Method for co-processing tyre oil and oil of natural origin

Abstract

The invention relates to a method for producing hydrocarbon fluids, the method comprising: a) a step of providing a tyre oil fraction having a final boiling point of no more than 400°C; b) a step of hydrotreatment, in which the tyre oil fraction is brought into contact with dihydrogen in the presence of a hydrocarbon feedstock of natural origin containing fatty acids and / or fatty acid esters, in a hydrotreatment zone in the presence of at least one catalyst, under conditions suitable for carrying out hydrotreatment and forming a hydrotreated effluent comprising a hydrotreated liquid fraction and a non-condensables fraction; c) a step of separating the hydrotreated effluent from step b), during which the non-condensables fraction is separated from the hydrotreated liquid fraction; the hydrotreated liquid fraction can then be further treated, for example by hydroisomerisation and / or hydrocracking, or separated into streams that can be used as fuel.

Description

[0001] PROCESS FOR CO-PROCESSING TIRE OIL AND OIL OF NATURAL ORIGIN

[0002] technical field

[0003]

[0001] The present invention relates to a coprocessing method for tire oil and oil of natural origin.

[0004] Context of the invention

[0005]

[0002] Due to the depletion of fossil resources and growing environmental concerns, the use of molecules derived from biomass is increasingly sought after to replace fossil-based molecules. In particular, some countries, such as France, are implementing taxes on aviation fuels. Furthermore, the regulation on levelling competition for a sustainable aviation sector within the European Union (also known as the "ReFuelEU Aviation initiative") aims to increase the use of sustainable fuels by aircraft and ships in order to reduce their environmental footprint. Thus, by 2025, 2% of jet fuel used in the European Union must be of renewable origin.

[0006]

[0003] Furthermore, there is an important need, also encouraged by regulations, to limit waste such as tires in landfills and to recycle them.

[0007]

[0004] One possible method for recycling tires is to obtain tire oil by pyrolysis, steam thermolysis, solvolysis, or hydrothermal liquefaction. However, the tire oil obtained generally contains large quantities of dienes and heteroatoms, including nitrogen, sulfur, silicon, and metals, which are contaminants for the catalysts in the hydrotreating processes typically used in subsequent recycling processes. These oils may also contain significant sediment content, which is also toxic to catalysts.

[0008]

[0005] Thus, the preparation of hydrocarbon fuels or fluids from molecules derived from biomass or tires constitutes a real economic, environmental and strategic challenge.

[0009] Previous art

[0010]

[0006] There are now many processes for manufacturing a fuel comprising a component of biological origin.

[0011]

[0007] A well-known process for manufacturing renewable fuels and other hydrocarbon fluids involves subjecting a vegetable or animal fat or oil and a fossil-based feedstock to hydrotreatment in the presence of dihydrogen and a catalyst. Such coprocessing helps to limit the high exothermicity of the hydrotreatment of triglycerides. However, corrosion phenomena are observed due to the acidity of the treated vegetable and / or animal oils.

[0012]

[0008] It is also known to hydrotreat a tire pyrolysis oil and an oil of animal or vegetable origin together. For example, document WO 2024 / 017593 A1 describes a coprocessing method for a tire oil containing 0.1 to 5% by mass of oxygen and an animal oil or fat. Prior to coprocessing, the tire oil may have undergone a stabilizing hydrotreatment to reduce the aromatic content and / or hydrodeoxygenation or deoxygenation and / or a toluene extraction step. This document states on page 20, lines 22-30, that coprocessing increases the cloud point of the resulting product due to the increased solubility of the heavy fraction of the tire oil.

[0013]

[0009] Tire oils contain significant amounts of sulfur and nitrogen that must be removed during recycling. The stabilization hydrotreatment described in WO 2024 / 017593 A1 probably allows their removal, but requires expensive dihydrogen.

[0014]

[0010] The applicant discovered that tire oil fractions with a final boiling point of 400°C or lower contain contaminants, including metals, sediments, sulfur, and nitrogen, that allow for their coprocessing with other feedstocks of natural origin. This eliminates the need for pre-coprocessing hydrotreatment. Furthermore, the absence of a heavy fraction (final boiling point above 400°C) in tire oil prevents pollution of the effluents produced, as the hydrotreatment of oils of natural origin does not generate this type of heavy fraction. Indeed, a heavy fraction present in tire oil would end up in the effluents, which is not necessarily desirable and would necessitate effluent distillation to remove this heavy fraction.

[0015] Description of the invention

[0016]

[0011] The invention proposes a process for manufacturing hydrocarbon fluids comprising: a) a step of supplying a fraction of tyre oil having a final boiling point of no more than 400 °C, b) a hydrotreating step, in which said fraction of tyre oil and a hydrocarbon feedstock of natural origin containing fatty acids and / or fatty acid esters are contacted in a hydrotreating zone with dihydrogen and at least one catalyst under conditions suitable for carrying out hydrotreating and forming a hydrotreated effluent comprising a hydrotreated liquid fraction and a fraction of non-condensable components, c) a step of separating the hydrotreated effluent from step b) in which the fraction of non-condensable components is separated from the hydrotreated liquid fraction.

[0017]

[0012] The process according to the invention thus makes it possible to manufacture hydrocarbon fluids (the hydrotreated liquid fraction), using bio-based and recycled feedstocks.

[0018]

[0013] The tire oil fraction may comprise one or more of the following characteristics: the tire oil fraction comprises one or more of the following fractions: (i) a naphtha fraction having a final boiling point of at most 150 °C, (ii) a kerosene fraction having an initial boiling point of at least 130 °C and a final boiling point of at most 270 °C, (iii) a diesel fraction having an initial boiling point of at least 230 °C and a final boiling point of at most 400 °C, a sulfur content of 100 ppm to 20,000 ppm, generally 200 to 20,000 ppm, most often 500 to 20,000 ppm, or even 3,000 to 20,000 ppm, a nitrogen content of 100 to 20,000 ppm, generally 200 to 20,000 ppm, most often from 500 to 20,000 ppm or even from 2,000 to 20,000 ppm, a sediment content of 1 ppm to 2,000 ppm, optionally from 1 to 500 ppm or from 1 to 200 ppm, a bio-based carbon content of 30 to 100% by mass (measured according to ASTM D6866-24,DI N 51637 (2014) or ASTM D7026), an aromatics content of 15 to 80% by mass.

[0019]

[0014] Step a) of supply may include: a step of obtaining tyre oil by a process selected from pyrolysis, vapothermolysis, solvolysis and hydrothermal liquefaction, a step of fractionating the tyre oil obtained in the previous step into a fraction having a final boiling point of not more than 400 °C and a heavier fraction, optionally into at least one fraction selected from (i) a naphtha fraction having a final boiling point of not more than 150 °C, (ii) a kerosene fraction having an initial boiling point of not more than 130 °C and a final boiling point of not more than 270 °C, (iii) a diesel fraction having an initial boiling point of not more than 230 °C and a final boiling point of not more than 400 °C, and into a heavier fraction.

[0020]

[0015] The naturally sourced hydrocarbon filler containing fatty acids and / or fatty acid esters used in the present invention may comprise, or be made up of, a naturally sourced oil, an esterified naturally sourced oil, or mixtures thereof.

[0021]

[0016] The process according to the invention may further include, prior to step b) of hydrotreatment, a pretreatment step of said tire oil, optionally mixed with said naturally sourced hydrocarbon feedstock, comprising at least one treatment selected from (i) a degumming treatment, optionally carried out under cavitation conditions, and (ii) a bleaching treatment. Such a treatment makes it possible to reduce the impurity content of the treated feedstock (tire oil possibly mixed with the naturally sourced hydrocarbon feedstock), and in particular its solids and / or oxygen content.

[0022]

[0017] The hydrotreatment step can be implemented under one or more of the following conditions:

[0023]

[0018] - a ratio of tire oil fraction / naturally derived hydrocarbon filler of

[0024] 0.1 to 50% by mass, preferably 5 to 40% by mass, more preferably 5 to 30% by mass, even more preferably 5 to 25% by mass or 1 to 25% by mass,

[0025]

[0019] - a temperature of 100 to 550°C, preferably 200 to 400°C, more preferably 250 to 380°C,

[0026]

[0020] - in the presence of dihydrogen at pressures ranging from 0.1 to 20 MPa, preferably from 4 to 15 MPa, more preferably from 5 to 12 MPa,

[0027]

[0021] - an hourly volumetric speed of 0.1 to 4 h' 1 , preferably from 0.2 to 3 hours 1 , preferably more from 0.2 to 2 h -1 ,

[0028]

[0022] - an H2 / HC ratio between the dihydrogen and the feed charge of 100 to 2000

[0029] NL / L, preferably 500 to 1500 NL / L, preferably more than 600 to 1200 NL / L,

[0030]

[0023] - in the presence of at least one catalyst selected from (i) oxides, phosphides or sulfides of Ni, Mo, W, Co or mixtures of NiW, NiMo, CoMo, NiCoW, NiCoMo, NiMoW and CoMoW, (ii) metals or mixtures of metal alloys of groups 8, 9, 10 and / or 11 of the periodic table, (iii) basic oxides such as alkali metal oxides, alkali-earth oxides, lanthanide oxides, zinc oxide, spinels, perovskites, calcium silicates.

