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WO2025214989A1 - Procédé de fabrication d'une huile de processus exemptée de l'obligation d'étiquetage et son utilisation - Google Patents

Procédé de fabrication d'une huile de processus exemptée de l'obligation d'étiquetage et son utilisation

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Publication number
WO2025214989A1
WO2025214989A1 PCT/EP2025/059537 EP2025059537W WO2025214989A1 WO 2025214989 A1 WO2025214989 A1 WO 2025214989A1 EP 2025059537 W EP2025059537 W EP 2025059537W WO 2025214989 A1 WO2025214989 A1 WO 2025214989A1
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WO
WIPO (PCT)
Prior art keywords
oil
din
measured according
extraction
content
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/EP2025/059537
Other languages
German (de)
English (en)
Inventor
Lukas HENTSCHEL
Herbert Schulze
Kirsten SKIBOROWSKI
Sebastian MOSSMANN
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hansen & Rosenthal & Co Kg GmbH
Original Assignee
Hansen & Rosenthal & Co Kg GmbH
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Filing date
Publication date
Application filed by Hansen & Rosenthal & Co Kg GmbH filed Critical Hansen & Rosenthal & Co Kg GmbH
Publication of WO2025214989A1 publication Critical patent/WO2025214989A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
    • C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
    • C10G67/04—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only including solvent extraction as the refining step in the absence of hydrogen
    • C10G67/0454—Solvent desasphalting
    • C10G67/0472—The hydrotreatment being a selective hydrogenation of diolefines or acetylenes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/002—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal in combination with oil conversion- or refining processes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/02—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by distillation
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/10—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal from rubber or rubber waste
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
    • C10G21/06—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents characterised by the solvent used
    • C10G21/12—Organic compounds only
    • C10G21/14—Hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
    • C10G21/06—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents characterised by the solvent used
    • C10G21/12—Organic compounds only
    • C10G21/16—Oxygen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
    • C10G21/06—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents characterised by the solvent used
    • C10G21/12—Organic compounds only
    • C10G21/20—Nitrogen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/44—Hydrogenation of the aromatic hydrocarbons
    • C10G45/46—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used
    • C10G45/48—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
    • C10G45/50—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum or tungsten metal, or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G53/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes
    • C10G53/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only
    • C10G53/04—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only including at least one extraction step
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
    • C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
    • C10G67/04—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only including solvent extraction as the refining step in the absence of hydrogen
    • C10G67/0454—Solvent desasphalting
    • C10G67/0481—The hydrotreatment being an aromatics saturation
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1003—Waste materials

Definitions

  • the invention relates to a process for producing a label-free aromatic process oil, the aromatic process oil and its use.
  • Used tires consist of several components, such as rubber, steel, carbon black, and additives.
  • the steel wire is extracted from the tires and can be reused as scrap metal.
  • the remaining rubber is shredded, finely ground, and pyrolyzed in a pyrolysis reactor at high temperatures of, for example, 700°C, i.e., separated into various components, including carbon black.
  • Byproducts include non-condensable gases and pyrolysis oil, also known as tire pyrolysis oil (TPO). Due to its low flash point and, in particular, its high content of polycyclic aromatics, this pyrolysis oil is of limited value and has no established application.
  • WO 2019/067311 Ai discloses a process for treating pyrolysis oil from scrap tires.
  • the process is used to improve the color of the pyrolysis oil and reduce the polycyclic aromatic hydrocarbon (PAH) content.
  • PAH polycyclic aromatic hydrocarbon
  • the pyrolysis oil is mixed with a solvent, brought into contact with clay, and the undesirable components are bound with clay.
  • the purified pyrolysis oil is used to clean oil drilling rigs or as fuel.
  • the object of the invention is therefore to provide a process that allows the utilization of pyrolysis oil from waste tires as a valuable material and, in particular, provides a label-free product that can be reused in industry as a raw material.
  • the object is achieved according to the invention by a process for producing a label-free aromatic process oil according to claim 1, a process oil according to claim 9 and the use of a process oil according to claim 11.
