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WO2025210070A1 - Procédé de recyclage de matériaux solides à base de caoutchouc à partir de déchets automobiles solides - Google Patents

Procédé de recyclage de matériaux solides à base de caoutchouc à partir de déchets automobiles solides

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Publication number
WO2025210070A1
WO2025210070A1 PCT/EP2025/058942 EP2025058942W WO2025210070A1 WO 2025210070 A1 WO2025210070 A1 WO 2025210070A1 EP 2025058942 W EP2025058942 W EP 2025058942W WO 2025210070 A1 WO2025210070 A1 WO 2025210070A1
Authority
WO
WIPO (PCT)
Prior art keywords
rubber
obtained according
obtaining
mixture
solid
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/EP2025/058942
Other languages
English (en)
Inventor
Hannah Stephanie MANGOLD
Miika FRANCK
Nok-Young Choi
Rainer Xalter
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.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of WO2025210070A1 publication Critical patent/WO2025210070A1/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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
    • B29B17/02—Separating plastics from other materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
    • B29B17/04—Disintegrating plastics, e.g. by milling
    • 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
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/40—Thermal non-catalytic treatment
    • 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
    • C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
    • B29B17/02—Separating plastics from other materials
    • B29B2017/0203—Separating plastics from plastics
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
    • B29B17/02—Separating plastics from other materials
    • B29B2017/0213—Specific separating techniques
    • B29B2017/0217—Mechanical separating techniques; devices therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
    • B29B17/02—Separating plastics from other materials
    • B29B2017/0213—Specific separating techniques
    • B29B2017/0262—Specific separating techniques using electrical caracteristics
    • B29B2017/0265—Electrostatic separation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
    • B29B17/02—Separating plastics from other materials
    • B29B2017/0213—Specific separating techniques
    • B29B2017/0279—Optical identification, e.g. cameras or spectroscopy
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
    • B29B17/02—Separating plastics from other materials
    • B29B2017/0213—Specific separating techniques
    • B29B2017/0293—Dissolving the materials in gases or liquids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
    • B29B17/04—Disintegrating plastics, e.g. by milling
    • B29B2017/0424—Specific disintegrating techniques; devices therefor
    • B29B2017/0496—Pyrolysing the materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2019/00—Use of rubber not provided for in a single one of main groups B29K2007/00 - B29K2011/00, as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2031/00—Other particular articles
    • B29L2031/30—Vehicles, e.g. ships or aircraft, or body parts thereof
    • B29L2031/3055—Cars
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/025—Processes for making hydrogen or synthesis gas containing a partial oxidation step
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • 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 solid automotive waste material W is obtained from end-of-life vehicles, preferably the solid waste material W is an automotive shredder residue ASR.
  • the automotive shredder residue may represent about 10 - 40 wt.-%, preferably from 15 - 35 wt.-%, and in particular from 20 - 30 wt.-% of the original vehicle weight.
  • the automotive shredder residue may comprise fragments of various polymeric vehicle parts, such as fragments of
  • the SHF can be present in an amount of 10 - 45 wt.-%, preferably 15 - 35 wt.-%, and in particular at 20 - 30 wt.-% of the automotive shredder residue.
  • the SLF may represent the remaining amount to 100 wt.-%.
  • the SLF usually contains a lower weight percentage of solid and sand than the SHF.
  • M1 has an halogen content in the range of from 0.5 to 5 weight-%, based on the weight of M1, determined as described in Analytics 2.
  • sorting according to (iii) is automated sorting.
  • Preferably sorting according to (iii) comprises using one or more of a conveyor, sensors, lights, a laser, an X-ray source, such as X-ray tubes, a radioisotopic source, a detector, and a camera.
  • a conveyor sensors, lights, a laser, an X-ray source, such as X-ray tubes, a radioisotopic source, a detector, and a camera.
  • sorting according to (iii) is an X-ray fluorescence sorting method.
  • the halogen content in the halogen-rich rubber-based materials fraction f 11 is superior to the halogen content in M1.
  • sorting according to (iii) comprises
  • the conveyor is a belt conveyor.
  • fillers refers to inorganic materials (inert materials) having a structural function which are typically added to a substance (e.g. a polymer) to improve certain characteristics such as physical and/or mechanical properties.
  • a substance e.g. a polymer
  • fillers are incorporated into polymer-based materials to improve strength, stiffness, thermal conductivity, reduce shrinkage, and so on.
  • fillers include glass fibers, carbon particles such as carbon black, or talc.
  • Fillers are not additives which are rather active (non-inert) substances.
