PROCESS FOR CONVERSION OF FOSSIL-DERIVED HYDROCARBONS FOLLOWED BY FRACTIONATION IN THE PRESENCE OF TIRE OIL

Abstract

The invention relates to a process for producing hydrocarbon fluids from a fossil hydrocarbon feedstock and tire oil, comprising: a) a step of supplying tire oil, b) a conversion step in which the fossil hydrocarbon feedstock undergoes conversion and a converted effluent is obtained, c) a fractionation step in which the converted effluent from step b) and the tire oil supplied by step a) are fractionated in the same fractionation section into at least one liquid hydrocarbon fraction, and optionally into at least one gaseous fraction. Abstract figure: Figure 1

Description

Title of the invention: METHOD FOR CONVERSING FOSSIL-DERIVED HYDROCARBONS FOLLOWED BY FRACTIONATION IN THE PRESENCE OF TIRE OIL technical field

[0001] The present invention relates to a process for converting hydrocarbons of fossil origin followed by fractionation in the presence of tire oil. Context of the invention

[0002] There is an important need, also encouraged by regulations, to limit 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 sulfur, nitrogen, 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 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] Document FR3091294A1 describes the desalting of a mixture of crude oil with a liquid derived from plastics and / or tires, followed by the distillation of the desalted mixture into one or more distillates and a bottomsl. The distillate(s) can then be hydrodesulfurized. The bottomsl can be subjected to vacuum distillation. The desalted mixture comprises 1 part of liquid derived from plastics and / or tires to 1 to 1000 parts of crude oil. In this process, the liquid derived from plastics and / or tires is found among the products of a refinery because it is mixed with the crude oil as soon as the latter is atmospherically distilled at the refinery inlet, which necessitates increasing the volumes of the processing units of existing refineries. Furthermore, the liquid derived from plastics and / or Tire oil is diluted upon entering the refinery, making it difficult to track the carbons from these liquids as the hydrocarbon feedstocks pass through the various units of a refinery. Furthermore, tire oil contains compounds that can cause clogging or polymerization in the refinery's inlet atmospheric distillation unit, potentially leading to refinery blockages. It also contains impurities (N, S, etc.) that require relatively advanced treatment, unlike typical products exiting a refinery's atmospheric distillation process.

[0007] There is therefore a need to propose a tire oil recycling process which limits the dilution of tire oil within the fossil hydrocarbon products of a refinery, limiting the risks of clogging and / or polymerization, while possibly allowing subsequent removal of impurities present in tire oils by downstream units. Description of the invention

[0008] The invention proposes a method for manufacturing hydrocarbon fluids from a fossil hydrocarbon feedstock and tire oil.

[0009] This process includes: a) a step of supplying tire oil, b) a conversion step during which the fossil hydrocarbon feedstock undergoes conversion and a converted effluent is obtained, c) a fractionation step in which the converted effluent from step b) and the tyre oil supplied by step a) are fractionated in the same fractionation section into at least one liquid hydrocarbon fraction, and optionally into at least one gaseous fraction.

[0010] The process according to the invention thus makes it possible to manufacture hydrocarbon fluids (liquid hydrocracked effluent) using in part recycled feedstocks.

[0011] By incorporating the recycled feed at the fractionation stage of an existing conversion unit, the process according to the invention allows for less dilution of the recycled feed in the fossil feed compared to an introduction further upstream in the refinery, for example at the atmospheric distillation stage of crude oil.

[0012] Furthermore, the hydrocarbon fractions of converted effluent usually contain sulfur, nitrogen, metal, or other pollutants that must be removed in subsequent treatments. Tire oils and their fractions also include impurities containing nitrogen, sulfur, and metals. By fractionating them along with the converted effluent, it is possible to introduce hydrocarbons from tire oils into each fossil fraction and send them to the usual subsequent treatments of fossil hydrocarbon fluids in which they will be rid of their impurities.

[0013] Advantageously, the tire oil can be introduced into the fractionation section mixed with the converted effluent, or separately at an introduction point higher than the introduction point of the converted effluent. A separate introduction as described can reduce the risk of polymerization and / or cracking of the tire oil components within the fractionation section.

