THERMAL CRACKING PROCESS OF FOSSIL-DERIVED HYDROCARBONS IN THE PRESENCE OF TIRE OIL

Abstract

The invention relates to a process for hydrocarbon fluids from a heavy hydrocarbon feedstock of fossil origin and tire oil, the process comprising: a) a step of supplying tire oil or at least a fraction thereof; b) a thermal cracking step in a visbreaking or coking unit in which said heavy hydrocarbon feedstock of fossil origin, or a fraction thereof, is subjected to thermal cracking under visbreaking or coking conditions in the presence of the tire oil or at least a fraction thereof supplied by step a), and an at least partially cracked effluent and a liquid or solid residue are produced; c) a fractionation step in which the effluent from step b) is fractionated into at least one liquid hydrocarbon fraction. (Abstract figure: Figure 1)

Description

Title of the invention: METHOD FOR THE THERMAL CRACKING OF FOSSIL-DERIVED HYDROCARBONS IN THE PRESENCE OF TIRE OIL technical field

[0001] The present invention relates to a process for the thermal cracking of hydrocarbons of fossil origin 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 nitrogen, sulfur, 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.

[0006] There is therefore a need to propose a process for recycling tire oil, particularly within the fossil hydrocarbon products of a refinery. Description of the invention

[0007] The invention proposes a process for manufacturing hydrocarbon fluids from a heavy hydrocarbon feedstock of fossil origin, for example from the vacuum distillation of a residue from the atmospheric distillation of crude oil and tire oil.

[0008] This process comprises: a) a step of supplying tire oil or at least a fraction of tire oil, (b) a thermal cracking step in a visbreaking unit or a coking unit in which said heavy fossil-based hydrocarbon feedstock, or a fraction thereof, is subjected to thermal cracking under visbreaking or coking conditions in the presence of tyre oil or at least a fraction of tyre oil supplied by step (a), and at least partially cracked effluent and liquid or solid residue are produced, in particular under the operating conditions of step (b); (c) a fractionation step in which the effluent from step (b) is fractionated into at least one liquid hydrocarbon fraction.

[0009] The process according to the invention thus makes it possible to manufacture hydrocarbon fluids (liquid hydrocarbon fraction) using, in part, recycled feedstocks. Furthermore, the volume of hydrocarbon fluids produced, and in particular light hydrocarbon fluids, is increased by the incorporation of one or more tire oils or tire oil fractions. Due to their high aromatic content, tire oils are also likely to form coke when step b) is carried out under coking conditions; this coke can then be used, for example, in the manufacture of tires and / or in the manufacture of adsorbents or catalysts.

[0010] By incorporating the recycled feed at the cracking stage of an existing unit, the process according to the invention allows 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 of crude oil.

[0011] Furthermore, the hydrocarbon fractions of the effluent exiting step b) 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 submitting them to step b) simultaneously with the fossil-based feedstock to be treated, it is possible to introduce hydrocarbons from the tire oils into each fossil fraction and send them to the usual subsequent treatments of fossil hydrocarbon fluids, where they will be freed of their impurities.

[0012] In one embodiment, prior to step b), said heavy fossil-based hydrocarbon feedstock may be fractionated into a heavy fraction and a fraction lighter than the heavy fraction, and said heavy fraction is sent to the coking step b) to be cracked with tire oil or at least a fraction of tire oil supplied in step a). This embodiment is particularly suitable for delayed coking units. This fractionation is typically implemented in the same splitting section as the one implementing step c) of splitting.

[0013] Step b) of thermal cracking can be implemented with a ratio of tire oil or fraction(s) of a tire oil / heavy hydrocarbon filler of fossil origin, or tire oil or fraction(s) of a tire oil / fraction of heavy hydrocarbon filler of fossil origin, of 0.1 to 50% by mass.

[0014] Said tire oil or at least a fraction thereof 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 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.

[0015] Step a) can provide at least one fraction of tire oil selected 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.

