing the purified composition and the solvent) and a raffinate (containing the heteroatoms), are formed and recovered separately (step c)).The contact between the two components can be achieved using a propeller, a counter-current flow circulation device, an agitation device, a Scheibel® column, a KARR® column, a centrifugal extractor or a mixer-decanter, in particular with two or three stages.

[0107] The composition can be contacted several times with new batches of extraction solvent, in particular with a single extraction solvent.

[0108] Thus, in one embodiment, the process may include:

[0109] -a second contacting step during which the recovered extract is brought into contact with a new batch of the same extraction solvent as that used during the first contacting step mentioned,

[0110] - followed by a second recovery step, separately, of a second immiscible extract and raffinate,

[0111] Optionally, these two steps are repeated i times on the extract recovered during the recovery step of the previous iteration, where i is a non-zero integer. The extract from the last iteration contains the solvent and the purified composition, which can then be subjected to further treatments (alone or in mixtures) after separation.

[0112] Hereafter, the term "extract" generally refers to the phase of the solvent enriched with the hydrocarbon compounds of interest, recovered during the recovery step when the process comprises a single contacting and recovery step, or the extract recovered during the second recovery step, or the extract recovered during the final iteration of the contacting and recovery steps. The raffinate is the phase depleted in hydrocarbon compounds of interest and enriched in polar compounds containing heteroatoms.

[0113] For example, the composition can be contacted with a first batch of extraction solvent to obtain a first raffinate and a first extract. After separating the raffinate from the extract, this first extract can be contacted with a second batch of extraction solvent to obtain a second raffinate and a second extract. This cycle can be repeated several times with new batches of the same extraction solvent or with different batches of extraction solvents, but preferably with batches of the same solvent, which facilitates the implementation of the process and the recovery of the raffinates.

[0114] In one embodiment, the contact cycle of the composition and its raffinate with an extraction solvent can be carried out from 1 to 9 times, in particular from 1 to 4 times. When this cycle is repeated from 2 to 9 times, the same extraction solvent or different extraction solvents can be used in each cycle, but preferably only one solvent.

[0115] Typically, the composition and the extraction solvent are brought into contact to a degree that allows for efficient extraction of the composition by the extraction solvent. These solutions are generally mixed intimately until an emulsion forms, which is then allowed to separate into two phases.

[0116] Step (c), the recovery of the two immiscible phases, namely the extract and the raffinate, can be carried out in the usual way, by separation, generally through a physical separation process. This separation usually consists of physically isolating the extract, or at least a portion of it. Thus, this separation generally consists of separating at least a portion of the raffinate from the extract.

[0117] Due to their immiscibility, the two phases (raffinate and extract) are generally separated within the contacting vessel or may be separated in a separate vessel. This separation may simply consist of removing (for example, by racking or decantation) at least a portion of the extract or raffinate.

[0118] Description of separation step (d)

[0119] This step allows the solvent to be separated from the rest of the first phase and thus the purified composition, depleted in heteroatoms, to be recovered.

[0120] This step can be carried out by distillation, separation, or compression. The type of separation used will be chosen depending on the nature of the solvent.

[0121] To separate the solvent, fractional distillation can be performed to recover only the fraction containing the extraction solvent, for example, with a purity of 99% of the initial purity. Those skilled in the art can typically determine the number of plates in the fractionation column based on the composition of the extract and the difference between the final boiling point of the extraction solvent and the initial boiling point of the extract. This difference is typically always positive. If the extract contains components sensitive to the solvent's boiling point, vacuum fractional distillation can be used to lower the boiling point below this critical temperature.

[0122] In particular, appropriate conditions can be chosen to obtain a purified composition with a desired distillation range. This distillation range can extend from the solvent's final boiling point to 450°C.

[0123] This step allows the extraction solvent to be recovered, which can then be reused in step (b).