[0014] Advantageously, the conversion step implemented in step b) can be a thermal cracking step implemented under visbreaking or coking conditions.

[0015] The conversion step b) can be chosen from a viscoreduction step and a coking step.

[0016] Step c) of fractionation can be implemented with a tire oil / converted effluent ratio of 0.1 to 50% by mass.

[0017] Said tire oil may comprise one or more of the following characteristics: - an initial boiling point of 15°C to 150°C, - a final boiling point of 250 °C to 850 °C, - a nitrogen content of 100 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 sulfur content of 100 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 (measured according to ASTM D6866-24, DIN 51637 (2014) or ASTM D7026), - an aromatic content of 15 to 80% by mass.

[0018] Step a) of supply may include, but is not limited to: - a step of obtaining tire oil by a process chosen from pyrolysis, vapothermolysis, solvolysis and hydrothermal liquefaction.

[0019] The process may further include a step d) of treating at least one liquid hydrocarbon fraction of step c), optionally of each hydrocarbon fraction of step c), step d) being selected from a hydrotreating step, a hydrocracking step and a fluid catalytic cracking step, and producing an effluent having a reduced content of heteroelements and / or olefins and / or dienes and / or aromatics, and / or more cracked.

[0020] The treatment in step d) may implement at least one reaction selected from hydrodesulfurization, hydrodeazotation, hydrodemetallation, hydrodearomatization, hydrodehalogenation, catalytic hydrogenation, a hydrodeoxygenation, decarboxylation, decarbonylation, hydrocracking and fluid catalytic cracking.

[0021] Advantageously, said fossil hydrocarbon feed treated in the process according to the invention can be a residue or a mixture of residues.

[0022] In one embodiment, prior to step b), said fossil hydrocarbon feedstock may be fractionated into a heavy fraction and a lighter fraction, and said heavy fraction is sent to the conversion step b). This embodiment is particularly suitable for delayed coking units. This fractionation is typically carried out in the same fractionation section as that carrying out the fractionation step c. In this case, the fossil hydrocarbon feedstock is preferably introduced at a lower inlet point than an inlet point of the converted effluent.

[0023] In one embodiment, wherein step b) of conversion is carried out under coking conditions producing the converted effluent and a solid residue, the solid residue produced can then be sent to a carbon black production unit for the manufacture of tires and / or to an activated carbon production unit for the manufacture of catalyst and / or adsorbent.

[0024] 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

[0025] 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.

[0026] 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.

[0027] Unless otherwise indicated, measurements given in parts per million (ppm) are expressed in mass.

[0028] 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. Determining the initial and final boiling points involves techniques known in the trade and several methods adapted according to the field. Distillation temperatures are applicable, for example NF EN 15199-1 (version 2020) or ASTM D2887 for the measurement of boiling points of petroleum fractions by gas chromatography, ASTM D7169 for heavy hydrocarbons, ASTM D7500, D86 or DI 160 for distillates.

[0029] The term "hydrocarbon" refers to both alkanes (saturated hydrocarbons), cycloalkanes, aromatics and unsaturated hydrocarbons.

[0030] By "heteroatom" is meant any element of an organic compound other than carbon and hydrogen.

[0031] 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.

[0032] The aromatic content can be measured by gas chromatography, for example by a GCxGC method or by liquid chromatography, or by proton NMR and / or carbon NMR.

[0033] 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.

[0034] 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.

[0035] Fossil hydrocarbon charge

[0036] The fossil hydrocarbon feedstock used in the present invention is typically a residue or a mixture of residues.

[0037] This charge does not include any component of biological origin, for example from biomass.

[0038] A fossil hydrocarbon feedstock usable in the process may advantageously be a residue from the atmospheric distillation of a crude oil, a residue from the vacuum distillation of a residue from the atmospheric distillation of a crude oil, and / or any other residue from fractionation sections of other units of the refinery and possibly treated, such as a heavy hydrocracking residue (commonly called "bleed"), deasphalting pitch, or other.