[0016] Preferably, step a) provides, in particular only, at least one residue type fraction and / or at least one vacuum diesel type fraction, more preferably at least one residue type fraction.

[0017] Step a) of supply may include: - 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 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.

[0018] 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), selected from a hydrotreating step, a hydrocracking step and a fluid catalytic cracking step, and producing a treated effluent having a reduced content of heteroelements (including metals) and / or olefins and / or dienes and / or aromatics, and / or further cracked.

[0019] The treatment in step d) can implement at least one reaction selected from hydrodesulfurization, hydrodeazotation, hydrodemetallation, hydrodearomatization, hydrodehalogenation, catalytic hydrogenation, hydrodeoxygenation, decarboxylation, decarbonylation, hydrocracking and fluid catalytic cracking.

[0020] Said heavy hydrocarbon filler of fossil origin used in the present invention can be chosen a residue or a mixture of residues.

[0021] Advantageously, step b) of cracking is carried out under coking conditions and the solid residue produced during this step 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.

[0022] 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

[0023] 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.

[0024] The expressions % by weight and % by mass have equivalent meanings and refer to the proportion of the mass of a product relative to 100g of a composition comprising it.

[0025] Unless otherwise indicated, measurements given in parts per million (ppm) are expressed in mass.

[0026] Boiling points as mentioned herein are measured at atmospheric pressure, unless otherwise specified. An initial boiling point is defined as the temperature value at which a first vapor bubble is formed. 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 field, 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, ASTM D7500, D86 or DI 160 for distillates.

[0027] The term "hydrocarbon" refers to both alkanes (saturated hydrocarbons), cycloalkanes, aromatics and unsaturated hydrocarbons.

[0028] By "heteroatom" is meant any element of an organic compound other than carbon and hydrogen.

[0029] 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.

[0030] 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.

[0031] 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.

[0032] 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.

[0033] Heavy hydrocarbon filler of fossil origin

[0034] The heavy hydrocarbon feedstock of fossil origin used in the present invention is typically a residue or a mixture of residues.

[0035] The heavy hydrocarbon feedstock of fossil origin used in the present invention typically has one or more of the following characteristics:

[0036] - a sulfur content of at least 1.5% by mass, for example from 1.5 to 10% by mass,

[0037] - a metal content of 1 to 5000 ppm,

[0038] - 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,

[0039] - 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,

[0040] - a final boiling point of 700 to 950 °C, preferably 700 to 900 °C, preferably from 700 to 850 °C.

[0041] By "fossil fuel" is understood a fuel which does not contain a component of biological origin, for example from biomass.

[0042] A hydrocarbon feedstock of fossil origin usable in the process may advantageously be selected from residues from the distillation of crude oil, in particular an atmospheric residue, a vacuum residue from the atmospheric distillation of crude oil, or from any other residue from fractionation sections of other units of the refinery and possibly treated, such as a heavy hydrocracking residue (commonly called "bleed"), a deasphalting pitch, or other.

[0043] 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.

[0044] Step a) of supplying at least one tire oil

[0045] The expression "tire oil" refers to hydrocarbon liquid products obtained from pyrolysis and / or vapothermolysis and / or solvolysis and / or hydrothermal liquefaction of tires, 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.

[0046] 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.

[0047] Biomass can be defined as an organic product of plant or animal origin.

[0048] 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.

[0049] 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, and 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, and organic waste. (forestry, agricultural, industrial and / or household waste), food waste, alone or mixed.

[0050] 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).

[0051] Tire oils contain, in particular, paraffins, i-paraffins (isoparaffins), dienes, alkynes, olefins, naphthenes, and aromatics. Tire oils also contain impurities containing heteroatoms, such as organic, oxygenated, sulfurous, nitrogenous, and / or silylated compounds, metals, salts, and phosphorus compounds.

[0052] 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.

[0053] 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.

[0054] 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.

[0055] A tire oil may comprise one or more of the following characteristics:

[0056] - A diene index of 1 to 10 g / L / 100g,

[0057] - An aromatic compound content of 15 to 80% by mass, most often of 20 to 80% by mass, or even 30 to 80% by mass,

[0058] - Heteroatom contents of 0 to 10% by mass.

