Method for recycling rubber-based solid material from solid automotive waste

Abstract

The present invention relates to a process for recycling a rubber-based solid material M1 from solid automotive waste W, a recycling unit for carrying out the process, and an automotive material comprising one or more products obtained by the process.

Description

[0001] The present invention relates to a method for recycling a rubber-based solid material M1 from solid automotive waste W, a recycling unit for carrying out the method, and an automotive material comprising one or more products obtained by the method.

[0002] The recycling of end-of-life vehicles has been ongoing for many years. In particular, research has been conducted on recycling tires, windows, motors, etc. However, very few methods have been developed for recycling automotive shredder residue (ASR). As is known in the art, ELVs (End-of-Life Vehicles) are processed according to a three-stage process: decontamination, dismantling, and shredding. Ferrous components comprise approximately 70-75% by weight of the shredded material, while non-ferrous metals comprise approximately 5% by weight. The remaining 20-25% by weight is referred to as automotive shredder residue (ASR), and this proportion in ELVs has increased in recent years and is likely to continue to increase, as can be seen in R. Cossu et al., “Automotive shredder residue (ASR) management: An overview”, Waste Management, Vol. 45, November 2015, pp. 143-151. Therefore, methods for recycling ASR must be developed.For example, EP0692356 proposes recycling automotive shredder residue by preparing composite materials containing ASR and virgin polymers; Vijayan, SK; Kibria, MA; Uddin, MH; Bhattacharya, S. “Pretreatment of Automotive Shredder Residues, Their Chemical Characterization, and Pyrolysis Kinetics.” Sustainability 2021, 13, 10549 proposes recycling automotive shredder residue through pyrolysis; and Juliana Argente Caetano, Valdir Schalch, Javier Mazariegos Pablos “Characterization and recycling of the fine fraction of automotive shredder residue (ASR) for concrete paving blocks production” Clean Technologies and Environmental Policy (2020). 22:835-847 proposes recycling ASR by solidifying it with cement, gravel, and sand used in paving brick production. As can be seen from the prior art, there is no technology that allows for the extraction of high-value pyrolysis oil from ASR, particularly for the production of high-value products. Therefore, there remains a need to provide improved methods for recycling solid automotive waste.

[0003] EP 3 907 267 A1 relates to a method for purifying crude pyrolysis oil derived from the pyrolysis of plastic waste to obtain purified pyrolysis oil with reduced nitrogen, sulfur and halogen content compared to the crude pyrolysis oil provided.

[0004] WO 2015 / 184343 A1 relates to the manufacture of a durable thermosetting in-mold finishing film (TIMFF) that combines in-mold decoration and in-mold coating capabilities, to molded articles having a TIMFF that adheres to its surface and both displays decoration and provides protection, and to thermosetting resin formulations for manufacturing TIMFF.

[0005] WO 2024 / 033212 A1 relates to a method for depolymerizing mixed automotive plastic waste via thermocatalytic degradation.

[0006] US 5,554,657 A relates to a method for recovering polyester polymers from a mixed polymer recycling stream using a solvent that selectively dissolves the polyester polymers and substantially does not dissolve most other polymers expected to be present in the mixed polymer recycling stream.

[0007] Zhao Yi-Bo et al., “Solvent-based separation and recycling of wasteplastics: A review”, CHEMOSPHERE, October 1, 2018, pp. 707-720, focus on an environmentally friendly and potentially profitable method for the separation and recycling of plastics and solvent extraction.

[0008] Therefore, the object of this invention is to provide an improved method for recycling solid automotive waste W, particularly automotive scrap (ASR), which allows for the production of high-value pyrolysis oils capable of producing high-value products. In fact, the aim is to develop a method for improving the sustainability of recycling methods in the automotive industry.

[0009] Therefore, the present invention relates to a method for recycling a rubber-based solid material M1 from solid automotive waste W, the method comprising:

[0010] (i) Provide a solid automotive waste W comprising a rubber-based solid material M1, wherein W further comprises one or more solid materials M2 having a chemical composition different from that of the rubber-based solid material M1, wherein the rubber-based solid material M1 comprises one or more halogens in addition to rubber and / or within rubber.

[0011] (ii) Separate M1 and M2 from W provided in (i), including

[0012] Material W is subjected to kinetic energy separation or electrostatic separation to obtain a mixture MS(1) containing rubber-based solid material M1 and a mixture MS(2) containing one or more solid materials M2 that is less M1 than W.

[0013] (iii) By sorting the rubber-based material M1 contained in MS(1) obtained in (ii) by elemental composition, a halogen-rich rubber-based solid material fraction f11 containing one or more halogens is obtained, and a halogen-poor rubber-based solid material fraction f12 containing rubber and depleted of one or more halogens compared to M1 is obtained.

[0014] (iv) Optionally, the halogen-poor fraction f12 obtained according to (iii) is subjected to purification treatment to obtain a purified solid mixture MP containing rubber;

[0015] (v) subjecting the halogen-poor rubber-based solid material fraction f12 containing rubber obtained according to (iii) or the purified solid mixture MP containing rubber obtained according to (iv) to pyrolysis in the pyrolysis reaction unit RU(p) to obtain pyrolysis oil.

[0016] Step (i)

[0017] Preferably, the solid automotive waste W is obtained from scrapped vehicles, and more preferably, the solid waste W is automotive shredded residue (ASR).

[0018] Automotive slag residue (ASR) can be obtained through vehicle shredding, preferably through it. More preferably, automotive slag residue can be obtained through vehicle decontamination, vehicle dismantling, vehicle shredding, and separation of metal particles from the shredded vehicle.

[0019] The vehicle is typically an end-of-life vehicle (also known as an "ELV"), typically at least 15 years old. The vehicle can be a passenger car, light or heavy-duty truck, motorcycle, multi-purpose vehicle, agricultural vehicle, or recreational vehicle. The vehicle can be an electric vehicle, such as a pure electric vehicle or a hybrid electric vehicle.

[0020] In vehicle decontamination, harmful liquids (such as fuel, lubricating oil, coolant, brake fluid) and batteries can be removed from the vehicle before crushing.

[0021] Vehicle dismantling can include the selective removal of parts such as engines, transmissions, tires, glass, and plastics for reuse as spare parts in the second-hand market. Dismantling can also include the removal of larger plastic components, such as bumpers, dashboards, and fluid containers, for individual recycling of the plastics.

[0022] ASR can include additional waste from other sources. For example, trash from a previous owner may be left in the trunk or inside the vehicle. The advantage of the method of this invention is that it can handle ASRs with a wide variety of compositions.

[0023] Crushing can be done using a vehicle crusher. Vehicle crushers are manufactured in various sizes. Typically, a vehicle crusher includes a heavy-duty, high-speed rotating rotor that can rotate in a vertical or horizontal plane and is usually equipped with a swing hammer. The vehicle crusher tears and crushes the vehicle wreckage until its parts are reduced to fragments with a desired size (e.g., up to 30 cm, preferably 1 mm to 15 cm). The fragments can then pass through a grid and exit the rotor housing.

[0024] After crushing, metal fragments (such as ferrous and non-ferrous metal fragments) can be separated from the crushed vehicle. Ferrous metal fragments can be removed using a magnetic separator. Non-ferrous metal fragments can be separated from the crushed vehicle using an eddy current separator, a density-based heavy media flotation device, or by manual sorting. Typically, 60-90 wt.% of the vehicle's weight is metal, which can be separated from the crushed vehicle.

[0025] Automotive debris can account for approximately 10-40 wt.% of the original vehicle weight, preferably 15-35 wt.%, and particularly 20-30 wt.%.

[0026] Automotive debris can include fragments of various polymer vehicle parts, such as bumpers, interior panels, dashboards, cable insulation, fuel tanks, electrical insulation materials, flexible foam seats, foam insulation panels, automotive suspension bushings, electrical potting compounds, body parts, pillar covers, spoilers, polymer parts coated with automotive paint, wheel covers, gears, bushings, cams, bearings, weather-resistant coatings, interior and exterior trim, fuel systems, gear housings, headlight retainers, engine hoods, connector housings, door handles, carburetor components, exterior mirror components, windshield wiper components, windshield wiper protection housings, decorative grilles, hood strips, roof rails, window frames, sliding roof frames, antenna covers, headlights and taillights, radiator grilles and exterior body parts, engine hoods, cylinder head covers, intake manifolds, engine hoods, turbocharger housings, and fragments of turbocharger valves.

[0027] Automotive debris can contain fragments of various polymer vehicle parts, such as the following:

[0028] - Bumpers, interior panels, dashboards, cable insulation, where these components are typically made of polypropylene;

[0029] - Fuel tanks, electrical insulation materials, where these fragments are typically made of polyethylene;

[0030] - Soft foam seats, foam insulation panels, automotive suspension bushings, electrical potting compounds, rigid plastic parts, transmission mounts, engine mounts, seals, and impact-resistant foam parts, among which these components are typically made of polyurethane;

[0031] - Body parts, dashboards, wheel covers, where these components are typically made of acrylonitrile-butadiene-styrene;

[0032] - Gears, bushings, cams, bearings, turbocharged air coolers, cylinder head covers, oil pans, engine cooling systems, thermostat and heater housings, exhaust systems including muffler and catalytic converter housings, intake manifolds, timing chain belt covers, where these components are typically made of nylon 6 or nylon 6.6.

[0033] - Interior and exterior trim, fuel systems, small gears, where these components are typically made of polyoxymethylene;

[0034] - Wiper arms and gear housings, headlight retainers, connector housings, where these components are typically made of polyethylene terephthalate; and

[0035] - Door handles, bumpers, carburetor parts, where these components are typically made of polybutylene terephthalate.

[0036] Automotive debris may contain at least 30 wt.-%, preferably at least 40 wt.-%, and particularly at least 50 wt.-%, of polymeric vehicle parts.

[0037] Automotive debris may contain at least 20 wt.% of, preferably at least 30 wt.% of, and particularly at least 40 wt.% of, fragments of polymer vehicle parts, which are black polymer vehicle parts. Black polymer vehicle parts typically contain carbon black pigment.

[0038] Automotive debris may contain up to 15 wt.-%, preferably up to 10 wt.-%, and particularly up to 5 wt.-%, of metal fragments, such as ferrous and nonferrous metal particles.

[0039] Automotive debris may contain up to 15 wt.% of wood and cardboard, preferably up to 10 wt.% and particularly up to 5 wt.% of wood and cardboard.

[0040] Automotive debris may contain up to 15 wt.-%, preferably up to 10 wt.-%, and particularly up to 5 wt.-%, of glass fragments, such as broken car window glass fragments.

[0041] Vehicle crushing residue can be separated into crushed light fraction (SLF) and crushed heavy fraction (SHF). The separation of SLF and SHF can be achieved through air classification. Another method of air classification is through the rotary movement of the vehicle crusher, which creates a fan-shaped motion that blows out the crushed light fraction, while the crushed heavy fraction exits the vehicle crusher through a grille.

[0042] SLF can be present in amounts of 55-90 wt.-%, preferably 65-85 wt.-%, and particularly 70-80 wt.-%, of automotive crush residue. SHF can represent a balance made up to 100 wt.-%.

[0043] SHF can be present in amounts of 10-45 wt.-%, preferably 15-35 wt.-%, and particularly 20-30 wt.-%, of automotive crush residue. SLF can represent a balance made up to 100 wt.-%.

[0044] SLF typically contains a lower weight percentage of rubber particles than SLF.

[0045] SLF typically contains a lower weight percentage of glass particles than SLF.

[0046] SLF typically contains a lower weight percentage of metal particles than SLF.

[0047] SLF typically contains a higher weight percentage of polyurethane foam particles than SLF.

[0048] SLF typically contains a lower weight percentage of solids and sand than SLF.

[0049] Preferably, at least 20% by weight, more preferably at least 30% by weight, more preferably at least 40% by weight, more preferably at least 50% by weight, and more preferably at least 60% by weight of M1 is composed of rubber.

[0050] Preferably, M2 can be one or more polymer-based materials, which are not rubber. Preferably, the polymer-based materials other than rubber include one or more of the following: polyurethane, polyamide-based materials such as polyamide 6 (PA6), polyolefin-based materials such as polyethylene (PE), polypropylene (PP), polymethylpentene (PMP), polybutene-1 (PB-1), ethylene-octene copolymers, stereoblock PP, olefin block copolymers and / or propylene-butane copolymers and polyisobutylene (PIB), and polyesters such as polyethylene terephthalate (PET) and polybutylene terephthalate (PBT).