[0039] A residue, or a mixture of residues, usable in the present invention typically has one or more of the following characteristics:

[0040] - a sulfur content of at least 1.5% by mass, for example from 1.5 to 10% by mass,

[0041] - a metal content of 1 to 5000 ppm,

[0042] - a Conradson carbon content of at least 2% by mass, preferably of at minus 10% by mass, preferably more of at least 15% by mass, and potentially up to 40% by mass,

[0043] - an initial boiling point of 230 °C to 550 °C, preferably of at least 400 °C, preferably more than at least 440 °C, even more preferably at least 500 °C, preferably at least 525 °C,

[0044] - a final boiling point of 700 to 950 °C, preferably 700 to 900 °C, preferably from 700 to 850 °C.

[0045] Atmospheric residues (noted RAT) and vacuum residues (noted RSV) are respectively the column bottoms from the atmospheric distillation of crude oil, and from the vacuum distillation of an RAT.

[0046] Step a) of supplying tire oil

[0047] The expression "tire oil" refers to 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.

[0048] 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.

[0049] Biomass can be defined as an organic product of plant or animal origin.

[0050] 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 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.

[0051] 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.

[0052] 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 shreds or granules (and therefore potentially without textiles or metals).

[0053] 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.

[0054] 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.

[0055] 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 can be determined by gas chromatography, liquid chromatography, proton NMR, and / or carbon NMR.

[0056] 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.

[0057] A tire oil shall comprise one or more of the following characteristics:

[0058] - A diene index of 1 to 100 g / L / 100g,

[0059] - 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,

[0060] - Heteroatom contents of 0 to 10% by mass.

[0061] 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).

[0062] 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% in large quantities, particularly for tires made from synthetic rubber of renewable origin (for example, from butadiene produced from ethanol derived from biomass). "Bio-based carbon" refers to carbon derived from biomass. Bio-based carbon does not include carbon from fossil fuels.

[0063] Step a) of supply may therefore include, in particular only:

[0064] - a step of obtaining tire oil by a process selected from pyrolysis, the vaporothermolysis, solvolysis and hydrothermal liquefaction.

[0065] 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 hydrocarbon fraction Cl to C4, and optionally an aqueous fraction, the remaining fraction being said tire oil.

[0066] 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 solely of tires.

[0067] 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, ...).

[0068] 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 byproducts.

[0069] The hydrothermal liquefaction (or HTL) process is a thermochemical conversion process using water as a solvent, reactant, and catalyst for the degradation reactions of a hydrocarbon feedstock, with the water typically 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.

[0070] 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.

[0071] The fractionation step can be implemented by distillation, for example by distillation at atmospheric pressure or under reduced pressure, or by staged condensation.

[0072] Conversion step b)

[0073] This conversion step makes it possible to obtain a converted effluent.

[0074] This conversion step can be chosen from a viscoreduction step and a coking stage.

[0075] This step then makes it possible to obtain an effluent that is at least partially cracked, namely consisting of the feed to be treated that is at least partially cracked.

[0076] Viscoreduction and coking are reactions well known to those skilled in the art.

[0077] Viscoreduction is a thermal cracking reaction carried out under moderate conditions to achieve partial cracking of the feed to be treated. It reduces the viscosity and the pour point of the treated feed.

[0078] The visbreaking process is a treatment of heavy hydrocarbon feedstocks, consisting of bringing these feedstocks (in liquid form) into a furnace at a temperature that cracks the heaviest hydrocarbons and then introducing them into a maturation tank, in which, without further heating, they move at such a speed that, at the specified temperature, they have a residence time sufficient to achieve the desired cracking of the heavy molecules into lighter molecules. The cracking results in a reduction of the viscosity of the treated feedstock, hence the terms visbreaking for the process implemented, and viscoreducer for the equipment used.

[0079] The feedstock processed can be heavy crude oil, atmospheric distillation residue (though this is uncommon, as other types of recovery exist), vacuum distillation residue, bleed, deasphalting pitch, or other. The products resulting from visbreaking are a vaporized effluent and a liquid residue generally called visbreaking vacuum residue.