  • the process according to the invention for producing a label-free aromatic process oil comprises at least the steps a) providing a pyrolysis oil from used tires (tire pyrolysis oil), wherein the tire pyrolysis oil has an aromatics content according to DIN 51378: 2020 of 30 wt% to 50 wt%, as well as a "Bureau of Minerals Correlation Index" (BMCI for short) according to API Technical Data Book of greater than 55, a bio-based carbon content according to ASTM D6866 Method B:2022 of 40% (pme) to 55% (pme), a density at 15°C of 880-970 kg/m 3 measured according to DIN 51757 Method 3 (2011), a sulfur content of 0.8-1.1 wt% measured according to DIN EN ISO 14596: 2007, a nitrogen content of 3500-6000 mg/kg measured according to DIN 51444: 2020, a benzo[a]pyrene content between 5 mg/kg and 150 mg/kg measured according to DIN EN 16143: 2023 and a PAH content determined
  • a PAH content determined as a sum according to Directive 2005/69/EU includes the sum of the following eight polycyclic aromatics: Benzo(a)pyrene (CAS No. 50-32-8), Benzo(e)pyrene (CAS No. 192-97-2), Benzo(a)anthracene (CAS No. 56-55-3), Chrysene (CAS No. 218-01-9), Benzo(b)fluoranthene (CAS No. 205-99-2), Benzo(j)fluoranthene (CAS No. 205-82-3), Benzo(k)fluoranthene (CAS No. 207-08-9), Dibenz(a,h)anthracene (CAS No. 53-70-3), which according to Federal Council document 190/06 of 09.03.2006, Section 29 are limited in use in tires.
  • the aromatic oil may have a sulfur content of less than 2 wt.% measured according to DIN EN ISO 14596: 2007, preferably less than 1.5 wt.%, particularly preferably less than 1 wt.%.
  • the raffinate obtained is an aromatic oil having a polycyclic aromatic hydrocarbon content according to IP346 of ⁇ 3 wt%.
  • pyrolysis oil from used tires is understood to mean an oil that is obtained as a liquid by-product during the pyrolysis of used tires or a thermal depolymerization, also called hydrothermal liquefaction.
  • pyrolysis oil from used tires is understood to mean a liquid, aromatic oil that is produced under the exclusion of oxygen by means of thermal decomposition of used tires, in particular thermal depolymerization of the rubber contained in tires, selected from natural rubber and synthetic rubber, such as styrene-butadiene rubber or other copolymers of styrene, butadiene and/or Isoprene monomers, isoprene rubber, butadiene rubber, ethylene-propylene-diene rubber, halobutyl and butyl rubber, as well as the dissolution and degradation of the various components that make up the complex structure of a tire.
  • the thermal decomposition and depolymerization of waste tires can be achieved by pyrolysis, solvolysis,
  • TPO Tire Pyrolysis Oil
  • BMCI Bureau of Minerals Correlation Index
  • the tire pyrolysis oil has a bio-based carbon content according to ASTM D6866 Method B:2022 of 40% (pme) to 55% (pme), a density at 15°C of 880-970 kg/m 3 measured according to DIN 51757 Method 3 (2011), a sulfur content of 0.8 wt.%-1.1 wt.% measured according to DIN EN ISO 14596: 2007, a nitrogen content of 3500-6000 mg/kg measured according to DIN 51444: 2020, a benzo[a]pyrene content between 5 mg/kg and 150 mg/kg measured according to DIN EN 16143: 2023 and a PAH content determined as a sum according to Directive 2005/69/EU of greater than 40 mg/kg and up to 850 mg/kg measured according to DIN EN 16143: 2023.
  • pyrolysis involves shredding entire tires.
  • the steel is separated after pyrolysis. This process also produces carbon soot, non-condensable gases, and pyrolysis oil.
  • a label-free aromatic process oil is understood to be a hydrocarbon mixture that has a proportion of aromatic hydrocarbons according to DIN 51378: 2020 of at least 15 wt.%, i.e. a CA content of at least 15.
  • the aromatic process oil is considered to be label-free if it has a benzo(a)pyrene content of less than 1 mg/kg measured according to DIN EN 16143: 2023 and a sum of polycyclic aromatics of less than 10 mg/kg measured according to DIN EN 16143: 2023 according to Directive 2005/69/EC, i.e.
  • the pyrolysis oil from waste tires is separated into several fractions in a distillation step (step b).