[0031]

[0024] The process according to the invention may further include a step d) of hydroisomerizing and / or hydrocracking the hydrotreated liquid fraction. The incorporation of tire oil into the naturally occurring hydrocarbon feedstock during the hydrotreatment step makes it possible to obtain a hydroisomerized and / or hydrocracking effluent with a lower cloud point than when the naturally occurring hydrocarbon feedstock does not contain tire oil.

[0032]

[0025] Step d) of hydroisomerization and / or hydrocracking can be carried out under at least one of the following conditions: a temperature of 150°C to 500°C, a pressure of 1 MPa to 20 MPa.

[0033]

[0026] The process according to the invention may further include a separation step e) in which the hydrotreated liquid fraction from step c) or the effluent from step d), preferably the effluent from step d), is separated into at least one fraction selected from a naphtha fraction, a kerosene fraction and a diesel fraction.

[0034]

[0027] In one embodiment, the process according to the invention comprises only steps a) to c), and optionally one or more of the other steps previously described.

[0035] Detailed description of the invention

[0036]

[0028] 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.

[0037]

[0029] The expressions % by weight and % by mass (also noted %m) have an equivalent meaning and refer to the proportion of the mass of a product relative to 100g of a composition comprising it.

[0038]

[0030] Unless otherwise indicated, measurements given in parts per million (ppm) are expressed in mass.

[0039]

[0031] 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 D1160 for distillates.

[0040]

[0032] The term "hydrocarbon" refers to alkanes (saturated hydrocarbons), cycloalkanes, aromatics, and unsaturated hydrocarbons.

[0033] The term "heteroatom" means any element of an organic compound other than carbon and hydrogen.

[0041]

[0034] The concentration of heteroatoms in the hydrocarbon matrix can be determined by any method known in the art. In particular, relevant characterization methods include X-ray fluorescence (XRF), inductively coupled plasma mass spectrometry (ICP-MS), and inductively coupled plasma atomic emission spectrometry (ICP-AES). Analytical scientists are able to identify the most suitable method for measuring each metal and, more generally, each heteroatom, depending on the hydrocarbon matrix considered. The oxygen content can be measured according to ASTM D5622-17 / D2504-88 (2015). The nitrogen content can be measured according to ASTM D4629-17. The sulfur content can be measured according to ISO 20846:2011. The halogen content, including chlorine, bromine, fluorine, can be measured according to the standard: ASTM D7359-18.

[0042]

[0035] The aromatic content can be measured by gas chromatography, for example by a GCxGC or GC method, or by liquid chromatography, or by proton NMR and / or carbon NMR.

[0043]

[0036] The sediment content can be measured according to ASTM D7579-09, using tetrahydrofuran instead of the solvents mentioned in the standard (dichloromethane-methanol mixture and methanol).

[0044]

[0037] The diene index (DV) or "diene index" is a measure of conjugated double bonds and refers to the analytical method by titration, expressed in grams of diiodine per 100 g of sample. This molar quantity of diiodine is equivalent to the molar quantity of maleic anhydride that reacts with 100 g of sample (based on two moles of iodine atoms per mole of maleic anhydride, one mole of maleic anhydride corresponding to one conjugated double bond). It can be measured by the UOP-326-82 method.

[0045]

[0038] In the following description, the different embodiments described, and in particular the preferred embodiments of each step, can be combined according to the objective sought.

[0046]

[0039] Naturally derived hydrocarbon filler containing fatty acids and / or fatty acid esters

[0047]

[0040] By "naturally sourced hydrocarbon filler" is meant a hydrocarbon filler comprising carbon, hydrogen and oxygen atoms, which is not of fossil origin. In other words, this filler does not contain components of fossil origin.

[0048]

[0041] The naturally sourced hydrocarbon filler containing fatty acids and / or fatty acid esters used in the present invention may comprise, or consist of, a naturally sourced oil, an esterified naturally sourced oil, or mixtures thereof.

[0049]

[0042] The naturally sourced hydrocarbon filler used in the present invention may thus comprise, or consist of, a naturally sourced oil or a mixture of naturally sourced oils, esters resulting from the trans-esterification of fatty acid esters and / or the esterification of fatty acids contained in one or more naturally sourced oils, as well as mixtures thereof.

[0050]

[0043] The oil of natural origin may be chosen from a vegetable oil, an animal oil or fat, a used oil, an oil produced by microorganisms, as well as mixtures thereof.

[0051]

[0044] A naturally sourced oil is defined as an oil that does not contain mineral oil of fossil origin.

[0052]

[0045] Typically, an oil of natural origin may contain 50% by mass or more, preferably 60% by mass or more, preferably 70% by mass or more, of fatty acids and / or fatty acid esters (mono-, di-, triglycerides).

[0053]

[0046] In one embodiment, a naturally derived oil may contain fatty acid esters (mono-, di-, or triglycerides) and / or free fatty acids, containing one to three C8-C24 acyl groups, saturated or unsaturated. When several acyl groups are present, they may be identical or different.

[0054]

[0047] The vegetable oil may be chosen from pine oil, rapeseed oil, sunflower oil, castor oil, peanut oil, linseed oil, babassu oil, hemp oil, linola oil, jatropha oil, peanut oil, rice bran oil, mustard oil, carinata oil, coconut oil, copra oil, olive oil, palm oil, cottonseed oil, corn oil, palm kernel oil, soybean oil, pumpkin seed oil, grapeseed oil, argan oil, jojoba oil, sesame oil, walnut oil, hazelnut oil, tung oil, rice oil, safflower oil, oil algae, used oils, nut shell oil (especially cashew nut shell oil), and any combination thereof.

[0055]

[0048] Used oil includes used cooking oils or used food oils and oils recovered from wastewater, such as trap and drain grease / oils, gutter oils, sewage oils, for example from wastewater treatment plants, used grease from the food industry, and used cooking oils which are animal by-products.

[0056]

[0049] Animal fat can be chosen from tallow, lard, fat (yellow and brown fat), fish oil / fat, milk fat, used cooking oils and / or animal fats which are animal by-products.

[0057]

[0050] In particular, animal fats and used cooking oils which are animal by-products have the status of animal by-products within the meaning of Regulation (EC) No 1069 / 2009 of the European Parliament and of the Council of 21 October 2009 and of Commission Regulation (EU) No 142 / 2011 (implementing Regulation of EC No 1069 / 2009).

[0058]

[0051] Animal fats having the status of animal by-product are fatty residues of animal origin, other than used cooking oils, coming for example from food industries or rendering plants.

[0059]

[0052] Used cooking oils classified as animal by-products are used cooking oils (used cooking oils or UCOs), namely residues of fats of vegetable or animal origin used for human consumption in the food processing industry, in institutional or commercial catering.

[0053] Oil of natural origin can also be oil produced by microorganisms, natural or genetically modified, such as bacteria, yeasts, particularly oleaginous yeasts, algae, prokaryotes, or eukaryotes. In particular, these oils can be recovered by well-known mechanical or chemical extraction methods.

[0060]

[0054] The aforementioned oils, most of which are rich in triglycerides, also contain varying amounts of non-triglyceride components such as free fatty acids, mono- and diglycerides, and many other organic and inorganic components, including phosphatides, sterols, tocopherols, tocotrienols, hydrocarbons, pigments (gossypol, chlorophyll), vitamins (carotenoids), sterol glucosides, glycolipids, protein fragments, traces of pesticides and traces of metals, as well as resinous and mucilaginous materials.

[0061]

[0055] Compositions resulting from the trans-esterification of fatty acid esters and / or from the esterification of fatty acids contained in the aforementioned natural oils, such as compositions comprising alkyl esters of fatty acids, and in particular methyl esters of fatty acids or ethyl esters of fatty acids, and comprising impurities from the oils, may also be part of the naturally sourced hydrocarbon fillers considered in the present invention.

[0062]

[0056] The naturally derived hydrocarbon filler used in the present invention may thus contain 50% by mass or more, preferably 60% by mass or more, preferably 70% by mass or more, of fatty acids and / or fatty acid esters (mono-, di-, triglycerides, alkyl esters of fatty acids, and in particular ethyl esters of fatty acids, methyl esters of fatty acids). In general, the naturally derived hydrocarbon filler comprises at most 99% by mass of fatty acids and / or fatty acid esters.

[0063]

[0057] The phosphorus content of the naturally occurring hydrocarbon load can be 20 ppm or more or 50 ppm or more, for example from 50 ppm to 1500 ppm, or from 200 ppm to 1200 ppm, measured for example by X-ray fluorescence or ICP by the UOP 389 method, or by ICP AES Dilution or ICP microwave digestion in a closed medium.

[0064]

[0058] The nitrogen content of the naturally occurring hydrocarbon feed can be 20 ppm or more, for example from 50 ppm to 1200 ppm or from 200 ppm to 2000 ppm, measured for example by X-ray fluorescence or by chemiluminescence.

[0065]

[0059] The naturally occurring hydrocarbon filler may further comprise one or more other heteroatoms such as alkali metals, in particular potassium, alkaline earth metals, and / or chlorine. The content of these heteroatoms may vary depending on the constituents of the composition. It may be determined by elemental analysis such as X-ray fluorescence or by ICP.