[0080] The vaporized effluent can be separated into gaseous hydrocarbons and non-condensable gas, naphtha, diesel and distillate(s), during step b) of fractionation.

[0081] The liquid residue, particularly under the implementation conditions of step b), can be used for the production of fuel oil type fuel.

[0082] Typical visbreaking conditions include a temperature of 350 to 550 °C, preferably 400 to 500 °C, for a duration generally of 1 to 60 minutes, preferably 10 to 45 minutes, a total pressure generally less than 10 MPa, preferably less than 5 MPa, and more preferably less than 2 MPa. The cracking rate is controlled by adjusting the residence time. hydrocarbons in the ripening tank. This process can be implemented using the devices described in documents FR2741888A1 or FR2741889A1.

[0083] Coking is a thermal cracking reaction carried out under severe conditions capable of reducing the viscosity and pour point of the treated feed.

[0084] In a coking step, the fossil hydrocarbon feedstock is advantageously an RSV, or any other heavy feedstock from a refinery process, such as a heavy hydrocracking residue, a deasphalting pitch, or other.

[0085] Typical coking conditions include a temperature of 400 to 600 °C, a pressure of 0 to 30 bar gauge, preferably 1 to 20 bar gauge, more preferably 1 to 15 bar gauge.

[0086] The products resulting from coking are a vaporized effluent and a solid residue (coke).

[0087] The vaporized effluent can be separated into gaseous hydrocarbons and non-condensable gases, naphtha, distillate(s) and residue during step c) of fractionation.

[0088] The solid residue, in particular under the implementation conditions of step b), here coke, can be sent to a carbon black production unit for the manufacture of tires, and / or to an activated carbon production unit for the manufacture of catalyst and / or adsorbent, or other.

[0089] The coking step can be implemented in a coking unit according to a delayed coking process or a fluid coking process.

[0090] The delayed coking process consists of heating the feedstock to the thermal cracking temperature in a furnace before introducing it into coke drums where the cracking reactions take place. In these drums, long-chain hydrocarbon molecules are cracked into an effluent consisting of hydrocarbon vapors containing essentially diesel fuel and lighter components, and solid coke. The solid coke remains in the coke drum, which fills up in 16 to 24 hours. Once the drum is full of solid coke, the process switches to the second drum. While the second drum is filling with solid coke, the top and bottom heads of the first drum are removed, and the solid coke is extracted, for example, using a high-pressure water jet.Before being heated in a furnace and introduced into the coke drums, the feedstock is fractionated into a heavy fraction which is sent to the furnace and then to the coke drums, the remaining gases being recondensed and returned to fractionation with the incoming feedstock. This fractionation is usually carried out in the same fractionation section as the one to which the effluents from the coke drums are sent.

[0091] Step b), when it is a coking step, can thus be preceded by a step of fractionating the feedstock to be treated, namely the fossil hydrocarbon feedstock alone (without tire oil), into a heavy fraction and a lighter fraction. The heavy fraction is then sent to the coking step b) to be cracked in the presence of tire oil or at least a fraction of tire oil. A person skilled in the art will know how to choose the cutting point between the heavy fraction returned to the coking step and the lighter fraction in the usual way under the conditions of implementation of the coking step.

[0092] The fluid bed process consists of bringing the feedstock to be treated into contact with a fluidized bed containing hot particles, generally coke particles. This produces an effluent consisting of hydrocarbon vapor and coke that deposits on the particles. These particles can then be regenerated by combustion, and some of the coke particles can then be returned to the coking zone, for example, a fluidized bed reactor. In this case, the entire fossil hydrocarbon feedstock is sent to the coking stage to undergo thermal cracking.

[0093] Step c) of splitting

[0094] During this step, the converted effluent from step b) is separated into at least one liquid hydrocarbon fraction, and optionally at least one gaseous fraction, in a fractionation section.

[0095] The fractionation step is preferably implemented on the converted effluent coming directly from step b) of conversion, without an intermediate step.

