COPROCESSING PROCESS OF TIRE OIL AND FOSSIL-DERIVED HYDROCARBONS

Abstract

The invention relates to a process for manufacturing hydrocarbon fluids comprising: a) a step of supplying tire oil or at least a fraction of tire oil, b) a hydrotreating step, in which said tire oil or at least a fraction of tire oil and a fossil hydrocracking feedstock are contacted in a hydrotreating zone with dihydrogen and at least one catalyst under conditions suitable for hydrotreating and forming a hydrotreated effluent, c) a step of hydroisomerizing and / or hydrocracking the hydrotreated effluent from step b) to form a liquid hydrocracking effluent. The liquid hydrocracking effluent can then be further treated, for example by hydroisomerization and / or hydrocracking, or separated into streams usable as fuel. Abstract figure: Figure 1

Description

Title of the invention: COPROCESSING METHOD OF TIRE OIL AND FOSSIL-DERIVED HYDROCARBONS technical field

[0001] The present invention relates to a coprocessing method for tire oil and fossil-based hydrocarbons. Context of the invention

[0002] There is an important need, also encouraged by regulations, to limit plastic and tire waste in landfills and to recycle it.

[0003] Tires have the advantage of possessing a non-negligible biogenic fraction (rubber from the Hevea tree), which allows them to be recycled into hydrocarbon products that are partly bio-based.

[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 silicon and metals, which are contaminants for the catalysts in the hydrotreating processes typically used in subsequent recycling processes. The presence of dienes in these oils also makes them unstable, with a high risk of gum formation during high-temperature treatments, and consequently, of clogging the installation and / or fouling of the catalysts used.

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

[0006] There are co-treatment processes for pyrolysis oil of plastics with a fossil feedstock.

[0007] Thus, an article entitled "Continuons upgrading of a plastics pyrolysis liquid to an environmentally favorable gasoline range product", H. S. Joo et al., Fuel Processing Technology, January 1, 1998 (1998-01-01), pages 25-40, describes the upgrading of a residual liquid from the pyrolysis of plastics into a gasoline range product using a three-step sequential process consisting of hydrotreating, hydrocracking, and distillation. This publication describes the hydrocracking of a residual liquid from a plastics pyrolysis process. The liquid products from the pyrolysis process are distilled to produce a distillate fraction (48% by weight) and a residual liquid fraction. (52% by weight). This residual liquid fraction, which contains 29% by weight of naphtha hydrocarbons and 71% by weight of hydrocarbons with a boiling point above 205°C, feeds the hydrocracking process. The product contained 46% by weight of matter in the gasoline boiling range.

[0008] This publication does not describe any treatment of the residual fraction of the pyrolysis liquid mixed with a fossil-based feedstock. Furthermore, the residual fraction originates from the pyrolysis of a mixture of plastics.

[0009] WO2015 / 128033A1 describes a coprocessing method for pyrolysis oil of plastic waste with a hydrocracking feedstock, in which the pyrolysis oil is separated into a low-aromatic fraction and a high-aromatic fraction, and the low-aromatic fraction is sent to hydrocracking without prior hydrogenation treatment. This document does not address the issue of the presence of hydrocracking poisons in the treated pyrolysis oils.

[0010] However, plastics are very different from tires: their liquefaction and the oils resulting from their liquefaction are very different. For example, during a pyrolysis process, plastic waste melts while approximately 30% of the tire material (carbon black) does not react. Tire rubber also does not contain the same type of inorganic compounds (metals and halogens), so the products resulting from tire liquefaction do not have the same type of contaminants as the products resulting from plastic waste liquefaction, which implies different subsequent processing. Finally, the products resulting from tire liquefaction are mainly aromatic (mono) and partially saturated and branched rings, whereas plastics tend to form linear, more olefinic molecules.

[0011] There is therefore a need to propose an efficient tire oil recycling process that makes it possible to limit, or even eliminate, the poisoning of the catalysts used. Description of the invention

[0012] The invention proposes a method for manufacturing hydrocarbon fluids comprising: a) a step of supplying tire oil or at least a fraction of tire oil containing nitrogen, sulfur and metals, b) a hydrotreating step, in which said tyre oil or at least a fraction of tyre oil and a fossil hydrocracking feedstock 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 having a reduced content of nitrogen, sulfur and metals, c) a hydrocracking step of the hydrotreated effluent from step b) to form a liquid hydrocracking effluent.