[0124] Step (d) thus allows the recovery of a purified composition, depleted in heteroatoms. Preferably, this purified composition contains at most 4% by mass of heteroatoms, in particular oxygen, preferably more than 3% by mass, preferably more than 1% by mass, or even an undetectable content.

[0125] The process according to the invention can in particular make it possible to obtain a rate of removal of heteroatoms contained in polar compounds of 30 to 99%, in particular greater than 40%, this rate of removal being defined, for each element, by equation 1:

[0126] [Equation 1]

[0127] Discount rate = 100 . ((x_H-x_R)) / x_H

[0128] Or :

[0129] x_H is the content in mg / kg of the element in the composition before treatment.

[0130] x_R is the content in mg / kg of the element in the purified composition.

[0131] The process according to the invention can thus make it possible to obtain one or more of the following reduction rates:

[0132] from 30 to 99% for oxygen,

[0133] from 20 to 90% for nitrogen,

[0134] from 10 to 60% for sulfur,

[0135] from 40 to 95% for halogens, including chlorine, bromine, and fluorine,

[0136] from 10 to 99% for metals, especially transition metals, particularly iron, but also alkali and alkaline earth metals.

[0137] Oxygen content can be measured according to the standard: ASTM D5622 / D2504.

[0138] Nitrogen content can be measured according to the standard: ASTM D4629.

[0139] Sulfur content can be measured according to ISO 20846.

[0140] The halogen content can be measured according to the standard: ASTM D7359

[0141] The alkali metal content can be measured according to the standard: ASTM D5708 A or IP 501.

[0142] The alkaline earth metal content can be measured according to the standard: ASTM D5708 A or IP 501.

[0143] Transition metal content can be measured according to the standard: ASTM D5708 A or IP 501.

[0144] The versions of the standards cited in this patent application are, where not specified, those as of the filing date of this application.

[0145] Advantageously, the purified composition according to the invention may exhibit at least one of the following characteristics:

[0146] an oxygen content of 100 mg / kg or less,

[0147] a nitrogen content of 75 mg / kg or less,

[0148] a sulfur content of no more than 700 ppm (by mass),

[0149] an alkali metal content, particularly K and Na, of less than or equal to 4 mg / kg,

[0150] a halogen content of less than or equal to 15 mg / kg, in particular a chlorine content of less than or equal to 1 ppm (by mass),

[0151] a total metal content of no more than 2 mg / kg.

[0152] Description of the optional second phase separation step

[0153] The second phase from step (c) (the raffinate) contains hydrocarbon compounds containing heteroatoms, some of which can be valuable, such as oxygenated compounds. This is particularly the case when the composition contains biomass oil, which typically contains phenols or other valuable oxygenated compounds.

[0154] In this case, the process according to the invention advantageously includes a step for separating the oxygenated compounds present in the second phase resulting from step (c). This separation step can be chosen according to the nature of the oxygenated compounds. It may consist of one or more separation steps by distillation, under atmospheric pressure or under vacuum.

[0155] Solids can form during the liquid-liquid extraction step, settling at the bottom in the second phase. It is therefore preferable to implement a solids removal step prior to this separation, for example by decantation, filtration and / or centrifugation.

[0156] Detailed description of the optional purification step (e)

[0157] The process may also include a purification step (e) by passing through a solid adsorbent. This is therefore a trapping step.

[0158] The purified composition from step (d) can be further purified by passing over a solid adsorbent in order to decrease 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.

[0159] Typically, the purified composition from step (d) 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.

[0160] The adsorbent can be operated in regenerative or non-regenerative mode, at a temperature below 400°C, preferably below 100°C, and more preferably below 60°C, selected from: (i) silica gel, (ii) clay, (iii) crushed clay, (iv) apatite, (v) hydroxyapatite and their combinations, (vi) alumina, for example, alumina obtained by boehmite precipitation, calcined alumina such as Sasol's Ceralox®, (vii) boehmite, (viii) bayerite, (ix) hydrotalcite, (x) spinel such as Sasol's Pural® or Puralox®, (xi) promoted alumina, for example, BASF's Selexsorb®, acid-promoted alumina, alumina promoted by a zeolite and / or by a metal such that 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 sieves 3A, 4A, 5A,13X, for example marketed under the brand name Siliporite ® by 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.