  • the one or more fillers F are present in M1 in an amount in the range of from 0.05 to 75 weight-%, based on the weight of W.
  • the one or more fillers F are present in the halogen-poor rubber-based solid materials fraction f12 in an amount in the range of from 0.1 to 75 weight-%, more preferably in the range of from 5 to 70 weight-%, based on the weight of the fraction f 12.
  • Preferably subjecting the halogen-poor rubber-based solid fraction f12 obtained according to (iii) to a purification treatment according to (iv) comprises
  • SD has a Hansen solubility parameter 5H in the range of from 0 to 10 MPa 1/2 , more preferably in the range of from 0 to 8 MPa 1/2 , more preferably in the range of from 0 to 7 MPa 1/2 .
  • the Hansen solubility parameter ⁇ 5 H is a known parameter which characterizes the solubility of a compound. ⁇ 5 H relates to the energy from hydrogen bonds between molecules. For numerous compounds, such as xylene, toluene and cyclohexane, the Hansen parameter bn can be found in standard chemical books.
  • the Hansen solubility parameters 5H mentioned in the present invention refers to values tabulated in: Hansen, C.M., Hansen Solubility Parameters - A user’s handbook, 2. Edition, CRC Press, Boca Raton, USA, 2007.
  • the rubber-dissolution treatment according to (iv.1 ) is performed at a pressure in the range of from 800 to 200 000 hPa, more preferably in the range of from 800 to 10000 hPa.
  • the dissolution treatment according to (iv.1 ) is performed in a reactor unit RD.
  • the rubber-dissolution treatment according to (iv.1 ) comprising, bringing in contact f 12 with the solvent SD at a weight ratio of the solid fraction f 12 relative to the solvent SD being in the range of from 1 : 1 to 1 :20, more preferably in the range of from 1 :3 to 1 : 15, more preferably in the range of from 1 :4 to 1 :12, obtaining an intermediate mixture comprising the impurities and/or the one or more fillers F and further comprising rubber dissolved in SD.
  • the temperature of the intermediate mixture obtained according to (iv.1 ) is essentially maintained, more preferably maintained, via one or more heated tubes used for transferring said intermediate mixture into Sil.
  • the filtration unit is operated under a pressure pp, with pp s 1 bar(abs), more preferably pp is in the range of from 1 to 30 bar(abs), more preferably in the range of from 1 to 10 bar(abs), more preferably in the range of from 1 to 6 bar(abs).
  • the precipitated rubber is in the form of powder, the particles having an average size in the range of from 1 micrometer to 1 millimeter, more preferably in the range of from 10 micrometers to 100 micrometers, the particles average size being determined as defined in Analytics 1 .
  • MP obtained according to (iv.3) has a halogen content of at most 1000 ppmw, more preferably at most 500 ppmw, more preferably at most 250 ppmw, more preferably at most 100 ppmw, based on the weight of MP, the content being determined as described in Analytics 2.
  • the precipitated rubber obtained according to (iv.3) has a halogen content of at most 1000 ppmw, more preferably at most 500 ppmw, more preferably at most 250 ppmw, more preferably at most 100 ppmw, based on the weight of the precipitated rubber, the content being determined as described in Analytics 2.
  • MP obtained according to (iv.3) has a O content of at most 1000 ppmw based on the weight of MP.
  • MP obtained according to (iv.3) has a N content of at most 1000 ppmw based on the weight of MP.
  • (iv.3) comprises
  • TP ⁇ TD - 5 °C more preferably TP ⁇ TD - 10 °C, more preferably TP ⁇ TD - 30 °C, more preferably TP ⁇ TD - 30 °C.
  • cooling according to (iv.3) comprises
  • (iv.3) comprises subjecting MD comprising the rubber dissolved in SD obtained according to (iv.2) to precipitation by contacting MD with a polar solvent, also called “anti-solvent”, obtaining an intermediate mixture IM’ comprising SD, the polar solvent and the precipitated rubber; passing IM’ in a solid-liquid separation unit SU2, obtaining the purified mixture MP comprising the precipitated rubber, and a liquid mixture comprising SD and the polar solvent.
  • a polar solvent also called “anti-solvent
  • (iii) further comprises. washing MP, more preferably the solid mixture MP is washed with one or more of methanol, ethanol, propanol, isopropanol, acetonitrile, ethyl acetate, acetone and water; and optionally drying the washed solid mixture MP comprising the precipitated rubber.
  • contacting MD with the polar solvent is performed at a temperature in the range of from 10 to 120 °C, more preferably in the range of from 20 to 60 °C.