[0051] Optionally, the method further includes

[0052] M2 is sorted by chemical composition to obtain one or more fractions according to polymer type, where M2 is one or more of the following: polyurethane, polyamide-based materials and polyolefin-based materials such as polyethylene (PE), polypropylene (PP), polymethylpentene (PMP), polybutene-1 (PB-1), ethylene-octene copolymers, stereoblock PP, olefin block copolymers and / or propylene-butane copolymers and polyisobutylene (PIB), and polyesters such as polyethylene terephthalate (PET) and polybutylene terephthalate (PBT). For example, fractions containing polyurethane, fractions containing polyamide, fractions containing polyolefin-based materials such as PE and PP, and / or fractions containing polyester.

[0053] According to this option, the method further includes subjecting each of one or more fractions obtained from M2 to depolymerization conditions.

[0054] Preferably, according to (i), the solid automotive waste W comprising a rubber-based solid material M1, W further comprises one or more solid materials M2 having a chemical composition different from that of the rubber-based solid material M1.

[0055] W is crushed and / or cut in crushing unit US1.

[0056] Preferably, the length of each side of the broken and / or cut material W is in the range of 0.5 to 10 cm, more preferably in the range of 0.5 to 5 cm.

[0057] Step (ii)

[0058] Preferably, the separation according to (ii) includes a kinetic energy separation method, which is a ballistic separation method or a size separation method, more preferably a ballistic separation method.

[0059] Alternatively, preferably, the separation according to (ii) includes an electrostatic separation method, which is a buoyancy separation method.

[0060] Any ballistic separation method known in the art (sorting by size and density) can be used for the kinetic energy separation method according to (ii). For example, the ballistic separation method may be as disclosed in DE 19535296 A1.

[0061] Any size separation method (sorting by size) known in the art can be used for the kinetic energy separation method according to (ii). For example, the separation method may be as disclosed in WO 2012 / 015299 A1.

[0062] Any sink-float separation method known in the art can be used for the kinetic separation method according to (ii). The sorting will depend on the density, surface properties, and hydrophobicity of the material to be sorted. For example, sink-float separation methods can be disclosed as in Markus Bauer et al., “Sink-float density separation of post-consumer plastics for feedstock recycling”, November 6, 2017, Journal of Material Cycles and Waste Management (2018) 20:1781-1791, https: / / doi.org / 10.1007 / s10163-018-0748-z

[0063] More preferably, the separation according to (ii) includes a ballistic separation method, and more preferably consists of such a method.

[0064] Step (iii)

[0065] Preferably, M1 has a halogen content in the range of 0.5 to 5 wt% based on the weight of M1, as determined as described in Analysis 2.

[0066] For example, X-ray measurement methods can be as disclosed in Cecilia Chaine et al., “Optimized industrial sorting of WEEE plastics: Development of fast and robust h-XRF technology for hazardous components”, Case Studies in Chemical and Environmental Engineering 7 (2023) 100292.

[0067] Optionally, after (ii) and before (iii), the method further includes

[0068] The washing of the rubber-based solid material M1 contained in MS(1) obtained according to (ii) is more preferably carried out with water, or one or more caustic agents, or one or more detergents, wherein the washed material M1 is dried after washing.

[0069] Alternatively, washing can be performed during the separation according to (ii).

[0070] Preferably, the sorting according to (iii) is automatic sorting.

[0071] Preferably, the sorting according to (iii) includes the use of one or more of a conveyor, sensor, light source, laser, X-ray source such as X-ray tube, radioactive isotope source, detector and camera.

[0072] Preferably, the sorting according to (iii) is an X-ray fluorescence sorting method.

[0073] In the context of this invention, the halogen content in halogen-rich rubber-based material fraction f11 is higher than the halogen-poor rubber-based material fraction f12.

[0074] Preferably, the halogen content in the halogen-rich rubber-based material fraction f11 is higher than the halogen content in M1.

[0075] Preferably, the halogen content in fraction f12 is lower than that in M1 and lower than that in f11. In fact, due to the separation by elemental composition according to (iii), the fraction to be pyrolyzed is halogen-poor or even halogen-free.

[0076] Without being bound by any theory, it has been found that this sorting (iii) is beneficial to downstream processing, especially pyrolysis, because it will allow for the delivery of high-quality pyrolysis, which will preferably not require additional processing, such as very expensive hydrogenation, before cracking (steam cracking) or conversion into syngas as in (vi).

[0077] This treatment before (v) or (vi) can also allow for reduced corrosion of equipment used for pyrolysis oil, such as pipes and containers.

[0078] The halogen-poor rubber-based solid material fraction f12, preferably up to 1000 ppmw, more preferably up to 500 ppmw, more preferably up to 250 ppmw, and more preferably up to 100 ppmw, is composed of halogens, the content of which is determined as described in Analysis 2.

[0079] Preferably, at least 20% by weight, more preferably at least 30% by weight, more preferably at least 40% by weight, more preferably at least 50% by weight, more preferably at least 60% by weight, and preferably at least 70% by weight of fraction f12 is composed of rubber.

[0080] Optionally, the sorting according to (iii) includes crushing the rubber-based solid material M1 contained in MS(1) obtained according to (ii) to obtain M1 sheet.

[0081] Preferably, the sorting according to (iii) includes

[0082] (iii.1) Spread the M1 sheet contained in MS(1) or the M1 sheet obtained as described in Example 10 onto the conveyor;

[0083] (iii.2) Automatic analysis of the rubber-based solid material M1 contained in MS(1) obtained according to (ii) and spread on the conveyor according to (iii.1), or the rubber-based solid material M1 sheet contained in MS(1) as defined in Example 10:

[0084] Use one or more of sensors, light sources, detectors and X-ray sources to identify the elemental composition of rubber-based materials or sheets of rubber-based materials;

[0085] (iii.3) Based on the presence of halogens, these materials are separated into at least two distinct fractions, thereby obtaining

[0086] - A fraction of halogen-rich rubber-based solid materials containing one or more halogens, f11, and

[0087] - A fraction of halogen-poor rubber-based solid materials f12, which is depleted of one or more halogens compared to M1;

[0088] (iii.4) Remove the fraction f12 obtained from (iii.3) from the conveyor.

[0089] Preferably, the conveyor is a belt conveyor.

[0090] Step (iv)

[0091] Optionally, in addition to rubber, M1 may also contain one or more fillers F, which preferably include one or more of the following: magnesium silicate hydrate, glass fiber, aluminum hydroxide (inorganic flame retardant), ammonium polyphosphate (inorganic flame retardant), barium sulfate, calcium carbonate, wollastonite, carbon black, and titanium dioxide.

[0092] In the context of this invention, the term "filler" (as is also known in the art) refers to an inorganic material (inert material) that has a structural function and is typically added to a substance (e.g., a polymer) to improve certain characteristics, such as physical and / or mechanical properties. For example, fillers are incorporated into polymer-based materials to improve strength, stiffness, thermal conductivity, and reduce shrinkage. Examples of fillers include glass fibers, carbon particles such as carbon black, or talc. Fillers are not additives; additives are, in fact, active (non-inert) substances.

[0093] Preferably, one or more fillers F are present in M1 in an amount ranging from 0.05 to 75 wt% based on W.

[0094] Preferably, in addition to rubber, the halogen-poor rubber-based solid material fraction f12 also contains one or more fillers F; more preferably, the one or more fillers F contain one or more of the following: magnesium silicate hydrate, glass fiber, aluminum hydroxide (inorganic flame retardant), ammonium polyphosphate (inorganic flame retardant), barium sulfate, calcium carbonate, wollastonite, carbon black, and titanium dioxide.

[0095] Preferably, one or more fillers F are present in fraction f12 in an amount ranging from 0.1 to 75 wt%, more preferably from 5 to 70 wt%, based on the weight of the halogen-poor rubber-based solid material fraction f12.

[0096] Preferably, according to (iv), the halogen-poor rubber-based solid fraction f12 obtained according to (iii) undergoes purification treatment including

[0097] (iv.1) subject fraction f12 containing impurities and / or one or more fillers F to rubber dissolution conditions in the presence of solvent SD, wherein the impurities and F are inert to the rubber dissolution treatment, thereby obtaining an intermediate mixture containing impurities and / or one or more fillers F and further containing rubber dissolved in SD.

[0098] (iv.2) The intermediate mixture obtained according to (iv.1) is fed into the solid-liquid separation unit SU to obtain a mixture M(F) containing impurities and / or one or more fillers F, and a mixture MD containing rubber dissolved in SD that is leaner in impurities and one or more fillers F (if any) compared to f12.

[0099] (iv.3) subject the MD containing rubber dissolved in SD obtained according to (iv.2) to precipitation conditions to obtain a purified solid mixture MP containing precipitated rubber.

[0100] Preferably, the solvent SD used in (iv) is selected from the group consisting of: n-hexane, n-heptane, 2,2-dimethylbutane, toluene, benzene, cyclohexane, methylcyclohexane, cyclopentane, methylcyclopentane, and mixtures of two or more thereof, more preferably selected from the group consisting of: n-hexane, n-heptane, 2,2-dimethylbutane, methylcyclohexane, and methylcyclopentane.

[0101] In the context of this invention, the rubber dissolution process is carried out at a temperature below the boiling temperature of SD.

[0102] Preferably, the SD has a pressure range of 0 to 10 MPa. 1 / 2 Within the range, more preferably within 0 to 8 MPa 1 / 2 Within the range, more preferably within 0 to 7 MPa1 / 2 Hansen solubility parameter δ within the range H .

[0103] In the context of this invention, the Hansen solubility parameter δ H δ is a known parameter characterizing the solubility of a compound. H This involves the energy derived from hydrogen bonds between molecules. For many compounds, such as xylene, toluene, and cyclohexane, the Hansen parameter δ... H It can be found in standard chemistry books. The Hansen solubility parameter δ mentioned in this invention... H This refers to the values ​​listed below: Hansen, CM, Hansen Solubility Parameters - A user's handbook, 2nd edition, CRC Publishing, Boca Raton, USA, 2007.

[0104] -- (iv.1)

[0105] Preferably, according to (iv.1), the rubber dissolution process does not involve solvents other than SD.

[0106] Preferably, 5 to 99% by weight, more preferably 20 to 98.5% by weight, and even more preferably 30 to 98% by weight of W is composed of M1.

[0107] Preferably, the rubber melting treatment according to (iv.1) is carried out at a temperature in the range of 55°C to 200°C, more preferably in the range of 100°C to 160°C.

[0108] Preferably, the rubber dissolution treatment according to (iv.1) is carried out under a pressure in the range of 800 to 200,000 hPa, more preferably in the range of 800 to 10,000 hPa.

[0109] The method of the present invention features an improved polymer extraction and separation process, which is carried out by: extracting the desired polymer using solvent SD at a high temperature (i.e., preferably 55°C to 200°C, more preferably 100°C to 160°C), and then obtaining these polymers by precipitation (e.g., by cooling) of the desired polyolefin / rubber from a supersaturated solution of a single nonpolar solvent. This method simplifies the entire process (including solvent recycling) and the equipment required to carry out the process on a continuous, large-scale basis, while reducing energy consumption compared to methods known in the art.

[0110] Preferably, the dissolution treatment according to (iv.1) is carried out in reactor unit RD.

[0111] Preferably, fraction f12 is fed into reactor unit RD via gravity or pneumatic conveying.

[0112] Preferably, the rubber dissolution treatment according to (iv.1) includes:

[0113] The solid fraction f12 is contacted with the solvent SD at a weight ratio of 1:1 to 1:20, more preferably 1:3 to 1:15, and even more preferably 1:4 to 1:12, to obtain an intermediate mixture containing impurities and / or one or more fillers F and further containing rubber dissolved in SD.

[0114] Preferably, the temperature of the intermediate mixture obtained according to (iv.1) is substantially maintained, more preferably maintained, via one or more heating pipes for transferring the intermediate mixture into the SU.

[0115] -- (iv.2)

[0116] Preferably, the solid-liquid separation unit SU used in (iv.2) is a filtration unit or a centrifugation unit, more preferably a filtration unit, which more preferably has a mesh size in the range of 1 to 100 micrometers, more preferably in the range of 10 to 50 micrometers.