[0013] The process according to the invention thus makes it possible to produce hydrocarbon fluids (the liquid hydrocracked effluent) using, in part, recycled feedstocks. Hydrotreating reduces the nitrogen, sulfur, and metal content initially present in the tire oil or at least a fraction of tire oil, as well as in the fossil feedstock, thereby protecting the catalyst in the subsequent hydrocracking step. Furthermore, diluting the tire oil or at least a fraction of tire oil with the hydrocracking fossil feedstock limits the overall quantity of dienes present in the treated mixture and thus reduces the risk of gum formation during hydrotreating.

[0014] In a particularly advantageous embodiment, during step b) of hydrotreating, the feeds to be treated are successively brought into contact with at least one first demetallization catalyst and then with at least one deazotation catalyst.

[0015] Step a) can provide one or more of the following fractions:

[0016] (i) a naphtha-type fraction having a final boiling point of at most 150 °C,

[0017] (ii) a kerosene-type fraction having an initial boiling point of at least 130 °C and a final boiling point of at most 270 °C,

[0018] (iii) a diesel-type fraction having an initial boiling point of at least 230 °C and a final boiling point of at most 400 °C,

[0019] (iv) a vacuum diesel-type fraction having an initial boiling point of at least 350 °C and a final boiling point of at most 550 °C,

[0020] (v) a residue-type fraction having an initial boiling point of at least 490 °C.

[0021] In one embodiment, step a) provides a tire oil in its entirety (not having undergone fractionation), or at least a fraction that boils above 230 °C, for example one or more of fractions (iii), (iv) and / or (v).

[0022] In a preferred embodiment, step a) provides, in particular only, a diesel-type fraction (iii) and / or a vacuum diesel-type fraction (iv).

[0023] Said tire oil or at least a fraction of tire oil may comprise one or more of the following characteristics: - a sulfur content of 100 ppm to 30,000 ppm, generally 200 to 25,000 ppm, most often 500 to 20,000 ppm or even 3,000 to 20,000 ppm, - a nitrogen content of 100 ppm to 30,000 ppm, generally 200 to 25,000 ppm, most often 500 to 20,000 ppm or even 3,000 to 20,000 ppm, - a bio-based carbon content of 30 to 100% by mass, - an aromatics content of 15 to 80% by mass.

[0024] Step a) of supply may include, but is not limited to: - a step of obtaining tire oil by a process chosen from pyrolysis, vapor-thermolysis, solvolysis and hydrothermal liquefaction, - an optional step of fractionating the tire oil obtained in the previous step into at least one fraction chosen from: (i) a naphtha-type fraction having a final boiling point of not more than 150 °C, (ii) a kerosene-type fraction having an initial boiling point of at least 130 °C and a final boiling point of not more than 270 °C, (iii) a diesel-type fraction having an initial boiling point of at least 230 °C and a final boiling point of at most 400 °C, (iv) a vacuum diesel-type fraction having an initial boiling point of at least 350 °C and a final boiling point of at most 550 °C, (v) a residue type fraction having an initial boiling point of at least 490 °C.

[0025] Said hydrocracking fossil feed can be selected from a distillate cut, for example an atmospheric distillation distillate, a vacuum distillation distillate and / or a coking distillate; and a residue, for example a hydrocracking residue and / or an atmospheric distillation residue, alone or in mixture.

[0026] Step b) of hydrotreating can be implemented with a ratio of tire oil or at least a fraction of tire oil / hydrocracking fossil feed of 0.1 to 50% by mass.

[0027] Step b) of hydrotreatment can be carried out:

[0028] - in a single step at a temperature of 200 to 500 °C, preferably from 200 to 450 °C, preferably from 200 to 425 °C, in the presence of hydrogen at an absolute pressure of 20 to 200 bar, preferably from 30 to 180 bar, and in the presence of at least one hydrotreating catalyst, or

[0029] - in a first step (b-1) 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 200 bar, preferably 20 to 180 bar, and in the presence of at least one first hydrotreating catalyst, preferably at least one first demetallization catalyst, and in a second step (b-2) in which the effluent from step (b-1) is hydrotreated at a temperature of 200 to 500 °C, preferably 250 to 450 °C, in the presence of hydrogen at an absolute pressure of 20 to 200 bar, preferably 30 to 180 bar, and in the presence of at least one second hydrotreating catalyst, preferably at least one second deazotation catalyst.