[0059] 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 30,000 ppm of sulfur, generally from 200 ppm to 25,000 ppm of sulfur, most often from 500 to 20,000 ppm of sulfur or even from 3,000 to 20,000 ppm of sulfur (measured according to ISO 20846), from 1 to 1,000 ppm of metals (measured by ICP), from 0 to 100 ppm of chlorine (measured according to ASTM D7359-18), 0 to 200 ppm of bromine (measured according to ASTM D7359-18), 0 to 40 ppm of fluorine (measured according to ASTM D7359-18), 1 to 200 ppm of silicon (measured by XRF).

[0060] 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.

[0061] Step b) of supply may therefore include, in particular only:

[0062] - a step of obtaining tire oil by a process selected from pyrolysis, the Vapor-thermal lysis, solvolysis and hydrothermal liquefaction,

[0063] - an optional step of fractionating the tire oil obtained into at least one of the following fractions:

[0064] (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,

[0065] (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,

[0066] (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, and

[0067] (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,

[0068] (v) a residue-type fraction having an initial boiling point of at least 490 °C, for example from 490 to 550, and typically an endpoint of 750 to 850 °C.

[0069] Advantageously, step a) may include, in particular only, the preliminary step a1) of providing a waste tire stream optionally mixed with biomass 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.

[0070] 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. Preferably, the waste consists of tires.

[0071] 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, ...).

[0072] 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.

[0073] 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.

[0074] 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.

[0075] The fractionation step can be implemented by distillation, for example by distillation at atmospheric pressure, or under reduced pressure, or by staged condensation or by decantation.

[0076] Fractionation can be implemented to separate one or more of the following fractions (i) to (v), preferably the vacuum diesel type fraction (v) and / or the residue type fraction (v), more preferably the fraction (v).

[0077] One or more of the fractions (i) to (v) are then sent to the thermal cracking step b).

[0078] Alternatively, all of the tire oil obtained by the liquefaction process can be sent to step b) of thermal cracking.

[0079] 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.

[0080] 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.

[0081] 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.

[0082] 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.

[0083] The residue-type fraction typically exhibits one or more of the following characteristics: - a sulfur content of 200 to 30000 ppm, generally 500 to 30000 ppm, - a nitrogen content of 200 to 30000 ppm, generally 500 to 30000 ppm - a metal content of 1 to 3000 ppm.

[0084] Step b) of thermal cracking

[0085] This step 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.

[0086] This step can be chosen from a viscoreduction step and a coking step.

[0087] According to the invention, this step is carried out in the presence of tire oil or at least a fraction of tire oil supplied by step a) described above.

[0088] Step b) of thermal cracking can be implemented with a ratio of tire oil or tire oil fraction(s) / heavy hydrocarbon filler of fossil origin (or tire oil or tire oil fraction(s) / heavy hydrocarbon filler of fossil origin) 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.

[0089] Tire oil or at least a fraction of tire oil can be introduced into the viscoelastic or coking unit mixed with the heavy hydrocarbon feedstock of fossil origin, or separately.

[0090] Viscoreduction and coking are reactions well known to those skilled in the art.

[0091] 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.

[0092] 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.

[0093] 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.

[0094] The vaporized effluent can be separated into gaseous hydrocarbons and non-condensable gas, naphtha, diesel and distillate(s), and residue during step b) of fractionation.

[0095] The liquid residue, particularly under the implementation conditions of step b), can be used for the production of fuel oil type fuel.

[0096] 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, and 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 of the hydrocarbons in the maturation tank. This process can be implemented using the devices described in documents FR2741888A1 or FR2741889A1.

[0097] Coking is a thermal cracking reaction carried out under severe conditions capable of reducing the viscosity and pour point of the treated feed.

[0098] 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 (commonly called "bleed"), a deasphalting pitch, or other.

[0099] 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.

[0100] The products resulting from coking are a vaporized effluent and a solid residue (coke).