[0161] 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 VVH 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.

[0162] The (e) purification step on adsorbent can be implemented continuously or in batch, in one or more reactors, such as fixed bed reactors, fluidized bed reactors or any other suitable type of reactor or device.

[0163] Detailed description of the optional catalytic hydrotreatment step (f)

[0164] The hydrotreating of step (f) can be carried out in one step or in two steps.

[0165] When carried out in a single step, the purified composition from step (d), optionally further purified in step (e), 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.

[0166] Alternatively, the hydrotreating of step (f) can be carried out in a first step (f-1) in which the purified composition from step (d), optionally further purified in step (e), 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% by weight), and in a second step (f-2) in which the effluent from step (f-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, for example a NiMo (0.1-60% by weight) and / or CoMo (0.1-60% by weight) type catalyst.

[0167] When carried out in two stages, the first hydrotreating stage can hydrogenate dienes, particularly conjugated dienes, and acetylenic bonds. The decrease in diene value observed between the inlet and outlet of the first hydrotreating stage is typically at least 10%, preferably at least 25%, measured according to UOP 326. In the second stage, a catalyst known to hydrogenate olefins and convert sulfur and nitrogen components to H₂S and NH₃, respectively, can advantageously be used.

[0168] During the first step, the composition can pass through one or more catalytic beds, preferably with an overall temperature increase of no more than 150°C, preferably no more than 100°C, and / or a temperature increase of no more than 100°C, preferably no more than 50°C, for each catalytic bed. Advantageously, an intermediate quenching step can be provided between the catalytic beds, preferably carried out with H2 or with the hydrotreated composition recovered in step (f). This first step can be carried out in a fixed-bed reactor, preferably in the presence of at least one catalyst, typically a hydrogenation catalyst. This catalyst can comprise at least one metal from groups 8-10, preferably selected 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. Alternatively, a catalyst comprising at least one group 6 metal, such as Mo or W, may be used, in combination or not with a promoter selected from at least one group 8-10 metal, such as Ni and / or Co, and / or a mixture thereof. These metals are used in sulfide form and preferably supported on alumina, titanium, zirconia, silica, carbon, and / or mixtures thereof.

[0169] During the second step, the composition can pass through one or more catalytic beds, preferably with an overall temperature increase of no more than 100°C, and / or a temperature increase of no more than 50°C on each catalytic bed. Advantageously, an intermediate quenching step can be provided between the catalytic beds, this quenching being preferably carried out with H2 or with the hydrotreated composition recovered in step f). This second step can be carried out in a fixed-bed reactor, preferably in the presence of at least one catalyst, typically a hydrogenation catalyst similar to that described for the first step. The catalyst can also have a trapping function and, for this purpose, have a BET surface area of ​​150 m² / g to 400 m² / g.

[0170] In addition, guard reactors can be provided to remove any remaining chlorine, metals, and silicon. A silicon trap can be installed (for example, at the inlet of the hydrotreating stage or at the inlet of the second hydrotreating stage when there are two stages), which can be in a separate reactor or form the upper bed of a reactor. This trap can operate at a temperature of at least 200°C, and / or at a VVH of 1 to 10 h⁻¹, and / or at an absolute pressure of 10 to 160 bar in the presence of H₂; optionally, a metal trap can be used in conjunction with a metal trap operating at a temperature of at least 200°C, at a VVH of 1 to 10 h⁻¹, and at an absolute pressure of 10 to 160 bar in the presence of H₂.

[0171] Thus, in general, step (f) 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.

[0172] This hydrotreating step can also have a demetallization, cracking, and dearomatization function depending on the characteristics of the catalyst and the hydrotreating conditions.