[0066]

[0060] Step a) of supplying tire oil

[0067]

[0061] The expression "tire oil" refers to hydrocarbon liquid products obtained from pyrolysis and / or vapothermolysis and / or solvolysis and / or hydrothermal liquefaction of tyres, alone or possibly mixed with other elastomers, and generally in the form of waste, optionally mixed with at least one other feedstock, in particular in the form of waste, such as plastic waste and / or biomass, for example selected from lignocellulosic biomass, herbaceous biomass, aquifer biomass, paper and cardboard, organic waste (forestry, agricultural, industrial and / or household waste), food waste, alone or mixed.

[0068]

[0062] 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 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.

[0069]

[0063] Biomass can be defined as an organic product of plant or animal origin.

[0070]

[0064] Biomass can thus include (i) biomass produced from surplus agricultural land, preferably not used for human or animal consumption: dedicated crops, called energy crops (short-rotation coppice (SRC), very short-rotation coppice (VSRC); (ii) biomass produced by deforestation (forest maintenance) or the clearing of agricultural land, ...; (iii) agricultural residues from crops, in particular cereal crops, vines, orchards, olive trees, fruits and vegetables including nuts, agri-food residues, ...; (iv) forestry residues from silviculture and wood processing; (v) agricultural residues from livestock farming (manure, slurry, bedding, droppings, ...); (vi) household organic waste (paper, cardboard, green waste, ...); (vii) industrial organic waste (paper, cardboard, wood, putrescible waste, ...(viii) algal biomass, namely biomass formed from algae, for example microalgae (algal biomass can be an algae suspension obtained by harvesting algae from, for example, a bioreactor, or an algae residue obtained by dehydrating an algae suspension) or macroalgae; (ix) herbaceous biomass; (x) vegetable oils contained in certain waste (cashew nut shells or other), (xi) industrial waste (type B wood), (xii) sewage sludge, (xiii) digestate from a methanizer.

[0071]

[0065] In one embodiment, the tire oil is obtained from waste comprising at least 60% by mass, preferably at least 70% by mass, more preferably at least 80% by mass, even more preferably at least 90% by mass of tire waste, the remainder coming from waste of other elastomers and / or plastics and / or biomass, in particular lignocellulosic biomass, herbaceous biomass, aquifer biomass, paper, cardboard, organic waste (forestry, agricultural, industrial and / or household waste), food waste, alone or in mixture.

[0072]

[0066] In a preferred embodiment, the tire oil is obtained exclusively from waste consisting of tires.

[0073]

[0067] Tire oils contain, in particular, paraffins, i-paraffins (isoparaffins), dienes, alkynes, olefins, naphthenes, and aromatics. Tire oils also contain impurities containing heteroatoms, such as oxygenated, sulfurous, nitrogenous, and / or silylated organic compounds, metals, salts, and phosphorus compounds.

[0074]

[0068] The composition of tire oil 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. Tire waste can be whole (including metals and textiles) or in the form of more or less coarse shredding or granules (and therefore potentially without textiles or metals).

[0075]

[0069] A tire oil typically comprises 5 to 80% by mass of paraffins (including cycloparaffins), 10 to 95% by mass of unsaturated compounds (including olefins, dienes, and acetylenes), 15 to 80% by mass of aromatics (mono-, di-, and / or tria-aromatics), most often 20 to 80% by mass, or even 30 to 80% by mass, of aromatics. These contents can be determined by gas chromatography, liquid chromatography, proton NMR, and / or carbon NMR.

[0076]

[0070] A tire oil may have an initial boiling point of at least 15 °C, typically from 15 to 150 °C, and a final boiling point of at most 850 °C, most often at most 800 °C, generally from 250 to 750 °C (measured according to standard NF EN 15199-1 / 2), most often from 350 to 700 °C or from 350 to 600 °C.

[0077]

[0071] A tire oil may comprise one or more of the following characteristics:

[0078]

[0072] - a diene index of 1 to 100 gl2 / 100g,

[0079]

[0073] - an aromatic compound content of 15 to 80% by mass, most often 20 to 80% by mass, or even 30 to 80% by mass,

[0080]

[0074] - heteroatom contents of 0 to 10% by mass,

[0081]

[0075] - a sediment content of 1 to 2000 ppm.

[0082]

[0076] A tire oil may in particular comprise one or more of the following heteroatom contents: from 0 to 30,000 ppm of oxygen (measured according to ASTM D5622); from 100 ppm to 30,000 ppm of nitrogen, generally from 200 ppm to 25,000 by mass of nitrogen, and most often from 500 to 20,000 ppm of nitrogen or even from 3,000 ppm to 20,000 ppm of nitrogen (measured according to ASTM D4629); from 100 ppm to 30000 ppm of sulfur, generally from 200 ppm to 25000 ppm of sulfur, most often from 500 to 20000 ppm of sulfur or even from 3000 to 20000 ppm of sulfur (measured according to ISO 20846), from 1 to 1000 ppm of metals (measured by ICP), from 0 to 100 ppm of chlorine (measured according to ASTM D7359-18), from 0 to 200 ppm of bromine (measured according to ASTM D7359-18), from 0 to 40 ppm of fluorine (measured according to ASTM D7359-18), 1 to 200 ppm of silicon (measured by XRF).

[0083]

[0077] Generally, the bio-based carbon content of a tire oil, measured according to ASTM D6866-24, DI N 51637 (2014), or ASTM D7026, is at least 30% by mass, preferably at least 40% by mass, and can reach 100% by mass, particularly for tires made from synthetic rubber of renewable origin (for example, from butadiene produced from ethanol derived from biomass). "Bio-based carbon" means carbon derived from biomass. Bio-based carbon does not include carbon derived from fossil materials.

[0084]

[0078] Step a) of supply may therefore include, in particular only:

[0085]

[0079] - a step of obtaining tire oil by a process selected from pyrolysis, vapothermolysis, solvolysis and hydrothermal liquefaction,

[0086]

[0080] - a step of fractionating the tire oil obtained into a fraction having a final boiling point of no more than 400 °C and a heavier fraction.

[0087]

[0081] Advantageously, step a) may include, in particular only, the preliminary step a1) of providing a waste tire stream, optionally mixed with biomass and / or plastics and / or other elastomers; a2) liquefying said waste stream by pyrolysis, hydrothermal liquefaction, vapothermolysis or solvolysis at a temperature of at least 200°C; a3) recovering a liquefaction effluent and separating said liquefaction effluent into a solid fraction, a C1 to C4 hydrocarbon fraction, and optionally an aqueous fraction, the remaining fraction being said tire oil.

[0088]

[0082] The waste may comprise at least 60% by mass, preferably at least 70% by mass, more preferably at least 80% by mass, and even more preferably at least 90% by mass of tire waste, the remainder being from waste of other elastomers and / or biomass and / or plastics. Preferably, the waste consists of tires.

[0089]

[0083] The pyrolysis process should be understood as a thermal cracking process in the absence of air, typically carried out at a temperature of 300 to 1000 °C or 400 to 700 °C, implemented in the presence or absence of a catalyst and / or a gas (rapid pyrolysis, slow pyrolysis, flash pyrolysis, catalytic pyrolysis, hydropyrolysis, steam pyrolysis, ...).

[0090]

[0082] The steam thermolysis process consists of injecting steam into the pyrolysis reactor. This steam partially or completely replaces the inert gases usually used, such as nitrogen, CO2, noble gases, or non-condensable pyrolysis gases.

[0091]

[0083] The hydrothermal liquefaction (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 being in a subcritical or supercritical state. The hydrothermal liquefaction process is typically carried out at a temperature of 250 to 500 °C and at pressures of 10 to 25-40 MPa in the presence of water.

[0092]

[0084] Solvolysis is a process similar to hydrothermal liquefaction but uses a solvent other than water and usually milder conditions, namely a temperature of 150 to 400 °C and a pressure of 1 to 25 MPa.

[0085] The fractionation step can be carried out by distillation, for example by distillation at atmospheric pressure or under reduced pressure, or by staged condensation.

[0093]

[0086] Fractionation can be implemented to separate one or more of the following fractions:

[0094]

[0087] (i) a naphtha fraction having a final boiling point of at most 150 °C, for example from 130 to 150 °C, and typically an initial boiling point of at least 15 °C, for example from 15 to 30 °C,

[0095]

[0088] (ii) a kerosene fraction having an initial boiling point of at least 130 °C, for example from 130 to 150 °C and a final boiling point of at most 270 °C, for example from 230 to 270 °C,

[0096]

[0089] (iii) a diesel fraction having an initial boiling point of at least 230 °C, for example from 230 °C to 270 °C, and a final boiling point of at most 400 °C, for example from 350 to 400 °C, preferably from 350 to 375 °C, and

[0097]

[0090] a heavier fraction than the previous ones.

[0098]

[0091] One or more of the fractions (i) to (iii) are then sent to step b) of hydrotreating, for example fractions (i), (ii), (iii), (i) and (ii) or (ii) and (iii), or a single fraction having a final boiling point of not more than 400 °C, for example from 350 to 400 °C, preferably from 350 to 375 °C, and typically an initial boiling point of at least 15 °C, for example from 15 to 30 °C, is sent to step b).