[0101] The vaporized effluent can be separated into gaseous hydrocarbons and non-condensable gases, naphtha, distillate(s) and residue during step c) of fractionation.

[0102] 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 tyres, and / or to an activated carbon production unit for the manufacture of catalyst and / or adsorbent, or other.

[0103] The coking step can be implemented in a coking unit according to a delayed coking process or a fluid coking process.

[0104] 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.

[0105] Step b) of coking can thus be preceded by a step of fractionating the feedstock to be treated, namely heavy hydrocarbon feedstock of fossil origin alone (without at least a fraction of 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.

[0106] The fluid bed process consists of bringing the feed to be treated into contact with a fluidized bed zone containing hot particles, generally coke particles. This produces an effluent consisting of hydrocarbon vapor and coke. which is deposited 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-based hydrocarbon feedstock is cracked in the presence of tire oil or at least a fraction thereof.

[0107] Step c) of splitting

[0108] During this step, the effluent from step b) is separated into at least one liquid hydrocarbon fraction, and optionally at least one gaseous fraction.

[0109] The fractionation step is preferably implemented on the effluent directly from step b) of thermal cracking, without an intermediate step.

[0110] When step b) is a coking step implemented in a delayed coking unit, this fractionation step also usually receives the coking charge before the implementation of step b), as previously described.

[0111] The nature and number of hydrocarbon fractions separated in step c) depends on the nature of the reaction carried out in step b) and the objective sought.

[0112] 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.

[0113] 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.

[0114] 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.

[0115] 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.

[0116] The recovered kerosene fraction preferably has a final boiling point below 300 °C, in particular 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.

[0117] The gas oil fraction under vacuum typically exhibits a distillation range from 350-375 °C up to 525 °C - 540 °C.

[0118] In the context of a viscoreduction step, the fractionation implemented typically allows the separation of a naphtha, kerosene, diesel fraction, a diesel fraction under vacuum and a viscoreduction residue.

[0119] In a coking step, the fractionation implemented typically allows the effluent to be separated into naphtha (with typically a final boiling point of about 170 °C), light diesel (distilling typically in the range of 170-370 °C), heavy diesel (distilling typically in the range of 370-525 °C), and residue (typically having an initial boiling point of 520 °C to 540 °C).

[0120] Typically, fractionation is carried out under the usual fractionation conditions following a coking or viscoreduction step.

[0121] 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 mbar, more preferably from 0.5 to 10 mbar.

[0122] Processing step d)

[0123] 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.

[0124] These heteroatoms can be nitrogen, sulfur, oxygen, silicon, halogens, and / or metals.

[0125] 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).

[0126] 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.

[0127] 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.

[0128] 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.

[0129] Advantageously, step d) of hydrotreating and / or hydrocracking and / or fluid catalytic cracking can thus be implemented in one or more hydrotreating units and / or hydrocracking units and / or catalytic cracking units existing fluids of a refinery, usually used to process feedstocks of fossil origin, and in particular specific fractions thereof.

[0130] The present invention can therefore be implemented in an existing refinery, without having to modify it. Detailed description of the figures

[0131] 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:

[0132] Figure 1 schematically represents a first possible embodiment of the invention,

[0133] Fig. 2 schematically represents a second possible embodiment of the invention.

[0134] In the figures, identical elements are designated by the same reference numerals.

[0135] In a possible embodiment of [Fig. 1], a heavy hydrocarbon feedstock of fossil origin of the type previously described (1) is at least partially cracked in a Cunit thermal cracking unit (visbreaking or coking unit). The thermal cracking unit is suitable for carrying out step b) of the process. Any type of unit 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.

[0136] According to the invention, a tire oil, or at least a fraction of tire oil (10), is sent into the Cunit thermal cracking unit, mixed with the heavy hydrocarbon feedstock of fossil origin (1) or separately.

[0137] The effluent (2) exiting the thermal cracking unit is then fractionated, in particular directly, without an intermediate step, in a Funit fractionation unit, capable of implementing step c), to be fractionated there into at least one liquid hydrocarbon fraction.