[0117] Preferably, the filtration unit includes a filter for blocking a mixture M(F) containing impurities and / or one or more fillers F and a receiving container for containing a mixture MD of rubber dissolved in SD.

[0118] Preferably, the filter unit is under pressure p F The following operation, where p F ≥ 1 bar (absolute value), more preferably p F The range is from 1 to 30 bar (absolute value), more preferably from 1 to 10 bar (absolute value), and even more preferably from 1 to 6 bar (absolute value).

[0119] -- (iv.3)

[0120] Preferably, the precipitated rubber is in the form of powder, with particles having an average size in the range of 1 micrometer to 1 millimeter, more preferably in the range of 10 micrometers to 100 micrometers, the average particle size being determined as defined in Analysis 1.

[0121] Preferably, the halogen content in the MP obtained according to (iv.3) is lower than the halogen content in the W provided in (i).

[0122] Preferably, the MP obtained according to (iv.3) has a halogen content of up to 1000 ppmw, more preferably up to 500 ppmw, more preferably up to 250 ppmw, and more preferably up to 100 ppmw based on the weight of MP, which is determined as described in Analysis 2.

[0123] Preferably, the precipitated rubber obtained according to (iv.3) has a halogen content of up to 1000 ppmw, more preferably up to 500 ppmw, more preferably up to 250 ppmw, and more preferably up to 100 ppmw based on the weight of the precipitated rubber, which is determined as described in Analysis 2.

[0124] Preferably, the MP obtained according to (iii) has a Cl content of up to 1000 ppmw, more preferably up to 500 ppmw, more preferably up to 250 ppmw, and more preferably up to 100 ppmw based on the weight of MP, which is determined as described in Analysis 2.

[0125] Preferably, the precipitated rubber obtained according to (iii) has a Cl content of up to 1000 ppmw, more preferably up to 500 ppmw, more preferably up to 250 ppmw, and more preferably up to 100 ppmw based on the weight of the precipitated rubber, the content being determined as described in Analysis 2.

[0126] Preferably, the MP obtained according to (iv.3) has an O content of up to 1000 ppmw based on the weight of MP.

[0127] Preferably, the MP obtained according to (iv.3) has an N content of up to 1000 ppmw based on the weight of MP.

[0128] Temperature drop

[0129] Preferably, (iv.3) includes

[0130] - MD containing rubber dissolved in SD, obtained according to (iv.2), is subjected to temperature T. P and pressure p P The lower part undergoes precipitation, in which T P < T D T D It is based on the dissolution temperature (iv.1), and T P < 100°C, thereby obtaining an intermediate mixture IM containing SD and precipitated rubber;

[0131] - The IM is transferred to the solid-liquid separation unit SU1 to obtain a purified mixture MP containing precipitated rubber and a liquid mixture containing SD.

[0132] Preferably, (iv.3) includes

[0133] - at temperature T P and pressure p P The MD containing rubber dissolved in SD, obtained by cooling according to (iv.2), is used for precipitation, where T P < T D T D It is based on the dissolution temperature (iv.1), and T P < 100°C

[0134] This yields an intermediate mixture IM containing SD and precipitated rubber;

[0135] - The IM is transferred to the solid-liquid separation unit SU1 to obtain a purified mixture MP containing precipitated rubber and a liquid mixture containing SD.

[0136] Preferably, T P < T D -5°C, more preferably T P ≤ T D -10°C, more preferably T P ≤ T D - 30°C, more preferably T P < T D - 30°C.

[0137] Preferably, the cooling according to (iv.3) includes

[0138] (iv.3.a) The cooling medium is transferred to the cooling jacket of the precipitation unit containing MD; or

[0139] (iv.3.b) Allow MD to stand in the precipitation unit.

[0140] Preferably, the cooling rate is in the range of 2 to 200 K / h, more preferably in the range of 3 to 150 K / h, even more preferably in the range of 20 to 120 K / h, and even more preferably in the range of 10 to 60 K / h.

[0141] Antisolvent addition

[0142] Preferably, (iv.3) includes

[0143] - An intermediate mixture IM' containing SD, a polar solvent and precipitated rubber is obtained by subjecting MD, which contains rubber dissolved in SD, obtained according to (iv.2), to precipitation by contacting MD with a polar solvent (also known as an "antisolvent");

[0144] - The IM' is conveyed to the solid-liquid separation unit SU2 to obtain a purified mixture MP containing precipitated rubber, and a liquid mixture containing SD and a polar solvent.

[0145] Optionally, (iii) further includes

[0146] The solid mixture MP is washed, more preferably with one or more of methanol, ethanol, propanol, isopropanol, acetonitrile, ethyl acetate, acetone and water; and optionally the washed solid mixture MP containing precipitated rubber is dried.

[0147] Preferably, the contact between MD and the polar solvent is carried out at a temperature in the range of 10°C to 120°C, more preferably in the range of 20°C to 60°C.

[0148] Preferably, the contact between the MD and the polar solvent is carried out at a pressure of 0 to 10 bar (absolute value), more preferably at a pressure of 0.5 to 2 bar (absolute value).

[0149] Preferably, the polar solvent is selected from the group consisting of: water, ethanol, methanol, propanol, butanol, acetone, dimethyl sulfoxide, acetonitrile, dimethylformamide, ethyl acetate, sulfolane, dichloromethane, tetrahydrofuran, and mixtures of two or more thereof; more preferably, it is selected from the group consisting of: water, acetone, ethanol, methanol, and mixtures of two or more thereof.

[0150] Preferably, the polar solvent has a strength greater than 5 MPa. 1 / 2 Preferably between 6 and 50 MPa 1 / 2 Within the range, more preferably within 10 to 30 MPa 1 / 2 Hansen solubility parameter δ within the range H .

[0151] Flash evaporation

[0152] Preferably, (iv.3) includes

[0153] By subjecting the MD containing rubber dissolved in SD, obtained according to (iv.2), to precipitation in a flash evaporator, a gaseous stream G3 containing evaporated solvent is obtained, and a purified mixture MP containing precipitated rubber is further obtained.

[0154] Optionally, the method further includes

[0155] At least a portion of the solvent SD recovered after (iv.3) will be recycled to the rubber dissolution treatment according to (iv.1);

[0156] Wherein recycling preferably includes

[0157] At least a portion of the solvent SD recovered after (iv.3) is transferred to distillation unit D to obtain purified solvent;

[0158] Purified solvents are used for the rubber dissolution treatment according to (iv.1).

[0159] Preferably, the distillation unit D is heated by a heating source, more preferably by steam. This heating source is preferably generated by the recirculated gas stream obtained after pyrolysis according to (v).

[0160] Optionally, the method further includes recycling both the solvent SD and the polar solvent by fractionation.

[0161] Step (v)

[0162] Preferably, the solid fraction f12 obtained according to (iii) or the purified mixture MP obtained according to (iv) contains an amount of rubber in the range of 90 to 100 wt%, more preferably in the range of 95 to 100 wt%, based on the weight of the solid mixture.

[0163] Preferably, (v) includes

[0164] (v.1) The solid fraction f12 obtained according to (iii) or the purified mixture MP obtained according to (iv) is fed into the pyrolysis reactor R(p);

[0165] (v.2) The rubber entering the pyrolysis reactor R(p) is heated at a temperature in the range of 350°C to 900°C, more preferably in the range of 400°C to 550°C, and at a pressure in the range of 0.5 to 2 bar (absolute value), more preferably in the range of 0.9 to 1.5 bar (absolute value);

[0166] (v.3) Remove the gas stream GS from the top of R(p) and subject GS to condensation conditions in the gas-liquid separation unit LGU to obtain pyrolysis oil.

[0167] Preferably, the feeding according to (v.1) is carried out via a metering unit, which is more preferably one or more of a screw, an extruder, and a rotary valve.

[0168] Another possibility is that the feed according to (v.1) is introduced into the pyrolysis reactor R(p) via a pneumatic conveyor or a liquid injector.

[0169] Preferably, the pyrolysis reactor R(p) is selected from the group consisting of: fluidized bed, moving bed, entrained fluidized bed, auger, screw reactor, extruder, stirred tank reactor, moving bed rotor-stator reactor, and rotary kiln, more preferably a fluidized bed. Preferably, the fluidized bed is bubbling, turbulent, rapid, or circulating.

[0170] Preferably, the pyrolysis is carried out in a pyrolysis reactor R(p) under an oxygen-free atmosphere.

[0171] Preferably, pyrolysis is carried out by thermal cracking (in the absence of a catalyst) or catalytic cracking, more preferably thermal cracking.

[0172] It should be noted that this catalyst is used to affect the properties of the pyrolysis products as known to those skilled in the art.

[0173] Preferably, the pyrolysis according to (v) is not a hydrothermal treatment.

[0174] Optionally, according to (v), the pyrolysis reactor R(p) contains trace amounts of water, wherein preferably the trace amounts of water are based on precipitated polyolefin P. P The total weight of water is less than 2 wt.%, more preferably less than 1 wt.%, and more preferably less than 0.1 wt.%.

[0175] Preferably, the pyrolysis reactor R(p) is water-free.

[0176] It is conceivable that, prior to the pyrolysis according to (v), the solid fraction f12 obtained according to (iii), or the purified mixture MP obtained according to (iv), could be subjected to pre-pyrolysis at a temperature in the range of 220°C to 360°C. If PVC is present in the solid mixture, such low-temperature pyrolysis allows for the pyrolysis of PVC. However, in the context of this invention, this step can be avoided given the specific method steps (i) to (iii) preceding (iv) of the method according to the invention.

[0177] Alternatively, in the pyrolysis reactor R(p), the solid fraction f12 obtained according to (iii), or the purified mixture MP obtained according to (iv), is mixed with one or more of CaO, Ca(OH)2, and CaCO3. Such additives allow for reaction with the resulting HCl and thus remove impurities such as chlorine from the PVC.

[0178] Alternatively, one could consider passing the gas stream GS leaving the pyrolysis reactor through a catalyst bed or adsorption bed to reduce the concentration of impurities and atoms other than C and H.

[0179] Preferably, in (v.3), after the GS is removed from R(p) and before the GS is subjected to condensation conditions in the LGU, the gas stream GS is passed through a filter unit, more preferably a filter, or a cyclone separator. Such a filter unit or cyclone separator allows dust particles to be removed from the gas stream GS before condensation. In addition to this dust removal, a catalyst bed or adsorption bed can be used upstream or downstream thereto to reduce the concentration of impurities and atoms other than C and H.

[0180] Preferably, according to (v.3), the GS is subjected to a condensation step in the LGU at a temperature ranging from 0°C to 80°C; more preferably, the LGU is a condenser, a scrubber, or a quencher.

[0181] Preferably, the gas stream GS in (v.3) undergoes a first condensation step at a temperature ranging from 50°C to 150°C and a second condensation step at a temperature ranging from 35°C to 0°C to obtain pyrolysis oil; each of the first and second condensation steps is more preferably carried out in a separate condenser or quencher. Alternatively, the gas stream GS in (v.3) preferably undergoes only one condensation step at a temperature ranging from 0°C to 80°C.

[0182] The non-condensable "permanent" gas G leaving the LGU can be used to generate process heat / electricity by combustion in a gas burner, gas engine, or combined heating and power generation unit. This combustion flue gas may require cleaning to remove dust, ash, and other components in accordance with emission regulations.

[0183] Preferably, the method further includes, after (v), using the pyrolysis oil obtained according to (v) as stream S O It is then transferred to the purification unit (PU) to obtain purified pyrolysis oil.

[0184] Preferably, the purification unit PU includes one or more of a filter, a centrifuge, a decanter, and a decanter-centrifuge; more preferably, it includes one or more of a filter, a centrifuge, and a decanter.

[0185] The pyrolysis oil obtained according to (v), more preferably (v.3), can be filtered, including possibly using a filter to remove solids. Alternatively, the pyrolysis oil can be centrifuged to remove solids.

[0186] Furthermore, in the purification unit (PU), water residue can be removed from the pyrolysis oil by decantation or centrifugation. Additionally, the pH can be adjusted to a maximum of 3, or alternatively, to at least 8, preferably at least 9. Preferably, this adjustment is made by adding an acid or base, such as an alkali metal hydroxide, for example sodium hydroxide (NaOH), potassium hydroxide (KOH), an alkaline earth metal hydroxide, for example calcium hydroxide (Ca(OH)2), NH3 or mixtures thereof, sulfuric acid (H2SO4), nitric acid (HNO3), or phosphoric acid (H3PO4).

