PROCESS FOR PURIFYING OIL, PLASTIC AND / OR ELASTOMER COMPOSITIONS BY LIQUID-LIQUID EXTRACTION

Abstract

The invention relates to a process 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 liquid-liquid extraction step by contacting the composition provided in step (a) with a solvent consisting of at least one hydrocarbon compound free of heteroatoms, (c) a recovery step of a first and a second immiscible phase, the first phase containing the heteroatom-depleted composition 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. Figure for the abstract: Figure 1,

Description

Title of the invention: METHOD FOR PURIFYING OIL, PLASTICS AND / OR ELASTOMERS 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, particularly when this plastic and / or elastomer waste contains, in varying proportions, other types of waste such as, for example, lignocellulosic biomass. Technological background

[0002] Plastic and / or elastomeric 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 the amount of plastic and / or elastomeric waste in landfills. On the other hand, disposing of plastic waste in landfills is becoming increasingly difficult. Therefore, recycling is necessary.

[0003] One possible method for recycling this waste is liquefaction by pyrolysis or hydrothermal liquefaction. However, the resulting 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 coke precursors in processes involving high temperatures, such as steam cracking. Advanced waste sorting can be carried out before liquefaction to maximize the presence of polyolefins and to avoid plastics such as PET, PA, PVC, PS, and biomass. Nevertheless, this sorting is not optimal, and these plastics 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 recycle them.

[0004] Numerous treatment processes exist for reducing the heteroatom content of plastic liquefaction oils. Liquid-liquid extraction is a known method, 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... These are found in water or polar solvents. Hydrotreating the oil (possibly mixed with a fossil-based filler) is also known 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, notably to allow for the efficient removal of heteroatoms, particularly silicon. While treatments in a basic medium allow for the efficient removal of silicon, chlorine, and other heteroatoms, such as oxygen and nitrogen, the high temperatures employed can lead to secondary reactions such as the formation of gums by diene polymerization, and when there is a high proportion of biomass in the feed, the high temperature also leads to 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 sorting 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 eliminate 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. Summary of the invention

[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 composition of hydrocarbon compounds supplied in step (a) with a solvent consisting of at least one hydrocarbon compound free of heteroatoms,

[0012] (c) a recovery step of a first phase and a second phase not miscible, the first phase containing the hydrocarbon compound composition 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 rest of the first phase forming a purified composition.

[0014] The composition of hydrocarbon compounds comprising a plastic and / or elastomer liquefaction oil optionally mixed with treated biomass in the present invention thus comprises hydrocarbon compounds devoid of heteroatoms, namely paraffins, isoparaffins, olefins, di-olefins, naphthenes, aromatics, ..., 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 which it is preferable to eliminate. These compounds, which are 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 specific solvent chosen. The impurities are found in a phase immiscible with the phase containing the solvent and the heteroatom-free hydrocarbon compounds of the composition. It is then sufficient to remove the solvent 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, with the other hydrocarbon compounds from the biomass remaining 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, 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 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 silicon, preferably at most 1,000 ppm by weight of silicon, relative to the total weight of said liquefaction oil. - said plastic liquefaction oil contains at least 1 ppm by weight of Cl, preferably at most 6000 ppm by weight, and / or at least 1 ppm by weight of P, preferably at most 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 step of liquefying plastics and / or elastomers, optionally in mixture with biomass.

[0018] In particular, step (a) of supply may include: - (al) 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 Cl 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 mainly (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 / compound ratio of 5 to 95% by mass, preferably 20 to 80% by mass, - a contact period ranging from a few seconds to 1 hour, - temperature and pressure conditions under which the solvent is in the liquid phase, - temperature and pressure conditions below the critical point of each component of the solvent, - the addition of water and / or a polar solvent with the solvent, in such a quantity 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 method according to the invention may further include: - a separation step of oxygenated compounds present in the second phase from step (c), optionally preceded by a solids removal step.

[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 life of the catalysts 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 from 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 catalytic fluidized bed 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, petrol, 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, comprise only steps (a) to (d) described above, and optionally steps (e) to (k). Definitions

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

[0029] 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.

[0030] The specification of a decimal-free numeric domain includes all integers and, where appropriate, fractions thereof (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 1.0 and 5.0). Any range of numeric values ​​recited herein 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 indicated, 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 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-".

[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 both alkanes (saturated hydrocarbons), cycloalkanes, aromatics and unsaturated hydrocarbons.