[0030] Step c) of 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 25 MPa, - an hourly volumetric velocity of 0.1 at 20h*.

[0031] The process according to the invention may further include a separation step d) in which the hydrocracked liquid effluent from step c) is separated into at least one fraction selected from a naphtha fraction, a kerosene fraction and a diesel fraction.

[0032] The effluent exiting step b) or c) can further be washed with water to remove non-hydrocarbon compounds such as hydrosulfide, hydrogen chloride, ammonia, carbon dioxide, carbon monoxide, and ammonium chloride salts before being sent to the next step. The washed hydrocracked effluent can then optionally be sent to the separation step d).

[0033] The hydrotreating and hydrocracking steps can be carried out successively in separate reactors or in the same reactor.

[0034] 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. Detailed description of the invention

[0035] 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.

[0036] 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.

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

[0038] 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.

[0039] The term "hydrocarbon" refers to both alkanes (saturated hydrocarbons), cycloalkanes, aromatics and unsaturated hydrocarbons.

[0040] By "heteroatom" is meant any element of an organic compound other than carbon and hydrogen.

[0041] 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] The aromatic content can be measured by gas chromatography, for example by a GCxGC or GC method, by liquid chromatography, or by proton NMR and / or carbon NMR.

[0043] 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.

[0044] 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.

[0045] Hydrocracking fossil charge

[0046] The fossil feedstock for hydrocracking is a hydrocarbon feedstock of fossil origin.

[0047] It typically consists of at least one distillate cut and / or at least one residue. The distillate cut may be an atmospheric distillation distillate of crude oil, a vacuum distillation distillate of an atmospheric distillation residue of crude oil, and / or a coking distillate. The residue may be a hydrocracking residue and / or an atmospheric distillation residue. Preferably, the fossil feedstock is a distillate cut and / or a hydrocracking residue. Even more preferably, the fossil feedstock is a distillate cut.

[0048] Fossil-derived distillate fractions typically have boiling points ranging from 375 to 600 °C. According to ASTM D86-12, they typically have an initial boiling point of 375 to 450 °C and a final boiling point of 500 to 600 °C. Such distillate fractions typically comprise C20-C55 compounds.

[0049] The residues usable in the present invention typically have boiling points of 350 °C to 750 °C. Hydrocracking residues have the advantage of not containing heteroatom-type contaminants, or very few, unlike other residues.

[0050] Step a) of supplying tire oil

[0051] 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.

[0052] Elastomers are linear or branched polymers transformed by vulcanization into a weakly cross-linked, infusible and insoluble three-dimensional network. These include natural or synthetic rubbers. They can be found in tire-type waste or any other household or industrial waste containing elastomers, natural and / or synthetic rubber, mixed or not with other components, such as plasticizers, fillers, vulcanizing agents, vulcanization accelerators, additives, etc. Examples of elastomeric polymers include ethylene-propylene copolymers, ethylene-propylene-diene terpolymer (EPDM), polyisoprene (natural or synthetic), polybutadiene, styrene-butadiene copolymers, isobutene-based polymers, isobutylene-isoprene copolymers (chlorinated or brominated), acrylonitrile butadiene copolymers (NBR), and polychloroprenes (CR), polyurethanes, silicone elastomers, etc.

[0053] Biomass can be defined as an organic product of plant or animal origin.

[0054] 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 clearing agricultural land, ...; (iii) agricultural residues from crops, including cereal crops, vineyards, orchards, olive groves, fruits and vegetables including nuts, 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) industrial organic waste (paper, cardboard, wood, putrescible waste, etc.).(viii) algal biomass, namely biomass formed from algae, for example microalgae (algal biomass can be an algal suspension obtained by harvesting algae from, for example, a bioreactor, or an algal residue obtained by dehydrating an algal 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 methanizers.

[0055] 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.

[0056] In a preferred embodiment, the tire oil is obtained exclusively from waste consisting of tires. The 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).

[0057] 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.

[0058] The composition of a 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.

[0059] 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 tri-aromatics), most often 20 to 80% by mass, or even 30 to 80% by mass, of aromatics. These contents may be determined by gas chromatography, liquid chromatography, proton NMR and / or carbon NMR.