[0173] Preferably, the feed for hydrotreatment, containing at least a portion of the purified composition from step (d), optionally purified in step (e), can be diluted with a portion of the hydrotreatment effluent that 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 components present in the purified composition and preheats the feed.

[0174] The purified composition from step (d), optionally further purified in step (e), can be treated alone or diluted with a feed of fossil hydrocarbons, in order to obtain a concentration of purified composition ranging from 0.01 wt% to a maximum of 50 wt%; preferably from 0.1 wt% to 25 wt%, even more preferably from 1 wt% to 20 wt%.

[0175] At the outlet of step f) of hydrotreating, 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 still at most 0.5 gBr2 / 100g, measured according to ASTM D1159.

[0176] Detailed description of the optional washing step

[0177] The effluent exiting the hydrotreatment step (f), 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.

[0178] Use of the purified composition

[0179] The purified composition from step (d), optionally purified in step (e) and / or hydrotreated in step (f), and optionally washed with water, can be fractionated into usable streams. The cut points at these streams 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, and kerosene. These streams can then be processed in a steam cracker and / or a catalytic cracker and / or a hydrocracker (and possibly then 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 most suitable cuts for the subsequent processing units according to the desired outcome.

[0180] The purified composition from step (d), optionally purified in step (e) and / or hydrotreated in step (f), optionally washed with water, can also be used diluted, for example mixed with naphtha, diesel or crude oil to obtain a concentration of purified composition 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.

[0181] Detailed description of the optional steam cracking step

[0182] The purified composition from step (d), optionally purified in step (e) and / or hydrotreated in step (f), optionally washed with water, with or without dilution with a conventional steam cracking feed, preferably without dilution.

[0183] Prior to this steam cracking stage, a separation step by distillation can be implemented depending on the technology of the steam cracking furnaces.

[0184] This steam cracking step allows the production of olefins such as ethylene and propylene, as well as aromatics. The ethylene and propylene can then be advantageously converted into polyethylene and polypropylene, respectively, in a polymerization section.

[0185] The steam cracking step involves 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.

[0186] Steam cracking is carried out in the presence of steam typically 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.

[0187] 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, and 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.

[0188] The reaction time is usually very short, typically from 0.005 to 0.5 seconds, preferably from 0.01 to 0.4 seconds, for example on the order of a few hundred milliseconds.

[0189] These conditions allow the carbon-carbon bonds to break, producing unsaturated hydrocarbons with molecules smaller than the feedstock introduced into the reactor(s). The effluent exiting 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.

[0190] The purified composition from step (d), optionally purified in step (e) and / or hydrotreated in step (f), and optionally washed with water, can be sent to the steam cracker undiluted or can be blended with ethane, liquefied petroleum gas, naphtha, or gas oils to obtain a purified composition 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. Liquefied petroleum gas (LPG) consists primarily of propane and butanes. The term "naphtha" or "naphtha fraction" refers to the general definition used in the oil and gas industry. In particular, it is a hydrocarbon derived from the distillation of crude oil and whose boiling point is between 15 and 145 °C, according to the ASTM D2887 standard.Naphtha contains virtually no olefins because the hydrocarbons are derived from crude oil. Naphtha is generally considered to have a carbon number between C5 and C11, although in some cases the carbon number can reach C15. Gas oils have a boiling range of approximately 200 to 350 °C and consist of hydrocarbons ranging from C10 to C22, including primarily linear and branched paraffins, cyclic paraffins, and aromatics (including mono-, naphtho-, and poly-aromatics).

[0191] Because the purified composition exhibits 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 residual hydrocarbon vapors by a flash tank. In this flash tank, the liquid flows out by gravity from the bottom, while the hydrocarbon vapors flow out from the top. Optionally, the hydrocarbon liquid can be returned to the plastics liquefaction unit or to the optional hydrocracking stage.

[0192] Detailed description of the optional hydrocracking step

[0193] Prior to the steam cracking step, the purified composition from step (d), optionally purified in step (e) and / or hydrotreated in step (f) 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.

