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WO2025109327A1 - Procédé de production d'un produit d'huile de pyrolyse valorisée - Google Patents

Procédé de production d'un produit d'huile de pyrolyse valorisée Download PDF

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Publication number
WO2025109327A1
WO2025109327A1 PCT/GB2024/052945 GB2024052945W WO2025109327A1 WO 2025109327 A1 WO2025109327 A1 WO 2025109327A1 GB 2024052945 W GB2024052945 W GB 2024052945W WO 2025109327 A1 WO2025109327 A1 WO 2025109327A1
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Prior art keywords
pyrolysis oil
water
alcohol
base
hydroxide
Prior art date
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Pending
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PCT/GB2024/052945
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English (en)
Inventor
Benjamin Paul Williams
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Refiniti Ltd
Original Assignee
Refiniti Ltd
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Filing date
Publication date
Priority claimed from GBGB2317929.4A external-priority patent/GB202317929D0/en
Priority claimed from GBGB2412622.9A external-priority patent/GB202412622D0/en
Application filed by Refiniti Ltd filed Critical Refiniti Ltd
Publication of WO2025109327A1 publication Critical patent/WO2025109327A1/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
    • C10G1/002—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
    • C10G1/10—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
    • C10G19/00—Refining hydrocarbon oils in the absence of hydrogen, by alkaline treatment
    • C10G19/02—Refining hydrocarbon oils in the absence of hydrogen, by alkaline treatment with aqueous alkaline solutions
    • 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
    • C10G31/00—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for
    • C10G31/08—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for by treating with water
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
    • C10B53/07—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form of solid raw materials consisting of synthetic polymeric materials, e.g. tyres
    • 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
    • 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
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/201—Impurities
    • 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
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/201—Impurities
    • C10G2300/202—Heteroatoms content, i.e. S, N, O, P
    • 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
    • C10G2300/40—Characteristics of the process deviating from typical ways of processing
    • C10G2300/44—Solvents

Definitions

  • Described herein is an improved process for producing an upgraded pyrolysis oil product.
  • the process is of particular use for upgrading pyrolysis oil derived from the pyrolysis of plastic or rubber, or a combination thereof.
  • the process uses low cost materials to efficiently and sustainably produce stable pyrolysis oil, allowing safe storage, transportantion and/or its use as fuel, as a component of fuels and/or as a chemical feedstock.
  • Pyrolysis is a conversion process where hydrocarbon-based material, including plastics, are heated to high temperatures, in the absence of oxygen, to thermally crack large molecules to produce shorter chain molecules. This process could be carried out with or without a catalyst to promote cracking.
  • Post consumer plastics such as municipal wastes, are not pure substances. They contain many substances in addition to the polymer themselves. These can include dyes, additives, adhesives and contamination such as organic material. These materials are a source of heteroatoms in the pyrolysis system and ultimately the pyrolysis oil. Elements such as sulphur, chlorine, oxygen, nitrogen and silicon and metals are present in both organic and inorganic forms 3 .
  • the liquid stream can also often contain solid residue such as char carried over from the reactor which can be removed by means of filtration or centrifuge.
  • Silicon is also found within pyrolysis oils and is known to be a hydrotreatment catalyst poison causing irreversible deactivation 5 .
  • Hydrotreatment is a known refining step to improve the quality of the oil to the extent that it can be used without hinderance in steam cracking or in fuels by saturation of olefin and diolefin components, denitrification, deoxygenation and desulfurization.
  • Polar aprotic solvents do not remove silicon and are of concern from environmental and health and safety grounds. In particular, restrictions on the use of commonly employed dipolar aprotic solvents, such as NMP and DMF, have been recently introduced 7 .
  • new methods will provide higher quality pyrolysis oil in improved yield which have at least one or more advantages selected from improved impurity profile (e.g. decreased levels of heteroatoms, such as silicon) and improved stability.
  • the upgraded pyrolysis oil products may be utilised as a transportation fuel, for blending with fuels and/or as a chemical feedstock.
  • the present invention relates to a process for producing an upgraded pyrolysis oil product comprising:
  • the present invention relates to the use of a solution comprising a C1-3 alcohol, a base selected from a Group I hydroxide or oxide and a Group II hydroxide or oxide; and water for decreasing the heteroatom content of a pyrolysis oil, wherein the pyrolysis oil is derived from the pyrolysis of plastic or rubber, or a combination thereof.
  • the present invention relates to an upgraded pyrolysis oil obtainable by a process according to the first aspect of the invention.
  • the present invention relates to the use of a C1-3 alcohol, a base selected from a Group I hydroxide or oxide and a Group II hydroxide or oxide; and water in combination to stabilise a pyrolysis oil, wherein the pyrolysis oil is derived from the pyrolysis of plastic or rubber, or a combination thereof.
  • Figure 1 provides a schematic diagram of an embodiment of the claimed process involving liquid/liquid extraction and distillation of the extract phase.
  • Figure 2 provides a schematic diagram of an embodiment of the claimed process involving liquid/liquid extraction, further extraction of the raffinate with aqueous KOH and distillation of the extract phase.
  • Figure 3 provides a schematic diagram of an embodiment of the claimed process involving liquid/liquid extraction, further extraction of the raffinate with water and distillation of the extract phase.
  • Figure 4 provides a schematic diagram of an embodiment of the claimed process involving liquid/liquid extraction, further extractions of the raffinate with methanol and water and distillation of the extract phase(s).
  • Figure 5 provides a schematic diagram of an embodiment of the use of a C1-3 alcohol, a base selected from a Group I hydroxide or oxide and a Group II hydroxide or oxide; and water in a method to stabilise a pyrolysis oil, wherein the pyrolysis oil is derived from the pyrolysis of plastic or rubber, or a combination thereof.
  • the term “upgrading” and “upgraded” used in relation to a pyrolysis oil refers to removing or reducing the concentration of one or more unwanted substances in the pyrolysis oil.
  • plastic refers to a solid material which comprises one or more thermoplastic or thermosetting polymers.
  • the plastic essentially consists of one or more thermoplastic or thermosetting polymers.
  • the plastic essentially consists of one or more thermoplastic polymers.
  • the plastic is waste plastic which may be a mixture of various plastics. Plastics may be referred to by the name of the polymer of which they consist of. Examples of common plastics are polyethylene, polypropylene and polystyrene.
  • thermoplastic polymer refers to a polymer which becomes pliable or mouldable above a certain temperature and solidifies upon cooling but can be remelted on heating.
  • thermoplastic polymers have a melting temperature from about 60°C. to about 300°C, from about 80°C to about 250°C, or from about 100°C to about 250°C.
  • thermoplastic polymer is one which is commonly comprised in commercial plastic products.
  • Suitable thermoplastic polymers generally include polyolefins, polyesters, polyamides, copolymers thereof, and combinations thereof.