[0138] In the example shown, the effluent (2) is fractionated into a gaseous fraction (3), and here into four liquid hydrocarbon fractions, for example into a naphtha fraction (4), a kerosene fraction (5), a diesel fraction (6), and a residue (7). 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 thermal cracking reaction implemented. Depending on the conditions of the thermal cracking reaction, the fractionation unit may be integrated into the thermal cracking unit (for example, comprising one or more side draw-offs) or be a separate unit, in particular a fractionation column.

[0139] Depending on the nature of any impurities present, a separated hydrocarbon liquid fraction may be sent to a hydrotreating unit and / or a hydrocracking unit and / or a fluid catalytic cracking (FCC) unit, either alone or mixed with at least one other separated hydrocarbon liquid fraction, or with another refinery effluent. One or more hydrotreating and / or hydrocracking and / or fluid catalytic cracking units may thus be provided, each dedicated to one or more separated hydrocarbon liquid fractions. In the example, three separate hydrotreating units, HDTi, HDT2, and HDT3, are planned, treating fractions (4), (5), and (6) separately, respectively, and a hydrocracking unit (HCKi) or a fluid catalytic cracking unit (FCCi) is planned to treat residue (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.

[0140] 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.

[0141] During the implementation of step b), a solid or liquid residue (11) (under the operating conditions of step b) is produced according to the thermal cracking implementation conditions, as previously described. The solid residue (coke) can be reused for the manufacture of tires, adsorbents and / or catalysts, while the liquid residue can be used for the manufacture of heavy fuel oils (fuel oil, etc.).

[0142] The embodiment shown [Fig. 1] can in particular be implemented in a viscoreduction unit or a coking unit comprising a fluidized bed reactor.

[0143] Figure 2 represents another possible embodiment of the process according to the invention implemented in a CRunit delayed coking unit. In this embodiment, the residue (11) is therefore solid (coke).

[0144] The feed (1) is first sent into the Funit fractionation unit. The feed (1) generally enters the lower part of the Funit fractionation unit, below the effluent inlet (2).

[0145] The heaviest fraction (residue) (7) separated in this fractionation unit Funit is sent in whole to the delayed coking unit CRunit, typically to one of the two coke drums that this type of unit usually comprises, in which it undergoes thermal cracking.

[0146] The effluent (2) exiting the coke drums is sent to the Funit fractionation unit. The Funit fractionation unit allows the separation of the heaviest fraction (7), a heavy gas oil (6), a light gas oil (5), a coke naphtha (4) and gases (3).

[0147] In the embodiment shown, the entirety of the heaviest fraction (7) is sent to the CRunit delayed coking unit. However, the invention is not limited to this embodiment, and it would be conceivable to send only a portion of the heaviest fraction (7) to the CRunit delayed coking unit, the other portion being sent, for example, to an HCKi hydrocracking unit, or other.

[0148] According to the invention, tire oil, or at least a fraction thereof, (10), is introduced into the CRunit delayed coking unit, here mixed with the heavy fraction (7) of the feedstock. The tire oil, or at least a fraction thereof, could also be introduced directly, separately, into the CRunit delayed coking unit.

[0149] 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.

[0150] The invention is illustrated by the following examples given by way of non-limiting example. Examples

[0151] A non-limiting example of implementation of the invention is now described.

[0152] Conversion by delayed coking

[0153] A vacuum residue (denoted RSV) is converted in a delayed coking unit (hereafter referred to as a "delayed coker") under the following conditions:

[0154] Quantity of RSV processed: 2.8 kg

[0155] Temperature: 440 °C

[0156] Absolute pressure: 1.5 bar

[0157] Maturation: 3 hours

[0158] Nitrogen flow rate at the head: 50 L / hour

[0159] Nitrogen flow rate at the bottom: 300 L / hour

[0160] The characteristics of the RSV are summarized in Table 1

[0161] [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

[0162] In this example, a tire oil is used that has been previously distilled in order to retain only the 375+ cut (noted TPO 375+), exhibiting the properties gathered in Table 2.