[0096] This fractionation is carried out in the presence of the tire oil supplied by step a) described above. The tire oil can be introduced into the fractionation section mixed with the converted effluent or separately. In the latter case, it is preferable to introduce the tire oil into a cooler part of the fractionation section, for example, at an introduction point higher than the introduction point of the converted effluent.

[0097] Step c) of fractionation can be implemented with a tire oil / converted effluent ratio of 0.1 to 50% by mass, preferably 1 to 40% by mass, more preferably 2 to 30% by mass, or even 2 to 15% by mass.

[0098] The nature and number of hydrocarbon fractions separated during step c) depends on the nature of the conversion reaction implemented in step b) and the objective sought.

[0099] In one embodiment, the effluent from step b) is fractionated into at least one liquid hydrocarbon fraction selected from a naphtha fraction, a kerosene fraction, a diesel fraction, a vacuum diesel fraction, and a residue.

[0100] According to the process, this fractionation can be carried out by adding a separation column, for example a distillation column, atmospheric or under reduced pressure, or by lateral withdrawal.

[0101] Preferably, the fractionation section is a distillation column, atmospheric or under reduced pressure.

[0102] 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, after undergoing hydrotreatment, in particular hydrodesulfurization, as feed for a steam cracker, in particular to produce olefins such as ethylene and propylene.

[0103] The recovered diesel fraction preferentially has an initial boiling point of 230 to 260 °C and a final boiling point less than or equal to 380 °C.

[0104] 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, generally after hydrotreating.

[0105] The gas oil fraction under vacuum typically exhibits a distillation range from 350-375 °C up to 525 °C - 540 °C.

[0106] In a visbreaking step, the fractionation process typically separates a naphtha, kerosene, and diesel fraction, a vacuum diesel fraction, and a visbreaking residue. The visbreaking residue can then be sent to a partial oxidation (POX) unit or a bitumen pool. The naphtha fraction can be hydrotreated and then optionally steam cracked. The other fractions can be sent to dedicated hydrotreating units and / or hydrocracking units and / or sent to a fluid catalytic cracking unit.

[0107] In a coking step, the fractionation process typically separates the effluent into naphtha (typically with a final boiling point of approximately 170 °C), light diesel (typically distilling in the range of 170–370 °C), heavy diesel (typically distilling in the range of 370–525 °C), and residue (typically with an initial boiling point of 520 °C to 540 °C). The residue can be returned to the coking step input. The naphtha fraction can be hydrotreated and then optionally steam cracked. The diesel fractions can be sent to dedicated hydrotreating units and / or hydrocracking and / or sent to a fluid catalytic cracking unit.

[0108] Typically, fractionation is carried out under the usual fractionation conditions following a coking or viscoreduction step.

[0109] The fractionation step can in particular be carried out under atmospheric pressure or under reduced pressure, for example at an absolute pressure of 0.1 mbar to 500 mbar, preferably from 0.1 mbar to 100 mb, more preferably from 0.5 to 10 mbar.

[0110] Processing step d)

[0111] The at least one liquid hydrocarbon fraction separated in step c) generally contains impurities containing heteroatoms and / or dienes and / or olefins and / or aromatics, and / or relatively long hydrocarbon chains.

[0112] These heteroatoms can be nitrogen, sulfur, oxygen, silicon, halogens, and / or metals.

[0113] Step d) of treatment makes it possible to reduce the content of heteroatoms and / or dienes and / or olefins and / or aromatics, and / or to further crack at least one liquid hydrocarbon fraction separated in step c).

[0114] Step d) may implement one or more of the following reactions: hydrodesulfurization, hydrodeazotation, hydrodemetallation, hydrodearomatization, hydrodehalogenation, catalytic hydrogenation, hydrodeoxygenation, decarboxylation, decarbonylation, hydrocracking, fluid catalytic cracking.

[0115] Depending on the reactions implemented, step d) can be carried out in the presence of dihydrogen and at least one catalyst under suitable usual conditions.