[0037] By "heteroatom" is meant 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, the methods of Relevant characterization techniques 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. 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 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 (version 2020) 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.

[0040] 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.

[0041] 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.

[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 "liquefaction oil of plastic waste and / or elastomers 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 polymers. and / or thermosetting, and / or elastomers (for example, possibly vulcanized latex or tires), with the plastics and / or elastomers optionally mixed with biomass.

[0043] 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.

[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, 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.).

[0045] Elastomers are linear or branched polymers transformed by vulcanization into a weakly cross-linked, infusible, and insoluble three-dimensional network. They include natural or synthetic rubbers. They may be part of 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] 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).

[0047] 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. Detailed description of the invention

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

[0049] The composition provided in step (a) comprises 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 comprise at least 1% by mass of plastic liquefaction oil and / or elastomers, optionally mixed with biomass. 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 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 mixed 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 mixed with biomass. The mass content of plastic and / or elastomer liquefaction oil(s), optionally mixed with biomass composition can be included in any interval defined by two of the previously fixed 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 come 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 or 80 or 75 or 50 or 30 or 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 waste, and the remainder being made up of plastic waste and / or elastomers, in particular in the form of waste.

[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 or 80 or 75 or 50 or 30 or 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.

[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 comprise a diluent miscible with plastic and / or elastomer liquefaction oil, optionally mixed with biomass. This diluent preferably has a diene number of not more than 0.5 g I₂ / 100 g, measured according to UOP 326, and a bromine number 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% sulfur, preferably not more than 0.1 wt% sulfur, and / or a hydrocarbon stream having a boiling range between 50°C and 150°C or an interval 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 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.

[0059] 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.

[0060] 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.

[0061] The composition may also have a heteroatom content of at least 1% by mass and generally of no more than 60% by mass.

[0062] Step (a) of supplying the composition may include:

[0063] (al) a step of supplying a stream of plastic waste and / or elastomers, optionally mixed with biomass,

[0064] (a2) a step of liquefying waste containing plastics and / or elastomers, and optionally in mixture with biomass, and the obtaining of a hydrocarbon product comprising a gaseous phase, a liquid phase and a solid phase,

[0065] (a3) ​​a step of recovering the liquefaction effluent and separating said effluent in a hydrocarbon fraction Cl to C4, and optionally in an aqueous fraction, said remaining fraction forming a composition comprising, or consisting of, a plastic and / or elastomer liquefaction oil, optionally mixed with biomass,

[0066] (a4) an optional step of mixing the composition, namely oil of liquefaction of plastic and / or elastomers, optionally in mixture with biomass, with a diluent and / or a biomass liquefaction oil.

[0067] The diluent can be as previously defined.

[0068] 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 being, for example, rapid pyrolysis or flash pyrolysis or pyrolysis Catalytic or hydropyrolysis, steam pyrolysis. The pyrolysis process should be understood as a thermal cracking process, carried out with or without a catalyst and / or a gas.

[0069] 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 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, the water typically being in a subcritical or supercritical state.

[0070] The waste supplied at step (al) may be plastic waste and / or elastomer waste, including tires, possibly mixed with biomass as previously described.

[0071] 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.

[0072] Plastic and / or elastomer liquefaction oils, optionally blended with biomass, contain, in particular, paraffins, i-paraffins (isoparaffins), dienes, alkynes, olefins, naphthenes, and aromatics. Plastic and / or elastomer liquefaction oils, optionally blended with biomass, 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 be chlorinated, oxygenated, sulfurous, nitrogenous, and / or silylated organic compounds, metals, salts, and phosphorus compounds.

[0073] 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.

[0074] 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 levels can be determined by gas chromatography or by NMR.

[0075] In particular, a plastic and / or elastomer liquefaction oil optionally mixed with biomass may have a Bromine number of 10 to 130 g Br / 100 g, as measured according to ASTM DI 159 based on its olefin content, and / or a maleic anhydride number (UOP 326) of 1 to 55 mg maleic anhydride / 1 g.

[0076] A plastic and / or elastomer liquefaction oil optionally mixed with biomass may have a diene index of at most 50 gI2 / 100 g, preferably at most 25 gI2 / 100 g, preferably even more at most 10 gI2 / 100 g, in particular measured according to UOP 326 standard.

[0077] 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).

[0078] 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.