  • thermoplastic polymers include polyethylene (PE), polypropylene (PP), polystyrene (PS), polyvinylchloride (PVC), polyamideimide, polymethylmethacrylate (PMMA), polytetrafluoroethylene, polyethylene terephthalate (PET), natural rubber (NR), and polycarbonate (PC), polyvinylidene chloride (PVDC), acrylonitrile butadiene styrene (ABS), polyurethanes (PU).
  • PE polyethylene
  • PP polypropylene
  • PS polystyrene
  • PVC polyvinylchloride
  • PMMA polyamideimide
  • PMMA polymethylmethacrylate
  • PC polycarbonate
  • PVDC polyvinylidene chloride
  • ABS acrylonitrile but
  • thermosetting polymer refers to a polymer which is irreversibly cured and cannot be reworked upon reheating.
  • thermosetting polymers are polyurethane and polyoxybenzylmethylenglycolanhydride (BakeliteTM).
  • liquid refers to the liquid matter state at standard ambient temperature and pressure (SATP) (i.e. at a temperature of about 298.15 K (25 °C) and a pressure of about 100,000 Pa (1 bar, 14.5 psi, 0.9869 atm)) unless otherwise provided.
  • SATP standard ambient temperature and pressure
  • the present invention relates to a process for producing an upgraded pyrolysis oil product comprising:
  • “upgraded” used in relation to a pyrolysis oil refers to the removal or reduction the concentration of one or more unwanted substances in the pyrolysis oil.
  • upgraded/upgrading is assessed relative to the pyrolysis to be upgraded, i.e. the starting pyrolysis oil prior to being subjected to the process of the invention.
  • the unwanted substances to be removed or reduced are selected from one or more compounds containing heteroatoms, such as sulphur, nitrogen, oxygen, halogens, transition metals and/or silicon.
  • the unwanted substances comprise or (essentially) consist of compounds containing heteroatoms, suitably the compounds containing heteroatoms are selected from one or more of sulphur compounds, nitrogen compounds, oxygen compounds, halogen compounds, silicon compounds, transition metal compounds; or combinations thereof.
  • the compounds containing heteroatoms are sulphur, nitrogen, oxygen, chlorine and silicon compounds.
  • the compounds containing heteroatoms are silicon compounds.
  • the sulphur compounds reduced/removed by the process of the invention comprise or essentially consist of organic sulphur compounds (OSCs).
  • the sulphur compounds reduced/removed comprise compounds selected from thiols, thioethers, disulphides, thiophenes and benzothiophenes.
  • the sulphur compounds reduced/removed are selected from thiols, thioethers, disulphides, thiophenes and benzothiophenes.
  • the halogen compounds are halogen compounds commonly found in plastic or rubber pyrolysis oils. These compounds include for instance halogenated acids (such as HCI and HBr) and halogenated aromatics, such a polyhalogenated dibenzodioxins and dibenzofurans.
  • halogenated acids such as HCI and HBr
  • halogenated aromatics such as a polyhalogenated dibenzodioxins and dibenzofurans.
  • the nitrogen compounds are molecules containing nitrogen which are commonly found in pyrolysis products.
  • the nitrogen compounds reduced/removed by the process of the invention comprise organic nitrogen compounds, such as ammonia and organic amines and imines.
  • the transition metal compounds are molecules containing transitional metals which are commonly found in pyrolysis products.
  • the transition metals reduced/removed by the process of the invention comprise copper or iron or compounds thereof which are often used in dyes, inks and additives within plastics.
  • the silicon compounds are molecules containing silicon which are commonly found in pyrolysis products.
  • the silicon compounds reduced/removed by the process of the invention comprise one or more of a siliane, an organosilane and a siloxane.
  • the oxygen compounds are molecules containing oxygen which are commonly found in pyrolysis products.
  • the oxygen compounds reduced/removed by the process of the invention comprise phenols and carboxylic acids.
  • step (I) the pyrolysis oil, C1-3 alcohol, the base selected from a Group I hydroxide or oxide and a Group II hydroxide or oxide; and water may be combined by any means known in the art.
  • each component will be delivered (e.g. pumped) to a vessel, reactor or mixer commonly used in the art, either simultaneously, sequentially or in combination, suitably in combination.
  • the C1-3 alcohol, the base and the water are added simultaneously to the pyrolysis oil.
  • one or more of the C1-3 alcohol, the base, and the water may be added in combination with one or more of the others.
  • the C1-3 alcohol is added in one entry stream and the water and alkali metal hydroxide are added in a second entry stream.
  • the C1-3 alcohol, the base and the water are added in combination.
  • the C1-3 alcohol, the base and the water are pre-mixed before they are combined with the pyrolysis oil. Pre-mixing may be achieved using any suitable technique known in the art. For instance, the C1-3 alcohol, the base and the water may be combined in an agitate tank before being transferred to pyrolysis oil in a separate vessel. Alternatively, the C1-3 alcohol, the base and the water can be combined by an in-line mixing step.
  • the pyrolysis oil is combined with the C1-3 alcohol, the base and the water at a temperature of between about 10°C to about 50°C, suitably between about 15°C and about 45°C, suitably between about 18°C and about 40°C, suitably between about 25°C and about 40°C.
  • the pyrolysis oil is combined with the C1-3 alcohol, the base and the water at ambient pressure, for instance a pressure of about 1 atm (101 kPa). Accordingly, expense and other problems associated with high pressure conditions are avoided.
  • the C1-3 alcohol, the base and the water are combined at a pressure of about 101 kPa to about 160 KPa, suitably about 101 KPa to about 140 KPa.
  • the base and water are added to the pyrolysis oil together, suitably in the form of an aqueous base solution.
  • the aqueous base solution has a concentration of about 0.3 M to about 4 M.
  • the concentration in the aqueous solution is about 0.3 M to about 2 M, suitably about 0.3 M to about 1 M, suitably about 0.5 M to about 0.8 M.
  • the C1-3 alcohol, the base and the water are added together via a single entry stream.
  • the C1-3 alcohol, the base and the water may be each added separately, suitably separately but simultaneously.
  • the C1-3 alcohol is added in an amount such that the mass ratio of C1-3 alcohol to pyrolysis oil is about 5:1 to about 1 :2.
  • the mass ratio of C1-3 alcohol to pyrolysis oil is about 3:1 to about 1 :2.
  • the mass ratio of C1-3 alcohol to pyrolysis oil is about 3:1 to about 2:3.
  • the mass ratio of C1-3 alcohol to pyrolysis oil is about 2:1 to about 2:3.
  • the mass ratio of C1-3 alcohol to pyrolysis oil is about 1 :1 to about 2:3.
  • the mass ratio of C1-3 alcohol to pyrolysis oil is about 1 :1 to about 4:5 .