[0116] Depending on the objective sought, a hydrocarbon liquid fraction separated in step b) may be sent to a hydrotreating unit and / or a hydrocracking unit to remove one or more of the specific impurities, and / or to a dedicated fluid catalytic cracking (FCC) unit for further cracking, alone or mixed with one or more other hydrocarbon liquid fractions separated in step c), or with other refinery effluents.

[0117] Advantageously, step d) of hydrotreating and / or hydrocracking and / or fluid catalytic cracking can thus be implemented in one or more existing hydrotreating units and / or hydrocracking units and / or fluid catalytic cracking units of a refinery, usually used to treat feedstocks of fossil origin, and in particular specific fractions thereof.

[0118] The present invention can therefore be implemented in an existing refinery, without having to modify it. Detailed description of the figures

[0119] 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 attached drawing in which:

[0120] Figure 1 schematically represents a first possible embodiment of the invention,

[0121] Figure [Fig. 2] schematically represents a second possible embodiment of the invention,

[0122] Figure 3 schematically represents a third possible embodiment of the invention.

[0123] In the figures, identical elements are designated by the same reference numerals.

[0124] In the possible embodiment of [Fig. 1], a fossil hydrocarbon feedstock of the type previously described (1) is converted in a Cunit conversion unit. The conversion unit is capable of carrying out step b) of the process. For this purpose, it may comprise one or more reactors in parallel and / or in series. Any type of reactor commonly used for the type of reaction envisaged may be used, for example, a fixed-bed reactor, a stirred-tank reactor, a bubbling-bed reactor, a slurry-type reactor, a plug-flow reactor, a batch reactor, etc.

[0125] The converted effluent (2) exiting the Cunit conversion unit is then fractionated, in particular directly, without an intermediate step, in a Funit fractionation section, capable of implementing step b), to be fractionated there into at least one liquid hydrocarbon fraction.

[0126] According to the invention, tire oil (TPO) is introduced into the Funit fractionation section to be fractionated along with the converted effluent (2). This tire oil can be introduced into the fractionation section mixed with the converted effluent, or separately, as shown in the figure. In this case, the tire oil (TPO) can advantageously be introduced at a point located above the point of introduction of the converted effluent, in other words, in a part of the fractionation section whose temperature is lower than the temperature at the point of introduction of the converted effluent (2). This limits the heating of the tire oil and thus limits secondary reactions such as polymerization and / or cracking.

[0127] In the example shown, the converted effluent (2) is fractionated, for example, into a gaseous fraction (3) and several liquid hydrocarbon fractions, for example, a naphtha fraction (4), a kerosene fraction (5), a diesel fraction (6), a VGO fraction (7), and a residue (8). The latter can optionally be recycled upstream of the Cunit reactor for further conversion or sent to a hydrotreating and / or hydrocracking and / or fluid catalytic cracking unit. Of course, the invention is not limited by the number and nature of the separated fractions, which will be chosen by those skilled in the art according to the nature of the conversion reaction implemented and the desired products. Depending on the nature of the conversion reaction, the fractionation section can be integrated into the unit of conversion (e.g. include one or more side draws) or be a separate unit, notably a splitting column.

[0128] Depending on the nature of any impurities present, a separated hydrocarbon liquid fraction may be sent to a hydrotreating unit, either alone or mixed with at least one other separated hydrocarbon liquid fraction, or with another refinery effluent. One or more hydrotreating units may thus be provided, each dedicated to one or more separated hydrocarbon liquid fractions. In the embodiment shown [Fig. 1], three separate hydrotreating units HDTi, HDT2, and HDT3 are provided, treating fractions (4), (5), and (6) separately, respectively, and a hydrocracking unit HCKi or a fluid catalytic cracking unit FCCi is provided to treat the VGO (7).Each unit can then be operated to remove one or more specific impurities by one or more reactions chosen from hydrodesulfurization, hydrodeazotation, hydrodemetallation, hydrodearomatization, hydrodehalogenation, catalytic hydrogenation, hydrodeoxygenation, decarboxylation, decarbonylation, hydrocracking, and / or be operated to carry out additional cracking by fluid catalytic cracking and / or hydrocracking.