[0079] A plastic and / or elastomer liquefaction oil optionally blended with biomass may, in particular, comprise one or more of the following heteroatom contents: from 0 to 60% by mass of oxygen, in particular from 0.1 to 50% by mass (e.g., measured according to ASTM D5622), from 1 ppm to 6% of nitrogen, in particular from 5 ppm to 4% of nitrogen (e.g., measured according to ASTM D4629), from 2 to 30,000 ppm of sulfur, in particular from 50 to 30,000 ppm of sulfur, preferably not exceeding 20,000 ppm (e.g., measured according to ISO 20846), from 1 to 10,000 ppm of metals, in particular exceeding 2 ppm (e.g., measured by ICP), from 1 to 6,000 ppm of chlorine, preferably not exceeding 5,000 ppm, in particular from 5 to 3000 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.

[0080] Detailed description of the optional pre-treatment step of the composition provided in step (a)

[0081] 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 can help 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 can prevent the formation of solids and / or gels during a subsequent hydrotreating step.

[0082] The polar solvent used for washing can be chosen from (i) water, (ii) alcohols in Cl to C4, preferably methanol, ethanol, propan-l-ol, propan-2-ol, butan-l-ol, butan-2-ol, 2-methylpropan-l-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.

[0083] The use of a washing step with a polar solvent can help to promote step b) of liquid-liquid extraction.

[0084] Detailed description of steps (b) of liquid-liquid extraction and (c) of recovery

[0085] 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.

[0086] 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 essentially of hydrocarbon compounds containing heteroatoms. This second phase may also include a portion of the heavy fraction of the hydrocarbon compounds initially present in the composition, as well as water if the composition contains it.

[0087] In general, the first phase is lighter than the second phase.

[0088] In order to improve the separation of hydrocarbon compounds devoid of 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.

[0089] Thus, the final boiling point of the solvent (namely the boiling point of the hydrocarbon compound Cn) corresponds to the initial boiling point of the hydrocarbon compounds devoid of heteroatoms that will be separated at the end of step (d). This extraction can, in particular, allow the extraction of all paraffin organic compounds, isoparaffins, naphthenes, aromatics, (di)-olefins... whose initial boiling point begins at the final boiling point of the solvent and having a final boiling point of 450 °C.

[0090] 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.

[0091] In particular, a solvent may be chosen comprising 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 then advantageously consists of olefins and / or aromatics. Preferably, the solvent has an olefin and / or aromatic content of less than 4% by mass, preferably less than 3% by mass.

[0092] A usable extraction solvent is a solvent composed of C3-C10 hydrocarbon compounds, preferably C3-C6. This solvent may consist mainly of alkanes, particularly 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.

[0093] Examples of usable alkanes include propane, butane, isobutane, pentane and its isomers, hexane and its isomers and mixtures thereof.

[0094] The contact of the composition with the solvent can in particular be carried out for a period ranging from a few seconds to 1 hour.

[0095] The contact can be made under temperature and pressure conditions in which the solvent is in liquid phase.

[0096] Advantageously, the contact can be made under temperature and pressure conditions below the critical point of each constituent of the solvent.

[0097] In general, the maximum conceivable temperature is around 350 °C and the maximum conceivable pressure is 42 bars.

[0098] Contacting can be carried out with a solvent / composition mass ratio of 5 to 95%, preferably 20 to 80%.

[0099] The implementation conditions of 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 will be varied to determine which ratio yields a desired target content.

[0100] Step (c) can thus allow for the separate recovery of a composition depleted in heteroatoms, having a heteroatom content, in particular oxygen, less than 4% by mass, preferably less than 3% by mass, more preferably less than 1% by mass, or even zero.

[0101] In order to improve the separation of the phases, and in particular when the composition contains little or no water, it may be provided, in step b), that water and / or a polar solvent be added with the solvent, in an amount such 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.

[0102] 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 composition-solvent mixture into two phases. Suitable polar solvents include alcohols, particularly C1-C3 alcohols, such as methanol and ethanol.

[0103] The composition and the extraction solvent can be brought into contact during step b) by any means known in the prior art.

[0104] For example, the composition and the extraction solvent can be introduced into tanks, reactors, or mixers commonly used in the industry, and the two components can be mixed. This mixing can involve vigorous agitation of the two components by a mixing device. For example, the two components can be blended together by stirring or shaking. Alternatively, the mixing can be carried out in a chamber in which the composition and the extraction solvent flow in opposite directions.

[0105] The contacting of the two components can occur more than once. For example, after the composition and the 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, particularly with two or three stages.

[0106] The composition can be contacted several times with new batches of extraction solvent, in particular with one and the same extraction solvent.