[0187] Steps (vi) and (vii)

[0188] Preferably, the method further includes

[0189] (vi) subject at least a portion of the pyrolysis oil obtained according to (v) to

[0190] (vi.1) Cracking, thereby obtaining a stream P1 containing cracked hydrocarbons; and / or

[0191] (vi.2) Partial oxidation, thereby obtaining a synthesis gas flow P2 containing CO and H2.

[0192] Optionally, prior to the cracking according to (vi.1), at least a portion of the pyrolysis oil obtained according to (v) is mixed / blended with one or more of the following: pyrolysis oil other than the pyrolysis oil obtained according to (v), bio-oil, hydrotreated bio-oil, naphtha, and feedstock other than those listed above suitable for this type of (steam) cracking.

[0193] Optionally, prior to partial oxidation according to (vi.2), at least a portion of the pyrolysis oil obtained according to (v) is mixed / blended with one or more of the following: pyrolysis oil other than the pyrolysis oil obtained according to (v), bio-oil, hydrotreated bio-oil, and fossil co-processes suitable for partial oxidation, such as heating oil, vacuum residue, preferably vacuum distillation residue, crude oil residue, heavy crude oil, extra-heavy crude oil, oil sands bitumen, viscosity-reducing bottom residue, deasphalting bottom residue, C5 bitumen fraction, high-viscosity residue, fuel oil, pyrolysis gasoline, waste oil, and tar.

[0194] Preferably, the pyrolysis according to (vi.1) is carried out in a pyrolyzer, more preferably a steam pyrolyzer.

[0195] Preferably, the pyrolyzer is supplied with gas or electricity, more preferably electricity, and even more preferably electricity from a renewable source.

[0196] In the context of this invention, flow P1 is a gaseous flow.

[0197] Preferably, the pyrolysis according to (vi.1) is carried out at a temperature in the range of 400°C to 1000°C, more preferably in the range of 500°C to 900°C.

[0198] The cracking is preferably carried out according to methods known in the art, such as those cited in Ullmann's Encyclopedia of Industrial Chemistry, Ethylene, Chapter 5.1, pp. 469-475 (2012).

[0199] Preferably, the partial oxidation according to (vi.2) is carried out in a gasifier such as an entrained flow reactor and / or a fluidized bed reactor.

[0200] Partial oxidation is preferably performed according to methods known in the art.

[0201] Preferably, the method further includes

[0202] (vii) Preparation of polymer PA, including

[0203] One or more of the following are used: pyrolysis oil obtained according to (v), cracked hydrocarbons contained in stream P1 obtained according to (vi) as described herein, and CO and / or H2 synthesis gas contained in stream P2 obtained according to (vi) as described herein.

[0204] Preferably, the polymer PA is rubber.

[0205] Polymers PA that are rubber can be prepared using any method known in the art, such as the method disclosed in Ullmann's Encyclopedia of Industrial Chemistry, Rubber, 3. Synthetic Rubbers, Introduction and Overview, pp. 602-604 (2011), DOI10.1002 / 14356007.a23_239.pub5.

[0206] Preferably, the method further includes

[0207] (viii) Preparation of automotive materials, including

[0208] The use of one or more of the following: pyrolysis oil obtained according to (v), cracked hydrocarbons contained in stream P1 obtained according to (vi) as described herein, CO and / or H2 contained in syngas stream P2 obtained according to (v) as described herein, and polymer PA obtained according to (vii) as described herein.

[0209] The present invention further relates to a recycling unit for performing the method according to the invention, the recycling unit comprising:

[0210] The first separation unit SU(a) is used for kinetic energy separation or electrostatic separation;

[0211] The second separation unit SU(b) is used for sorting by element composition;

[0212] The means for conveying MS(1) to SU(b) is preferably one or more conveyors;

[0213] The pyrolysis reaction unit RU(p);

[0214] An outlet device for removing pyrolysis oil from RU(p);

[0215] Optional purification unit PU;

[0216] An inlet device optionally used to introduce f12 into the PU;

[0217] An outlet device optionally used to remove purified mixture MP from PU;

[0218] An inlet device used to introduce f12 or MP into RU(p).

[0219] Preferably, the PU includes a dissolution unit DU, a solid-liquid separation unit SU, and a precipitation unit PPU. Preferably, the SU is as disclosed herein.

[0220] Preferably, RU(p) is selected from the group consisting of: fluidized bed, moving bed, entrained fluidized bed, auger, screw reactor, extruder, stirred tank reactor, moving bed rotor-stator reactor, and rotary kiln, more preferably fluidized bed. Preferably, the fluidized bed is bubbling, turbulent, rapid, or circulating.

[0221] The present invention further relates to an automotive material, preferably a motor vehicle, comprising a polymer PA obtained according to the method of the present invention.

[0222] The present invention further relates to a method as described above, preferably a method as described above comprising (i) to (v) or (i) to (vi), wherein the method (further) comprises the step of converting a pyrolysis oil obtainable according to (v), or a cracked hydrocarbon contained in P1 obtainable according to (vi) as described herein, or CO and / or H2 contained in P2 obtainable according to (vi) as described herein, or a chemical material obtainable by the method described herein to obtain product Ω. The product Ω is preferably selected from...

[0223] - Building blocks or monoliths; or

[0224] - Polymer, preferably polymer A; polymer composition, preferably polymer composition A; or polymer product, preferably polymer product A; or

[0225] - Cleaning polymers, cleaning surfactants, descaling compounds, cleaning biocides, or combinations thereof; or

[0226] - Agricultural chemical compositions, agricultural chemical formulations, adjuvants, or agricultural chemical active ingredients; or

[0227] - Active pharmaceutical ingredients or intermediates thereof, pharmaceutical excipients, animal feed additives, human food additives, dietary supplements, aromatic chemicals or aromatic compositions; or

[0228] - Aqueous polymer dispersions, preferably polyurethane or polyurethane-poly(meth)acrylate hybrid polymer dispersions, emulsions, binders for paper and fiber coatings, UV-curable acrylic polymers for hot melts and coatings, polyisocyanates, hyperbranched polyester polyols, polymer dispersants for inorganic binder compositions, unsaturated polyester polyols, or 100% curable compositions; or

[0229] - Cosmetic surfactants, emollients, waxes, cosmetic polymers, UV filters, other cosmetic ingredients, or combinations thereof or formulations thereof; or

[0230] - Polymer B, polymer composition B, coating composition, other functional composition, foil, molded body, coating or coated substrate.

[0231] Further regarding the product Ω, it is preferred to be

[0232] The content of pyrolysis oil obtained or acquired according to (v) in product Ω, or cracked hydrocarbons contained in P1 obtained or acquired according to (vi) as described herein, or CO and / or H2 contained in P2 obtained or acquired according to (vi) as described herein, is 1 wt% or more, more preferably 2 wt% or more, more preferably 5 wt% or more, more preferably 15 wt% or more, more preferably 30 wt% or more, more preferably 40 wt% or more, more preferably 60 wt% or more, more preferably 80 wt% or more, more preferably 90 wt% or more, more preferably 95 wt% or more; and / or

[0233] The content of pyrolysis oil obtained or acquired according to (v) in product Ω, or cracked hydrocarbons contained in P1 obtained or acquired according to (vi) as described herein, or CO and / or H2 contained in P2 obtained or acquired according to (vi) as described herein, is 100 wt% or less, more preferably 95 wt% or less, more preferably 90 wt% or less, more preferably 50 wt% or less, more preferably 25 wt% or less, more preferably 10 wt% or less; and

[0234] The content is preferably determined based on a chain of custody model of identity preservation and / or separation and / or quality balance and / or certificate declaration, preferably based on quality balance, and preferably based on the International Sustainable Development and Carbon Certification (ISCC) standard.

[0235] The publicly disclosed prior art content; No. 684; paragraphs

[1000] to

[8005] ; ISSN: 2198-4786; publication date: February 12, 2024, shall be regarded as reference RF1, which is incorporated herein by reference in its entirety. Preferably, the product Ω mentioned in the preceding paragraph is the product as described in reference RF1; paragraphs

[1000] to

[8005] . Preferably, the method described herein is further a method for producing the product mentioned in the preceding paragraph.

[0236] The conversion step for obtaining product Ω preferably includes one or more steps as described below, and can be performed by conventional methods well known to those skilled in the art. The conversion step preferably includes one or more steps selected from the following:

[0237] Recycling, preferably through depolymerization, gasification, pyrolysis and / or steam cracking; and / or

[0238] Purification, preferably crystallization, (solvent) extraction, distillation, evaporation, hydrogenation, absorption, adsorption, and / or ion exchange; and / or

[0239] Assembling, preferably through foaming, synthesis, chemical transformation, chemical conversion, polymerization, and / or blending; and / or

[0240] Molding, preferably foaming, extrusion and / or molding; and / or

[0241] Finishing, preferably coating and / or smoothing.

[0242] In addition, one or more of these steps are described in detail in reference RF1; paragraphs

[1000] to

[8005] .

[0243] As used in the context of the product Ω herein, the term "building unit" refers to a compound that is in a gaseous or liquid state under standard conditions of 0°C and 0.1 MPa. Building units are typically used in the chemical industry to form secondary products that offer greater structural complexity and / or higher molecular weight than the building unit on which the secondary product is based. Building units are preferably selected from the group consisting of free hydrogen, carbon monoxide, carbon dioxide, ethylene oxide, ethylene glycol, syngas containing mixtures of hydrogen and carbon monoxide, alkanes, alkenes, alkynes, and aromatic compounds. Alkanes, alkenes, alkynes, and aromatic compounds particularly contain 1 to 12 carbon atoms, respectively.

[0244] As used in the context of the product Ω herein, the term "monomer" includes molecules that can react with each other to form polymer chains by polymerization. Monomers are preferably selected from the group consisting of: (meth)acrylic acid, salts of (meth)acrylic acid; particularly sodium, potassium, and zinc salts; (meth)acrylaldehyde and (meth)acrylates. (Meth)acrylates containing 1 to 22 carbon atoms, particularly 1 to 8 carbon atoms, are preferred. The terms (meth)acrylic acid, (meth)acrylaldehyde, or (meth)acrylate refer to acrylic acid, acrolein, or acrylates, and where applicable, also refer to methacrylic acid, methacrolein, or methacrylates. Furthermore, monomers may be selected from hexamethylenediamine (HMD) and adipic acid.

[0245] The building blocks may further be intermediate compounds. As used in the context of the product Ω herein, the term "intermediate compound" includes organic reagents that are applied to form compounds with higher molecular complexity. Intermediate compounds may, for example, be selected from the group consisting of phosgene, polyisocyanates, and propylene oxide. Polyisocyanates are particularly aromatic diisocyanates and polyisocyanates, preferably toluene diisocyanate (TDI) and / or diphenylmethane diisocyanate (MDI).

[0246] The building blocks and monomers, as well as one or more typical transformation steps used to obtain the building blocks or monomers, are described in more detail in paragraphs

[1000] through

[1012] of reference RF1.

[0247] As used in the context of product Ω herein, the term “polymer A” includes thermoplastics (e.g., polyamides or thermoplastic polyurethanes), thermosettings (e.g., polyurethanes), elastomers (e.g., polybutadiene) or copolymers or mixtures thereof, and is defined in more detail in paragraphs

[2001] through

[2007] of reference RF1.

[0248] As used in the context of product Ω herein, the term “polymer composition A” includes all compositions comprising the polymers described above and one or more additives (e.g., reinforcing agents, colorants, modifiers and / or flame retardants), and is defined in more detail in paragraph

[2008] of reference RF1.

[0249] As used in the context of product Ω herein, the term “polymer product A” includes any product comprising polymer A and / or polymer composition A as described above, and is defined in more detail in paragraphs

[2009] and

[2010] of reference RF1.

[0250] One or more steps for obtaining a polymer (preferably polymer A), a polymer composition (preferably polymer composition A), or a polymer product (preferably polymer product A) are described in more detail in paragraph

[2011] of reference RF1.