[0163] [Tables2] Distillation TPO 375+ mass % T (°C) PI 359 10 393 20 408 30 422 40 437 50 453 60 471 70 493 80 520 90 564 PF 687

[0164] 2.8 kg of RSV are introduced into the delayed coker with 0.7 kg of TPO 375+, which corresponds to an RSV:TPO 375+ ratio of 80:20.

[0165] The effluent from the delayed coker is fractionated in a distillation column. The fractions obtained are detailed in Table 3.

[0166] [Tables3] Outputs delayed coker 100% RSV RSV + TPO 3 75+ Gas (% by mass) 12.5 12.4 Naphtha (<145°C) (% by mass) 4.0 3.0 LCGO (145-375°C) (% by mass) 38.5 40.5 HCGO (375+) (% by mass) 8.4 11.1 Coke (% by mass) 36.6 33.0 Total 100.0 100.0

[0167] Table 4 lists the qualities of the effluent at the outlet of the distillation column.

[0168] [Tables4] Unit Charge Effluent RSV TPO 375+ 100% RSV RSV + TPO 375+ Density at 15 °C g / L — — 857.7 875.2 Carbon % by mass 83.5 87.7 84.5 85.6 Hydrogen % by mass 9.6 9.8 11.8 12.1 Calculated Oxygen % by mass 1.5 1.3 0.1 Nitrogen ppm 3615 8800 742 1975 Sulfur ppm 50660 9000 23430 19900

Claims

Demands

1. A process for manufacturing hydrocarbon fluids from a heavy hydrocarbon feedstock of fossil origin and a tire oil, the process comprising: a) a step of supplying a tire oil or at least a fraction of a tire oil, b) a thermal cracking step in a visbreaking unit or a coking unit during which said heavy hydrocarbon feedstock of fossil origin, or a fraction of said heavy fraction of said heavy hydrocarbon feedstock of fossil origin, is subjected to thermal cracking under visbreaking or coking conditions in the presence of the tire oil or at least a fraction of tire oil supplied by step a), and an at least partially cracked effluent and a liquid or solid residue are produced, c) a fractionation step in which the effluent from step b) is fractionated into at least one liquid hydrocarbon fraction.

2. A manufacturing process according to claim 1, wherein, prior to step b), said heavy hydrocarbon feedstock of fossil origin is fractionated into a heavy fraction and a fraction lighter than the heavy fraction, and said heavy fraction is sent to step b) of thermal cracking to be cracked there with tire oil or at least a fraction of tire oil supplied in step a).

3. A manufacturing process according to claim 1 or 2, wherein step b) of thermal cracking is carried out with a ratio of tire oil or tire oil fraction(s) / heavy hydrocarbon filler of fossil origin, or tire oil or tire oil fraction(s) / heavy hydrocarbon filler of fossil origin, of 0.1 to 50% by mass.

4. A manufacturing process according to any one of claims 1 to 3, wherein said tire oil or at least a fraction of tire oil comprises one or more of the following characteristics: - 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 aromatic content of 15 to 80% by mass.

5. A manufacturing process according to any one of claims 1 to 4, wherein step a) provides at least one tire oil 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 at most 550 °C, (v) a residue-type fraction having an initial boiling point of at least 490 °C.

6. A manufacturing process according to claim 5, characterized in that step a) provides at least one residue-type fraction and / or at least one vacuum-type diesel-type fraction.

7. A manufacturing process according to any one of claims 1 to 6, 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 obtained tire oil 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.

8. A manufacturing process according to any one of claims 1 to 7, 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 a treated effluent having a reduced content of heteroelements and / or olefins and / or dienes and / or aromatics, and / or further cracked.

9. A manufacturing process according to claim 8, 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.

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

11. A manufacturing process according to any one of claims 1 to 10, wherein step b) of cracking is carried out under coking conditions and the solid residue produced during this step 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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