[0194] 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 25MPa abs. and an hourly volumetric rate of 0.1 to 10h-1.

[0195] 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.

[0196] 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

[0197] Lad describes a possible embodiment of the invention. In this possible embodiment, the composition comprising a plastic and / or elastomer liquefaction oil optionally mixed with biomass (1) is first optionally pretreated in a pretreatment section (A) by (i) filtration, (ii) washing with 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 liquid-liquid extraction section (B) for the implementation of step (b) of the invention. This extraction section (B) receives an extraction solvent (3) for this purpose.The effluent (4) exiting this extraction section (B) is then sent to a recovery section (C) for the recovery of a first phase or extract (5) containing the solvent and the purified composition depleted in heteroatoms, and a second phase or raffinate (6) enriched in heteroatoms. This recovery section (C) can be integrated into the extraction section (B). The first phase (5) is sent to a separation section (D) to carry out the separation step (d) and separate the solvent (7), which can be returned to the extraction section (B), from the purified composition depleted in heteroatoms (8).

[0198] The purified composition (8) can then be sent to an optional purification section (E) for the implementation of the adsorbent treatment step (e). The effluent (9) exiting the optional purification section (E) or the purified composition (8), possibly after fractionation and / or dilution (not shown), can then be sent to an optional hydrotreatment section (F) for the implementation of a hydrotreatment step (f).

[0199] The effluent (10) exiting the hydrotreating section (F), possibly after fractionation and / or dilution (not shown), can be sent to one or more of the following optional sections: an optional hydrotreating section (S-HDT), 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, or an optional fuel, lubricant, or base oil preparation section (S-Pool). Preferably, the effluent (10) exiting the hydrotreating section (F) is then steam cracked to obtain olefins, which can then be polymerized.

[0200] Preferably, the effluent (11) exiting the hydrocracking section (S-HC) is then steam cracked to obtain olefins which can then be polymerized.

[0201] The purified composition (8) exiting step (d) may optionally be sent directly to the hydrotreating step (f) before being sent to the hydrocracking step (S-HC), advantageously followed by the fuel pool (S-Pool) or the steam cracking step (S-VAPO).

[0202] The purified composition (8) can be sent to hydrocracking, hydrotreating, fuel pooling or steam cracking, alone or mixed with a feedstock of fossil hydrocarbons.

[0203] The second phase (6) separated at the recovery section (D) can then be sent to a separation section (S) in order to separate the oxygenated compounds (12) present in the second phase.

[0204] Example

[0205] The composition tested is a plastic pyrolysis oil with a variable proportion of biomass, denoted HPP(+B), the main characteristics of which are summarized in Table 1.

[0206] [Table 1] Table 1 Pyrolysis Oil HPP(+B) Density (kg / m³ 3 850-1250 Chlorine (ppm by mass) 5-3000 Silicon (ppm by mass) 2-3000 Nitrogen (mg / L) 50-40000 Sulfur (mg / L) 50-30000 Oxygen (% by mass) 0.1-50 Aromatics (% by mass) 1-80

[0207] Liquid / liquid extraction tests were carried out by contacting HPP(+B) plastic pyrolysis oil with pentane at different HPP(+B) / pentane mass ratios.

[0208] The following protocol was used:

[0209] - contacting the HPP(+B) plastic pyrolysis oil with the solvent at room temperature;

[0210] - agitation at 500 rpm for 5 minutes to ensure good contact between the two phases;

[0211] - separation of phases after 12 to 14 hours of rest and obtaining a light phase and a heavy phase.

[0212] The light phase containing pentane and the heavy phase were then subjected to evaporation under the following conditions: the flasks opened on a hot plate at 60°C were each subjected to a flow of dry nitrogen with a pipette (1L / min) above each liquid until the weight stabilized (a few hours) in order to remove the pentane.

[0213] The mass yields of extraction are shown in Table 2, the mass yields of evaporation are shown in Table 3.