  • contacting MD with the polar solvent is performed at a pressure in the range of from 0 to 10 bar(abs), more preferably in the range of from 0.5 to 2 bar(abs).
  • the polar solvent is selected from the group consisting of water, ethanol, methanol, propanol, butanol, acetone, dimethylsulfoxide, acetonitrile, dimethylformamide, ethylacetate, sulfolane, dichloromethane, tetrahydrofurane, and a mixture of two or more thereof, more preferably selected from the group consisting of water, acetone, ethanol, methanol and a mixture of two or more thereof.
  • the polar solvent has an Hansen solubility parameter ⁇ 5 H of more than 5 MPa 1/2 , preferably in the range of from 6 to 50 MPa 1/2 , more preferably in the range of from 10 to 30 MPa 1/2 . Flash evaporation
  • (iv.3) comprises subjecting MD comprising the rubber dissolved in SD obtained according to (iv.2) to precipitation by passing MD in a flash evaporator, obtaining a gaseous stream G3 comprising the evaporated solvent, and further obtaining the purified mixture MP comprising the precipitated rubber.
  • the process further comprises recycling at least a portion of the solvent SD recovered after (iv.3) to the rubber-dissolution treatment according to (iv.1); wherein recycling preferably comprises passing the at least a portion of the solvent SD recovered after (iv.3) in a distillation unit D, obtaining a purified solvent; using the purified solvent to the rubber-dissolution treatment according to (iv.1 ).
  • the distillation unit D is heated by a heating source, more preferably steam.
  • a heating source preferably is generated from the recycled gas stream obtained after pyrolysis according to (v).
  • the process further comprises recycling both the solvent SD and the polar solvent by fractional distillation.
  • the solid fraction f 12 obtained according to (iii), or the purified mixture MP obtained according to (iv) comprises rubber in an amount in the range of from 90 to 100 weight-%, more preferably in the range of from 95 to 100 weight-%, based on the weight of the solid mixture.
  • (v) comprises
  • feeding according to (v.1) is performed via a dosing unit, the dosing unit being more preferably one or more of a screw, an extruder and a rotary valve.
  • feeding according to (v.1) is performed via pneumatic conveyor or liquid injector into the pyrolysis reactor R(p).
  • the pyrolysis is performed by thermal cracking (absence of catalyst) or catalytic cracking, more preferably thermal cracking.
  • the pyrolysis according to (v) is not a hydrothermal treatment.
  • the pyrolysis reactor R(p) contains trace amounts of water, wherein preferably trace amounts of water is less than 2 wt.% water calculated on the basis of the total weight of the precipitated polyolefin PP, more preferably less than 1 wt.% water, more preferably less than 0.1 wt.% water.
  • the solid fraction f 12 obtained according to (iii), or the purified mixture MP obtained according to (iv) may be subjected to a prepyrolysis at a temperature in the range of from 220 to 360 °C.
  • a prepyrolysis at low temperature permits to pyrolysed PVC if present in the solid mixture.
  • such step can be avoided in view of the particular process steps (i) to (iii) prior to (iv) of the process according to the present invention.
  • the solid fraction f 12 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 CaCCh.
  • Such additives permit to react with formed HCI and thus remove impurities such as chlorine from PVC.
  • the gas stream GS exiting the pyrolysis reactor is passed through a catalyst bed or an adsorption bed, in order to reduce the concentration of impurities and atoms other than C and H.
  • the gas stream GS is passed through a filtration unit, more preferably a filter, or a cyclone.
  • a filtration unit or cyclone permits to remove dust particles from the gas stream GS before condensation.
  • a catalyst bed or an adsorption bed can be used upstream thereof or downstream thereof to reduce the concentration of impurities and atoms other than C and H.
  • GS is subjected to a condensation step in LGU at a temperature in the range of from 0 to 80 °C; wherein more preferably LGU is a condenser, a scrubber or a quench.
  • the gas stream GS in (v.3) is subjected to a first condensation step at a temperature in the range of from 50 to 150 °C and to a second condensation step at a temperature in the range of from 35 to 0°C, obtaining the pyrolysis oil; each of the first and second condensation steps more preferably being performed in a separate condenser or quench.
  • the gas stream GS in (v.3) is preferably subjected to only one condensation step at a temperature in the range of from 0 to 80 °C.
  • the non-condensable “permanent” gases G exiting LGU can be used to generate process heat /electricity by burning in a gas burner, gas motor or combined heat and power plant.
  • the flue gases of this combustion might need to be cleaned according to emission laws to remove dust, ashes and other components.
  • the process further comprises, after (v), passing the pyrolysis oil obtained according to (v), as a stream So, into a purification unit PU, obtaining a purified pyrolysis oil.