[0251] As used in the context of this product Ω, the term "industrial polymer" includes rheological polymers based on polycarboxylate, alkoxylated polyalkyleneamine, alkoxylated polyalkyleneimide, polyether, dye-inhibiting and dirt-releasing cleaning polymers, as defined in more detail in paragraphs

[3035] through

[3044] of reference RF1. The term "industrial surfactant" as used in the context of this product Ω includes nonionic, anionic, and amphoteric industrial surfactants, as defined in more detail in paragraphs

[3008] through

[3034] of reference RF1. The term "industrial descaling compound" as used in the context of this product Ω includes nonphosphate-based detergent builders (NPB) and phosphonates (CoP), as described in more detail in paragraphs

[3001] through

[3005] of reference RF1. As used herein, the term "industrial biocide" refers to compounds that kill or inhibit the growth or reproduction of microorganisms, as defined in more detail in paragraphs

[3006] through

[3007] of reference RF1. As used in the context of product Ω herein, the term “industrial solvent” includes alkylamides, alkyl lactamides, alkyl esters, lactates, alkyl diesters, cyclic alkyl diesters, cyclic carbonates, aromatic aldehydes, and aromatic esters, as defined in more detail in paragraphs

[3045] through

[3055] of reference RF1. As used in the context of product Ω herein, the term “industrial dispersant” includes anionic and nonionic industrial dispersants, as defined in more detail in paragraphs

[3056] through

[3058] of reference RF1. The term “compositions and / or formulations thereof” with respect to industrial polymers, industrial surfactants, scale-removing compounds, and / or industrial biocides refers to industrial compositions and / or institutional products and / or textile and household care products and / or personal care products, as defined in more detail in paragraph

[3059] of reference RF1. One or more conversion steps for obtaining industrial polymers, industrial surfactants, scale-removing compounds, and / or industrial biocides are defined in more detail in paragraph

[3060] of reference RF1. The conversion steps for obtaining industrial compositions or formulations of industrial polymers, industrial surfactants, scale-removing compounds and / or industrial biocides are defined in more detail in paragraph

[3061] of reference RF1.

[0252] As used in the context of the product Ω herein, the term "agrochemical composition" typically refers to a composition comprising an agrochemical active ingredient and at least one agrochemical formulation adjuvant. Examples of agrochemical compositions, active ingredients, and adjuvants are described in more detail in paragraph

[4001] of reference RF1.

[0253] Agricultural chemical compositions can be in any conventional formulation form. These agricultural chemical compositions are prepared in known ways, for example, as described in: Mollet and Grubemann, Formulation technology, Wiley VCH, Weinheim, 2001; or Knowles, New developments in crop protection product formulation, Agrow Reports DS243, T&F Informa, London, 2005. One or more conversion steps to obtain agricultural chemical active ingredients and adjuvants can be similar to one or more production steps of their analogues based on petrochemicals or other precursors not obtained through recycling processes. Additionally, the conversion of compounds mentioned in the sections “Polymers” and “Cosmetic Surfactants, Emollients, Waxes, Cosmetic Polymers, UV Filters, Other Cosmetic Ingredients or Combinations or Formulations thereof” can be carried out as described in those sections and the corresponding paragraphs in reference RF1.

[0254] As used in the context of product Ω herein, the terms active pharmaceutical ingredient and / or intermediate thereof include substances that provide pharmacological activity or other direct effects or influence the structure or any function of the body in the diagnosis, cure, relief, treatment or prevention of a disease. Intermediates are isolated products generated during a multi-step synthetic route of the active pharmaceutical ingredient. As used in the context of product Ω herein, the term pharmaceutical excipient includes compounds or mixtures of compounds used in compositions for various pharmaceutical applications that are substantially non-pharmaceutical in themselves. Active pharmaceutical ingredients and / or intermediates thereof, as well as pharmaceutical excipients, are defined in more detail in paragraph

[5001] of reference RF1.

[0255] One or more conversion steps for obtaining an active pharmaceutical ingredient and / or its intermediates and pharmaceutical excipients may include one or more synthetic steps and may be carried out by conventional synthesis and techniques well known to those skilled in the art.

[0256] As used in the context of the product Ω herein, the terms animal feed additive, human food additive, and dietary supplement include vitamins, provitamins, and their active metabolites, including intermediates and precursors, particularly vitamins A, B, E, D, K, and their esters (like acetates, propionates, palmitates) or their alcohols (like retinol) or their salts or any combination thereof; tetraterpenes, particularly isoprene-like substances, such as carotenoids and lutein, including their intermediates and precursors, as well as mixtures and derivatives thereof, particularly β-carotene, canthaxanthin, hesperidin, astaxanthin, zeaxanthin, and lutein. Voxel, lycopene, apocarotenoids and any combination thereof; organic acids, especially formic acid, propionic acid and their salts (such as sodium, calcium or ammonium salts) and any combination thereof, such as, but not limited to, formic acid and sodium formate, propionic acid and ammonium propionic acid, formic acid and propionic acid, formic acid and sodium formate, and mixtures of propionic acid, propionic acid and sodium propionic acid and formic acid and sodium formate; glycerides of carboxylic acids and short and medium chain fatty acids, conjugated linoleic acid (such as omega-6 fatty acid (C18:2) methyl ester) and 1,2-propanediol; and beverage stabilizers such as polyvinylpyrrolidone polymers or polyvinylimazole / polyvinylpyrrolidone copolymers. Animal feed additives, human food additives and dietary supplements are defined in more detail in paragraph

[5002] of reference RF1.

[0257] One or more conversion steps used to obtain animal feed additives, human food additives, or dietary supplements may include one or more synthetic steps and may be carried out by conventional synthesis and techniques well known to those skilled in the art.

[0258] As used in the context of the product Ω herein, the terms aromatic chemicals and aromatic compositions include volatile organic compounds with a molecular weight between 70 and 250 g / mol, including those with a carbon skeleton of C5-C6. 16 Functional groups of carbon atoms, the carbon skeleton including straight chains, branches, and rings (e.g., rings with a size of C5-C). 18 The aromatic chemicals are bicyclic or tricyclic aliphatic chains, but do not necessarily contain one or more unsaturated structural elements such as double bonds, triple bonds, aromatic or heteroaromatic groups, and preferably, one or more additional functional groups are selected from alcohols, ethers, esters, ketones, aldehydes, acetals, carboxylic acids, nitriles, thiols, and amines. In one aspect, aromatic chemicals are terpenoid-based aromatic chemicals, selected from monoterpenes and monoterpenoids, sesquiterpenes and sesquiterpenoids, diterpenes, triterpenes, or tetraterpenes. Aromatic chemicals can be combined with other aromatic chemicals to obtain aromatic compositions. Aromatic chemicals and aromatic compositions are defined in more detail in paragraph

[5003] of reference RF1.

[0259] One or more conversion steps for obtaining aromatic chemicals and aromatic compositions may include one or more synthetic steps and may be carried out by conventional synthesis and techniques well known to those skilled in the art.

[0260] As used herein in the context of product Ω, the term “aqueous polymer dispersion” includes an aqueous composition comprising a dispersed polymer, and is defined in more detail in the section entitled “Aqueous Polymer Dispersions” of reference RF1

[6001] . One or more dispersed polymers may be selected from one or more acrylic emulsion polymers, one or more styrene acrylic emulsion polymers, one or more styrene butadiene dispersions, one or more aqueous dispersions comprising composite particles, one or more acrylate alkyd hybrid dispersions, one or more polyurethanes (including UV-curable polyurethanes), and one or more polyurethane-poly(meth)acrylate hybrid polymers. As used herein, the term “emulsion polymer” includes one or more polymers prepared by free radical emulsion polymerization. One or more aqueous polyurethane dispersions are defined in more detail in the section entitled “Polyurethane Dispersions” of reference RF1

[6002] . One or more UV-curable polyurethanes are defined in more detail in the section entitled “Polyurethane Dispersions” of reference RF1

[6017] . One or more polyurethane-poly(meth)acrylate hybrid polymers are defined in more detail in the section entitled “Polyurethane Dispersions” of reference RF1

[6016] .

[0261] As used in the context of product Ω herein, the term “polymer dispersant” preferably includes polymers containing polyether side chains, particularly polycarboxylate ether polymers and condensation products as defined in more detail in the paragraph entitled “Polymer Dispersants” in reference RF1

[6020] .

[0262] One or more conversion (polymerization) steps for obtaining one or more aqueous polymer dispersions comprising one or more emulsion polymers are defined in more detail in the section entitled “Emulsion Polymerization” in reference RF1

[6003] .

[0263] One or more conversion (polymerization) steps for obtaining one or more waterborne polyurethane dispersions are defined in more detail in the section entitled “Methods for preparing waterborne polyurethane dispersions”

[6014] and the section entitled “UV-curable waterborne polyurethane dispersions, their preparation and use and compositions containing them”

[6017] of reference RF1.

[0264] Compositions and uses of one or more aqueous polymer dispersions and one or more polymer dispersants are defined in more detail in the following sections of reference RF1:

[0265] The section titled "Applications of Aqueous Polymer Dispersions"

[6004]

[0266] The section titled "Adhesives for Building and Construction Coatings"

[6005]

[0267] The section titled "Adhesives for Paper Coatings"

[6006]

[0268] The section titled "Adhesives for Fiber Bonding"

[6007]

[0269] The section titled "Adhesive Polymers and Adhesive Compositions"

[6008]

[0270] The section titled "Aqueous Polyurethane Dispersions Suitable for Coating Compositions"

[6015]

[0271] The section titled "Waterborne polyurethane-poly(meth)acrylate mixed polymer dispersions suitable for coating compositions"

[6016]

[0272] The section titled "Waterborne UV-curable polyurethane dispersions, their preparation and uses, and compositions containing them"

[6017]

[0273] Section entitled “Inorganic binder compositions containing polymer dispersants and their uses”

[6018]

[6019] 100% curable coating compositions.

[0274] UV-crosslinkable poly(meth)acrylates and their uses are defined in more detail in the section entitled “UV-crosslinkable poly(meth)acrylates for UV-curable solvent-free hot melt adhesives and their use in the preparation of pressure-sensitive self-adhesive products” in reference RF1

[6009] .

[0275] One or more polyisocyanates, one or more compositions comprising them, and their uses are defined in more detail in the section entitled “Polyisocyanates” in reference RF1

[6010] .

[0276] One or more hyperbranched polyester polyols and their uses are defined in more detail in the section entitled "Organic solvent-based hyperbranched polyester polyols suitable for coating compositions" in reference RF1

[6011] . One or more conversion steps for obtaining hyperbranched polyester polyols are defined in more detail in the section entitled "Preparation of organic solvent-based hyperbranched polyester polyols" in reference RF1

[6012] . One or more coating compositions comprising one or more hyperbranched polyester polyols, one or more polyisocyanates and one or more additives, and the substrates coated thereon are defined in more detail in the section entitled "Organic solvent-based two-component coating compositions comprising hyperbranched polyester polyols and polyisocyanates" in reference RF1

[6013] .

[0277] One or more unsaturated polyester polyols, one or more solvent-based coating compositions comprising said unsaturated polyester polyols, and one or more substrates for coating with said one or more coating compositions are defined in more detail in the section entitled “Organic solvent-based coating compositions comprising unsaturated polyester polyols” in reference RF1

[6018] .

[0278] One or more 100% curable coating compositions are defined in more detail in section

[6019] of reference RF1.

[0279] One or more polymeric dispersants for use in inorganic binder compositions are defined in more detail in section

[6020] of reference RF1. One or more inorganic binder compositions comprising polymeric dispersants and their uses are defined in more detail in section

[6021] of reference RF1. One or more conversion steps for obtaining one or more polymeric dispersants are defined in more detail in section

[6020] of reference RF1. As used herein, the term "inorganic binder composition" comprising one or more polymeric dispersants preferably includes, in particular, hydraulic coagulating compositions and compositions comprising calcium sulfate, and is defined in more detail in section

[6021] of reference RF1 entitled "Inorganic Binder Compositions Containing Polymer Dispersants and Their Uses Therein". Specific one or more building material formulations comprising one or more polymeric dispersants, or one or more building products produced from building material formulations containing polymeric dispersants, are disclosed in more detail in section

[6021] of reference RF1.