[0099]

[0092] The naphtha fraction typically has one or more of the following characteristics: a sulfur content of 100 to 8000 ppm, preferably 500 to 8000 ppm, a nitrogen content of 100 to 12000 ppm, preferably 500 to 12000 ppm, a metal content of 0 to 100 ppm, a sediment content of 1 to 500 ppm.

[0100]

[0093] The kerosene fraction typically has one or more of the following characteristics: a sulfur content of 200 to 12000 ppm, generally 500 to 12000 ppm, a nitrogen content of 200 to 15000 ppm, generally 500 to 15000 ppm, a sediment content of 1 to 1000 ppm, a metal content of 1 to 200 ppm.

[0101]

[0094] The diesel fraction typically has one or more of the following characteristics: a sulfur content of 500 to 15000 ppm, generally 1000 to 15000 ppm, a nitrogen content of 500 to 20000 ppm, generally 1000 to 20000 ppm, a sediment content of 1 to 2000 ppm, a metal content of 2 to 500 ppm.

[0102]

[0095] Optional pretreatment step

[0103]

[0096] Before hydrotreating, the tire oil fraction may undergo pretreatment to remove at least some of the impurities present in the tire oil, including sulfur, nitrogen, oxygen, metals, and possibly solids content.

[0097] When present, this pretreatment step is preferably carried out on the tire oil fraction mixed with the naturally occurring hydrocarbon feedstock to further remove at least some of the impurities (phospholipids, phosphate salts, gums, metals, sulfur, ash, water, pigments, and other undesirable materials) present in the naturally occurring hydrocarbon feedstock.

[0104]

[0098] The mass ratio of tire oil fraction / naturally occurring hydrocarbon filler can be from 0.1 to 50% by mass, preferably from 5 to 40% by mass, more preferably from 5 to 30% by mass, even more preferably from 5 to 25% by mass or from 1 to 25% by mass.

[0105]

[0099] This pretreatment step may include, in particular, only one or more of the following treatments: (i) a degumming treatment, optionally carried out under cavitation conditions, and (ii) a bleaching treatment, each treatment being followed by a separation of the organic and aqueous phases, the final recovered organic phase forming a partially refined effluent with a reduced content of heteroatoms, in particular nitrogen, sulfur and / or oxygen, and / or a reduced solids content. This separation may be carried out using any conventional separation technique. In particular, the pretreatment of tire oil, alone or in a mixture with a naturally occurring hydrocarbon feedstock, by one of the aforementioned pretreatments, and especially by bleaching, makes it possible to significantly reduce the nitrogen and / or oxygen and solids content of the pretreated feedstock.Reducing the solids and / or nitrogen content helps to protect the catalyst used in a subsequent hydrotreating step from the presence of solids leading to deactivation, while reducing the oxygen content helps to reduce the consumption of dihydrogen during hydrotreating.

[0106]

[0100] Degumming is a process well known to the person skilled in the art.

[0107]

[0101] The degumming treatment is typically carried out in the presence of at least one degumming agent chosen from water, a saline solution such as EDTA, enzymes, a base such as sodium hydroxide, an acid such as phosphoric acid, citric acid or maleic acid.

[0108]

[0102] This degumming treatment can be water degumming, acid degumming, dry degumming, enzymatic degumming, EDTA degumming, deep degumming, membrane degumming, cavitation degumming.

[0109]

[0103] In one embodiment, the degumming treatment (i) may include one or more water washes with the optional addition of an acid. Preferably, the acid is added during a first step when there are several steps.

[0110]

[0104] The degumming treatment (i) may be a water degumming treatment in which the oil to be treated is typically heated to 50-70 °C or 60-70 °C, for example, at 50-60 °C, water to which a basic (e.g., NaOH) or acidic (e.g., citric or phosphoric acid) compound has been added and mixed for about 30 minutes, then the hydrated gums are separated by centrifugation and the degummed composition is dried under vacuum. This process may involve the addition of live steam to the product to be treated for a short period. The appropriate amount of water normally represents about 75% by mass of the phosphatide content of the oil to be treated. Insufficient water produces dark, viscous gums, while excessive water leads to excessive losses of the oil by hydrolysis. Water-degummed oil generally still contains phosphatides (between 50 and 200 ppm by mass).

[0111]

[0105] The degumming treatment (i) can be an acid treatment in which the oil to be treated is typically heated to 50-70 °C or 60-70 °C, for example 50-60 °C, and a water-acid mixture is added and mixed for about 30 minutes. Phosphoric acid or citric acid is typically used.

[0112]

[0106] The degumming process can be a dry degumming process, that is, in the presence of an acid without the addition of water. The filler is treated with an acid (the principle being that strong acids displace weaker acids from their salts) to decompose the metal ion / phosphatide complexes and form a mixture, which is then mixed with bleaching earth (bleaching agent). The bleaching earth containing the degumming acid, phosphatides, pigments, and other impurities is removed by filtration. Filler materials degummed with water or acid can also be dry degummed to ensure a low phosphorus content.

[0113]

[0107] The degumming treatment (i) may be an enzymatic degumming treatment in which an enzyme, for example phospholipase A1, the most recent degumming enzyme, transforms phospholipids into lysophospholipids and free fatty acids. This process involves three important steps:

[0114]

[0108] (1) adjusting the pH of the aqueous solution with a buffer;

[0115]

[0109] (2) enzymatic reaction in retention basins; and

[0116]

[0110] (3) the separation of the mud and the oil.

[0117]

[0111] The oil to be degumed enzymatically in this way can be crude or previously degumed with water.

[0118]

[0112] The degumming treatment can be an EDTA degumming treatment. A chelating agent (such as EDTA) is used to chelate the Ca, Mg, and Fe ions. EDTA has a much stronger affinity for Ca and Mg ions than phosphatidic acid, and non-hydratable phosphatides are decomposed by the action of EDTA.

[0119]

[0113] The degumming treatment may be a deep degumming which uses a reagent such as an acid to chelate non-hydratable phosphatide complexes of Fe, Ca and Mg.

[0120]

[0114] The degumming treatment can be membrane degumming. Membrane technology, including nanofiltration and ultrafiltration, can also be used to remove phospholipids from vegetable oils.

[0121]

[0115] The Lipid Handbook (edited by Frank D. Gunstone, John L. Harwood, Albert J. Dijkstra, 3rd ed.) describes many variations and details of degumming treatments.

[0122]

[0116] The degumming treatment can be carried out under cavitation conditions, in particular hydrodynamic cavitation. Typically, cavitation conditions are applied to the mixture obtained following contact between the oil to be treated, in particular the tire oil / natural hydrocarbon filler mixture, and an aqueous solution.

[0123]

[0117] Cavitation is a phenomenon of nucleation, growth and implosion (collapse) of cavities filled with vapor or gas, which can be obtained by the passage of ultrasound (acoustic cavitation), by a laser, by the injection of vapor into a cold fluid or by modifications of the flow and pressure (hydrodynamic cavitation), via appropriate cavitation devices.

[0124]

[0118] A cavitation device can, for example, be used to improve extraction yields and / or operate under less severe conditions (lower temperature). In this case, hydrodynamic cavitation treatment of the oil to be treated can be carried out, possibly in the presence of a degumming agent, under conditions effective in generating cavitation characteristics and transferring at least some of the impurities contained in the oil into the degumming agent.

[0125]

[0119] Hydrodynamic cavitation can be generated by passing the mixture to be treated through one or more cavitation devices.

[0126]

[0120] Suitable cavitation devices that can be used are disclosed for example in WO201098783A1, US8911808B2, US7762715B2, US8042989B2.

[0127]

[0121] For example, a suitable cavitation device includes a flow path through which the fluid is pumped, such as that disclosed in US8911808B2, in which a predetermined pump pressure is preferably applied in the range of 340 kPa-34 MPa.

[0128]

[0122] In hydrodynamic cavitation treatment, phosphatides are hydrated into gums, which are insoluble in oil and can be easily separated as sludge forming an aqueous phase, for example by decantation, filtration or centrifugal action.

[0129]

[0123] In one embodiment, cavitation treatment, in particular hydrodynamic cavitation, can be carried out in the presence of a degumming agent. This agent can be chosen from water, steam, acids, complexing agents, and mixtures thereof.

[0130]

[0124] Acids are for example strong acids, in particular inorganic acids, such as phosphoric acid, sulfuric acid.

[0131]

[0125] Complexing agents are for example weak organic acids (or their corresponding anhydrides) such as acetic acid, citric acid, oxalic acid, tartaric acid, malic acid, maleic acid, fumaric acid, aspartic amino acid, ethylenediaminetetraacetic acid (EDTA).

[0132]

[0126] Preferably, the degumming agent comprises water, steam, phosphoric acid, acetic acid, citric acid, oxalic acid, tartaric acid, malic acid, fumaric acid, aspartic amino acid, ethylenediaminetetraacetic acid, a base, salts, chelating agents, crown ethers or maleic anhydride.