  • the water is added in an amount such that the mass ratio of water to pyrolysis oil is about 1 :2 to about 1 :20.
  • the mass ratio of water to pyrolysis oil is about 1 :2 to about 1 :15.
  • the mass ratio of water to pyrolysis oil is about 1 :2 to about 1 :12.
  • the mass ratio of water to pyrolysis oil is about 1 :5 to about 1 :12.
  • the mass ratio of water to pyrolysis oil is about 1 :8 to about 1 :10.
  • the base is added in an amount such that the mass ratio of base to pyrolysis oil is about 1 :4 to about 1 :250.
  • the mass ratio of base to pyrolysis oil is about 1 :10 to about 1 :200.
  • the mass ratio of base to pyrolysis oil is about 1 :10 to about 1 :175.
  • the mass ratio of base to pyrolysis oil is about 1 :50 to about 1 :150.
  • the mass ratio of base to pyrolysis oil is about 1 :75 to about 1 :150.
  • the mass ratio of base to pyrolysis oil is about 1 :90 to about 1 :110.
  • the mass ratio of base to pyrolysis oil is about 1 : 100.
  • the mass ratio of C1-3 alcohol to pyrolysis oil is about 3:1 to about 1 :2, the mass ratio of water to pyrolysis oil is about 1 :2 to about 1 :15 and the mass ratio of alkali metal hydroxide to pyrolysis oil is about 1 :50 to about 1 :200.
  • the mass ratio of C1-3 alcohol to pyrolysis oil is about 3:1 to about 2:3, the mass ratio of water to pyrolysis oil is about 1 :2 to about 1 :12 and the mass ratio of alkali metal hydroxide to pyrolysis oil is about 1 :10 to about 1 :175.
  • the mass ratio of C1-3 alcohol to pyrolysis oil is about 1 :1 to about 4:5, the mass ratio of water to pyrolysis oil is about 1 :8 to about 1 :10, and the mass ratio of alkali metal hydroxide to pyrolysis oil is about 1 :90 to about 1 :110.
  • the C1-3 alcohol, the base and the water are added to the pyrolysis oil simultaneously as a combined solution.
  • the combined solution comprises about 5% to about 20% (w/w) of water, suitably about 5% to about 15% (w/w) water, suitably about 12.5% (w/w) of water.
  • the combined solution comprises about 80% to about 95% (w/w) of C1-3 alcohol, suitably about 85% to about 90% (w/w) C1-3 alcohol, suitably about 86.5% (w/w) of C1-3 alcohol.
  • the combined solution comprises about 0.5% to about 5% (w/w) of the base, suitably about 0.5% to about 3% (w/w) of the base, suitably about 0.5% to about 1 .2% (w/w) of the base, suitably about 1 % (w/w) of the base.
  • the base is present in a concentration of about 0.05 M to about 1 M in the combined solution.
  • concentration in the combined solution is about 0.05 M to about 0.5 M, suitably about 0.05 M to about 0.2 M, suitably about 0.09 M to about 0.2 M.
  • the combined solution comprises: about 70% to about 95% (w/w) of the C1-3 alcohol; about 3% to about 20% (w/w) of the water; and about 0.5% to about 10% (w/w) of the base.
  • the combined solution comprises: about 80% to about 95% (w/w) of the C1-3 alcohol; about 5% to about 20% (w/w) of the water; and about 0.5% to about 5% (w/w) of the base.
  • the combined solution comprises: about 85% to about 90% (w/w) of the C1-3 alcohol; about 5% to about 15% (w/w) of the water; and about 0.5% to about 3% (w/w) of the base.
  • the combined solution comprises: about 85% to about 90% (w/w) of the C1-3 alcohol; about 5% to about 15% (w/w) of the water; and about 0.5% to about 1 .5% (w/w) of the base.
  • the combined solution comprises: about 85% to about 90% (w/w) of the C1-3 alcohol; about 5% to about 15% (w/w) of the water; and about 0.5% to about 1 .2% (w/w) of the base.
  • the combined solution comprises: about 85% to about 90% (w/w) of the C1-3 alcohol; about 8% to about 15% (w/w) of the water; and about 0.5% to about 1 .2% (w/w) of the base.
  • the combined solution comprises: about 80% to about 90% (w/w) of the C1-3 alcohol; about 8% to about 15% (w/w) of the water; and about 0.5% to about 2% (w/w) of the base.
  • the C1-3 alcohol is selected from methanol, ethanol and 1- propanol. In another embodiment, the C1-3 alcohol is methanol or ethanol. Suitably, the C1-3 alcohol is methanol.
  • the base is a Group I hydroxide or oxide or a Group II hydroxide or oxide selected from the group consisting of potassium hydroxide, sodium hydroxide, lithium hydroxide, potassium oxide, sodium oxide, lithium oxide, caesium hydroxide, caesium oxide, barium hydroxide, barium oxide, calcium hydroxide, calcium oxide, magnesium hydroxide and magnesium oxide.
  • the base is a Group I hydroxide or a Group II hydroxide.
  • the base is selected from potassium hydroxide, sodium hydroxide, lithium hydroxide, caesium hydroxide, barium hydroxide, calcium hydroxide and magnesium hydroxide.
  • the base is a Group I hydroxide.
  • the base is selected from potassium hydroxide, sodium hydroxide, lithium hydroxide and caesium hydroxide.
  • the base is an alkali metal hydroxide.
  • the base is an alkali metal hydroxide selected from potassium hydroxide or sodium hydroxide, suitably potassium hydroxide.
  • step (i) comprises or (essentially) consists of combining the pyrolysis oil with methanol, potassium hydroxide and water.
  • a combined solution (essentially) consisting of methanol, potassium hydroxide and water.
  • the combined solution of step (i), (essentially) consists of about 85% to about 90% (w/w) methanol, about 0.5% to about 3% (w/w) of potassium hydroxide and about 5% to about 15% (w/w) water.
  • the combined solution of step (I) (essentially) consists of about 85% to about 90% (w/w) methanol, about 0.5% to about 3% (w/w) of potassium hydroxide and about 5% to about 15% (w/w) water.
  • the combined solution of step (I) (essentially) consists of about 85% to about 90% (w/w) methanol, about 0.5% to about 1.2% (w/w) of potassium hydroxide and about 5% to about 15% (w/w) water.
  • the combined solution of step (I) (essentially) consists of about 86.5% (w/w) methanol, about 1.0% (w/w) of potassium hydroxide and about 12.5% (w/w) water.
  • the combined solution of step (I) (essentially) consists of about 85% (w/w) methanol, about 1 .5% (w/w) of potassium hydroxide and about 13.5% (w/w) water.
  • the mass ratio of pyrolysis oil to C1-3 alcohol, the base and water combined is from about 95:5 to about 10:90. In one embodiment, the mass ratio of pyrolysis oil to C1-3 alcohol, base and water combined is about 60:40 to about 30:70, or suitably about 50:50 to about 30:70, or suitably about 50:50.