[0107] Thus, in one embodiment, the process may comprise:

[0108] - a second contacting step during which the recovered extract is contacted with a new batch of the same extraction solvent as that used in the first contacting step mentioned,

[0109] - followed by a second recovery step separately from a second extract and of a second, immiscible refinement,

[0110] - optionally, these two steps are repeated i times on the extract retrieved during the recovery step from 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.

[0111] 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 last 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.

[0112] 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 a single solvent, which facilitates the implementation of the process and the recovery of the raffinates.

[0113] In one embodiment, the cycle of contacting 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 one and the same solvent.

[0114] Typically, the composition and the extraction solvent are brought into contact to an extent that allows 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.

[0115] Step (c) of recovering the two immiscible phases, namely the extract and the raffinate, can be carried out in the usual way, by separation, generally by a physical separation process. This separation generally consists of isolating physically the extract, or at least a part of it. Thus, this separation generally consists of separating at least a part of the raffinate from the extract.

[0116] Due to their immiscibility, the two phases (raffinate and extract) are generally separated in the contacting chamber or may be separated in another chamber. This separation may simply consist of removing (for example by racking or decantation) at least a portion of the extract or raffinate.

[0117] Description of separation step (d)

[0118] This step allows the solvent to be separated from the rest of the first phase and thus to recover the purified composition, depleted in heteroatoms.

[0119] This step can be carried out by distillation, separation or compression. The type of separation used can be chosen according to the nature of the solvent.

[0120] To separate the solvent, fractional distillation can be performed to recover only the fraction containing the solvent used for extraction, 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 fractionating 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 boiling point of the solvent, fractional distillation under vacuum can be applied to reduce the boiling point below this critical temperature.

[0121] In particular, appropriate conditions can be chosen to recover a purified composition with a desired distillation range. This distillation range can extend from the final boiling point of the solvent to 450°C.

[0122] This step allows the extraction solvent to be recovered, which can then be reused in step (b).

[0123] Step (d) thus makes it possible to recover a purified composition, depleted in heteroatoms. Preferably, this purified composition contains at most 4% by mass of heteroatoms, in particular oxygen, more preferably at most 3% by mass, more preferably at most 1% by mass.

[0124] 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:

[0125] [Equation 1]

[0126] Reduction rate = 100 . ((x_H-x_R)) / x_H

[0127] Where:

[0128] x_H is the content in mg / kg of the element in the composition before treatment,

[0129] x_R is the content in mg / kg of the element in the purified composition.

[0130] The process according to the invention can thus make it possible to obtain one or more of the following abatement rates:

[0131] from 30 to 99% for oxygen,

[0132] from 20 to 90% for nitrogen,

[0133] from 10 to 60% for sulfur,

[0134] from 40 to 95% for halogens, including chlorine, bromine, fluorine,

[0135] from 10 to 99% for metals, particularly transition metals, especially the iron, but also alkali metals and alkaline earth metals.

[0136] Oxygen content can be measured according to the standard: ASTM D5622 / D2504.

[0137] The nitrogen content can be measured according to the standard: ASTM D4629.

[0138] Sulphur content can be measured according to ISO 20846.

[0139] The halogen content can be measured according to the standard: ASTM D7359

[0140] The alkali metal content can be measured according to the standard: ASTM D5708 A or IP 501.

[0141] The alkaline earth metal content can be measured according to the standard: ASTM D5708 Aou IP 501.

[0142] The transition metal content can be measured according to the standard: ASTM D5708 Aou IP 501.

[0143] The versions of the standards cited in this patent application are, where not specified, those as of the filing date of this application.

[0144] Advantageously, the purified composition according to the invention may have at least one of the following characteristics:

[0145] an oxygen content less than or equal to 100 mg / kg,

[0146] a nitrogen content less than or equal to 75 mg / kg,

[0147] a sulfur content of at most 700 ppm (by mass),

[0148] an alkali metal content, in particular K and Na, less than or equal to 4 mg / kg

[0149] a halogen content less than or equal to 15 mg / kg, in particular a chlorine content less than or equal to Ippm (by mass),

[0150] a total metal content of no more than 2 mg / kg.

[0151] Description of the optional second phase separation step

[0152] The second phase resulting from step (c) (the raffinate) contains hydrocarbon compounds containing heteroatoms, some of which may 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.

[0153] In this case, the process according to the invention advantageously comprises 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.

[0154] Solids may form during the liquid-liquid extraction step, these solids 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.