[0280] As used in the context of this product Ω, the term "cosmetic surfactant" includes nonionic, anionic, cationic, and amphoteric surfactants, and is defined in more detail in paragraph

[7002] of reference RF1. As used in the context of this product Ω, the term "emollient" refers to a compound used to protect, moisturize, and / or lubricate the skin, and is defined in more detail in paragraph

[7003] of reference RF1. As used in the context of this product Ω, the term "wax" includes pearlescent agents and opacifiers, and is defined in more detail in paragraph

[7004] of reference RF1. As used in the context of this product Ω, the term "cosmetic polymer" includes any polymer that can be used as an ingredient in cosmetic formulations, and is defined in more detail in paragraph

[7005] of reference RF1. As used in the context of this product Ω, the term "UV filter" refers to a compound that blocks or absorbs ultraviolet light, and is defined in more detail in paragraph

[7006] of reference RF1. As used in the context of product Ω herein, the term “additional cosmetic ingredient” includes any ingredient suitable for the preparation of cosmetic formulations. Several sources disclose ingredients acceptable for cosmetics. For example, the database Cosing on the European Commission’s internet page discloses cosmetic ingredients, and the International Dictionary and Handbook of Cosmetic Ingredients edited by the Personal Care Products Association (PCPC) discloses cosmetic ingredients. The term “compositions and / or formulations thereof” with respect to cosmetic surfactants, emollients, waxes, cosmetic polymers, UV filters and / or other cosmetic ingredients refers to personal care and / or cosmetic compositions or formulations as defined in more detail in paragraph

[7007] of reference RF1. One or more conversion steps used to obtain cosmetic surfactants, emollients, waxes, cosmetic polymers, UV filters or other cosmetic ingredients are defined in more detail in paragraph

[7008] of reference RF1.

[0281] The terms “polymer B”, “polymer composition B”, “coating composition”, “other functional composition”, “foil”, “molded body”, “coating” and “coated substrate” are well known to those skilled in the art and are defined in more detail from paragraphs

[8000] to

[8005] of reference RF1.

[0282] The invention is further illustrated by the following set of embodiments and combinations of embodiments derived from the dependent relationships and reverse references shown. In particular, it should be noted that in each instance of reference to a series of embodiments, such as in the context of the term "method as described in any one of Embodiments 1 to 3," each embodiment in this series is intended to clearly disclose to those skilled in the art that the wording of this term should be understood by those skilled in the art to be synonymous with "method as described in any one of Embodiments 1, 2, and 3." Furthermore, it should be clearly noted that the following set of embodiments represents appropriate structural portions of the general description of preferred aspects of the invention and therefore appropriately supports, but does not represent, the claims of the invention.

[0283] 1. A method for recycling a rubber-based solid material M1 from solid automotive waste W, the method comprising:

[0284] (i) Providing the solid automotive waste W comprising the rubber-based solid material M1, W further comprising one or more solid materials M2 having a chemical composition different from that of the rubber-based solid material M1, wherein the rubber-based solid material M1 contains one or more halogens in addition to rubber and / or within rubber;

[0285] (ii) Separate M1 and M2 from W provided in (i), including

[0286] The material W is subjected to a kinetic energy separation method or an electrostatic separation method to obtain a mixture MS(1) containing the rubber-based solid material M1 and a mixture MS(2) containing one or more solid materials M2 that is less M1 than W.

[0287] (iii) By sorting the rubber-based material M1 contained in MS(1) obtained in (ii) by elemental composition, a halogen-rich rubber-based solid material fraction f11 containing one or more halogens is obtained, and a halogen-poor rubber-based solid material fraction f12 containing rubber and depleted of one or more halogens compared to M1 is obtained.

[0288] (iv) Optionally, the halogen-poor fraction f12 obtained according to (iii) is subjected to purification treatment to obtain a purified solid mixture MP containing rubber;

[0289] (v) The halogen-poor rubber-based solid material fraction f12 containing rubber obtained according to (iii), or the purified solid mixture MP containing rubber obtained according to (iv), is subjected to pyrolysis in the pyrolysis reaction unit RU(p) to obtain pyrolysis oil.

[0290] 2. The method as described in Example 1, wherein the solid automotive waste W is obtained from scrapped vehicles, preferably, the solid waste W is automotive shredded residue (ASR).

[0291] 3. The method as described in Example 1 or 2, wherein the separation according to (ii) includes the kinetic energy separation method, which is a ballistic separation method or a size separation method, preferably a ballistic separation method; or

[0292] The separation according to (ii) includes the electrostatic method, which is a buoyancy separation method.

[0293] 4. The method as described in any one of Examples 1 to 3, wherein, after (ii) and before (iii), the method further comprises washing the rubber-based solid material M1 contained in MS(1) obtained according to (ii), preferably with water, or one or more caustic agents, or one or more detergents, wherein the washing is followed by drying the washed material M1.

[0294] 5. The method as described in any one of Examples 1 to 4, wherein the sorting according to (iii) is automatic sorting.

[0295] 6. The method as described in any one of Examples 1 to 5, wherein the sorting according to (iii) includes the use of one or more of the following: a conveyor, a sensor, a light source, a laser, an X-ray source, a radioactive isotope source, a detector, and a camera.

[0296] 7. The method as described in any one of Examples 1 to 6, wherein the sorting according to (iii) is an X-ray fluorescence sorting method.

[0297] 8. The method as described in any one of Examples 1 to 7, wherein the halogen-poor rubber-based solid material fraction f12, comprising up to 1000 ppmw, preferably up to 500 ppmw, more preferably up to 250 ppmw, and even more preferably up to 100 ppmw, is composed of halogens, the content of which is determined as described in Analysis 2.

[0298] 9. The method as described in any one of Examples 1 to 8, wherein at least 60% by weight, preferably at least 70% by weight, of the fraction f12 is composed of rubber.

[0299] 10. The method of any one of Examples 1 to 8, wherein the sorting according to (iii) includes crushing the rubber-based solid material M1 contained in MS(1) obtained according to (ii) to obtain a sheet of M1.

[0300] 11. The method as described in any one of Examples 1 to 10, wherein the sorting according to (iii) includes

[0301] (iii.1) Spread the M1 sheet contained in MS(1) or the M1 sheet obtained as described in Example 10 onto the conveyor;

[0302] (iii.2) Automatic analysis of the rubber-based solid material M1 contained in MS(1) obtained according to (ii) and spread on the conveyor according to (iii.1), or the sheet of the rubber-based solid material M1 contained in MS(1) as defined in Example 10:

[0303] Use one or more of sensors, light sources, detectors and X-ray sources to identify the elemental composition of rubber-based materials or sheets of rubber-based materials;

[0304] (iii.3) Based on the presence of halogens, these materials are separated into at least two distinct fractions, thereby obtaining

[0305] - A fraction of halogen-rich rubber-based solid materials f11 containing one or more of the halogens, and

[0306] - A fraction of halogen-poor rubber-based solid materials f12, which is depleted of one or more halogens compared to M1;

[0307] (iii.4) Remove the grade f12 obtained according to (iii.3) from the conveyor.

[0308] 11. The method of any one of Examples 1 to 10, wherein, in addition to rubber, the halogen-poor rubber-based solid material fraction f12 further comprises one or more fillers F; wherein preferably, the one or more fillers F comprises one or more of the following: magnesium silicate hydrate, glass fiber, aluminum hydroxide, ammonium polyphosphate, barium sulfate, calcium carbonate, wollastonite, carbon black, and titanium dioxide.

[0309] 12. The method as described in any one of Examples 1 to 11, wherein, according to (iv), the halogen-poor rubber-based solid fraction f12 obtained according to (iii) is subjected to purification treatment comprising:

[0310] (iv.1) subjecting fraction f12 containing impurities and / or one or more fillers F to rubber dissolution conditions in the presence of solvent SD, wherein the impurities and F are inert to the rubber dissolution treatment, thereby obtaining an intermediate mixture containing the impurities and / or the one or more fillers F and further containing rubber dissolved in SD;

[0311] (iv.2) The intermediate mixture obtained according to (iv.1) is conveyed to the solid-liquid separation unit SU to obtain a mixture M(F) containing these impurities and / or the one or more fillers F, and a mixture MD containing rubber dissolved in SD that is depleted of these impurities and the one or more fillers F—if any—compared to f12;

[0312] (iv.3) subject the MD containing rubber dissolved in SD obtained according to (iv.2) to precipitation conditions to obtain a purified solid mixture MP containing precipitated rubber.

[0313] 13. The method as described in Example 12, wherein the solvent SD used in (iv) is selected from the group consisting of: n-hexane, n-heptane, 2,2-dimethylbutane, toluene, benzene, cyclohexane, methylcyclohexane, cyclopentane, methylcyclopentane, and mixtures of two or more thereof, more preferably selected from the group consisting of: n-hexane, n-heptane, 2,2-dimethylbutane, methylcyclohexane, and methylcyclopentane.

[0314] 14. The method as described in Example 12 or 13, wherein the rubber dissolution treatment according to (iv.1) is carried out at a temperature in the range of 55°C to 200°C, preferably in the range of 100°C to 160°C.

[0315] 15. The method as described in any one of Examples 12 to 14, wherein the rubber dissolution treatment according to (iv.1) includes

[0316] The solid fraction f12 is brought into contact with the solvent SD at a weight ratio of 1:1 to 1:20, preferably 1:3 to 1:15, and more preferably 1:4 to 1:12, to obtain an intermediate mixture containing these impurities and / or one or more fillers F and further containing rubber dissolved in SD.

[0317] 16. The method of any one of Examples 12 to 15, wherein the solid-liquid separation unit SU used in (iv.2) is a filtration unit or a centrifugation unit, preferably a filtration unit, which more preferably has a mesh size in the range of 1 to 100 micrometers, more preferably in the range of 10 to 50 micrometers.

[0318] 17. The method of any one of Examples 12 to 16, wherein the filtration unit comprises a filter for blocking the mixture M(F) containing the impurities and / or the one or more fillers F and a receiving container for the mixture MD containing the rubber dissolved in SD.

[0319] 18. The method as described in Example 16 or 17, wherein the filter unit is at pressure p F The following operation, where p F ≥ 1 bar (absolute value), preferably p F The range is from 1 to 30 bar (absolute value), more preferably from 1 to 10 bar (absolute value), and even more preferably from 1 to 6 bar (absolute value).

[0320] 19. The method as described in any one of Examples 12 to 18, wherein (iv.3) comprises

[0321] - MD containing the rubber dissolved in SD obtained according to (iv.2) is subjected to temperature T. P and pressure p P The lower part undergoes precipitation, in which T P < T D T D It is based on the dissolution temperature (iv.1), and T P < 100°C, thereby obtaining an intermediate mixture IM containing SD and precipitated rubber;

[0322] - The IM is transferred to the solid-liquid separation unit SU1 to obtain a purified mixture MP containing the precipitated rubber and a liquid mixture containing SD.

[0323] 20. The method as described in Example 19, wherein (iv.3) includes

[0324] - at temperature T P and pressure p P The MD containing the rubber dissolved in SD, obtained by cooling according to (iv.2), is used for precipitation, wherein T P < T D T D It is based on the dissolution temperature (iv.1), and T P < 100°C

[0325] This yields an intermediate mixture IM containing SD and the precipitated rubber;

[0326] - The IM is transferred to the solid-liquid separation unit SU1 to obtain a purified mixture MP containing the precipitated rubber and a liquid mixture containing SD.

[0327] 21. The method as described in any one of Examples 12 to 18, wherein (iv.3) includes

[0328] - By subjecting the MD containing the rubber dissolved in SD obtained according to (iv.2) to precipitation by contacting the MD with a polar solvent, an intermediate mixture IM' containing SD, the polar solvent and the precipitated rubber is obtained;

[0329] - The IM' is transferred to the solid-liquid separation unit SU2 to obtain the purified mixture MP containing the precipitated rubber, and the liquid mixture containing SD and the polar solvent.

[0330] 22. The method as described in any one of Examples 12 to 18, wherein (iv.3) includes

[0331] By passing the MD containing the rubber dissolved in SD obtained according to (iv.2) into a flash evaporator to subject the MD to precipitation, a gaseous stream G3 containing the evaporated solvent is obtained, and a purified mixture MP containing the precipitated rubber is further obtained.