  • the first fraction is a low-boiling fraction that boils at temperatures between 40 and 300°C. This low-boiling fraction is collected separately and not further processed in the process according to the invention.
  • Another fraction is a high-boiling fraction that boils at temperatures between 300 and 700°C.
  • This high-boiling fraction is collected and further processed in the process according to the invention.
  • the high-boiling fraction has a higher flash point and is therefore more suitable for further processing.
  • the distillation in step b) is carried out at atmospheric pressure or under vacuum, preferably in several distillation steps, either at the same pressure or at different pressures in the different distillation steps.
  • the distillation can be carried out in two distillation steps, with atmospheric pressure in a first distillation step and under vacuum in a second distillation step.
  • Distillation can be carried out in one or more distillation steps. If multiple distillation steps are involved, the high-boiling fraction from the last distillation step is used as the high-boiling fraction for the extraction step.
  • the high-boiling fraction of the pyrolysis oil is subjected to an extraction process.
  • the extraction process is carried out under typical pressures and residence times for a liquid-liquid extraction, e.g., at atmospheric or slightly elevated pressure.
  • the extractant in step c) is preferably selected from furfural, n-methylpyrrolidone, n-methylpyrrolidone-water mixtures, n-pentane, iso-pentane, n-hexane, n-heptane, n-octane, iso-octane, cyclohexane and mixtures thereof, preferably selected from furfural, n-methylpyrrolidone, n-methylpyrrolidone-water- Mixtures, n-heptane, and mixtures thereof, particularly preferably a polar solvent such as furfural or n-methylpyrrolidone, assuming that the extractants are of at least technical purity. Extractants in step c) refer to all solvents added to the extraction reactor. If n-methylpyrrolidone is used, it can be used mixed with 0-10 wt.% water, preferably with 0-7 wt.% water.
  • the ratio of extractant to pyrolysis oil fraction is from 30 wt.% to 300 wt.%, preferably from 50 wt.% to 250 wt.%, particularly preferably from 80 wt.% to 200 wt.% extractant to pyrolysis oil, wherein the ratio refers to extractant to pyrolysis oil, i.e. at a ratio of 80 wt.%, 0.8 kg of extractant is added to 1 kg of pyrolysis oil.
  • the extraction process can be carried out as a single-stage or multi-stage extraction process.
  • the pyrolysis oil from waste tires can be mixed with a mineral oil-based process oil, preferably selected from distilled aromatic extract (DAE), residual aromatic extract (RAE), and mixtures thereof, and then transferred to extraction with an extraction agent.
  • a mineral oil-based process oil preferably selected from distilled aromatic extract (DAE), residual aromatic extract (RAE), and mixtures thereof
  • DAE distilled aromatic extract
  • RAE residual aromatic extract
  • a homogeneous mixture of pyrolysis oil and mineral oil-based process oil is first prepared, and this mixture is then mixed with an extraction agent.
  • the ratio of The ratio of mineral oil-based process oil to pyrolysis oil in the mixture is preferably between 99-70 wt.% mineral oil-based and 1-30 wt.% pyrolysis oil-based. This mixture is mixed in the same ratio of extractant to extracting mixture as the pure pyrolysis oil.
  • the extraction process can be carried out on an industrial scale in an extraction column.
  • Suitable extraction columns are designed, for example, as: a. packed column b. packed column c. tray column or d. rotating disc extractor (RDC).
  • RDC rotating disc extractor
  • Both the distillation step and the extraction step can be carried out either with the pure pyrolysis oil or in a mixture with mineral oil-based products, such as DAE or RAE, whereby the extraction step is carried out starting from the heavy fraction of the pure pyrolysis oil or the mixture of the heavy fraction of the pyrolysis oil with a mineral oil-based product.
  • Solvent extraction with a polar solvent such as furfural or N-methyl-2-pyrrolidone at the temperatures and solvent ratios used preferentially extracts the polycyclic aromatics.
  • the resulting process oil is still aromatic, allowing it to be used in tire compounds, for example, while also being label-free.
  • the pyrolysis oil from waste tires is hydrogenated in an additional step a2), wherein the hydrogenation of the entire pyrolysis oil can take place before the distillation or of the heavy fraction after the distillation of step b).