[0133]

[0127] Cavitation treatment can be carried out at temperatures close to or below ambient temperature, for example at 15-25°C. However, hydrodynamic cavitation can be carried out between 10 and 90°C, preferably between 25 and 75°C and more preferably between 30 and 60°C.

[0128] This can be carried out, for example, as described in document WO2019229035A1.

[0134]

[0129] The product from the degumming step recovered after separation from the aqueous solution is an organic phase which constitutes a purified effluent with a reduced content of heteroatoms which can then be subjected to the hydrotreatment step, in particular directly, without an intermediate step.

[0135]

[0130] Bleaching is a process well known to those skilled in the art.

[0136]

[0131] Bleaching is a treatment consisting of bringing the product to be treated into contact with a bleaching agent, such as absorbent clays, synthetic amorphous silica, and activated carbons. The bleaching agent acts, in particular, as an absorbent. After separation, the resulting effluent has a reduced heteroatom content compared to the effluent before bleaching.

[0137]

[0132] Acid-activated fuller's earth (bentonite clay) is an effective bleaching agent with a high absorption capacity. It can be treated with an inorganic acid (sulfuric acid, hydrochloric acid or phosphoric acid) or organic acids such as oxalic acid, citric acid or acetic acid.

[0138]

[0133] Filtration then allows the recovery of a purified effluent with a reduced content of heteroatoms and sediments which can then be subjected to the hydrotreatment step, in particular directly, without an intermediate step.

[0139]

[0134] Bleaching generally ensures the removal of soaps, residual phosphatides, trace metals, sediments, and certain oxidation products, and catalyzes the removal of carotene; the adsorbent also catalyzes the decomposition of peroxides. Another function is the removal of peroxides and secondary oxidation products.

[0140]

[0135] The key parameters of the bleaching process are the procedure, the type and dosage of the adsorbent, the temperature, the duration, the humidity and the filtration, as indicated in The Lipid Handbook (edited by Frank D. Gunstone, John L. Harwood, Albert J. Dijkstra. 3rd edition, chapter 3.7).

[0141]

[0136] Step b) of hydrotreatment

[0142]

[0137] The tire oil fraction supplied in step a) is subjected to a step b) of hydrotreatment in the presence of a naturally sourced hydrocarbon feedstock containing fatty acids and / or fatty acid esters, of the type previously described.

[0143]

[0138] This hydrotreatment is carried out in a hydrotreatment zone in the presence of dihydrogen and at least one catalyst under suitable conditions to transform into paraffins, in particular linear or substantially linear paraffins, or into hydrocarbons at least partly deoxygenated, free fatty acids and / or fatty acid esters, contained in the naturally occurring hydrocarbon feedstock, as well as fatty chain compounds, phenolic compounds and / or carboxylic acids, or other oxygenated compounds, contained in the tire oil fraction, and to form a hydrocarbon-rich effluent with a limited or even zero oxygen content such as paraffins or other deoxygenated hydrocarbons.

[0144]

[0139] Furthermore, during this step, impurities, particularly sulfur, nitrogen, and metals present in the tire oil fraction, can be at least partially removed. Olefins and / or dienes present in the tire oil can also be at least partially hydrogenated.

[0145]

[0140] The mass ratio of tire oil fraction(s) / naturally occurring hydrocarbon filler can be from 0.1 to 50% by mass, preferably from 5 to 40% by mass, more preferably from 5 to 30% by mass, even more preferably from 5 to 25% by mass or from 1 to 25% by mass.

[0146]

[0141] The catalyst can be selected from (i) oxides, phosphides or sulfides of Ni, Mo, W, Co or mixtures of NiW, NiMo, CoMo, NiCoW, NiCoMo, NiMoW and CoMoW, (ii) metals or mixtures of metal alloys of groups 8, 9, 10 and / or 11 of the periodic table, (iii) basic oxides such as alkali metal oxides, alkali-earth oxides, lanthanide oxides, zinc oxide, spinels, perovskites, calcium silicates.

[0147]

[0142] The catalyst may have a supported or unsupported catalytic active phase.

[0148]

[0143] When the catalyst includes a support for the catalytic active phase, it is preferable that the support have a high specific surface area. In one embodiment, the specific surface area should be at least 5 m². 2 / g, preferably at least 50 m 2 / g and more preferably at least 75 m 2 / g, this specific surface area can be measured by methods known in the art such as the BET method where the adsorption of nitrogen allows the specific surface area of ​​the solid material to be estimated.

[0149]

[0144] It is also preferable that the support of the catalytic active phase has a low acidity, preferably neutral or basic, in order to avoid hydroisomerization reactions which would give rise to branched paraffins and cracking at high temperature and pressure in the presence of dihydrogen.

[0150]

[0145] A freshly prepared catalyst or a regenerated catalyst may be used, namely a spent catalyst that has undergone regeneration under conventional and known regeneration conditions, for example under conditions similar to those described in patent EP2174712A2, including for example treatment in the presence of oxygen or air and at a temperature ranging from 350°C to 550°C.

[0151]

[0146] Hydrotreating can be carried out at a temperature of 100 to 550°C in the presence of dihydrogen at pressures ranging from 0.1 to 20 MPa. The ratio (H2 / HC) between dihydrogen and feedstock can be from 100 to 2000 NL / L. Typically, the hourly volumetric velocity (WH) is from 0.1 to 4 h' 1 .

[0152]

[0147] In one embodiment, the hydrotreating can be carried out at a temperature of 200 to 400 °C in the presence of dihydrogen at pressures ranging from 4 to 15 MPa, with an H2 / HC ratio of 500 to 1500 NL / L and a WH of 0.2 to 3 IT 1 .

[0153]

[0148] In another embodiment, the hydrotreating can be carried out at a temperature of 250 to 380 °C in the presence of dihydrogen at pressures ranging from 5 to 12 MPa, with an H2 / HC ratio of 600 to 1200 NL / L and a WH of 0.2 to 2 h' 1 .

[0154]

[0149] The various operating conditions described above can be implemented regardless of the tire oil content of the load subjected to hydrotreatment and the nature of the fraction used.

[0155]

[0150] Step b) of hydrotreating can be carried out in one or more reactors. Any type of reactor commonly used for this type of reaction may be used, for example a fixed-bed reactor, a stirred-tank reactor, a bubbling-bed reactor, a slurry-type reactor, etc., preferably a fixed-bed reactor.

[0156]

[0151] The hydrotreated effluent exiting the hydrotreatment zone typically comprises a liquid portion and a gaseous portion. The liquid portion essentially comprises a mixture of n-paraffins, typically containing 5 to 25 carbon atoms. The gaseous portion comprises H2, H2S, CO2, and possibly CO, NH3. The hydrotreated effluent also contains water.

[0157]

[0152] During this step b) of hydrotreating, various reactions can take place in the transformation of fatty acid esters and free fatty acids, as well as other fatty chain compounds (carboxylic acids and / or esters) and / or phenolic compounds, or other oxygenated compounds, into hydrocarbons with a limited or even zero oxygen content (paraffins or other deoxygenated hydrocarbons):

[0158]

[0153] - a hydrodeoxygenation (HDO), which removes oxygen from the treated oils and leads to the formation of linear paraffins while preserving the number of carbons of the initial fat chains and is accompanied by the formation of water and possibly propane, this reaction can be carried out on fatty acid esters, free fatty acids, carboxylic acids and fatty chain esters, or mixtures thereof; a deoxygenation of other oxygenated compounds such as phenolic compounds can also occur;

[0159]

[0154] - a decarboxylation and / or a decarbonylation (COD) X), which leads to the formation of paraffins with one less carbon atom than the initial fat chain and is accompanied by the formation of carbon oxides (CO and CO2) and possibly propane, this reaction can be carried out on glycerides, any esters or with free fatty acids, or even with carboxylic acids, for example benzoic acid.

[0160]

[0155] This hydrotreatment step b) can thus comprise one or more steps selected from hydrodeoxygenation, decarboxylation and decarbonylation, namely, this step b) can be carried out under hydrodeoxygenation and / or decarboxylation and / or decarbonylation conditions.

[0161]

[0156] Hydrodeoxygenation

[0162]

[0157] Several reactions occur under hydrodeoxygenation conditions. The easiest is the hydrogenation of the double bonds in the alkyl chain. The most difficult reaction is the removal of oxygen atoms from the C-O bonds. The carboxyl group of the fatty acid and the hydroxyl group of the glycerol fraction are hydrodeoxygenated. This results in the production of linear paraffin, from the acyl fraction, and propane, from the glycerol. Depending on the conditions (catalyst, temperature, dihydrogen, etc.), the carboxyl group can also be decomposed into CO / CO2 (decarboxylation or decarbonylation), which can in turn be hydrogenated to methane. These hydrodeoxygenation reactions consume a large amount of dihydrogen.

[0163]

[0158] The catalyst is typically a solid catalyst which can be selected from oxides, phosphides or sulfides of Ni, Mo, W, Co or mixtures such as NiW, NiMo, C0M0, NiCoW, NiCoMo, NiMoW and C0M0W as a catalytic phase, preferably supported on carbon, alumina, silica, titanium oxide or zirconia.