[0332] 23. The method of any one of Examples 12 to 21, further comprising recycling at least a portion of the solvent SD recovered after (iv.3) to the rubber dissolution treatment according to (iv.1);

[0333] Wherein recycling preferably includes

[0334] At least a portion of the solvent SD recovered after (iv.3) is transferred to distillation unit D to obtain purified solvent;

[0335] The purified solvent was used for the dissolution treatment of the rubber according to (iv.1).

[0336] 24. The method as described in any one of Examples 1 to 23, wherein (v) includes

[0337] (v.1) The solid fraction f12 obtained according to (iii) or the purified mixture MP obtained according to (iv) is fed into the pyrolysis reactor R(p);

[0338] (v.2) The rubber entering the pyrolysis reactor R(p) is heated at a temperature in the range of 350°C to 900°C, preferably in the range of 400°C to 550°C, and at a pressure in the range of 0.5 to 2 bar (absolute value), preferably in the range of 0.9 to 1.5 bar (absolute value);

[0339] (v.3) The gas stream GS is removed from the top of R(p) and subjected to condensation conditions in the gas-liquid separation unit LGU to obtain the pyrolysis oil.

[0340] 25. The method as described in any one of Examples 1 to 24, wherein the method further comprises, after (v), using the pyrolysis oil obtained according to (v) as stream S O It is then transferred to the purification unit (PU) to obtain purified pyrolysis oil.

[0341] 26. The method as described in any one of Examples 1 to 25, wherein the method further comprises

[0342] (vi) subject at least a portion of the pyrolysis oil obtained according to (v) to [a process / treatment].

[0343] (vi.1) Cracking, thereby obtaining a stream P1 containing cracked hydrocarbons; and / or

[0344] (vi.2) Partial oxidation, thereby obtaining a synthesis gas flow P2 containing CO and H2.

[0345] 27. The method as described in Example 26, wherein the pyrolysis according to (vi.1) is carried out in a pyrolyzer, preferably a steam pyrolyzer.

[0346] 28. The method as described in Example 26 or 27, wherein the partial oxidation according to (vi.2) is carried out in a gasifier such as an entrained flow reactor and / or a fluidized bed reactor.

[0347] 29. The method as described in any one of Examples 1 to 28, further comprising:

[0348] (vii) Preparation of polymer PA, including

[0349] The pyrolysis oil obtained according to (v), the cracked hydrocarbon contained in the stream P1 contained according to (vi) as described in any one of Examples 26 to 28, and the CO and / or H2 synthesis gas contained in the stream P2 contained according to (vi) as described in any one of Examples 26 to 28 are used.

[0350] 30. The method as described in any one of Examples 1 to 29, further comprising:

[0351] (viii) Preparation of automotive materials, including

[0352] The pyrolysis oil obtained according to (v), the cracked hydrocarbon contained in the stream P1 obtained according to (vi) as described in any one of Examples 26 to 28, the CO and / or H2 contained in the synthesis stream P2 obtained according to (v) as described in any one of Examples 26 to 28, and the polymer PA obtained according to (vii) as described in Example 29.

[0353] 31. A recycling unit for performing the method according to any one of embodiments 1 to 30, the recycling unit comprising:

[0354] The first separation unit SU(a) is used for kinetic energy separation or electrostatic separation;

[0355] The second separation unit SU(b) is used for sorting by element composition;

[0356] The means for conveying MS(1) to SU(b) is preferably one or more conveyors;

[0357] The pyrolysis reaction unit RU(p);

[0358] An outlet device for removing pyrolysis oil from RU(p);

[0359] Optional purification unit PU;

[0360] An inlet device optionally used to introduce f12 into the PU;

[0361] An outlet device optionally used to remove purified mixture MP from PU;

[0362] An inlet device used to introduce f12 or MP into RU(p).

[0363] 32. An automotive material, preferably for motor vehicles, comprising a polymer PA obtained according to the method of Example 29.

[0364] 33. A method, preferably according to any one of Examples 1 to 28, comprising the step of converting the pyrolysis oil that is available or obtainable according to (v), or the cracked hydrocarbon contained in P1 that is available or obtainable according to (vi) as in any one of Examples 26 to 28, or the CO and / or H2 contained in P2 that is available or obtainable according to (vi) as in any one of Examples 26 to 28, to obtain product Ω.

[0365] 34. The method as described in Example 33, wherein the product Ω is selected from:

[0366] - Building blocks or monoliths; or

[0367] - Polymer, preferably polymer A; polymer composition, preferably polymer composition A; or polymer product, preferably polymer product A; or

[0368] - Cleaning polymers, cleaning surfactants, descaling compounds, cleaning biocides, or combinations thereof; or

[0369] - Agricultural chemical compositions, agricultural chemical formulations, adjuvants, or agricultural chemical active ingredients; or

[0370] - Active pharmaceutical ingredients or intermediates thereof, pharmaceutical excipients, animal feed additives, human food additives, dietary supplements, aromatic chemicals or aromatic compositions; or

[0371] - Aqueous polymer dispersions, preferably polyurethane or polyurethane-poly(meth)acrylate hybrid polymer dispersions, emulsions, binders for paper and fiber coatings, UV-curable acrylic polymers for hot melts and coatings, polyisocyanates, hyperbranched polyester polyols, polymer dispersants for inorganic binder compositions, unsaturated polyester polyols, or 100% curable compositions; or

[0372] - Cosmetic surfactants, emollients, waxes, cosmetic polymers, UV filters, other cosmetic ingredients, or combinations thereof or formulations thereof; or

[0373] - Polymer B, polymer composition B, coating composition, other functional composition, foil, molded body, coating or coated substrate.

[0374] 35. The method as described in Examples 33 or 34,

[0375] Wherein, the content of the pyrolysis oil obtainable or acquireable according to (v) in the product Ω, or the cracked hydrocarbon contained in P1 obtainable or acquireable according to (vi) as described in any one of Examples 26 to 28, or the CO and / or H2 contained in P2 obtainable or acquireable according to (vi) as described in any one of Examples 26 to 28, is 1 wt% or more, preferably 2 wt% or more, more preferably 5 wt% or more, more preferably 15 wt% or more, more preferably 30 wt% or more, more preferably 40 wt% or more, more preferably 60 wt% or more, more preferably 80 wt% or more, more preferably 90 wt% or more, more preferably 95 wt% or more; and / or

[0376] Wherein, the content of the pyrolysis oil obtainable or acquireable according to (v) in the product Ω, or the cracked hydrocarbon contained in P1 obtainable or acquireable according to (vi) as described in any one of Examples 26 to 28, or the CO and / or H2 contained in P2 obtainable or acquireable according to (vi) as described in any one of Examples 26 to 28, is 100 wt% or less, preferably 95 wt% or less, more preferably 90 wt% or less, more preferably 50 wt% or less, more preferably 25 wt% or less, more preferably 10 wt% or less; and

[0377] Preferably, the content is determined based on an identity preservation and / or segregation and / or quality balance and / or ledger and declaration chain of custody model, preferably based on quality balance, preferred International Sustainable Development and Carbon Certification (ISCC) standards.

[0378] It should be clearly noted that the above set of embodiments represents appropriate structural portions of the general description of preferred aspects of the invention, and therefore appropriately supports but does not represent the claims of the invention.

[0379] In the context of this invention, the term "X is one or more of A, B, and C" (where X is a given feature and each of A, B, and C represents a specific implementation of said feature) should be understood to disclose that X is A, or B, or C, or A and B, or A and C, or B and C, or A and B and C. In this respect, it should be noted that those skilled in the art can translate the above abstract terms into concrete examples, for example, where X is a chemical element and A, B, and C are specific elements such as Li, Na, and K, or X is a temperature and A, B, and C are specific temperatures such as 10°C, 20°C, and 30°C. In this regard, it should be further noted that those skilled in the art can extend the above terms to less specific implementations of the feature, such as "X is one or more of A and B," which discloses that X is A, or B, or A and B, or extend them to more specific implementations of the feature, such as "X is one or more of A, B, C, and D," which discloses that X is A, or B, or C, or D, or A and B, or A and C, or A and D, or B and C, or B and D, or C and D, or A and B and C, or A and B and D, or B and C and D, or A and B and C and D.

[0380] The invention is further illustrated by the following examples.

[0381] analyze

[0382] 1. Average particle size

[0383] The average particle size was measured using the Mastersizer 3000, which uses laser diffraction to measure particle size and particle size distribution. This is described in Particle Size Measurements: Fundamentals, Practice, Quality (Particle Technology Series Book 17), Henk G. Merkus, 2009.

[0384] 2. Halogen content, Cl content

[0385] 2.1 Calibration:

[0386] a. Prepare halogen-free samples whose composition and matrix are highly matched to the sample to be analyzed.

[0387] b. Use an XRF instrument to analyze halogen-free samples to establish calibration curves or calibration factors for halogen detection.

[0388] 2.2 Sample preparation:

[0389] a. If the sample is in solid form, grind it using a mortar and pestle to obtain a uniform powder.

[0390] b. Weigh an appropriate amount of sample using an analytical balance. The amount will depend on the expected halogen content and the sensitivity of the XRF instrument.

[0391] 2.3 XRF Analysis:

[0392] a. Turn on the XRF instrument and heat it according to the manufacturer's instructions.

[0393] b. Based on the expected halogen content and instrument capabilities, set the instrument to the appropriate X-ray tube voltage and current.

[0394] c. Load calibration standards onto the instrument, including halogen-free samples and any additional standards with moderate halogen concentrations (if available).

[0395] d. Analyze calibration standards to verify the accuracy and precision of calibration curves or calibration factors.

[0396] e. Load one or more prepared samples onto the instrument, ensuring that the samples are evenly distributed and cover the detection area as much as possible.

[0397] f. Analyze one or more samples using an XRF instrument, following the manufacturer's instructions for sample positioning and measurement duration.

[0398] g. Repeat the analysis for each sample to ensure reproducibility.

[0399] 2.4 Data Analysis:

[0400] a. Retrieve XRF data from the instrument software.

[0401] b. Apply the calibration curve or calibration factor to the measured XRF intensity to determine the halogen content in each sample.

[0402] c. Calculate the mean and standard deviation of halogen content for parallel samples (if any).

[0403] Example

[0404] 1. Preparation of the initial ASR sample (solid automotive waste W)

[0405] To prepare models ASR-1 through ASR-3, single components were collected from passenger vehicles approximately 15 years old from local end-of-life vehicle (ELV) recycling companies (authorized processing facilities for decontaminating ELVs). For example, glass was collected from the windshield and rear window, dirt was collected as dirt adhering to the exterior of the vehicle, PUR foam was collected from seat foam, and plastics were collected from selected plastic parts of the vehicle, such as wheel covers, dashboards, wiper arms, door handles, gears, and bushings, where the type of polymer was known.

[0406] Models ASR-1 to ASR-3 were prepared in 5 kg batches by weighing the components and first manually crushing them using a hammer and metal shears, as listed in Table 1, followed by crushing with a quadruped crusher (such as the "JFS 8080" from Jogindra, India, with a main blade rotation diameter of 245 mm, an auxiliary blade rotation diameter of 270 mm, 42 main blades, 20 auxiliary blades, a spindle speed of 25 rpm, and a capacity of 120-200 kg / hr). The maximum fragment size was 10 cm.

[0407] Table 1: Composition of ASR in the model (in wt.-%)

[0408]

[0409] 2. Preparation of SLF and SHF samples from ASR (solid automotive waste W)

[0410] To prepare models of crushed light fractions SLF-1 to SLF-3 and crushed heavy fractions SHF-1 to SHF-3, single components were collected from a local ELV recycling company, as described in Example 1.

[0411] The samples were prepared in 5 kg batches by weighing the components and first manually crushing them with a hammer and metal shears, as listed in Tables 2 and 3, followed by crushing with a quadrupole crusher. The maximum fragment size was 10 cm.

[0412] Table 2: Composition of SLF (in wt.-%)

[0413]

[0414] Table 3: Composition of SHF (in wt.-%)

[0415]

[0416] The method of the present invention is reproduced by using the materials in 1. and 2. as material W in (i). Attached Figure Description

[0417] Figure 1 A flowchart with a suitable process sequence for obtaining automotive shredded residue ASR is shown. Starting with the vehicle, followed by optional decontamination, then optional dismantling, then shredding the vehicle, then optional separation of metal fragments from the shredded vehicle, followed by obtaining the ASR, and then optionally separating the ASR into shredded light fractions and shredded heavy fractions.