[0060] 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.

[0061] A tire oil may comprise one or more of the following characteristics:

[0062] - A diene index of 1 to 100 g / L / 100g,

[0063] - An aromatic compound content of 15 to 80% by mass, most often 20 at 80% by mass, or even from 30 to 80% by mass,

[0064] - Heteroatom contents of 0 to 10% by mass.

[0065] 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 20,000 by mass of nitrogen, and most often from 500 to 20,000 ppm of nitrogen or even from 2,000 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 20000 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).

[0066] Generally, the bio-based carbon content of a tire oil, measured according to ASTM D6866-24, DIN 51637 (2014), or ASTM D7026, is at least 30% by mass, preferably at least 40% by mass, and can reach 100% by mass, particularly for tires made from synthetic rubber of renewable origin (e.g., 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.

[0067] Step a) of supply may therefore include, in particular only:

[0068] - a step of obtaining tire oil by a process selected from pyrolysis, the Vapor-thermal lysis, solvolysis and hydrothermal liquefaction,

[0069] - an optional step of fractionating the tire oil obtained in the step previous.

[0070] Advantageously, step a) may include, in particular only, the preliminary step a1) of providing a stream of waste tires, optionally mixed with other elastomers and / or biomass and / or plastics; a2) liquefying said waste stream by pyrolysis, hydrothermal liquefaction, vaporothermolysis or solvolysis at a temperature of at least 200°C; a3) recover a liquefaction effluent and separate said liquefaction effluent into a solid fraction, a hydrocarbon fraction Cl to C4, and optionally an aqueous fraction, and the remaining fraction being said tyre oil.

[0071] 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.

[0072] 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, flash pyrolysis, slow pyrolysis, catalytic pyrolysis, hydropyrolysis, steam pyrolysis, ...).

[0073] 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.

[0074] 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.

[0075] 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.

[0076] The fractionation step can be implemented by distillation, for example by distillation at atmospheric pressure or under reduced pressure, or by staged condensation.

[0077] Fractionation can be implemented to separate one or more of the following fractions:

[0078] (i) a naphtha-type fraction having a final boiling point of no more than 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,

[0079] (ii) a kerosene-type 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,

[0080] (iii) a diesel-type fraction having an initial boiling point of at least 230 °C, for example from 230 to 270 °C, and a final boiling point of at most 400 °C, for example from 350 to 400 °C,

[0081] (iv) a vacuum diesel-type fraction having an initial boiling point of at least 350 °C, for example from 350 to 400 °C, and a final boiling point of at most 550 °C, for example from 490 to 550 °C,

[0082] (v) a residue-type fraction having an initial boiling point of at least 490 °C, for example from 490 to 550 °C, and typically an endpoint of 750 to 850 °C.

[0083] One or more of the fractions (i) to (v) are then sent to step b) of hydrotreatment.

[0084] Preferably, step b) is sent an oil directly from a pyrolysis, hydrothermal liquefaction, vapothermolysis or solvolysis step, without fractionation, or a fraction that boils above 230 °C, such as one or more of fractions (iii), (iv) and / or (v), preferably a fraction (iii) and / or a fraction (iv), in particular for manufacturing aviation fuel or a naphtha cut.

[0085] The naphtha fraction typically exhibits one or more of the following characteristics: - a sulfur content of 100 to 8000 ppm, generally 500 to 8000 ppm, - a nitrogen content of 100 to 12000 ppm, generally 500 to 12000 ppm, - a metal content of 0 to 100 ppm.

[0086] The kerosene fraction typically exhibits 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 metal content of 1 to 200 ppm.

[0087] The diesel-type fraction typically exhibits 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 metal content of 2 to 500 ppm.

[0088] The vacuum-type diesel fraction typically exhibits one or more of the following characteristics: - a sulfur content of 150 to 20000 ppm, generally from 500 to 20000 ppm, - a nitrogen content of 150 to 25000 ppm, generally from 500 to 25000 ppm, - a metal content of 1 to 500 ppm.

[0089] The residue-type fraction typically exhibits one or more of the following characteristics: - a sulfur content of 200 to 30,000 ppm, generally 500 to 30,000 ppm, - a nitrogen content of 200 to 30000 ppm, generally 500 to 30000 ppm - a metal content of 1 to 3000 ppm.