[0159] Hydrodeoxygenation can be carried out at a temperature of 200 to 500°C, preferably 220 to 400°C, under a pressure of 1 MPa to 20 MPa (10 to 200 bars), for example 6 MPa, and with a dihydrogen / hydrocarbon feed ratio of 100 to 2000, but preferably 350 to 1500, for example 800 NI H2 / I of hydrocarbon feed.

[0164]

[0160] For optimal performance and stable continuous operation, it is preferable that the active metallic component of the catalyst, in the case of Ni, Mo, W, Co, or mixtures thereof, be in the form of sulfides or phosphides. Therefore, in the case of sulfides, it is preferable that traces of decomposable (thermally or catalytically) sulfide compounds be present or intentionally added to the feedstock to maintain the metallic sulfide in its sulfide state. For example, these sulfur compounds may be H₂S, COS, CS₂, mercaptans (e.g., methyl sulfide), thioethers (e.g., dimethyl sulfide), disulfides (e.g., dimethyl disulfide), thiophenic and tetrahydrothiophenic compounds. Sulfur compounds may also be supplied by the tire oil fraction, in which case it is not necessary to add other sulfur compounds.

[0165]

[0161] Hydrodeoxygenation is preferably carried out in continuous fixed bed reactors, continuous stirred tank reactors or slurry type reactors, particularly in the presence of a solid catalyst.

[0166]

[0162] Decarboxylation and / or decarbonylation

[0167]

[0163] Under decarboxylation and / or decarbonylation conditions, the following reactions may occur:

[0168]

[0164] Decarboxylation:

[0169]

[0165] R-CH2-CH2-COOH to R-CH2-CH3 + CO2

[0170]

[0166] [CI8H33O]3C3H5O3 + 6 H2 à 3 CI7H 36 + 3 CO2 + C3H8

[0171]

[0167] Decarbonylation:

[0172]

[0168] R-CH2-CH2-COOH to R-CH=CH2+ CO + H2O

[0173]

[0169] Other reactions that can occur under decarboxylation and / or decarbonylation conditions are:

[0174]

[0170] - hydrogenation of unsaturated bonds:

[0175]

[0171] R-CH=CH2+ H2 à R-CH2-CH3

[0176]

[0172] - the hydrodeoxygenation of fatty acids:

[0177]

[0173] R-CH2-CH2-COOH + 3 H2 to R-CH2-CH2-CH3 + 2 H2O

[0178]

[0174] Further hydrogenation of the CO / CO2 produced may take place depending on the amount of dihydrogen available, the catalyst and the reaction conditions:

[0179]

[0175] CO + 3 H2 → CH4 + H2O

[0180]

[0176] CO2 + 4 H2 → CH4 + 2 H2O

[0181]

[0177] Decarboxylation and / or decarbonylation is preferably carried out in the presence of a solid catalyst, generally in batch tank reactors, continuous fixed bed reactors, continuously stirred tank reactors or slurry reactors.

[0182]

[0178] The catalyst, regenerated or not, may be selected from:

[0179] - oxides, phosphides or sulfides of Ni, Mo, W, Co, NiW, NiMo, CoMo, NiCoW, NiCoMo, NiMoW and CoMoW as a catalytic phase, preferably supported on carbon, alumina, silica, titanium oxide or zirconia, or

[0183]

[0180] - metals or alloy mixtures of groups 8 (Ru), 9 (Rh), 10 (Ni, Pt and Pd) and / or group 11 (Cu and Ag), preferably supported by carbon, magnesia, zinc oxide, spinels (Mg2AhO4, ZnAhOt), perovskites (BaTiOs, ZnTiCh), calcium silicates (such as xonotlite), alumina, silica or silica-aluminas or mixtures thereof, or

[0184]

[0181] - basic oxides, such as alkali metal oxides (MgO, ZnO), alkali-earth oxides, lanthanide oxides, zinc oxide, spinels (Mg2AhO4, ZnAhOt), perovskites (BaTiCh, ZnTiCh), calcium silicates (such as xonotlite), either in bulk or dispersed on neutral or basic supports, on basic zeolites (such as low silica / alumina alkali or alkaline-earth zeolites obtained by exchange or impregnation).

[0185]

[0182] For optimal performance and stable continuous operation, it is preferable that the active metallic component of a catalyst containing Ni, Mo, W, Co, or mixtures thereof, be in the form of sulfides or phosphides. It is therefore preferable that traces of decomposable (thermally or catalytically) sulfide compounds be present (for example, contained in the tire oil fraction) or intentionally added to the feedstock to maintain the metallic sulfide in its sulfide state. The same compounds mentioned above may be used.

[0186]

[0183] The decarboxylation and / or decarbonylation step can be carried out at a temperature of 100 to 550°C in the presence of dihydrogen at pressures ranging from 0.1 to 20 MPa. The ratio between dihydrogen and feedstock can be from 100 to 2000 Nl / L.

[0187]

[0184] The hydrotreated liquid fraction exiting step (b) can then be further treated, for example by hydroisomerization and / or hydrocracking (step d), or separated into usable streams as fuel (step e).

[0188]

[0185] Separation step c)

[0189]

[0186] The hydrotreated effluent from step b) is subjected, before possibly being sent to step d) or e), to a separation step c) in which non-condensable components such as propane, CO2, CO, methane, dihydrogen and vaporized water are separated from the liquid fraction.

[0190]

[0187] In one embodiment, the dihydrogen can be separated from the other non-condensable components and returned in part or in full to the inlet of step b).

[0191]

[0188] In one embodiment, the effluent from step b) can thus be separated into:

[0192]

[0189] - a gaseous stream containing H2, H2S, CO2, and possibly small amounts of CO and NH3,

[0193]

[0190] - water,

[0194]

[0191] - a liquid fraction containing a mixture of paraffins.

[0195]

[0192] The gas stream can undergo further treatment to separate the dihydrogen from the other gases for reuse in the process.

[0193] A portion of this liquid fraction, after separation, can be used as hydrocarbon recycling to the hydrotreating zone to absorb the heat of reaction and / or dilute the deteriorating effect of the remaining impurities.

[0196]

[0194] This separation, implemented in a separation zone, can be a flash separation or be carried out in a stripping section. Depending on the operating conditions, some of the remaining water can be condensed and removed in this stage by sedimentation or drainage, for example in a high-pressure separator. The flash separation and the removal of the liquid water can be carried out simultaneously or not.

[0197]

[0195] A separator vessel may also be provided to separate the water, gases, and a liquid organic phase, the latter then being sent to a stripping section to remove light hydrocarbons. The gases can be sent to a treatment section, for example, to the amines, to separate the dihydrogen from the other gaseous components.

[0198]

[0196] Step d) of hydroisomerization and / or hydrocracking

[0199]

[0197] All or part of the hydrotreated liquid fraction of step c) may be subjected to a hydroisomerization step and / or a hydrocracking step in a hydroisomerization and / or hydrocracking zone in the presence of dihydrogen and at least one catalyst to produce an isomerized effluent rich in isoparaffins and / or to produce a hydrocraced effluent rich in hydrocarbons having less carbon in the chain than the feed, forming a hydrotreated and isomerized and / or hydrocraced oil.

[0200]

[0198] In particular, during hydroisomerization and / or hydrocracking, normal paraffins are isomerized and / or hydrocracked into branched and / or shorter paraffins.

[0201]

[0199] Hydroisomerization and / or hydrocracking of the paraffinic product can be accomplished in any manner known in the art or by using any suitable catalyst known in the art.

[0202]

[0200] The catalysts and the conditions for hydroisomerization and / or hydrocracking are well known in the art.

[0203]

[0201] Suitable hydroisomerization and / or hydrocracking catalysts used in hydroisomerization and / or hydrocracking processes are all of the bifunctional type, combining an acid function with a (de)hydrogenating function. The production of the bifunctional hydroisomerization and / or hydrocracking catalyst can be carried out by any method known in the art. The (de)hydrogenating function can be added to the acid support by impregnation with metal-containing solutions, by ion exchange, and by mixing.

[0204]

[0202] The acid function is typically provided by a support (amorphous or crystalline) whose specific surfaces are generally between 100 and 700 m 2 / g and which exhibits surface acidity, such as halogenated aluminas (especially sulfated, phosphated, chlorinated or fluorinated), aluminas, (possibly containing boron), amorphous silica-aluminas, amorphous silica-aluminas-titaniums, sulfated zirconias, tungsten zirconias and zeolites or mixtures thereof.Suitable support materials include amorphous alumina, amorphous silica-alumina, amorphous silica borate, amorphous silica-alumina-titanium, zeolites or modified zeolites having the following structures: ferrierite, beta zeolite, Y zeolite, mordenite zeolite and molecular sieves of the type SAPO-11, SAPO-31, SAPO-37, SAPO-41, SM-3, MgAPSO-31, FU-9, NU-10, NU-23, ZSM-12, ZSM-22, ZSM-23, ZSM-35, ZSM-38, ZSM-48, ZSM-50, ZSM-57, theta-1, EU-1, EU-13, ISI-1, KZ-2, ISI-4 and KZ-1, MeAPO-11, MeAPO-31, MeAPO-41, MeAPSO-11, MeAPSO-31, MeAPSO-41, MeAPSO-46, ELAPO-11, ELAPO-31, ELAPO-41, ELAPSO-11, ELAPSO-31, ELAPSO-41, each of which can be used alone or in combination.