[0418] Figure 2 This is a schematic diagram of a recycling unit for a method according to an embodiment of the present invention. The recycling unit includes a separation unit SU(a), a separation unit SU(b), a pyrolysis reaction unit RU(p), and optionally a purification unit PU. Solid material W (ASR) containing rubber-based solid material M1 is separated in SU(a) via a kinetic separation unit or an electrostatic separation method to obtain a mixture MS(1) containing rubber-based solid material M1, and a mixture MS(2) containing one or more solid materials M2 that is M1-poor compared to W, wherein W further contains one or more solid materials M2 having a chemical composition different from that of rubber-based solid material M1, wherein the rubber-based solid material M1 contains one or more halogens in addition to rubber and / or within the rubber. The mixture MS(1) is further conveyed to the separation unit SU(b) for sorting material M1 by elemental composition to obtain a halogen-rich rubber-based solid material fraction f11 containing one or more halogens, and a halogen-poor rubber-based solid material fraction f12 containing rubber that is one or more halogens-poor compared to M1. Alternatively, fraction f12 can be passed through purification unit PU to obtain a purified solid mixture MP containing rubber. The MP is then introduced into RU(p) for pyrolysis to obtain pyrolysis oil. Alternatively, f12 can be directly introduced into RU(p) for pyrolysis to obtain pyrolysis oil.

[0419] References

[0420] - R. Cossu, et al., “Automotive shredder residue (ASR) management: Anoverview”, Waste Management, Volume 45, November 2015, Pages 143-151. Therefore, methods for recycling ASR must be developed.

[0421] - EP0692356

[0422] - Vijayan, S.K.; Kibria, M.A.; Uddin, M.H.; Bhattacharya, S.“Pretreatment of Automotive Shredder Residues, Their ChemicalCharacterisation, and Pyrolysis Kinetics.” Sustainability 2021, 13, 10549

[0423] - Juliana Argente Caetano, Valdir Schalch, Javier Mazariegos Pablos“Characterization and recycling of the fine fraction of automotive shredderresidue (ASR) for concrete paving blocks production” Clean Technologies andEnvironmental Policy (2020) 22:835-847

[0424] - DE 19535296 A1

[0425] - WO 2012 / 015299 A1

[0426] - Markus Bauer, et al., “Sink-float density separation of post-consumer plastics for feedstock recycling”, November 6, 2017, Journal ofMaterial Cycles and Waste Management (2018) 20:1781-1791, https: / / doi.org / 10.1007 / s10163-018-0748-z

[0427] - Cecilia Chaine, et al., “Optimized industrial sorting of WEEEplastics: Development of fast and robust h-XRF technique for hazardouscomponents”, Case Studies in Chemical and Environmental Engineering 7 (2023)100292

[0428] - Hansen, C.M., Hansen Solubility Parameters - A user’s handbook, 2.Edition, CRC Press, Boca Raton, USA, 2007

[0429] - Ullmann’s Encyclopedia of Industrial Chemistry, Ethylene, Ch. 5.1,pages 469-475 (2012)

[0430] - Ullmann’s Encyclopedia of Industrial Chemistry, Rubber, 3.Synthetic Rubbers, Introduction and Overview, p. 602-604 (2011), DOI10.1002 / 14356007.a23_239.pub5

[0431] - Prior Art Disclosure; Issue 684; paragraphs

[1000] to

[8005] ; ISSN:2198-4786; published: 5 February 12, 2024

[0432] - Mollet and Grubemann, Formulation technology, Wiley VCH, Weinheim,2001

[0433] - Knowles, New developments in crop protection product formulation,Agrow Reports DS243, T&F Informa, London, 2005

[0434] - Database Cosing on the internet pages of the European Commissiondiscloses cosmetic ingredients and the International Cosmetic IngredientDictionary and Handbook, edited by the Personal Care Products Council (PCPC)

[0435] - EP 3 907 267 A1

[0436] - WO 2015 / 184343 A1

[0437] - WO 2024 / 033212 A1

[0438] US 5,554,657 A

[0439] Zhao Yi-Bo et al., “Solvent-based separation and recycling of wasteplastics: A review”, CHEMOSPHERE, 1 October 2018, pages 707 to 720。

Claims

1. A method for recycling a rubber-based solid material M1 from solid automotive waste W, the method comprising: (i) Providing the solid automotive waste W comprising the rubber-based solid material M1, W further comprising one or more solid materials M2 having a chemical composition different from that of the rubber-based solid material M1, wherein the rubber-based solid material M1 contains one or more halogens in addition to rubber and / or within rubber; (ii) Separate M1 and M2 from W provided in (i), including The material W is subjected to a kinetic energy separation method or an electrostatic separation method to obtain a mixture MS(1) containing the rubber-based solid material M1 and a mixture MS(2) containing one or more solid materials M2 that is less M1 than W. (iii) By sorting the rubber-based material M1 contained in MS(1) obtained in (ii) by elemental composition, a halogen-rich rubber-based solid material fraction f11 containing one or more halogens is obtained, and a halogen-poor rubber-based solid material fraction f12 containing rubber and depleted of one or more halogens compared to M1 is obtained. (iv) Optionally, the halogen-poor fraction f12 obtained according to (iii) is subjected to purification treatment to obtain a purified solid mixture MP containing rubber; (v) The halogen-poor rubber-based solid material fraction f12 containing rubber obtained according to (iii), or the purified solid mixture MP containing rubber obtained according to (iv), is subjected to pyrolysis in the pyrolysis reaction unit RU(p) to obtain pyrolysis oil.

2. The method according to claim 1, wherein, The solid automotive waste W is obtained from scrapped vehicles, and preferably, the solid waste W is automotive shredded residue (ASR).

3. The method as described in claim 1 or 2, wherein, The separation according to (ii) includes the kinetic energy separation method, which is a ballistic separation method or a size separation method, preferably a ballistic separation method.

4. The method according to any one of claims 1 to 3, wherein, After (ii) and before (iii), the method further includes washing the rubber-based solid material M1 contained in MS(1) obtained according to (ii), preferably with water, or one or more caustic agents, or one or more detergents, wherein the washing is followed by drying the washed material M1.

5. The method according to any one of claims 1 to 4, wherein, The sorting method according to (iii) is X-ray fluorescence sorting.

6. The method according to any one of claims 1 to 5, wherein, According to the sorting in (iii), including (iii.1) Spread M1 contained in MS(1) onto the conveyor; (iii.2) Automatic analysis of the rubber-based solid material M1 contained in MS(1) obtained according to (ii) and spread on the conveyor according to (iii.1): Use one or more of sensors, light sources, detectors and X-ray sources to identify the elemental composition of rubber-based materials or sheets of rubber-based materials; (iii.3) Based on the presence of halogens, these materials are separated into at least two distinct fractions, thereby obtaining - A fraction of halogen-rich rubber-based solid materials f11 containing one or more of the halogens, and - A fraction of halogen-poor rubber-based solid materials f12, which is depleted of one or more halogens compared to M1; (iii.4) Remove the grade f12 obtained according to (iii.3) from the conveyor.

7. The method according to any one of claims 1 to 6, wherein, According to (iv), the halogen-poor rubber-based solid fraction f12 obtained according to (iii) is subjected to purification treatment including (iv.1) subjecting the fraction f12, which further contains impurities and / or one or more fillers F, to rubber dissolution conditions in the presence of solvent SD, wherein the impurities and F are inert to the rubber dissolution treatment, thereby obtaining an intermediate mixture containing the impurities and / or the one or more fillers F and further containing rubber dissolved in SD. (iv.2) The intermediate mixture obtained according to (iv.1) is conveyed to the solid-liquid separation unit SU to obtain a mixture M(F) containing these impurities and / or the one or more fillers F, and a mixture MD containing rubber dissolved in SD that is depleted of these impurities and the one or more fillers F—if any—compared to f12; (iv.3) subject the MD containing rubber dissolved in SD obtained according to (iv.2) to precipitation conditions to obtain a purified solid mixture MP containing precipitated rubber.

8. The method of claim 7, wherein, The rubber dissolution treatment according to (iv.1) includes The solid fraction f12 is brought into contact with the solvent SD at a weight ratio of 1:1 to 1:20, preferably 1:3 to 1:15, and more preferably 1:4 to 1:12, to obtain an intermediate mixture containing these impurities and / or one or more fillers F and further containing rubber dissolved in SD.

9. The method of claim 7 or 8, wherein, (iv.3) Includes - MD containing the rubber dissolved in SD obtained according to (iv.2) is subjected to temperature T. P and pressure p P The lower part undergoes precipitation, in which T P < T D T D It is based on the dissolution temperature (iv.1), and T P < 100°C, thereby obtaining an intermediate mixture IM containing SD and precipitated rubber; - The IM is conveyed to the solid-liquid separation unit SU1 to obtain a purified mixture MP containing the precipitated rubber and a liquid mixture containing SD; Preferably, (iv.3) includes - at temperature T P and pressure p P The MD containing the rubber dissolved in SD, obtained by cooling according to (iv.2), is used for precipitation, wherein T P < T D T D It is based on the dissolution temperature (iv.1), and T P < 100°C, thereby obtaining an intermediate mixture IM containing SD and the precipitated rubber; - The IM is transferred to the solid-liquid separation unit SU1 to obtain a purified mixture MP containing the precipitated rubber and a liquid mixture containing SD; or (iv.3) includes - By subjecting the MD containing the rubber dissolved in SD obtained according to (iv.2) to precipitation by contacting the MD with a polar solvent, an intermediate mixture IM' containing SD, the polar solvent and the precipitated rubber is obtained; - The IM' is transferred to the solid-liquid separation unit SU2 to obtain the purified mixture MP containing the precipitated rubber, and the liquid mixture containing SD and the polar solvent.

10. The method of claim 7 or 8, wherein, (iv.3) Includes By passing the MD containing the rubber dissolved in SD obtained according to (iv.2) into a flash evaporator to subject the MD to precipitation, a gaseous stream G3 containing the evaporated solvent is obtained, and a purified mixture MP containing the precipitated rubber is further obtained.

11. The method according to any one of claims 1 to 10, wherein, (v) Includes (v.1) The solid fraction f12 obtained according to (iii) or the purified mixture MP obtained according to (iv) is fed into the pyrolysis reactor R(p); (v.2) The rubber entering the pyrolysis reactor R(p) is heated at a temperature in the range of 350°C to 900°C, preferably in the range of 400°C to 550°C, and at a pressure in the range of 0.5 to 2 bar (absolute value), preferably in the range of 0.9 to 1.5 bar (absolute value); (v.3) The gas stream GS is removed from the top of R(p) and subjected to condensation conditions in the gas-liquid separation unit LGU to obtain the pyrolysis oil.

12. The method according to any one of claims 1 to 11, wherein, The method further includes (vi) subject at least a portion of the pyrolysis oil obtained according to (v) to [a process / treatment]. (vi.1) Cracking, thereby obtaining a stream P1 containing cracked hydrocarbons; and / or (vi.2) Partial oxidation to obtain a synthesis gas flow P2 containing CO and H2; The process further includes (vii) Preparation of polymer PA, including The pyrolysis oil obtained according to (v), the cracked hydrocarbon contained in the stream P1 included according to (vi.1), and the CO and / or H2 synthesis gas contained in the stream P2 obtained according to (vi.2) are used.

13. A recycling unit for performing the method according to any one of claims 1 to 12, the recycling unit comprising: The first separation unit SU(a) is used for kinetic energy separation or electrostatic separation; The second separation unit SU(b) is used for sorting by element composition; The means for conveying MS(1) to SU(b) is preferably one or more conveyors; The pyrolysis reaction unit RU(p); An outlet device for removing pyrolysis oil from RU(p); Optional purification unit PU; An inlet device optionally used to introduce f12 into the PU; An outlet device optionally used to remove purified mixture MP from PU; An inlet device used to introduce f12 or MP into RU(p).

14. An automotive material, preferably for motor vehicles, comprising a polymer PA obtained by the method according to claim 12.

15. A method, preferably the method of any one of claims 1 to 12, comprising the step of converting the pyrolysis oil available or obtainable according to (v), or the cracked hydrocarbon contained in P1 available or obtainable according to (vi) as described in claim 12, or the CO and / or H2 contained in P2 available or obtainable according to (vi) as described in claim 12, to obtain product Ω.

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