  • the mass ratio of pyrolysis oil to C1-3 alcohol, base and water combined is from about 60:40 to about 20:80, suitably about 60:40 to about 40:60.
  • the mass ratio of pyrolysis oil to C1-3 alcohol, base and water combined is from about 2:1 to about 1 :2, suitably about 2:1 to about 1 :1.
  • the pyrolysis oil, C1-3 alcohol, base and water may be mixed by any means known in the art.
  • each component may be added to vessels, reactors or mixers commonly used in the art, either simultaneously or sequentially and the components may be mixed.
  • Mixing may comprise vigorous agitation of the components by a mixing means.
  • the components may be mixed together by stirring or by shaking.
  • the combination of pyrolysis oil with the C1-3 alcohol, the base and the water is allowed to mix for period of time, suitably about 1 minute to about 24 hours, suitably about 1 minute to 12 hours; suitably about 1 minute to about 6 hours.
  • the mixing may take place in a separate vessel.
  • the pyrolysis oil is mixed with the C1-3 alcohol, the base and the water at a temperature of between about 10°C to about 50°C, suitably between about 15°C and about 45°C, suitably between about 18°C and about 40°C, suitably between about 25°C and about 40°C.
  • the pyrolysis oil is mixed with the C1-3 alcohol, the base and the water at ambient pressure, for instance a pressure of about 1 atm (101 kPa). Accordingly, expense and other problems associated with high pressure conditions are avoided.
  • the C1-3 alcohol, the base and the water are mixed at a pressure of about 101 kPa to about 160 KPa, suitably about 101 KPa to about 140 KPa.
  • the mixing of the components may occur more than once. For instance, after mixing the pyrolysis oil with the C1-3 alcohol, base and water for the first time, the resulting two phases may be mixed again, possible numerous times. In one embodiment, the mixing results in two liquid phases, i.e. an extract phase and a raffinate phase.
  • the pyrolysis oil may be repeatedly mixed multiple times with fresh batches of C1-3 alcohol, base and water.
  • the pyrolysis oil may be mixed with a first batch to provide a first raffinate phase and a first extract phase.
  • the raffinate phase may be mixed with a second batch to provide a second raffinate phase and a second extract phase. This cycle may be repeated multiple times.
  • the cycle of mixing the pyrolysis oil or its raffinate with fresh batches of C1-3 alcohol, base and water is repeated between 1 and 9 times. In another embodiment, the cycle is repeated between 1 and 4 times. In another embodiment, the cycle is repeated 1 , 2, 3 or 4 times. In another embodiment, the cycle is repeated 4 times.
  • the steps of contacting and formation of two phases may be continuous.
  • the components may pass through a mixing means before entering a separating chamber in which the first and second phases are formed.
  • the contacting of the components may be performed using a propeller, in-line mixers, counter-current flow means, an agitation means, a column (e.g. a Scheibel® column or a KARR® column) or a centrifugal extractor.
  • each mixing is carried out at a temperature of between about 10°C to about 65°C, suitably each mixing is carried out at a temperature of between about 10°C to about 50°C, suitably between about 15°C and about 45°C, suitably between about 18°C and about 40°C.
  • raffinate phase refers to the phase comprising/consisting essentially of/consisting of the upgraded pyrolysis oil.
  • extract phase refers to the phase typically comprising the C1-3 alcohol, the base and water.
  • the extract phase will comprise the majority of the C1-3 alcohol, the base and water after mixing with the pyrolysis oil.
  • the extract phase will be denser than the raffinate phase and will form the lower layer.
  • the extract phase may comprise one or more undesirable substances extracted from the pyrolysis oil (e.g. such as heteroatom compounds).
  • the raffinate phase/upgraded pyrolysis oil will have a reduced concentration of undesirable substances compared to the pyrolysis oil prior to treatment with the C1-3 alcohol, the base and water.
  • the raffinate phase/upgraded pyrolysis oil will have a reduced concentration of one or more of heteroatoms compared to the pyrolysis oil prior to treatment with the C1-3 alcohol, the base and water.
  • the concentration of sulphur compounds in the raffinate phase/upgraded pyrolysis oil is reduced by about 10% to about 80% (wt.%) relative to the concentration of sulphur compounds in the starting pyrolysis oil. In another embodiment, the concentration of sulphur compounds in the raffinate phase/upgraded pyrolysis oil is reduced by about 10% to about 70% (wt.%) relative to the concentration of sulphur compounds in the starting pyrolysis oil. In another embodiment, the concentration of sulphur compounds in the raffinate phase/upgraded pyrolysis oil is reduced by about 30% to about 80% (wt.%) relative to the concentration of sulphur compounds in the starting pyrolysis oil.
  • the concentration of sulphur compounds in the raffinate phase/upgraded pyrolysis oil is reduced by about 30% to about 70% (wt.%) relative to the concentration of sulphur compounds in the starting pyrolysis oil. In another embodiment, the concentration of sulphur compounds in the raffinate phase/upgraded pyrolysis oil is reduced by about 40% to about 60% (wt.%) relative to the concentration of sulphur compounds in the starting pyrolysis oil. [0088] In one embodiment, the raffinate phase/upgraded pyrolysis oil will have a reduced concentration of chlorine compared to the pyrolysis oil prior to treatment with the C1-3 alcohol, the base and water.
  • the concentration of chlorine in the raffinate phase/upgraded pyrolysis oil is reduced by about 10% to about 80% (wt.%) relative to the concentration of chlorine in the starting pyrolysis oil. In another embodiment, the concentration of chlorine in the raffinate phase/upgraded pyrolysis oil is reduced by about 10% to about 70% (wt.%) relative to the concentration of chlorine in the starting pyrolysis oil. In another embodiment, the concentration of chlorine in the raffinate phase/upgraded pyrolysis oil is reduced by about 10% to about 60% (wt.%) relative to the concentration of chlorine in the starting pyrolysis oil.
  • the concentration of chlorine in the raffinate phase/upgraded pyrolysis oil is reduced by about 30% to about 80% (wt.%) relative to the concentration of chlorine in the starting pyrolysis oil. In another embodiment, the concentration of chlorine in the raffinate phase/upgraded pyrolysis oil is reduced by about 30% to about 70% (wt.%) relative to the concentration of chlorine in the starting pyrolysis oil. In another embodiment, the concentration of chlorine in the raffinate phase/upgraded pyrolysis oil is reduced by about 30% to about 60% (wt.%) relative to the concentration of chlorine in the starting pyrolysis oil.
  • the concentration of chlorine in the raffinate phase/upgraded pyrolysis oil is reduced by about 40% to about 60% (wt.%) relative to the concentration of chlorine in the starting pyrolysis oil. In another embodiment, the concentration of chlorine in the raffinate phase/upgraded pyrolysis oil is reduced by about 50% to about 60% (wt.%) relative to the concentration of chlorine in the starting pyrolysis oil.