[0090] Step b) of hydrotreatment

[0091] The tire oil fraction(s) supplied in step a) are subjected to a step b) of hydrotreating in a hydrotreating zone in the presence of a fossil hydrocracking feedstock, in particular of the type previously described.

[0092] This hydrotreatment is implemented in a hydrotreatment zone in the presence of dihydrogen and at least one catalyst under conditions suitable for carrying out hydrotreatment and forming a hydrotreated effluent.

[0093] 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.

[0094] This hydrotreatment step thus has a demetallization, hydrodesulfurization and / or hydrodeazotation function, and optionally a hydrogenation function.

[0095] The two charges can be introduced separately or together into the hydrotreatment zone.

[0096] The ratio of tire oil or fraction(s) of tire oil / hydrocracking fossil feedstock is advantageously from 0.1 to 50% by mass, preferably from 1 to 40% by mass, more preferably from 1 to 30% by mass, even more preferably from 5 to 25% by mass.

[0097] Preferably, the feeds to be treated are brought into contact successively with at least one first demetallation catalyst and then with at least one deazotation catalyst.

[0098] A usable demetallation catalyst may comprise one or more metals from groups 6, 9 and / or 10 of the periodic table, for example Pt and / or Pd (0.1-10 wt%) and / or Ni (0.1-60 wt%) and / or NiMo (0.1-60 wt%) and / or CoMo (0.1-60 wt%), generally on a support, for example chosen from zeolites, aluminas, silicas, refractory oxides, activated carbon, or other.

[0099] A usable deazotation catalyst may comprise one or more metals from groups 6, 9 and / or 10 of the periodic table, for example a NiMo (0.1-60 wt%) and / or CoMo (0.1-60 wt%) type catalyst, generally on a support, for example chosen from zeolites, aluminas, silicas, activated carbon, refractory oxides, or other.

[0100] This hydrotreatment can be carried out in one or two steps.

[0101] When this hydrotreatment is carried out in a single step, the feed consisting of tire oil fraction(s) and a fossil hydrocracking feed is hydrotreated at a temperature of 200 to 500 °C, preferably 200 to 450 °C, more preferably 200 to 425 °C, in the presence of hydrogen at an absolute pressure of 20 to 200 bar, preferably 30 to 180 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.

[0102] Alternatively, the hydrotreating can be carried out in a first step (b-1) in which the feed consisting of tire oil fraction(s) and a fossil hydrocracking feed 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 200 bar, preferably 20 to 180 bar, and in the presence of at least one first hydrotreating catalyst, preferably a hydrogenation catalyst, for example a hydrogenation catalyst comprising Pd and / or Pt (0.1-10 wt.%) and / or Ni (0.1-60 wt.%) and / or NiMo (0.1-60 wt%), and in a second step (b-2) in which the effluent from step (b-1) is hydrotreated at a temperature of 200 to 500 °C, preferably 250 to 450 °C, in the presence of hydrogen at an absolute pressure of 20 to 200 bar, preferably 30 to 180 bar, and in the presence of at least one second hydrotreating catalyst, for example a NiMo (0.1-60 wt%) and / or CoMo (0.1-60 wt%) type catalyst. The first step can then allow the hydrogenation of dienes initially present in the composition.

[0103] In one embodiment, the feedstock for hydrotreating can be diluted with a portion of the hydrotreating effluent and / or the hydrocracking effluent, which still has a temperature higher than the desired temperature at the hydrotreating inlet. This at least partial recycling of the hydrotreating effluent and / or the hydrocracking effluent allows for the dilution of unsaturated solids present in the purified composition and the preheating of the feedstock. Preferably, this dilution is carried out with a heavy fraction of the hydrocracking effluent in order to continue cracking the longer molecules.

[0104] This hydrotreating step can be carried out in a hydrotreating zone with one or more catalytic beds connected in series, possibly with hydrogen inter-bed loading. This hydrotreating zone can include one or more reactors in series, depending on the desired outcome. Any type of reactor commonly used for this type of reaction can 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.

[0105] The hydrotreated effluent exiting the hydrotreatment step is then hydrocracracked in step c).