[0129] The invention is not, however, limited to the number of hydrotreating and / or hydrocracking and / or fluid catalytic cracking units, nor to the nature of the reactions they employ. A person skilled in the art will be able to determine which treatment is necessary to remove one or more specific impurities from a given feedstock, or even to carry out other reactions, depending on the objective sought.

[0130] In the embodiment of [Fig.1], the tire oil is introduced into the Funit fractionation section separately from the converted effluent.

[0131] In another embodiment shown [Fig.2], the tire oil (TPO) is introduced inside the Funit fractionation section mixed with the converted effluent (2).

[0132] The embodiments shown [Fig. 1] and 2 can in particular be implemented in a viscoreduction unit or a coking unit comprising a fluidized bed reactor.

[0133] Figure 3 represents another possible embodiment of the process according to the invention implemented in a CRunit delayed coking unit.

[0134] In this embodiment, the feed (1) is first sent into the Funit fractionation section. The feed (1) generally enters the lower part of the Funit fractionation section, below the inlet of the converted effluent (2).

[0135] The heavier fraction (residue) (8) separated in this fractionation section F unit is sent to the delayed coking unit CRunit, typically to one of the two coke drums, which this type of unit usually includes, in which it undergoes thermal cracking. The coking stage produces a converted effluent (2) at least partially cracked and a solid residue (10), namely coke.

[0136] The converted effluent (2) exiting the coke drums is sent to the Funit fractionation section.

[0137] In the embodiment shown, the entirety of the heaviest fraction (8) is sent to the CRunit delayed coking unit. However, the invention is not limited to this embodiment, and a portion of the heaviest fraction (8) could be sent to the delayed coking unit, with the remainder being sent to an HCKi hydrocracking unit and / or an FCCi fluid catalytic cracking unit (not shown).

[0138] According to the invention, a tire oil (TPO) is introduced into the Funit fractionation section, separately from the converted effluent (2) at a point located above the point of introduction of the converted effluent (2). The tire oil could also be introduced mixed with the converted effluent, as shown [Fig. 2].

[0139] As explained above, the coke drums operate alternately: the coke from one drum is discharged while thermal cracking is in progress in the other drum. Water is typically used to discharge the coke from the coke drums. The coke can then be used to produce carbon black and / or activated carbon.

[0140] The invention is illustrated by the following examples given by way of non-limiting example. Examples

[0141] A non-limiting example of implementation of the invention is now described.

[0142] Conversion by delayed coking

[0143] A vacuum residue (denoted RSV) is converted in a delayed coking unit (hereafter referred to as a "delayed coker") under the following conditions:

[0144] Quantity of RSV processed: 3.5 kg

[0145] Temperature: 440 °C

[0146] Absolute pressure: 1.5 bar

[0147] Maturation: 3 hours

[0148] Nitrogen flow rate at the head: 50 L / hour

[0149] Nitrogen flow rate at the bottom: 300 L / hour

[0150] The characteristics of the RSV are summarized in Table 1

[0151] [Tables 1] RSV Carbon (% by mass) 83.5% Hydrogen (% by mass) 9.6% Sulfur (% by mass) 5.4% Oxygen (% by mass) 1.0% Total: 99.5% Distillation % by mass T (°C) PI 447 10 554 20 589 30 618 40 645 50 674 60 706 70 738 80 >750

[0152] The effluent from the delayed coker is fractionated in a distillation column. The fractions obtained are detailed in Table 2.

[0153] [Tables2] Outputs delayed coker 100% RSV Gas (% by mass) 12.5 Naphtha (<145°C) (% by mass) 4.0 LCGO (145-375°C) (% by mass) 38.5 HCGO (375+) (% by mass) 8.4 Coke (% by mass) 36.6 Total 100.0

[0154] A tire oil (denoted TPO) is fractionated alone under the same conditions as the delayed coker effluent. The fractions obtained are detailed in Table 3.