  • the invention further relates to a label-free aromatic process oil produced from pyrolysis oil from used tires, characterized in that the process oil has a proportion of aromatic hydrocarbons CA of 15-35, preferably 20-30, measured according to DIN 51378: 2020, a concentration of benzo(a)pyrene ⁇ 1 mg/kg measured according to DIN EN 16143: 2023, a PAH content determined as a sum according to Directive 2005/69/EU of less than 10 mg/kg measured according to DIN EN 16143: 2023, and that the process oil is a hydrocarbon mixture, wherein the carbons originate from fossil sources to a maximum of 99% by weight and at least 1% by weight from bio-based sources which have a bio-based carbon content measured according to ASTM D6866 Method B: 2022 greater than 1% (pMC), preferably greater than 10% (pMC), particularly preferably greater 40% (pMC) or even greater than 50% (pMC).
  • the process oil has a proportion of aromatic hydrocarbons CA of 15-35, preferably 20-30, measured according to
  • the origin of the bio-based carbon content is preferably natural rubber and other bio-based components of the tire, such as bio-based synthetic rubbers, bio-based fillers, bio-based plasticizers, bio-based resins, bio-based waxes, bio-based anti-aging agents or vulcanization chemicals as well as bio-based reinforcements.
  • the carbon contained in the process oil preferably comes from up to a maximum of 95% fossil sources and at least 5% (pMC) bio-based sources, particularly preferably from a maximum of 90% fossil sources and at least 10% (pMC) bio-based sources, further preferably from a maximum of 85% fossil sources and at least 15% (pMC) bio-based sources.
  • Bio-based sources can be of plant or animal origin.
  • a plant source of hydrocarbons can be natural rubber, which is found in used tires.
  • An animal source can be stearic acid, which is also found in used tires.
  • the label-free aromatic process oil has, for example, a density of 890 to 990 g/cm 3 , preferably 940 - 965 g/cm 3 at 15°C according to DIN 51757 Method 3: 2011, a kinematic viscosity of 17.5 - 37 mm 2 /s at 100°C measured according to DIN EN ISO 3104: 2024, and an aniline point of 68 - 79 °C measured according to DIN ISO 2977: 2020.
  • the label-free aromatic process oil can have a sulfur content of less than 2 wt.% measured according to DIN EN ISO 14596: 2007, preferably less than 1.5 wt.%, particularly preferably less than 1 wt.%.
  • the label-free aromatic process oil has a polycyclic aromatic hydrocarbon content of less than 3 wt.% measured according to IP346.
  • the aromatic process oil according to the invention is preferably produced by a process according to one of claims 1 to 8.
  • the invention relates to the use of a label-free aromatic process oil produced by a process according to one of claims 1 to 8 or a process oil according to one of claims 9 or 10 as a plasticizer in tires or rubber mixtures or as an extender oil, i.e. extender oil in polymers.
  • the process oil is preferably present in the rubber compound, tire, or polymer in an amount of up to 60 phr, preferably up to 40 phr.
  • the process oil is preferably used in an amount of up to 37.5 phr.
  • additional plasticizers can be added. When using oil-extended rubbers, these are in the low range, e.g., 10-20 phr. When using non-oil-extended rubbers (so-called dry grades), correspondingly high amounts of plasticizer can be used, e.g., up to 50-60 phr.
  • an extracted aromatic oil, treated distillated aromatic extract (TDAE) or naphthenic base oils are typically used as a plasticizer, i.e. as a process oil.
  • These conventional products are 100% mineral oil-based.
  • the present invention replaces mineral oil-based process oils with a product from the chemical recycling of used tires, which is obtained from pyrolysis oil (tire pyrolysis oil, TPO for short).
  • the concentration of polycyclic aromatics is reduced compared to TPO, with values of (benzo(a)pyrene ⁇ 1 mg/kg according to DIN EN 16143:2023, Directive 2005/69/EC total ⁇ 10 mg/kg according to DIN EN 16143:2023 and PCA according to IP346 ⁇ 3 wt.%).
  • the aromatic process oil can be used in tire and rubber compounds and replace conventional process oils such as TDAE.
  • FIG. 1 shows a first embodiment of the process.
  • a pyrolysis oil (TPO) 10 is provided.