[0106] Step d) of hydrocracking

[0107] The entire hydrotreated effluent from step b) is subjected to step d) of hydrocracking in a hydrocracking zone in the presence of dihydrogen and at least one catalyst in order to reduce the length of the carbon chains of the paraffins present.

[0108] Hydrocracking of the hydrotreated effluent can be accomplished in any manner known in the art or by using any suitable catalyst known in the art.

[0109] The catalysts and hydrocracking conditions are well known in the art.

[0110] Typically, this hydrocracking reaction is carried out at a temperature of 150 to 500 °C, a partial pressure of hydrogen of 1 to 25 MPa abs. and an hourly volumetric rate of 0.1 to 20 h-1.

[0111] Suitable hydrocracking catalysts used in hydrocracking processes are typically of the bifunctional type combining an acid function with a (de)hydrogenating function.

[0112] The production of the bifunctional hydrocracking catalyst can be carried out by any method known in the art. The (de)hydrogenation function can be added to the acid support by impregnation with solutions containing metals, by ion exchange, and by mixing.

[0113] The acid function is typically ensured by a support (amorphous or crystalline) whose specific surfaces are generally between 100 and 700 m2 / g and which has a surface acidity, such as halogenated aluminas (in particular 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, ISL4 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.

[0114] 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, CO₂, etc.), by a catalytic cracking test, or by hydroconversion using a model molecule.

[0115] Hydrocracking catalysts generally possess a strong acid function, preferably sulfated zirconias, tungsten zirconias and zeolites or mixtures thereof.

[0116] 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.

[0117] The distance between the two functions, acid and (de)hydrogenating, is one of the key parameters governing the activity and selectivity of the catalyst.

[0118] 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.

[0119] 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.

[0120] One type of conventional hydrocracking catalyst is based on crystalline supports such as zeolites and sulfated zirconia, which are highly acidic. These systems are used to reduce the number of carbons in the chain and provide good cold-flow properties. Hydrocracking produces non-condensable gases, naphtha, kerosene, and diesel fuel.

[0121] A usable hydrocracking catalyst typically comprises a support, for example 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.

[0122] Typical hydrocracking conditions include a temperature of 150°C to 500°C or more, preferably 220°C to 450°C and more preferably 250 to 420°C, and a pressure of 1 MPa to 25 MPa or more, preferably 1.5 MPa to 20 MPa or more, preferably 2 MPa to 18 MPa. The hourly space velocity can be approximately 0.1 to 20 h1, more preferably 0.2 to 10 h1, and most preferably 0.3 to 5 h1. The supplied dihydrogen-containing gases can be introduced simultaneously with the feed charge at a ratio of 75 to 2500 NI (H2) / L of charge, more preferably 150 to 1500 NI, or more preferably 250 to 1000 NI.

[0123] During a hydrocracking reaction, hydroisomerization can occur. A person skilled in the art will know how to choose appropriate conditions for treating the effluent under hydrocracking conditions, namely conditions under which hydrocracking reactions predominantly occur, according to the objective sought.

[0124] The 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.

[0125] This hydrocracking step can be carried out in a hydrocracking zone with one or more catalytic beds connected in series, possibly with hydrogen inter-bed loading. This hydrocracking zone can comprise one or more reactors in series, depending on the desired outcome. Any type of reactor commonly used for this type of reaction can be used, for example, a fixed-bed reactor, a stirred tank reactor, a bubbling-bed reactor, a slurry reactor, etc., preferably a fixed-bed reactor.

[0126] The feed for hydrocracking can be fed onto the catalyst with the hydrogen-containing gases in a downward flow mode. In an upward flow mode, the liquid feed can flow downwards while the hydrogen-containing gases flow upwards through the catalyst beds.

[0127] In one embodiment, the hydrocracking step can be carried out by adding at least one hydrocracking catalyst bed downstream of the last catalytic bed in the hydrotreating zone, in the same reactor.

[0128] Alternatively, the hydrocracking steps can be implemented in separate reactors, each comprising one or more suitable catalytic beds.

[0129] Optional washing step

[0130] At the outlet of the hydrocracking step, the hydrocracking liquid effluent from step c) can be washed with water to remove inorganic compounds such as hydrosulfide, hydrogen chloride, ammonia, NH4C1 (ammonium chloride) salts.

[0131] It can then be used as is, sent to the separation step e) or subjected to further processing.