[0155] Detailed description of the optional purification step (e)

[0156] The process may also include a purification step (e) by passing over a solid adsorbent. This is thus a trapping step.

[0157] 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.

[0158] 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.

[0159] 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 their combinations, (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, alumina promoted by a zeolite 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 Tonsil® from Clariant, (xiii) a molecular sieve in the form of an aluminosilicate containing an alkali or alkaline earth cation, for example 3A, 4A, 5A, 13X sieves, for example marketed under the brand name Siliporite® from 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.

[0160] 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.

[0161] The purification step (e) on adsorbent can be carried out continuously or in batch, in one or more reactors, such as fixed bed reactors, fluidized bed reactors or any other type of suitable reactor or device.

[0162] Detailed description of the optional catalytic hydrotreating step (f)

[0163] The hydrotreating in step (f) can be carried out in one step or in two steps.

[0164] 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.

[0165] 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.

[0166] When carried out in two steps, the first hydrotreating step can hydrogenate dienes, and in particular conjugated dienes, and 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, one could advantageously use a catalyst known to hydrogenate olefins and convert the sulfur and nitrogen components into H2S and NH3 respectively.

[0167] During the first step, the composition can 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 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. 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.

[0168] 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.

[0169] 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⁻¹, and / or at an absolute pressure of 10 to 160 bar in the presence of H₂; optionally with a metal trap. working at a temperature of at least 200°C, at a WH of between 1 and 10h-l, at an absolute pressure of 10 to 160 bar in the presence of H2.

[0170] Thus, in general, step (f) 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.

[0171] This hydrotreating step can also have a demetallization, cracking, dearomatization function depending on the characteristics of the catalyst and the hydrotreating conditions.

[0172] Preferably, the feed for hydrotreating, 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 hydrotreating effluent, which still has a temperature higher than the desired temperature at the hydrotreating inlet. This at least partial recycling of the hydrotreating effluent allows for the dilution of unsaturated components present in the purified composition and preheats the feed.

[0173] 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%.

[0174] At the outlet of the hydrotreating step f), 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 more at most 0.5 gBr2 / 100g, measured according to ASTM DI 159.

[0175] Detailed description of the optional washing step

[0176] 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.

[0177] Use of the purified composition

[0178] 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 whose cut points 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, 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. A skilled professional knows how to select the most suitable cuts for subsequent processing units, depending on the desired outcome.

[0179] 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 wt% to a maximum of 50 wt%; preferably from 0.1 wt% to 25 wt%, even more preferably from 1 wt% to 20 wt% at the inlet of the next treatment.

[0180] Detailed description of the optional steam cracking step

[0181] 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.

[0182] Prior to this steam cracking step, a separation step by distillation can be implemented depending on the technology of the steam cracking furnaces.

[0183] 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.

[0184] 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.

[0185] 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.

[0186] 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.

[0187] 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.

[0188] These conditions allow the carbon-carbon bonds to be broken and unsaturated hydrocarbons to be produced with molecules smaller than the charge introduced into the(s) 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 light C2-C5 olefins, such as ethylene, propylene, butadiene, isobutene, n-butene, and isoprene.

[0189] The purified composition from step (d), optionally purified in step (e) and / or hydrotreated in step (f), 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 essentially 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 Cl1, although the carbon number can reach C15 in some cases. Gas oils have a boiling range of approximately 200 to 350 °C and consist of hydrocarbons ranging from C10 to C22, including essentially linear and branched paraffins, cyclic paraffins, and aromatics (including mono-, naphtho-, and poly-aromatics).

[0190] 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.

[0191] Detailed description of the optional hydrocracking step

[0192] 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.

[0193] 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-l.

[0194] 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.

[0195] 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

[0196] [Fig-1] [Fig.1] describes one possible embodiment of the invention. In this In a possible embodiment, the composition comprising a plastic and / or elastomer liquefaction oil (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) which exits this extraction section (B) is then sent to a recovery section (C) allowing 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 implement the separation step (d) and separate the solvent (7), which can be returned to the extraction section (B), from the purified heteroatom-depleted composition (8).

[0197] The purified composition (8) can then be sent to an optional purification section (E) for the implementation of the treatment step (e) on an adsorbent. 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).

[0198] The effluent (10) exiting the hydrotreatment section (F), possibly after fractionation and / or dilution (not shown), can be sent to one or more The following optional sections are included: 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, and an optional preparation section (S-Pool) for a fuel, lubricant, or base oil. Preferably, the effluent (10) exiting the hydrotreating section (F) is then steam cracked to obtain olefins, which can then be polymerized.