  • the pyrolysis oil is separated in a distillation step 20, producing a low-boiling fraction 21 and a high-boiling fraction 22.
  • the high-boiling fraction is transferred to an extraction reactor 30, where it is extracted with solvent.
  • a label-free aromatic process oil 40 and an extract 41 are obtained.
  • FIG. 2 shows a further embodiment of the process.
  • the pyrolysis oil (TPO) 10 is again provided. It is hydrogenated 15 in a hydrogenation reactor in a first process step.
  • the hydrogenated pyrolysis oil is then separated again in a distillation step 20, producing a low-boiling fraction 21 and a high-boiling fraction 22.
  • the high-boiling fraction is transferred to an extraction reactor 30 and extracted there with solvent.
  • the result of the process is a label-free aromatic process oil 40 and an extract 41.
  • FIG. 3 shows a further embodiment of the process with a hydrogenation step.
  • the pyrolysis oil (TPO) 10 is again provided.
  • the pyrolysis oil is first separated in a distillation step 20, whereby a low-boiling Fraction 21 and a high-boiling fraction 22 are formed.
  • the high-boiling fraction is transferred to a hydrogenation reactor and hydrogenated there 15.
  • the hydrogenated fraction is then transferred to an extraction reactor 30 and extracted there with solvent.
  • a co-extraction 31 can be carried out with a mineral oil-based process oil, such as DAE.
  • the result of the process is a label-free aromatic process oil 40 and an extract 41.
  • a first step 40 l of pyrolysis oil were prepared according to Table 1 and fed into a distillation column (batch column).
  • the batch column was initially operated at atmospheric pressure up to 170°C.
  • the pressure was reduced to 30 mbar as the temperature increased.
  • a residue fraction with an initial boiling point greater than 350°C was obtained.
  • the residue fraction was distilled again using a D1160 apparatus to further remove low-boiling components.
  • the D1160 was operated at a pressure of 13.33 mbar up to an AET temperature of 424°C.
  • the high-boiling fraction obtained from the second distillation stage was subjected to a three-stage laboratory extraction. This was operated at a temperature of 55°C. Furfural was used as the solvent. This produced a label-free raffinate and an extract in which the polycyclic aromatics were preferentially found.
  • a furfural ratio of 110 wt% was used.
  • a process oil with the parameters listed in Table 1 was obtained. The results are listed in Table 1 as L-Ex-3 raffinate.
  • the process oil has a low content of polycyclic aromatic hydrocarbons, and relevant compounds such as benzo[a]pyrene and PAH are below the required limits.
  • sulfur contents in the process oil can be reliably achieved in the same range as in a mineral oil-based process oil.
  • the bio-based carbon content according to ASTM D6866 Method B: 2022 was 39% (pMC). The process thus transforms a waste product (tire) into a high-quality raw material with a reduced fossil carbon content and a high bio-based carbon content.
  • Example 1 the pyrolysis oil from Example 1 was used proportionally, so that the same distillation product (residue) was used for the subsequent steps.
  • a DAE sample was taken from a large-scale production facility. This was mixed in a ratio of 80% DAE to 20% TPO distillation residue from step 1 (Example 1).
  • the mixture was subjected to a three-stage laboratory extraction. This was carried out at a temperature of 55°C. Furfural was used as the solvent. A label-free raffinate and an extract containing the polycyclic aromatics were produced. A furfural ratio of 90% was used.
  • a DAE sample was taken from an ongoing production at the point of use of the extraction.
  • the pure DAE was subjected to a three-stage laboratory extraction. This was carried out at a temperature of 55°C. Furfural was used as the solvent. A label-free raffinate and an extract in which the polycyclic aromatics were preferentially found were produced. A furfural ratio of 80% was used. The results are listed in Table 2 as L-Ex-6 raffinate.
  • Another batch of pyrolysis oil was investigated. For this, 40 l of pyrolysis oil were again fed into a distillation column (batch column). The batch column was initially operated at atmospheric pressure to separate an initial low-boiling fraction. A maximum head temperature of 170°C was selected for the first fraction. For the subsequent fractions, the pressure was reduced to 30 mbar to prevent cracking of the pyrolysis oil. Distillation was stopped at a head temperature of 220°C. This corresponds to an AET temperature of 348°C.