[0132] When the hydrotreating and hydrocracking steps are carried out in separate reactors, this optional washing step may possibly be carried out on the hydrotreated effluent before it enters the hydrocracking step.

[0133] Separation step e)

[0134] In one embodiment of the invention, the process for manufacturing hydrocarbon fluids may further include a separation step d) in which the hydrocracked liquid effluent from step c), optionally washed with water, is separated into at least one fraction selected from a naphtha fraction, a kerosene fraction and a diesel fraction.

[0135] The hydrocracked liquid effluent from step c) can undergo fractionation, for example by adding a separation column, for example an atmospheric pressure or reduced pressure distillation column, or by lateral withdrawal.

[0136] 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 c).

[0137] 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. This fraction can also be used as feedstock for a steam cracker, particularly for the production of olefins such as ethylene and propylene.

[0138] The recovered diesel fraction preferably has an initial boiling point of 230 to 260 °C and a final boiling point of 360 to 380 °C. This fraction can be used as fuel for diesel engines.

[0139] The recovered kerosene fraction preferably has a final boiling point below 300 °C, notably measured 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.

[0140] In particular, the cutting points of the recovered fractions can be adapted in order to obtain products meeting particular specifications.

[0141] The invention makes it possible in particular to obtain fractions having sufficiently low N, S contents to be able to be used as fuel without dilution, or with limited dilution.

[0142] During this step, it will also be possible to separate a fraction heavier than the previous fractions, which can be sent to the input of the hydrotreatment step to dilute the feed to be treated.

[0143] Detailed description of the figures

[0144] Other features and advantages of the invention will become apparent from the following description of particular embodiments of the invention, given by way of example but not limitation, with reference to the accompanying drawings in which:

[0145] Figure 1 schematically represents a first possible embodiment of the invention,

[0146] Fig. 2 schematically represents a second possible embodiment of the invention.

[0147] In the embodiment of [Fig. 1], a tire oil (1), optionally fractionated in a fractionation section (SF) capable of performing fractionation to separate at least one tire oil fraction (1'), is first hydrotreated in a hydrotreatment section (HDT) to undergo hydrotreatment according to step b). This hydrotreatment is carried out with a fossil hydrocracking feedstock (2). The hydrotreated oil (3) is then sent to a hydrocracking section (HCK) for hydrocracking according to step (c) of the invention. The effluent (4) which exits this hydrocracking section (HCK) can then be sent to a fractionation section (E) for the implementation of step e) in order to be separated there for example into a naphtha fraction (7), a kerosene fraction (8) and a diesel fraction (9), which can be sent to fuel pools.The effluent (4) is sent to the fractionation section (E) directly or after washing in a washing section (L) to remove non-hydrocarbon compounds (6) such as hydrosulfide, hydrogen chloride, ammonia, etc., from a purified hydrocracked oil (5). Each hydrotreating and hydrocracking section then constitutes a hydrotreating zone, respectively a hydrocracking zone, within the meaning of the invention, each comprising one or more hydrotreating catalytic beds, respectively arranged in one or more reactors in series and / or in parallel.

[0148] Figure 2 schematically represents another possible embodiment of the invention. In this figure, the same reference numerals designate the same elements. In this embodiment, the hydrotreating (b) and hydrocracking (c) steps are carried out in a single treatment section (TT), comprising, in the direction of flow of the feed to be treated, namely tire oil (1) and a fossil hydrocracking feed (2), a hydrotreating zone ZHDT followed by a hydrocracking zone ZHck, each zone comprising one or more catalytic hydrotreating beds, respectively hydrocracking beds, arranged in one or more reactors in series. The separation between the two zones is symbolized by a horizontal dashed line in Figure 2.

[0149] In both embodiments, one or more fractions of tire oils can be treated in a mixture with a fossil hydrocracking feedstock. These two components can enter the hydrotreating zone separately or in a mixture.

Claims

Demands

1. A process for manufacturing hydrocarbon fluids comprising: a) a step of supplying tire oil or at least a fraction of tire oil containing nitrogen, sulfur and metals, b) a hydrotreating step, in which said tire oil or at least a fraction of tire oil and a fossil hydrocracking feedstock 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 having a reduced content of nitrogen, sulfur and metals, c) a step of hydrocracking the hydrotreated effluent from step b) to form a liquid hydrocracking effluent.