[0205]

[0203] Acidity can be measured by methods well known to those skilled in the art. It can, for example, be measured by temperature-programmed desorption (TPD) with ammonia, by infrared measurement of absorbed molecules (pyridine, CO . . .), by a catalytic cracking test or by hydroconversion using a model molecule.

[0206]

[0204] Hydroisomerization catalysts have a weak acid function, preferably halogenated aluminas (in particular sulfated, phosphated, chlorinated or fluorinated), aluminas (possibly containing boron), amorphous silica-aluminas, amorphous silica-aluminas-titaniums.

[0207]

[0205] Hydrocracking catalysts possess a strong acid function, preferably sulfated zirconias, tungsten zirconias and zeolites or mixtures thereof.

[0208]

[0206] The (de)hydrogenation function is typically ensured either by one or more metals from group 6 of the periodic table of elements, or by a combination of at least one metal from group 6 of the periodic table and at least one metal from groups 8, 9, 10.

[0209]

[0207] The distance between the two functions, acid and (de)hydrogenating, is one of the key parameters governing the activity and selectivity of the catalyst.

[0210]

[0208] A weak acid function and a strong (de)hydrogenating function result in catalysts with low activity, generally requiring a high temperature (greater than or equal to 390-400°C), and long residence times or low spatial velocity per hour (the VSLH expressed as the liquid volume of feed per unit volume of catalyst per hour is generally less than or equal to 2), but exhibiting very good selectivity for middle distillates (jet fuel and diesel). Generally, the term "middle distillates" as used in the present invention applies to one or more fractions whose initial boiling point is at least 150°C and whose final boiling point is generally less than about 350°C, preferably less than 370°C.

[0211]

[0209] Conversely, a strong acid function and a weak (de)hydrogenating function give catalysts which are active, but which have a lower selectivity for middle distillates and the result is more cracked hydrocarbons in the range of naphthas and jet fuels.

[0212]

[0210] A type of conventional hydroisomerization catalyst is based on moderately acidic amorphous supports, such as silica-alumina. These systems are used to maximize the yield of middle distillates with good cold-flow properties.

[0211] A type of conventional hydrocracking catalyst is based on highly acidic crystalline supports, such as zeolites and sulfated zirconia. These systems are used to reduce the number of carbons in the chain while maintaining good cold-flow properties. Hydrocracking produces non-condensable gases, naphtha, kerosene, and diesel fuel.

[0213]

[0212] The hydroisomerization and / or hydrocracking step can be carried out using one or more types of catalysts in one or more catalytic beds in the same reactor or in one or more different reactors. The feed for hydroisomerization and / or hydrocracking can be fed onto the catalyst simultaneously with the hydrogen-containing gases in a downward flow mode, in an upward flow mode, or the liquid feed can flow downward while the hydrogen-containing gases flow upward through the catalyst beds.

[0214]

[0213] A freshly prepared catalyst or a regenerated catalyst may be used, namely a spent catalyst that has undergone regeneration under conventional and known regeneration conditions, for example under conditions similar to those described in patent EP2174712A2, including for example treatment in the presence of oxygen or air and at a temperature ranging from 350°C to 550°C.

[0215]

[0214] Typical hydroisomerization and / or hydrocracking conditions include a temperature of 150°C to 500°C or more, preferably 220°C to 450°C and more preferably 250°C to 420°C, and a pressure of 1 MPa to 20 MPa or more, preferably 1.5 MPa to 18 MPa and more preferably 2 MPa to 17 MPa. The hourly space velocity can be about 0.1 to 20 h' 1 , preferably from 0.2 to 10 am -1 and preferably from 0.3 to 5 hours 1. The supplied dihydrogen-containing gases can be introduced simultaneously with the feed charge at a ratio of 75 to 2500 NI (hL) / ! of charge, more preferably 150 to 1500 NI or more preferably 250 to 1000 NI.

[0216]

[0215] During a hydroisomerization reaction, secondary hydrocracking reactions may occur. Similarly, during a hydrocracking reaction, hydroisomerization may occur. A person skilled in the art will be able to select appropriate conditions for treating the effluent under hydroisomerization conditions, or under hydrocracking conditions respectively—that is, conditions under which hydroisomerization reactions and hydrocracking reactions, respectively, predominantly occur, depending on the desired objective.

[0217]

[0216] Separation step e)

[0218]

[0217] In one embodiment of the invention, the process for manufacturing hydrocarbon fluids may further include a separation step e) in which the hydrotreated liquid fraction from step c) or the effluent from step d), preferably the effluent from step d), is separated into at least one fraction selected from a naphtha fraction, a kerosene fraction and a diesel fraction.

[0219]

[0218] The hydrotreated liquid fraction of step c) or the effluent of step d), preferably the effluent of step d), particularly under hydrocracking conditions, may undergo fractionation, for example by adding a separation column, for example a distillation column (atmospheric or under reduced pressure), or by lateral withdrawal.

[0220]

[0219] This fractionation allows the recovery of at least one selected fraction from a naphtha fraction, a kerosene fraction and a diesel fraction. This fractionation step can also allow the separation of condensable (propane, butane) and non-condensable (H2, methane, ethane) gaseous fractions, including unreacted dihydrogen, which can optionally be sent to the inlet of step b) or d).

[0221]

[0220] The recovered naphtha fraction preferably has an initial boiling point of 30 °C and a final boiling point of 120 °C to 160 °C. This fraction can be used as fuel for internal combustion engines, particularly without the addition of other components such as esters. This fraction can also be used as feedstock for a steam cracker, particularly for the production of olefins such as ethylene and propylene.

[0222]

[0221] The recovered diesel fraction preferably has an initial boiling point of 230 to 260 °C and a final boiling point less than or equal to a temperature ranging from 360 to 380 °C. This fraction can be used as fuel for diesel engines.

[0223]

[0222] The recovered kerosene fraction preferably has a final boiling point below 300 °C, measured in particular according to ASTM D86-12. The initial boiling point according to ASTM D86-12 can be from 120 to 160 °C. The kerosene fraction can be used as jet fuel, in particular without the addition of aromatic components. The necessary aromatic components, for example for seals, are in fact supplied by the tire oil fraction.

[0224]

[0223] In particular, the cutting points of the recovered fractions can be adapted in order to obtain products meeting particular specifications.

[0225] Detailed description of the figures

[0226]

[0224] Other features and advantages of the invention will become apparent from the following description of a particular embodiment of the invention, given by way of example but not limitation, with reference to the accompanying drawings in which:

[0227]

[0225] Figure 1 schematically represents one possible embodiment of the invention. In this possible embodiment, tire oil (1) is first fractionated in a fractionation section (SF) capable of performing fractionation (Frac) to separate a tire oil fraction (2) having a final boiling point of at most 400 °C or at least a naphtha, kerosene, and / or diesel fraction (not shown), and a heavier fraction (3). This tire oil fraction (2) is optionally pretreated in a pretreatment section (A) to undergo pretreatment (PTT) by (i) degumming and / or (ii) bleaching. This pretreatment is preferably carried out in a mixture with a naturally occurring hydrocarbon feedstock (4). The pretreated oil (5) is then sent to a hydrotreatment section (B) for hydrotreatment in accordance with step (b) of the invention.If a naturally occurring hydrocarbon feedstock has not already been mixed with the tire oil fraction, such a feedstock (4') is introduced into this hydrotreating section. The effluent (6) exiting this treatment section (B) can then be sent to a separation section (C) to separate the hydrotreated liquid fraction (7) from the non-condensables (8). The hydrotreated liquid fraction (7) can then be sent to a section (D) to carry out the hydroisomerization / hydrocracking step (d). The hydrocracracked and / or isomerized effluent (9) is then sent to a fractionation section (E) to carry out step (e) to be separated, for example, into a naphtha fraction (10), a kerosene fraction (11), and a diesel fraction (12), which can be sent to fuel pools.

[0228]

[0226] Depending on the objective sought, the hydrotreated liquid fraction (7) can be sent directly to the fractionation section (E).

[0229]

[0227] The invention is illustrated by the following examples, which are given by way of non-limiting example.

[0228] Examples

[0230]

[0229] Example 1: Hydrotreating a fraction of tire pyrolysis oil

[0231]

[0230] A fraction of tire pyrolysis oil (denoted TPO) was hydrotreated in a mixture with rapeseed oil. The TPO has boiling points ranging from 25 °C to 277 °C.

[0231] The properties of the rapeseed oil and the TPO are summarized in Tables 1 and 2, respectively.

[0232]

[0232] [Table 1]

[0233]

[0233] [Table 2]

[0234]

[0234] 225 ml of regenerated conventional NiMo-type catalyst mixed with carborundum (0.21 mm) in equal proportions (1:1 by volume) was introduced into a reactor. The catalyst used was regenerated under normal conditions.