  • the obtained high-boiling fraction was subjected to a three-stage laboratory extraction. This was carried out at a temperature of 55°C. Furfural was used as the solvent. A label-free raffinate and an extract in which the polycyclic aromatics were preferentially found were produced. A furfural ratio of 80% was used for this purpose.
  • Table 4 Composition of the rubber mixtures with process oils according to the invention: solution-polymerized styrene-butadiene copolymer, Sprintan SLR 4602, Synthos Nd-catalyzed butadiene polymer, Buna CB 24, Arlanxeo Ultrasil 7000 GR, Evonik
  • TESPT 3,3'-bis(triethoxysilylpropyl)tetrasulfide e TMQ, 2,2,4-trimethyl-i,2-dihydroquinoline, polymerized f 6PPD, N-(i,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine
  • the process oils prepared according to the above examples were tested in a rubber compound.
  • the compositions are shown in Table 4.
  • the compounds were vulcanized, and the properties of the resulting vulcanizates were measured. These are shown in Table 5.
  • TPO Pyrolysis oil

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Abstract

L'invention concerne un procédé de fabrication d'une huile de processus aromatique exemptée de l'obligation d'étiquetage à partir d'une huile de pyrolyse issue de pneus usagés. Le procédé comprend les étapes suivantes : distiller l'huile de pyrolyse issue de pneus usagés dans une distillation fractionnée, au moins une fraction à faible point d'ébullition et au moins une fraction à point d'ébullition élevé étant obtenues, mélanger ladite au moins une fraction à point d'ébullition élevé avec un solvant en tant qu'agent d'extraction et procéder à l'extraction, une huile aromatique étant obtenue sous forme de raffinat. En outre, l'invention concerne une huile de processus aromatique exemptée de l'obligation d'étiquetage et l'utilisation de l'huile de processus dans des pneus ou des mélanges de caoutchouc.
PCT/EP2025/059537 2024-04-09 2025-04-08 Procédé de fabrication d'une huile de processus exemptée de l'obligation d'étiquetage et son utilisation Pending WO2025214989A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1180755A (ja) * 1997-09-05 1999-03-26 Fuji Kosan Kk 溶剤抽出と水素化精製法による非発ガン性芳香族炭化水素油の製造法
CN106010631B (zh) * 2016-05-23 2017-10-03 中海沥青股份有限公司 一种橡胶增塑剂的溶剂精制方法
US20180355256A1 (en) * 2015-11-23 2018-12-13 Integrated Green Energy Singapore Pte Ltd Production of hydrocarbon fuels from plastics
DE102017211926A1 (de) * 2017-07-12 2019-01-17 Continental Reifen Deutschland Gmbh Kautschukmischung für die Innenschicht oder den Schlauch von Fahrzeugluftreifen und Fahrzeugluftreifen
WO2019067311A1 (fr) 2017-09-27 2019-04-04 Rj Lee Group, Inc. Procédés et appareil de clarification d'huiles de pyrolyse
CN109401780B (zh) * 2017-08-16 2021-02-02 中国石油大学(华东) 一种橡胶填充油的制备方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1180755A (ja) * 1997-09-05 1999-03-26 Fuji Kosan Kk 溶剤抽出と水素化精製法による非発ガン性芳香族炭化水素油の製造法
US20180355256A1 (en) * 2015-11-23 2018-12-13 Integrated Green Energy Singapore Pte Ltd Production of hydrocarbon fuels from plastics
CN106010631B (zh) * 2016-05-23 2017-10-03 中海沥青股份有限公司 一种橡胶增塑剂的溶剂精制方法
DE102017211926A1 (de) * 2017-07-12 2019-01-17 Continental Reifen Deutschland Gmbh Kautschukmischung für die Innenschicht oder den Schlauch von Fahrzeugluftreifen und Fahrzeugluftreifen
CN109401780B (zh) * 2017-08-16 2021-02-02 中国石油大学(华东) 一种橡胶填充油的制备方法
WO2019067311A1 (fr) 2017-09-27 2019-04-04 Rj Lee Group, Inc. Procédés et appareil de clarification d'huiles de pyrolyse

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
no. 207-08-9

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