  • the raffinate phase/upgraded pyrolysis oil will have a reduced concentration of silicon compared to the pyrolysis oil prior to treatment with the C1-3 alcohol, the base and water.
  • the concentration of silicon in the raffinate phase/upgraded pyrolysis oil is reduced by about 10% to about 80% (wt.%) relative to the concentration of silicon in the starting pyrolysis oil. In another embodiment, the concentration of silicon in the raffinate phase/upgraded pyrolysis oil is reduced by about 10% to about 70% (wt.%) relative to the concentration of silicon in the starting pyrolysis oil. In another embodiment, the concentration of silicon in the raffinate phase/upgraded pyrolysis oil is reduced by about 10% to about 60% (wt.%) relative to the concentration of silicon in the starting pyrolysis oil.
  • the concentration of silicon in the raffinate phase/upgraded pyrolysis oil is reduced by about 25% to about 80% (wt.%) relative to the concentration of silicon in the starting pyrolysis oil. In another embodiment, the concentration of silicon in the raffinate phase/upgraded pyrolysis oil is reduced by about 25% to about 70% (wt.%) relative to the concentration of silicon in the starting pyrolysis oil. In another embodiment, the concentration of silicon in the raffinate phase/upgraded pyrolysis oil is reduced by about 25% to about 60% (wt.%) relative to the concentration of silicon in the starting pyrolysis oil.
  • the raffinate phase/upgraded pyrolysis oil will have a reduced concentration of oxygen compared to the pyrolysis oil prior to treatment with the C1-3 alcohol, the base and water.
  • the concentration of oxygen in the raffinate phase/upgraded pyrolysis oil is reduced by about 50% to about 90% (wt.%) relative to the concentration of oxygen in the starting pyrolysis oil. In another embodiment, the concentration of oxygen in the raffinate phase/upgraded pyrolysis oil is reduced by about 50% to about 80% (wt.%) relative to the concentration of oxygen in the starting pyrolysis oil. In another embodiment, the concentration of oxygen in the raffinate phase/upgraded pyrolysis oil is reduced by about 50% to about 70% (wt.%) relative to the concentration of oxygen in the starting pyrolysis oil. In another embodiment, the concentration of oxygen in the raffinate phase/upgraded pyrolysis oil is reduced by about 60% to about 70% (wt.%) relative to the concentration of oxygen in the starting pyrolysis oil.
  • the raffinate phase/upgraded pyrolysis oil will have a reduced concentration of nitrogen compared to the pyrolysis oil prior to treatment with the C1-3 alcohol, the base and water.
  • the concentration of nitrogen in the raffinate phase/upgraded pyrolysis oil is reduced by about 50% to about 90% (wt.%) relative to the concentration of nitrogen in the starting pyrolysis oil. In another embodiment, the concentration of nitrogen in the raffinate phase/upgraded pyrolysis oil is reduced by about 60% to about 80% (wt.%) relative to the concentration of nitrogen in the starting pyrolysis oil. In another embodiment, the concentration of nitrogen in the raffinate phase/upgraded pyrolysis oil is reduced by about 70% to about 80% (wt.%) relative to the concentration of nitrogen in the starting pyrolysis oil.
  • the raffinate phase tends to be of lower density than the extract phase and thus the raffinate phase will typically be the upper phase and the extract phase will typically be the lower phase.
  • the process comprises an optional step of filtering the two liquid phases prior to separating the raffinate from the extract phase. Filtration may be carried by processes known in the art.
  • the process further comprises separating the raffinate phase to yield an upgraded pyrolysis oil (step (ill)).
  • the raffinate phase may be separated by any means used in the art and is typically separated by a physical process. Said separating typically comprises physically isolating the raffinate phase, or at least some of the raffinate phase. Thus, said separating typically comprises separating at least some of the raffinate phase from the extract phase.
  • said separating may simply comprise removing (e.g. by draining or decanting) at least part of the extract phase from the container comprising the extract phase and the raffinate phase.
  • the raffinate phase may be removed (e.g. by draining or decanting) from the container to leave the extract phase.
  • the separation of the raffinate and extract phase is conducted at a temperature of between about 10°C to about 65°C, or about 10°C to about 50°C, suitably between about 15°C and about 45°C, suitably between about 18°C and about 40°C, suitably between about 25°C and about 40°C.
  • the separation is conducted at ambient pressure, for instance a pressure of about 1 atm. (101 kPa).
  • the separation is conducted at a pressure of about 101 kPa to about 160 KPa, suitably about 101 KPa to about 140 KPa.
  • the raffinate is further treated with the base and/or water.
  • the raffinate is mixed with the base and/or water and allowed to form two layered phases.
  • the top layer being a further raffinate essentially consisting of the upgraded pyrolysis oil and the bottom layer being a further extract layer essentially consisting of aqueous base or water and potentially a small amount of extracted C1-3 alcohol.
  • this further extract may be recycled in order to treat further batches of pyrolysis oil.
  • the raffinate is further treated with the C1.3 alcohol and/or water.
  • the raffinate is mixed with the C1-3 alcohol and/or water and allowed to form two layered phases.
  • the top layer being a further raffinate essentially consisting of the upgraded pyrolysis oil and the bottom layer being a further extract layer essentially consisting of C1.3 alcohol and/or water and potentially a small amount of base, or Group I or II metal.
  • this further extract may be combined with preceding extract phases for further processing, e.g., distillation.
  • the raffinate is further treated with (i) a combination of Ci- 3 alcohol and water, and raffinate derived therefrom is further treated with water.
  • the present invention relates to a raffinate phase obtainable by a process as defined in any of the above embodiments.
  • the present invention relates to a raffinate phase obtained by a process as defined in any of the above embodiments.
  • the present invention relates to an upgraded pyrolysis oil obtained by a process as defined in any of the above embodiments.
  • the upgraded pyrolysis oil obtained/obtainable by the process of the invention is suitable for use as a substitute for naphtha used to produce fuel (e.g. gasoline and diesel) or hydrocarbon chemicals (e.g. ethylene and propylene).
  • fuel e.g. gasoline and diesel
  • hydrocarbon chemicals e.g. ethylene and propylene.
  • the upgraded pyrolysis has a reduced tendency to form gum on storage and thus can be stored or transported for longer periods than untreated pyrolysis oils.
  • Pyrolysis oil is a substance known to the skilled person. Pyrolysis oil may be obtained from a number of sources.
  • the present invention concerns pyrolysis oil derived from plastic, rubber or a combination thereof. In one embodiment, the pyrolysis oil is derived from plastic. In another embodiment, the pyrolysis oil is derived from rubber. In another embodiment, the pyrolysis oil is derived from a combination of plastic and rubber.