[0235]

[0235] Sulfur was added by DMDS injection to maintain the NiMo catalyst activated. A starting temperature of 280 °C was chosen. The presence of oxygen, found in esters and carboxylic acid compounds, was monitored by FTIR analysis. The reaction temperature was increased during the reaction to 290 °C to eliminate any oxygen (i.e., to be below the limit of quantification of 13 ppm of oxygen, i.e., 100 ppm of esters). By increasing the temperature from 280 °C to 290 °C, the oxygen content decreased from approximately 1200 ppm to less than 100 ppm. This temperature of 290 °C was maintained constant until the end of the study.

[0236]

[0236] The operating conditions are summarized in Table 3.

[0237]

[0237] [Table 3]

[0238]

[0238] 10 and 20% by mass of TPO, respectively, were hydrotreated with rapeseed oil. The chemical properties of the effluents obtained by H DT at different mixing ratios of the light fraction of TPO are summarized in Table 4.

[0239]

[0239] In feeds, when the TPO fraction is mixed with a lipid feed, higher nitrogen and sulfur levels are observed. Conversely, a decrease in oxygen content is analyzed.

[0240]

[0240] After hydrotreatment, only traces of sulfur are observable when 20 wt% of TPO is injected. For the other effluents, sulfur, oxygen, or nitrogen are no longer present (see Table 4). The oxygen content was determined by measuring the ester and acid bands using FTIR and thus corresponds to an acid and ester content, not a total oxygen content.

[0241]

[0241] [Table 4]

[0242] PI: Initial boiling point

[0243] PF: final boiling point

[0244]

[0242] While lipid raw materials produce only normal paraffins, the addition of TPO brings aromatics and naphthenes, as shown in Table 4. By calculation, extrapolating to 100% by weight of the tested TPO gives about 30% by mass of aromatics in the final product.

[0245]

[0243] During the tests, the mass balance and yield were calculated. As shown in Table 5, higher losses were observed during TPO injection, although they remained within an acceptable range.

[0244] [Table 5] Tl

[0246]

[0245] Cracking gases are not linear and monotonic and may contribute to the aforementioned losses. However, the proportion of gas produced increases with the TPO injection rate. This may be due to the lightness of the pyrolysis oil tested.

[0247]

[0246] Water production decreases with the TPO injection rate, which is consistent with the oxygen content of the raw material.

[0248]

[0247] In conclusion, the injection of the light fraction of TPO into the H₂DO co-treatment with a vegetable oil was carried out on a pilot scale. In this way, partially biogenic aromatics can be introduced into a fully paraffinic stream. Since TPO is contaminated with sulfur, oxygen, and nitrogen, the effluents were carefully analyzed.

[0249]

[0248] Under the tested operating conditions, nitrogen from TPO was reduced below the limit of quantification (< 3 ppm). Sulfur was also largely eliminated, except when a high TPO concentration was introduced. Indeed, a few ppm were still present with the injection of 20% by mass of TPO.

[0250]

[0249] A decrease in paraffins and an increase in aromatic and naphthenic molecules were observed with the incorporation of a light cut of tire pyrolysis oil.

[0251]

[0250] Example 2 Hydroisomerization of a hydrotreated effluent

[0252]

[0251] A test simulating the hydroisomerization of the effluents of example 1 was carried out.

[0253]

[0252] The hydroisomerization conditions are as follows:

[0254]

[0253] - NiW catalyst on zeolite

[0255]

[0254] - WH: 1h-1

[0256]

[0255] - P: 35 Bar

[0257]

[0256] - H2 / HC=500 NL / L

[0258]

[0257] The simulation was carried out assuming that aromatics and naphthenes pass through the reactor without reacting. Table 6 shows the simulated cloud point values ​​for the different effluents obtained after hydroisomerization for two hydroisomerization reactor temperatures (330 °C and 350 °C).

[0259]

[0258] [Table 6]

[0260]

[0259] The addition of TPO thus makes it possible to lower the cloud point of the final product. This allows the production of higher value-added products, such as kerosene fraction or winter diesel, these products requiring a low cloud point.

[0261]

[0260] In other words, at a constant cloud point, it is possible to carry out the hydroisomerization reaction at a lower temperature, and thus reduce energy consumption, and to use the catalyst on longer cycles, ...).

[0262]

[0261] Example 3: Pretreatment of a tire pyrolysis oil

[0262] The same fraction of tire pyrolysis oil as that used in Example 1 was pretreated to reduce the amount of impurities present. The pretreatment used is bleaching with activated earth, with one or two passes through the activated earth.

[0263]

[0263] Table 7 shows the nitrogen, sulfur and nitrogen contents before and after bleaching.

[0264]

[0264] Table 7

Claims

DEMANDS 1. A process for manufacturing hydrocarbon fluids comprising: a) a step of supplying a tire oil fraction having a final boiling point of no more than 400 °C, b) a hydrotreating step, in which said tire oil fraction and a naturally occurring hydrocarbon feedstock containing fatty acids and / or fatty acid esters are contacted in a hydrotreating zone with dihydrogen and at least one catalyst under conditions suitable for carrying out hydrotreating and forming a hydrotreated effluent comprising a hydrotreated liquid fraction and a fraction of non-condensable components, c) a step of separating the hydrotreated effluent from step b) in which the fraction of non-condensable components is separated from the hydrotreated liquid fraction.

2. A manufacturing process according to claim 1, wherein said tire oil fraction comprises one or more of the following characteristics: the tire oil fraction comprises one or more of the following fractions: (i) a naphtha fraction having a final boiling point of at most 150 °C, (ii) a kerosene fraction having an initial boiling point of at least 130 °C and a final boiling point of at most 270 °C, (iii) a diesel fraction having an initial boiling point of at least 230 °C and a final boiling point of at most 400 °C, a sulfur content of 100 ppm to 20000 ppm, a nitrogen content of 100 ppm to 20000 ppm, a sediment content of 1 ppm to 2000 ppm, a bio-based carbon content of 30 to 100% by mass, an aromatics content of 15 to 80% by mass.

3. A manufacturing process according to claim 1 or 2, wherein the supply step a) comprises: a step of obtaining tire oil by a process selected from pyrolysis, vapor thermolysis, solvolysis and hydrothermal liquefaction, a step of fractionating the tire oil obtained in the preceding step into a fraction having a final boiling point of not more than 400 °C and a heavier fraction, optionally into at least one fraction selected from (i) a naphtha fraction having a final boiling point of not more than 150 °C, (ii) a kerosene fraction having an initial boiling point of not more than 130 °C and a final boiling point of not more than 270 °C, (iii) a diesel fraction having an initial boiling point of not more than 230 °C and a final boiling point of not more than 400 °C, and into a heavier fraction.

4. A manufacturing process according to any one of claims 1 to 3, wherein said naturally sourced hydrocarbon filler containing fatty acids and / or fatty acid esters comprises a naturally sourced oil, an esterified naturally sourced oil, or mixtures thereof.

5. A manufacturing process according to any one of claims 1 to 4, further comprising: prior to step b) of hydrotreatment, a pretreatment step of said tire oil, optionally mixed with said hydrocarbon feedstock, comprising at less a treatment chosen from (i) a degumming treatment, optionally carried out under cavitation conditions, and (ii) a bleaching treatment.

6. A manufacturing process according to any one of claims 1 to 5, wherein step b) of hydrotreating is carried out under one or more of the following conditions: a tire oil fraction / natural hydrocarbon feedstock ratio of 0.1 to 50% by mass, preferably 5 to 40% by mass, more preferably 5 to 30% by mass, even more preferably 5 to 25% by mass or 1 to 25% by mass, a temperature of 100 to 550 °C, preferably 200 to 400 °C, more preferably 250 to 380 °C, in the presence of dihydrogen at pressures ranging from 0.1 to 20 MPa, preferably 4 to 15 MPa, more preferably 5 to 12 MPa, an hourly volumetric rate of 0.1 to 4 h' 1 preferably from 0.2 to 3 hours -1 , preferably more from 0.2 to 2 h -1, an H2 / HC ratio between dihydrogen and feed charge of 100 to 2000 NL / L, preferably 500 to 1500 NL / L, more preferably 600 to 1200 NL / L, in the presence of at least one catalyst selected from (i) oxides, phosphides or sulfides of Ni, Mo, W, Co or mixtures of NiW, NiMo, CoMo, NiCoW, NiCoMo, NiMoW and CoMoW, (ii) metals or mixtures of metal alloys of groups 8, 9, 10 and / or 11 of the periodic table, (iii) basic oxides such as alkali metal oxides, alkali-earth oxides, lanthanide oxides, zinc oxide, spinels, perovskites, calcium silicates.

7. A manufacturing process according to any one of claims 1 to 6, further comprising: d) a step of hydroisomerization and / or hydrocracking of the hydrotreated liquid fraction.

8. Manufacturing process according to claim 7, wherein the step d) of hydroisomerization and / or hydrocracking is carried out under at least one of the following conditions: a temperature of 150°C to 500°C, a pressure of 1 MPa to 20 MPa.

9. A manufacturing process according to any one of claims 1 to 8, further comprising: e) a separation step in which the hydrotreated liquid fraction from step c) or the effluent from step d), preferably the effluent from step d), is separated into at least one fraction selected from a naphtha fraction, a kerosene fraction and a diesel fraction.

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