[0214] Pentane / HPP(+B) mass ratio (%) Initial mass (g) HPP(+B) + pentane Mass (g) Light phase mass (g) Heavy phase mass (g) Extraction yield (% mass) Losses (g) 1060, 1856, 912, 1698, 91, 112060, 1451, 676, 9698, 51, 513060, 2750, 047, 8497, 62, 394060, 1437, 6619, 5897, 12, 95060, 1232, 5122, 594, 95, 116060, 9440, 3818, 2297, 7 2,346560,452,097,0298,71,297060,453,375,6198,61,427560,7753,65,498,21,778059,9346,1111,2897,52,548560,3853,794,5397,92,069060,1853,924,0797,82,19

[0215] Pentane / HPP(+B) Mass Ratio (%) Initial Mass (g) HPP(+B) + Pentane Mass (g) Light Phase Mass (g) Heavy Phase Mass (g) Losses (g) Total Losses (*) (g) 1059.0752.711.444.926.032058.6344.294.819.5311.043057.8842.55.1510.2312.624057.2436.784.0816.3819.385055.0119.5217.2118.2823.396058.633.510.5714.5316 ,876559,1127,962,9428,2129,57058,9841,52,1315,3516,77755935,551,7921,6623,438057,3928,664,4324,326,848558,3237,770,7919,7621,829057,9935,250,4122,3324,52

[0216] (*) cumulative losses from extraction and evaporation

Claims

A process for purifying a hydrocarbon compound composition comprising a plastic and / or elastomer liquefaction oil optionally mixed with biomass, comprising the following steps: (a) a step of supplying a hydrocarbon compound composition comprising a plastic and / or elastomer liquefaction oil optionally mixed with biomass, said composition containing at least 1% by mass of heteroatoms, this step (a) comprising: (a1) a step of supplying a stream of plastic and / or elastomer waste, optionally mixed with biomass, (a2) a step of liquefying waste containing plastics and / or elastomers, optionally mixed with biomass, and obtaining a hydrocarbon product comprising a gaseous phase, a liquid phase and a solid phase,- (a3) ​​a step of recovering the liquefaction effluent and separating said effluent into a C1 to C4 hydrocarbon fraction, and optionally into an aqueous fraction, said remaining fraction forming a composition comprising a plastic and / or elastomer liquefaction oil optionally mixed with biomass, - (a4) an optional step of mixing the composition with a diluent and / or a biomass liquefaction oil, (b) a liquid-liquid extraction step by contacting the hydrocarbon compound composition supplied in step (a) with a solvent consisting of at least one heteroatom-free hydrocarbon compound, (c) a step of recovering a first and a second immiscible phase, the first phase containing the hydrocarbon compound composition depleted in heteroatoms and the solvent, while the second phase is enriched in heteroatoms,(d) a separation step in which the solvent is separated from the remainder of the first phase forming a purified composition, wherein the solvent consists of C3-Cn hydrocarbon compounds, where n is an integer greater than three, and the Cn hydrocarbon compound has a final boiling point less than or equal to a predetermined boiling point corresponding to an initial boiling point of the composition or to an initial boiling point of hydrocarbon compounds of interest to be extracted present in said composition. A process according to claim 1, characterized in that said composition comprises at least one of the following characteristics: - said composition contains at least 10% by weight of plastic and / or elastomer liquefaction oil optionally mixed with biomass, the other part of said composition being a diluent, or said composition contains only plastic and / or elastomer liquefaction oil optionally mixed with biomass, - said composition comprises biomass liquefaction oil, - said plastic and / or elastomer liquefaction oil optionally mixed with biomass in said composition 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, preferably further at most 560°C, preferably at most 450°C, preferably further at most 350°C, preferably 250°C,- said plastic and / or elastomer liquefaction oil, optionally mixed with biomass, contains from 0 to 60% by weight of oxygen, and / or from 1 ppm to 6% by weight of nitrogen, and / or at least 2 ppm of sulfur, preferably not more than 30,000 ppm of sulfur, relative to the total weight of said liquefaction oil; - said plastic and / or elastomer liquefaction oil, optionally mixed with biomass, contains at least 1 ppm by weight of silicon, preferably not more than 5,000 ppm by weight of silicon, and / or at least 1 ppm by weight of silicon, preferably not more than 1,000 ppm by weight of silicon, relative to the total weight of said liquefaction oil; - said plastic and / or elastomer liquefaction oil, optionally mixed with biomass, contains at least 1 ppm by weight of chlorine, preferably not more than 6000 ppm by weight, and / or at least 1 ppm by weight of P, preferably not more than 5000 ppm by weight relative to the total weight of said liquefaction oil,- prior to step (b), said composition is subjected to (i) filtration, (ii) washing with a polar solvent, (iii) distillation, (vi) decantation, or (v) a combination of two or three of steps (i) to (iv). A process according to any one of claims 1 or 2, wherein the solvent has one or more of the following characteristics: - the solvent consists mainly of alkanes, optionally the solvent contains 90 to 100% by mass of alkanes, preferably 95 to 100% by mass, more preferably 96 to 100% by mass, even more preferably 97 to 100% by mass, - the solvent consists of C3-C10 hydrocarbon compounds, - the solvent has an olefin and / or aromatic content of less than 4% by mass, preferably less than 3% by mass. A process according to any one of claims 1 to 3, wherein step (b) comprises at least one of the following features: - a solvent / composition ratio of 5 to 95% by mass, preferably 20 to 80% by mass, - contact for a duration ranging from a few seconds to 1 hour, - temperature and pressure conditions in which the solvent is in the liquid phase, - temperature and pressure conditions below the critical point of each constituent of the solvent, - the addition of water and / or a polar solvent with the solvent, in an amount such that the mass ratio of water and / or polar solvent to heteroatoms present in the composition is 0.7 to 1.3, preferably 0.9 to 1.