  • the pyrolysis oil to be upgraded is obtainable or obtained by pyrolysis of plastic, rubber or a combination thereof.
  • pyrolysis is carried out at high temperature (greater than 400°C) and with very high heating rates in the absence of oxygen.
  • the pyrolysis oil is obtainable or obtained by pyrolysis of plastic.
  • the pyrolysis oil is obtainable or obtained by pyrolysis of rubber.
  • the pyrolysis oil is obtainable or obtained by pyrolysis of a combination of plastic and rubber.
  • the combination of rubber and plastic comprises at least about 50% w/w of plastic and rubber, suitably at least about 60% w/w of plastic and rubber, suitably at least about 70% w/w of plastic and rubber, suitably at least about 80% w/w of plastic and rubber, suitably at least about 90% w/w of plastic and rubber, suitably at least about 95% w/w of plastic and rubber.
  • the combination of plastic and rubber comprises about 50% to about 100% (w/w) of plastic and rubber, suitably about 60% to about 100% (w/w) of plastic and rubber, about 70% to about 100% (w/w) of plastic and rubber, about 80% to about 100% (w/w) of plastic and rubber, about 90% to about 100% (w/w) of plastic and rubber.
  • the rubber is obtained from tyres.
  • the plastic (essentially) consists of one or more thermoplastic polymers.
  • the plastic is waste plastic which may be a mixture of various plastics. Plastics may be referred to by the name of the polymer of which they consist of. Examples of common plastics are polyethylene, polypropylene and polystyrene.
  • the pyrolysis oil is obtainable or obtained by pyrolysis of waste plastic, for instance waste plastic from the residue of a material recovery facility (MRF).
  • waste plastic for instance waste plastic from the residue of a material recovery facility (MRF).
  • MRF material recovery facility
  • sources of waste plastic will additionally contain contamination from organic and inorganic materials which will be pyrolyzed and/or carried through into the resultant pyrolysis oil resulting in the pyrolysis oil containing water, organic acids, organic halides such as chlorides and bromides; oxygenated compounds such as phenol, alcohol, ketone carboxylic acids; silanes, organic sulphides; organic nitrogen compounds such as amides and amines; and transition metals, such as iron and vanadium.
  • the pyrolysis oil is obtainable or obtained by pyrolysis of plastic comprising one or more of polyethylene, polypropylene and polystyrene.
  • the waste plastic comprises at least about 50% w/w of plastic, suitably at least about 60% w/w of plastic, suitably at least about 70% w/w of plastic, suitably at least about 80% w/w of plastic, suitably at least about 90% w/w of plastic, suitably at least about 95% w/w of plastic.
  • the waste plastic comprises about 50% to about 100%
  • (w/w) of plastic suitably about 60% to about 100% (w/w) of plastic, about 70% to about 100% (w/w) of plastic, about 80% to about 100% (w/w) of plastic, about 90% to about 100% (w/w) of plastic.
  • the pyrolysis oil to be upgraded has a specific gravity (20/4) of about 1 or less, suitably about 0.95 or less, or about 0.90 or less. In one embodiment, the pyrolysis oil to be upgraded has a specific gravity (20/4) of from about 0.7 to about 0.95, suitably about 0.8 to about 0.95, or about 0.7 to about 0.85.
  • the pyrolysis oil to be upgraded is not miscible with water at standard ambient temperature and pressure (SATP), i.e. at a temperature of 298.15 K (25 °C) and at 100,000 Pa (1 bar, 14.5 psi, 0.9869 atm).
  • SATP standard ambient temperature and pressure
  • the pyrolysis oil to be upgraded is not miscible with water at standard ambient temperature and pressure (SATP), i.e. at a temperature of 298.15 K (25 °C) and at 100,000 Pa (1 bar, 14.5 psi, 0.9869 atm), and has a specific gravity (20/4) of from about 0.7 to about 0.95, suitably about 0.8 to about 0.95, or about 0.7 to about 0.85.
  • SATP standard ambient temperature and pressure
  • the process comprises a preceding step of pyrolyzing plastic, rubber or a combination thereof, before combining the pyrolysis oil derived therefrom with a C1-3 alcohol, an alkali metal hydroxide and water (i.e. step (i)).
  • the pyrolysis is conducted on plastic or a combination of plastics as defined in any of the above embodiments.
  • the pyrolysis is conducted using waste plastic, suitably waste plastic from the residue of a material recovery facility (MRF).
  • MRF material recovery facility
  • pyrolysis of polymers can occur with or without a catalyst in temperature range of about 300°C to about 900°C in the absence of oxygen.
  • the pyrolysis is conducted at a temperature in the range of about 300°C to about 500°C, suitably about 300°C to about 450°C, suitably about 400°C to about 450°C.
  • the reactor can be of batch or continuous design. Products produced include non-condensable gases, a (liquid) pyrolysis oil and char.
  • a filter system or gravitational method of separation may be employed to remove solids from the pyrolysis oil, such as char carried over via entrainment from the reactor.
  • the pyrolysis oil is or has been filtered prior to performing the claimed method. In another embodiment, the pyrolysis oil is or has been dewatered prior to performing the claimed method. In another embodiment, the pyrolysis oil is a dewatered, filtered and/or fractionated pyrolysis oil prior to performing the claimed method. In another embodiment, the pyrolysis oil is a dewatered, and/or filtered pyrolysis oil prior to performing the claimed method.
  • the pyrolysis oil suitably a plastic pyrolysis oil, used in step (i) is obtained directly from the pyrolysis reactor.
  • the process comprises the further step of recovering the C1-3 alcohol from the extract phase.
  • the recovered C1-3 alcohol from the extract is then recycled for use in step (i).
  • the C1-3 alcohol is recovered from the extract phase by distillation.
  • Distillation may be performed by conventional techniques familiar to the skilled person and may or may not take place under vacuum.
  • Suitably means of distillation would be known to the skilled person and include rotary evaporator, rising film evaporator and distillation tower.
  • the distillation is conducted at atmospheric pressure at a temperature of about 60°C to about 80°C, suitably about 65°C to about 70°C.
  • the present invention provides a process for producing an upgraded pyrolysis oil product comprising:
  • the process is carried out a temperature of about 50°C or less, suitably 45°C or less, suitably 40°C or less. In another embodiment, the process is carried out at a temperature of about 15°C to about 45°C, suitably about 18°C to about 40°C, about 25°C to about 40°C.
  • the process is carried out at ambient pressure, for instance a pressure of about 1 atm. (101 kPa). In one embodiment, the process is carried out at a pressure of about 101 kPa to about 160 KPa, suitably about 101 KPa to about 140 KPa.
  • the raffinate produced by the process disclosed herein is suitably purified for further processing, storage or transportation.
  • further processing is selected from one or more of hydrotreatment, cracking, adsorption, absorption and distillation.