  • the purification unit PU comprises one or more of a filter, a centrifuge, a decanter, and a decanter centrifuge, more preferably one or more of a filter, a centrifuge and a decanter.
  • the pyrolysis oil obtained according to (v), more preferably (v.3), can be filtered including the possible use of a filter agent to remove solids.
  • said pyrolysis oil can be centrifuged to remove solids.
  • water residue can be removed from the pyrolysis oil by decanting or centrifugation.
  • the pH can be adjusted to a pH value of at most 3 or, alternatively, a pH value of at least 8, preferably at least 9.
  • the adjustement is performed by the addition of an acid or a base such as an alkali metal hydroxide, for example sodium hydroxide (NaOH), potassium hydroxide (KOH), alkaline earth metal hydroxide, for example calcium hydroxide (Ca(0H)2, NH3, or mixtures thereof sulfuric acid (H2SO4), nitric acid (HNO3) or phosphoric acid (H3PO4).
  • an acid or a base such as an alkali metal hydroxide, for example sodium hydroxide (NaOH), potassium hydroxide (KOH), alkaline earth metal hydroxide, for example calcium hydroxide (Ca(0H)2, NH3, or mixtures thereof sulfuric acid (H2SO4), nitric acid (HNO3) or phosphoric acid (H3PO4).
  • an acid or a base such as an alkali metal hydroxide, for example sodium hydroxide (NaOH), potassium hydroxide (KOH), alkaline earth metal hydroxide, for example calcium hydrox
  • the process further comprises
  • the filtration unit comprises a filter for blocking the mixture M(F) comprising the impurities and/or the one or more fillers F and a receiving vessel for the mixture MD comprising the rubber dissolved in SD.
  • (vi.2) partial oxidation, obtaining a syngas stream P2 comprising CO and H2.
  • a cracker preferably a steam cracker.
  • (viii) preparing an automotive material, comprising using one or more of the pyrolysis oil obtained according to (v), the cracked hydrocarbons comprised in the stream P1 obtained according to (vi) as described in any one of embodiment 26 to 28, and the CO and/or H2 comprised in the syngas stream P2 obtained according to (v) as described in any one of embodiments 26 to 28, and the polymer PA obtained according to (vii) as described in embodiment 29.
  • An automotive material preferably an automotive vehicle, comprising a polymer PA obtained according to the process of embodiment 29.
  • a process preferably according to any one of embodiments 1 to 28, comprising the step of converting the pyrolysis oil obtainable or obtained according to (v), or the cracked hydrocarbons comprised in P1 obtainable or obtained according to (vi) as described in any one of embodiments 26 to 28, or the CO and/or H2 comprised in P2 obtainable or obtained according to (vi) as described in any one of embodiments 26 to 28, to obtain a product Q.
  • X is a chemical element and A, B and C are concrete elements such as Li, Na, and K, or X is a temperature and A, B and C are concrete temperatures such as 10 °C, 20 °C, and 30 °C.
  • X is one or more of A and B” disclosing that X is either A, or B, or A and B, or to more specific realizations of said feature, e.g. “X is one or more of A, B, C and D”, disclosing that X is either 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, or A and B and C and D, or A and B and C and D, or A and B and C and D, or A and B and C and D.
  • the average particle size was measured with a Mastersizer 3000 which uses laser diffraction to measure the particle size, and size distribution. This is described in Particle Size Measurements: Fundamentals, Practice, Quality (Particle Technology Series Book 17), Henk G. Merkus, 2009 Edition.
  • 2.3 XRF Analysis a. Turn on the XRF instrument and allow it to warm up according to the manufacturer's instructions. b. Set the instrument to the appropriate X-ray tube voltage and current based on the expected halogen content and the instrument's capabilities. c. Load the calibration standards onto the instrument, including the halogen-free sample and any additional standards for intermediate halogen concentrations if available. d. Analyze the calibration standards to verify the accuracy and precision of the calibration curve or calibration factors. e. Load the prepared sample(s) onto the instrument, ensuring that the sample is evenly distributed and covers the detection area as much as possible. f. Analyze the sample(s) using the XRF instrument, following the manufacturer's instructions for sample positioning and measurement duration. g. Repeat the analysis for each sample to ensure reproducibility.
  • the single components are collected from a local End-of- Life Vehicles “ELV” collector company (an authorized treatment facility which depollutes ELV) from about 15 year-old passenger cars.
  • ELV End-of- Life Vehicles
  • glass is the glass from front windshields and rear windows
  • dirt is collected as attached to the car exterior
  • PUR foam is collected from the seat foam
  • plastic is collected from selected plastic parts of the cars, such as wheel covers, dashboard, wiper arm, door handle, gears, and bushes, where the type of polymer is known.