[0199] Preferably, the effluent (11) exiting the hydrocracking section (S-HC) is then steam cracked to obtain olefins which can then be polymerized.

[0200] The purified composition (8) exiting step (d) can 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).

[0201] The purified composition (8) can be sent to hydrocracking, hydrotreating, fuel pooling or steam cracking, alone or mixed with a feedstock of fossil hydrocarbons.

[0202] 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.

[0203] Example

[0204] The tested composition is a plastic pyrolysis oil with a variable proportion of biomass, denoted HPP(+B), the main characteristics of which are summarized in Table 1

[0205] [Table 1] Table 1 HPP(+B) Pyrolysis Oil Density (kg / m³) 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

[0206] Liquid / liquid extraction tests were carried out by contacting HPP(+B) plastic pyrolysis oil with pentane at different HPP(+B) / pentane mass ratios

[0207] The following protocol was used:

[0208] - contacting the HPP(+B) plastic pyrolysis oil with the solvent at room temperature;

[0209] - stirring at 500 rpm for 5 minutes to ensure good contact between the two phases;

[0210] - separation of phases after 12 to 14 hours of rest and obtaining a light phase and a heavy phase.

[0211] The light phase containing pentane and the heavy phase are 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 (IL / min) above each liquid until the weight stabilized (a few hours) in order to remove the pentane.

[0212] The mass yields of the extraction are presented in Table 2, the mass yields of the evaporation are presented in Table 3.

[0213] [Tables2] Pentane / HPP(+B) Mass Ratio (%) Initial Mass (g) HPP (+B) + pentane Mass (g) Light Phase Mass (g) Heavy Phase Extraction Yield (% Mass) Losses (g) 10 60.18 56.91 2.16 98.9 1.11 20 60.14 51.67 6.96 98.5 1.51 30 60.27 50.04 7.84 97.6 2.39 40 60.14 37.66 19.58 97.1 2.9 50 60.12 32.51 22.5 94.9 5.11 60 60.94 40.38 18.22 97.7 2.34 65 60.4 52.09 7.02 98.7 1.29 70 60.4 53.37 5.61 98.6 1.42 75 60.77 53.6 5.4 98.2 1.77 80 59.93 46.11 11.28 97.5 2.54 85 60.38 53.79 4.53 97.9 2.06 90 60.18 53.92 4.07 97.8 2.19

[0214] [Tables3] Pe ntane / HPP(+B) mass ratio (%) Initial mass (g) HPP(+ B) + pentane Mass (g) light phase Mass (g) heavy phase Losses (g) Total losses (*) (g) 10 59.07 52.71 1.44 4.92 6.03 20 58.63 44.29 4.81 9.53 11.04 30 57.88 42.5 5.15 10.23 12.62 40 57.24 36.78 4.08 16.38 19.38 50 55.01 19.52 17.21 18.28 23.39 60 58.6 33.5 10.57 14.53 16.87 65 59.11 27.96 2.94 28.21 29.5 70 58.98 41.5 2.13 15.35 16.77 75 59 35.55 1.79 21.66 23.43 80 57.39 28.66 4.43 24.3 26.84 85 58.32 37.77 0.79 19.76 21.82 90 57.99 35.25 0.41 22.33 24.52

[0215] (*) cumulative losses from extraction and evaporation

Claims

Demands

1. 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, (b) a liquid-liquid extraction step by contacting the hydrocarbon compound composition supplied in step (a) with a solvent consisting of at least one hydrocarbon compound free of heteroatoms, (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.

2. 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 not more than 700°C, preferably not more than 600°C, preferably even more than 560°C, preferably not more than 450°C, preferably even more 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).

3. A method according to claim 1 or 2, wherein step (a) comprises: - (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 Cl to C4, 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.

4. A process according to any one of claims 1 to 3, wherein the solvent has 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 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.

5. A process according to any one of claims 1 to 4, 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 of 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.

6. A process according to any one of claims 1 to 5, 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.

7. A method according to any one of claims 1 to 6, further comprising: - a separation step of oxygenated compounds present in the second phase from step (c), optionally preceded by a solids removal step.

8. A process according to any one of claims 1 to 7, 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.

9. A process according to any one of claims 1 to 8, 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.

10. A process according to claim 9, 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 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 9 or 10, wherein the hydrotreated composition exiting step (f) 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 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, petrol, dieselheavy fuel oil and / or for the preparation of lubricants and / or base oils.

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