1. A process according to any one of claims 1 to 4, wherein the second separation step comprises at least one of the following features: - step (d) is a separation step by distillation, evaporation or compression, - the separated solvent is returned to step (b), - the purified composition from step (d) contains at most 4% by mass of heteroatoms, preferably at most 3% by mass of heteroatoms, more preferably at most 1% by mass. A process according to any one of claims 1 to 5, further comprising: - a step separating the oxygenated compounds present in the second phase from step (c), optionally preceded by a step removing the solids. A process according to any one of claims 1 to 6, characterized in that the purified composition from step (d) undergoes a purification step (e) 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. A process according to any one of claims 1 to 7, wherein: (f) the purified composition from step (d), optionally further purified in step (e), undergoes catalytic hydrotreatment in one or two steps to provide a purified hydrotreated composition. A process according to claim 8, characterized in that the hydrotreating in step (f): - is carried out in a single step in which the purified composition from step (d), optionally further purified in step (e), 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 (f-1) in which the purified composition from step (d), optionally further purified in step (e), 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 (f-2) in which the effluent from step (f-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. A process according to any one of claims 8 or 9, wherein the hydrotreated composition exiting step (f) is washed with water to remove inorganic compounds such as hydrosulfide, hydrogen chloride, ammonia. A process according to any one of claims 1 to 10, wherein the purified composition separated in step (d), optionally further purified in step (e), or the hydrotreated composition of step (f), optionally washed with water, is: (g) subjected, pure or diluted, optionally after separation into usable streams, to a steam cracking step, and / or (h) subjected, pure or diluted, optionally after separation into usable streams, to a fluidized bed catalytic cracking step, and / or (i) subjected, pure or diluted, optionally after separation into usable streams, to a hydrocracking step, and / or (j) subjected, pure or diluted, optionally after separation into usable streams, to a catalytic hydrogenation step, and / or (k) used as is or separated into usable streams for the preparation of fuels and combustibles such as LPG, gasoline, diesel, and heavy fuel oil and / or for the preparation of lubricants and / or base oils.

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