  • the process further comprises a step of recovering water from the residue of the extract phase after methanol has been recovered from the extract phase via distillation.
  • Suitable techniques for water recovery would be known to the skilled person, such as passing the distillation residue through a membrane or by a further distillation step.
  • the present invention provides a process for producing an upgraded pyrolysis oil product comprising:
  • step (vi) recovering water from the residue of step (v); wherein the pyrolysis oil is derived from the pyrolysis of plastic or rubber, or a combination thereof.
  • the recovered water from the extract is then recycled for use in step (i) or (iv).
  • Figure 1 provides a schematic of a process according to the present invention.
  • the process comprises pumping methanol (101) and aqueous potassium hydroxide solution
  • the separator (103) is suitably a column, mixer settler or centrifuge.
  • separator (103) the pyrolysis oil is intensely mixed with the methanol (101) and the aqueous potassium hydroxide solution (102) in order to extract contaminants from the oil via a reactive liquid-liquid extraction and then allowed to settle. Said contaminants include sulphur, silicon, nitrogen, oxygen and chlorine containing compounds.
  • the extraction in separator (103) may take place at ambient temperature to about 40°C and at substantially ambient pressure (i.e. about 1 atm.).
  • the upper raffinate phase (104) comprising upgraded pyrolysis oil is isolated via one exit stream and the lower extract phase (105) from separator
  • the distillation is typically performed at atmospheric pressure and at a temperature of about 60°C to about 80°C.
  • FIG. 2 provides a schematic of a process according to the present invention.
  • the process comprises pumping methanol (201) and aqueous potassium hydroxide solution (202) via a shared entry stream to a separator with heating device (203) charged with pyrolysis (212) oil derived from plastic, rubber or a combination thereof.
  • the separator (203) is suitably a column, mixer settler or centrifuge.
  • separator (203) the pyrolysis oil is intensely mixed with the methanol (201 ) and the aqueous potassium hydroxide solution (202) in order to extract contaminants from the oil via a reactive liquid-liquid extraction and then allowed to settle.
  • the upper phase (204) comprising extracted pyrolysis oil exits separator (203) and is fed to another separator (205) for further extraction with aqueous potassium hydroxide solution (207). Any residual methanol remaining in the oil is removed and the lower phase extract can be recycled as part of the aqueous KOH feed (202) to be combined with methanol (201 ) for use in separator (203).
  • the upgraded pyrolysis oil (206) product is isolated as an exit stream from separator (205).
  • the extractions in separators (203) and (205) may take place at ambient temperature to about 40°C and at substantially ambient pressure (i.e. about 1 atm.).
  • the lower extract phase (208) from separator (203) comprising mostly methanol, water and potassium hydroxide along with impurities extracted from the pyrolysis oil is fed via an exit stream to a distillation device (209) in order to separate a recycle stream of methanol (211 ) which may be combined with or used as methanol stream (201 ) for use in the extraction of separator (203).
  • the distillation is typically performed at atmospheric pressure and at a temperature of about 60°C to about 80°C.
  • the process comprises pumping methanol (301 ) and aqueous potassium hydroxide solution (302) via a shared entry stream to a separator with heating device (303) charged with pyrolysis oil (312) derived from plastic, rubber or a combination thereof.
  • the separator (303) is suitably a column, mixer settler or centrifuge.
  • separator (303) the pyrolysis oil is intensely mixed with the methanol (301) and the aqueous potassium hydroxide solution (302) in order to extract contaminants from the oil via a reactive liquid-liquid extraction and then allowed to settle.
  • the upper phase (304) comprising extracted pyrolysis oil exits separator (303) and is fed to another separator (305) for further extraction with water (307). Any residual methanol remaining in the oil is removed and the lower phase extract from separator (305) can be recycled as part of the aqueous KOH feed (302) to be combined with methanol (301 ) for use in separator (303).
  • the upgraded pyrolysis oil (306) product is isolated as an exit stream from separator (305).
  • Distillation of the lower phase (308) from separator (303) is conducted in a similar manner as the process described in Figure 2.
  • lower extract phase (308) comprising mostly methanol, water and potassium hydroxide along with impurities extracted from the pyrolysis oil is fed via an exit stream to a distillation device (309) in order to separate a recycle stream of methanol (311) which may be combined with or used as methanol stream (301 ) for use in the extraction of separator (303).
  • a feed stream of aqueous potassium hydroxide (402), an water stream (401 ) and a methanol stream (403) is delivered, suitably pumped, to a mixer tank (404).
  • the combined methanol, KOH and water solution is then transferred to a reaction tank (405) where it is combined with the pyrolysis oil derived from plastic, rubber or a combination thereof (406).
  • the reaction tank (405) comprises a heating device.
  • the contents are mixed (e.g. stirred) for 1 minute to 6 hours at a temperature of about 15°C to about 40°C in order to extract contaminants from the oil via a reactive liquid-liquid extraction.
  • the contents of the reaction tank (405) is transferred to a separator with heating device (407).
  • the separator (407) is suitably a column, mixer settler or centrifuge.
  • the separator (407) the oil, methanol, KOH and water mixture is allowed to settle under gravity for a desired time, typically 30 minutes to 24 hours and typically at a temperature of about 15°C to about 40°C.
  • the upper phase (408) comprising upgraded pyrolysis oil exits the separator (407) and is fed to another separator with heating device (409) for further extraction with methanol and water (418).
  • the separator (409) is suitably a column, mixer settler or centrifuge. After mixing the inputs the contents are allowed to settle under gravity for a desired time, typically 30 minutes to 24 hours and typically at a temperature of about 15°C to about 40°C.
  • any residual potassium and other heteroatoms remaining in the oil are removed to the extract phase.
  • the lower phase extract (413) from the separator (409) can be combined with the extract from the previous separator (407) to form a feed (414) to a distillation apparatus (415).
  • the upper phase (410) comprising extracted pyrolysis oil exits separator (409) and is fed to a further separator (411 ) for washing with a water (420).
  • the further separator (411 ) is suitably a column, mixer settler or centrifuge.
  • the water is fed (420) to the separator (411 ) and after mixing the inputs the contents are allowed to settle under gravity for a desired time, typically 30 minutes to 24 hours and typically at a temperature of about 15°C to about 40°C.
  • Any residual methanol from the oil is removed to a lower aqueous extract phase (419) which may be combined with recovered methanol (417) as a methanol and water feed (418).
  • the upgraded pyrolysis oil (412) product is isolated as an exit stream from the further separator (411 ).
  • Distillation of the lower extract phase (414) from separator (407) and optionally the lower phase (413) from the next separator (409) is conducted in a similar manner as the process described in Figure 2.
  • the lower extract phase(s) comprising mostly methanol, water and potassium hydroxide along with impurities extracted from the pyrolysis oil is fed to a distillation device (415) in order to separate extracted impurities, KOH and water (416) from the methanol.