2. A manufacturing process according to claim 1, wherein, during step b) of hydrotreating, the feeds to be treated are successively brought into contact with at least one first demetallization catalyst and then with at least one deazotation catalyst.

3. A manufacturing process according to claim 1 or 2, wherein step a) provides one or more of the following fractions: (i) a naphtha-type fraction having a final boiling point of not more than 150 °C, (ii) a kerosene-type fraction having an initial boiling point of not less than 130 °C and a final boiling point of not more than 270 °C, (iii) a diesel-type fraction having an initial boiling point of not less than 230 °C and a final boiling point of not more than 400 °C, (iv) a vacuum diesel-type fraction having an initial boiling point of not less than 350 °C and a final boiling point of not more than 550 °C, (v) a residue-type fraction having an initial boiling point of not less than 490 °C.

4. The manufacturing process according to claim 3, in step a) provides a diesel-type fraction (iii) and / or a vacuum diesel-type fraction (iv).

5. A manufacturing method according to any one of claims 1 to 4, wherein said tire oil or at least a fraction thereof Tyre oil includes one or more of the following characteristics: - a sulfur content of 100 ppm to 30000 ppm, - a nitrogen content of 100 ppm to 30000 ppm, - a bio-based carbon content of 30 to 100% by mass, - an aromatics content of 15 to 80% by mass.

6. A manufacturing process according to any one of claims 1 to 5, wherein the supply step (a) comprises: - a step of obtaining tire oil by a process selected from pyrolysis, vapor thermolysis, solvolysis, and hydrothermal liquefaction, - an optional step of fractionating the tire oil obtained in the preceding step into at least one fraction selected from: (i) a naphtha-type fraction having a final boiling point of at most 150 °C, (ii) a kerosene-type fraction having an initial boiling point of at least 130 °C and a final boiling point of at most 270 °C, (iii) a diesel-type fraction having an initial boiling point of at least 230 °C and a final boiling point of at most 400 °C, (iv) a vacuum diesel-type fraction having an initial boiling point of at least 350 °C and a final boiling point of no more than 550 °C,(v) a residue-type fraction having an initial boiling point of at least 490 °C.

7. A manufacturing process according to any one of claims 1 to 6, wherein said hydrocracking fossil feedstock is selected from a distillate cut, such as an atmospheric distillation distillate, a vacuum distillation distillate and / or a coking distillate; and a residue, such as a hydrocracking residue and / or an atmospheric distillation residue, alone or in mixture.

8. A manufacturing process according to any one of claims 1 to 7, wherein hydrotreating step b) is carried out with a ratio of tire oil or at least a fraction of tire oil / hydrocracking fossil feed of 0.1 to 50% by mass.

9. A manufacturing process according to any one of claims 1 to 8, wherein step b) of hydrotreating: - is carried out in a single step at a temperature of 200 to 500 °C, preferably 200 to 450 °C, more preferably 200 to 425 °C, in the presence of hydrogen at an absolute pressure of 20 to 200 bar, preferably 30 to 180 bar, and in the presence of at least one hydrotreating catalyst, or - is carried out in a first step (b-1) 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 200 bar, preferably 20 to 180 bar, and in the presence of at least one first hydrotreating catalyst, and in a second step (b-2) in which the effluent from step (b-1) is hydrotreated at a temperature of 200 to 500 °C, preferably 250 to 450 °C, in the presence of hydrogen at an absolute pressure of 20 to 200 bars, preferably 30 to 180 bars, and in the presence of at least one second hydrotreating catalyst.

10. A manufacturing process according to any one of claims 1 to 9, wherein step c) of 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 25 MPa, - an hourly volumetric rate of 0.1 to 20 h1.

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

12. A process according to any one of claims 1 to 11, wherein the effluent exiting step b) or c) is further washed with water to remove non-hydrocarbon compounds such as hydrosulfide, hydrogen chloride, ammonia, carbon dioxide, carbon monoxide, ammonium chloride salts, before being sent to the next step.

13. A manufacturing process according to any one of claims 1 to 12, wherein the hydrotreating and hydrocracking steps are carried out successively in separate reactors.

14. A manufacturing process according to any one of claims 1 to 12, wherein the hydrotreating and hydrocracking steps are carried out successively in the same reactor.

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