  • the model ASR-1 to ASR-3 are prepared in 5 kg batches by weighing in the components and by shredding the components listed in Table 1 first by hand with a hammer and metal scissors, followed by shredding with a four-shaft shredder (like Model “JFS 8080” from Jogindra, India with main blade rotation diameter 245 mm, assistant rotation diameter 270 mm, 42 main blades, 20 assistant blades, 25 rpm main axle rotation speed, 120-200 kg/hr capacity).
  • the maximum fragment size is 10 cm.
  • Table 1 Composition of model ASR (amounts in wt.-%)
  • FIG. 1 shows a possible flow scheme with a suitable process sequence for obtaining the automotive shredder residue ASR. Starting from the vehicles, followed by optional depollution, followed by optional dismantling, followed by shredding the vehicles, followed by optional separating the metal fragments from the shredded vehicle, then the ASR is obtained, followed by optional separation of the ASR in shredder light fraction and shredder heavy fraction.
  • FIG. 2 is a schematic representation of a recycling unit used for the process according to embodiments of the present invention.
  • the recycling unit comprises a separation unit Sll(a), a separation unit Sll(b), a pyrolysis reaction unit Rll(p) and optionally a purification unit Pll.
  • the solid material W comprising a rubber-based solid materials M1 , W further comprising one or more solid materials M2 having a chemical composition different to the rubber-based solid materials M1 , wherein the rubber-based solid materials M1 comprises, in addition to rubber and/or within rubber, one or more halogens, is separated in Sll(a) via a kinetic energy separation unit or electrostatic separation method, obtaining a mixture MS(1) comprising the rubberbased solid materials M1, and a mixture MS(2), depleted in M1 compared to W, comprising the one or more solid materials M2.
  • the mixture MS(1) is further passed in the separation unit Sll(b) for sorting the materials M1 by elemental composition, obtaining an halogen-rich rubberbased solid materials fraction f 11 comprising the one or more halogens, and obtaining an halo- gen-poor rubber-based solid materials fraction f12, being depleted in the one or more halogens compared to M1 , comprising rubber.
  • the fraction f12 is optionally passed through the purification unit Pll for obtaining a purified solid mixture MP comprising rubber. Said MP being then introduced into Rll(p) for pyrolysis, obtaining a pyrolysis oil.
  • f12 can directly be introduced into Rll(p) for pyrolysis, obtaining a pyrolysis oil.
  • PCPC Personal Care Products Council

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Thermal Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Environmental & Geological Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)

Abstract

La présente invention concerne un procédé de recyclage de matériaux solides à base de caoutchouc M1 à partir de déchets automobiles solides W, une unité de recyclage pour mettre en oeuvre ledit procédé et un matériau automobile comprenant le ou les produits obtenus par ledit procédé.
PCT/EP2025/058942 2024-04-03 2025-04-02 Procédé de recyclage de matériaux solides à base de caoutchouc à partir de déchets automobiles solides Pending WO2025210070A1 (fr)

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WO2012015299A1 (fr) 2010-07-28 2012-02-02 Inashco R&D B.V. Appareil de séparation
WO2015184343A1 (fr) 2014-05-30 2015-12-03 Absolute Exhibits, Inc. Film de finissage en moule thermodurci
EP3907267A1 (fr) 2020-05-08 2021-11-10 Basf Se Procédé de purification d'une huile de pyrolyse brute provenant de la pyrolyse de déchets plastiques
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EP0692356A2 (fr) 1994-07-12 1996-01-17 Jack Lazareck Méthode pour la préparation des déchets provenant d'un concasseur d'automobiles, contenant des matériaux composites
US5554657A (en) 1995-05-08 1996-09-10 Shell Oil Company Process for recycling mixed polymer containing polyethylene terephthalate
DE19535296A1 (de) 1995-09-22 1997-03-27 Hamos Elektronik Gmbh Verfahren und Vorrichtung zum Trennen eines Gemisches aus unterschiedlichen Stoffen in die einzelnen Stoffe
WO2012015299A1 (fr) 2010-07-28 2012-02-02 Inashco R&D B.V. Appareil de séparation
WO2015184343A1 (fr) 2014-05-30 2015-12-03 Absolute Exhibits, Inc. Film de finissage en moule thermodurci
EP3907267A1 (fr) 2020-05-08 2021-11-10 Basf Se Procédé de purification d'une huile de pyrolyse brute provenant de la pyrolyse de déchets plastiques
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