[0155] [Tables3] TPO alone Yield (% mass) Naphtha (<145°C) 13 LCGO (145-375°C) 61 HCGO (375-525°C) 23

[0156]

[0157]

[0158]

[0159] Residue returned to the coker (525+) 3 Considering that the effluent resulting from the treatment of 100 kg of RSV in the delayed coker is mixed with 10 kg of TPO before entering a distillation column, the fractions obtained at the outlet of the distillation column are in the proportions shown in Table 4. An increase in the quantity of naphtha, LOGO and HCGO cuts is observed, for a quantity of coke formed that is substantially the same compared to the treatment of a feed without the addition of TPO. [Tables 4] Fractionation outputs (100 kg delayed input Coke + 10 kg TPO in fractionation) Gas (% by mass) 12.5 Naphtha (<145°C) (% by mass) 5.3 LCGO (145-375°C) (% by mass) 44.6 HCGO (375+) (% by mass) 10.7 Coke (% by mass) 36.9 Total 110.0 Table 5 summarizes the characteristics of the effluents obtained at the outlet of the distillation column. [Tables 5] TPO Unit Effluent 100% RSV Effluent with TPO Mixture Carbon % by mass 87.9 84.5 85.0 Hydrogen % by mass 10.8 11.8 11.6 Oxygen calculated % by mass 0.0 1.3 1.1 Nitrogen ppm 6203 742 1638 Sulfur ppm 9000 23430 21062 Liquid yield in kg 10 51 61

Claims

Demands

1. A process for manufacturing hydrocarbon fluids from a fossil hydrocarbon feedstock and tire oil, the process comprising: a) a step of supplying tire oil, b) a conversion step in which the fossil hydrocarbon feedstock is subjected to conversion and a converted effluent is obtained, c) a fractionation step in which the converted effluent from step b) and the tire oil supplied by step a) are fractionated in the same fractionation section into at least one liquid hydrocarbon fraction, and optionally into at least one gaseous fraction.

2. A manufacturing method according to claim 1, wherein the tire oil is introduced into the fractionation section mixed with the converted effluent, or separately at an introduction point higher than an introduction point of the converted effluent.

3. A manufacturing process according to claim 1 or 2, wherein the conversion step b) is selected from a viscoreduction step and a coking step.

4. A manufacturing process according to any one of claims 1 to 3, wherein step b) of fractionation is carried out with a tire oil / converted effluent ratio of 0.1 to 50% by mass.

5. A manufacturing process according to any one of claims 1 to 4, wherein said tire oil comprises one or more of the following characteristics: - an initial boiling point of 15 °C to 150 °C, - a final boiling point of 250 °C to 850 °C, - a nitrogen content of 100 to 30,000 ppm, - a sulfur content of 100 to 30,000 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, vapothermolysis, solvolysis and hydrothermal liquefaction.

7. A manufacturing process according to any one of claims 1 to 6, further comprising: d) a treatment step of at least one liquid hydrocarbon fraction of step c), selected from a hydrotreating step, a hydrocracking step and a fluid catalytic cracking step, and producing an effluent having a reduced content of heteroelements and / or olefins and / or dienes and / or aromatics, and / or more cracked.

8. A manufacturing process according to claim 7, wherein the treatment step implements at least one reaction selected from hydrodesulfurization, hydrodeazotation, hydrodemetallation, hydrodearomatization, hydrodehalogenation, catalytic hydrogenation, hydrodeoxygenation, decarboxylation, decarbonylation, hydrocracking and fluid catalytic cracking.

9. A manufacturing process according to any one of claims 1 to 8, wherein said fossil hydrocarbon feedstock is a residue or a mixture of residues.

10. A manufacturing process according to any one of claims 1 to 9, wherein, prior to step b), said fossil hydrocarbon feedstock is fractionated into a heavy fraction and a fraction lighter than the heavy fraction, and said heavy fraction is sent to step b) of conversion.

11. A manufacturing process according to any one of claims 1 to 10, wherein conversion step b) is carried out under coking conditions producing the converted effluent and a solid residue, and the solid residue produced is then sent to a carbon black production unit for the manufacture of tires and / or to an activated carbon production unit for the manufacture of catalyst and / or adsorbent.

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