  • the recycle stream of purified methanol (417) obtained from the distillation may be combined with water for use as extractant stream (418) in a separator (409), and/or may be recycled as the methanol feed (403) to the mixer tank (404).
  • the residue (416) of the distillation device (415) is fed to a water recovery system (421) in order to recover water (422) which may be recycled as one or more of the water feeds (401 , 420).
  • the raffinate may be treated with a sorbent.
  • the present invention relates to a process for producing an upgraded pyrolysis oil product comprising:
  • step (iv) treating the separated raffinate phase of step (iii) with a sorbent; wherein the pyrolysis oil is derived from the pyrolysis of plastic or rubber, or a combination thereof.
  • the raffinate/upgraded pyrolysis oil may be treated with the sorbent by any means known in the art. For instance, the raffinate/upgraded pyrolysis oil and sorbent may be combined and either left to stand, stirred or shaken together, or a combination thereof. Alternatively, the raffinate/upgraded pyrolysis oil may be flowed over a bed of the sorbent.
  • the sorbent is capable of absorbing and/or adsorbing one or more heteroatoms (suitably sulfur and/or chloride) from the raffinate/upgraded pyrolysis oil.
  • heteroatoms suitable sorbents are zeolites, aluminosilicates, activated carbon and mixtures thereof.
  • the sorbent is a commercially available molecular sieve.
  • the sorbent is a microporous molecular sieve (i.e. pore diameter of 2nm or less).
  • the sorbent is a zeolite molecular sieves suitably selected from 3A, 4A, 5A, 10X, 13X.
  • the sorbent is zeolite molecular sieves 13X.
  • the zeolite is a zeolite of the faujasite series, suitably a zeolite Y (e.g. zeolite Na-Y or La-Y).
  • zeolite Y e.g. zeolite Na-Y or La-Y.
  • the sorbent is an adsorbent.
  • the sorbent treated raffinate may be further subjected to hydrotreatment.
  • the process of the invention utilises a C1-3 alcohol, a base selected from a Group I hydroxide or oxide and a Group II hydroxide or oxide; and water in combination to upgrade the pyrolysis oil.
  • a base selected from a Group I hydroxide or oxide and a Group II hydroxide or oxide removes polar heteroatom containing compounds but has minimal impact on silicon containing compounds and can lead to mass loss from the hydrocarbon oil, in part due to poor phase separation.
  • the addition of water and a base selected from a Group I hydroxide or oxide and a Group II hydroxide or oxide maintains effective removal of polar heteroatom containing compounds, vastly improves removal of silicon containing compounds whilst increasing the selectivity of the extraction and subsequent yield of the upgraded pyrolysis oil.
  • a C1-3 alcohol, a base selected from a Group I hydroxide or oxide and a Group II hydroxide or oxide; and water in combination is capable of removing or reducing the concentration of undesirable substances in the pyrolysis oil, wherein the undesirable substances are selected from one or more of polar heteroatom compounds (e.g. compounds containing sulphur, nitrogen, oxygen and halogens) and silicon containing compounds.
  • polar heteroatom compounds e.g. compounds containing sulphur, nitrogen, oxygen and halogens
  • the present invention relates to the use of a C1-3 alcohol, a base selected from a Group I hydroxide or oxide and a Group II hydroxide or oxide; and water in combination for decreasing the heteroatom content of a pyrolysis oil, wherein the pyrolysis oil is derived from the pyrolysis of plastic or rubber, or a combination thereof.
  • the heteroatoms are selected from sulphur, nitrogen, oxygen, halogens (e.g. chlorine) and silicon.
  • the heteroatoms include sulphur, nitrogen, oxygen, halogens (e.g. chlorine) and silicon.
  • the present invention relates to the use of C1-3 alcohol, a base selected from a Group I hydroxide or oxide and a Group II hydroxide or oxide; and water in combination for decreasing the silicon content of a pyrolysis oil, wherein the pyrolysis oil is derived from the pyrolysis of plastic or rubber, or a combination thereof.
  • the silicon content is decreased by about 25% to about 80% (wt.%) relative to the silicon content in the pyrolysis oil initially. In another embodiment, the silicon content is decreased by about 25% to about 70% (wt.%) relative to the silicon content in the pyrolysis oil initially. In another embodiment, the content is decreased by about 25% to about 60% (wt.%) relative to the silicon content in the pyrolysis oil initially.
  • the combination (essentially) consists of a C1-3 alcohol, a base selected from a Group I hydroxide or oxide and a Group II hydroxide or oxide; and water.
  • the C1-3 alcohol is methanol or ethanol.
  • the C1-3 alcohol is methanol.
  • the base is an alkali metal hydroxide, suitably selected from potassium hydroxide or sodium hydroxide, suitably potassium hydroxide.
  • the C1-3 alcohol, the base and water are used as a combined solution.
  • the combined solution (essentially) consists of about 85% to about 90% (w/w) methanol, about 0.5% to about 3% (w/w) of potassium hydroxide and about 5% to about 15% (w/w) water.
  • the combined solution (essentially) consists of about 85% to about 90% (w/w) methanol, about 0.5% to about 1 .2% (w/w) of potassium hydroxide and about 5% to about 15% (w/w) water.
  • the combined solution (essentially) consists of about 86.5% (w/w) methanol, about 1 .0% (w/w) of potassium hydroxide and about 12.5% (w/w) water.
  • the present invention relates to the use of a C1-3 alcohol, a base selected from a Group I hydroxide or oxide and a Group II hydroxide or oxide; and water in combination to stabilise a pyrolysis oil wherein the pyrolysis oil is derived from the pyrolysis of plastic or rubber, or a combination thereof.
  • addition of the C1-3 alcohol, a base selected from a Group I hydroxide or oxide and a Group II hydroxide or oxide; and water in combination can prevent gum formation within the pyrolysis oil, thus small amounts of C1-3 alcohol, a base selected from a Group I hydroxide or oxide and a Group II hydroxide or oxide; and water in combination may be added to the pyrolysis oil during storage or transport in order to reduce or prevent gum formation and thus stabilise the oil.
  • the present invention relates to a method of stabilising a pyrolysis oil wherein the pyrolysis oil is derived from the pyrolysis of plastic or rubber, or a combination thereof, wherein said method comprises combining a mixture of C1-3 alcohol, a base selected from a Group I hydroxide or oxide and a Group II hydroxide or oxide; and water with the pyrolysis oil.
  • the pyrolysis oil and mixture of C1-3 alcohol, a base selected from a Group I hydroxide or oxide and a Group II hydroxide or oxide; and water are combined in a suitable container, such as a bulk tank, drum or intermediate bulk container (IBC).
  • a suitable container such as a bulk tank, drum or intermediate bulk container (IBC).
  • the pyrolysis oil and mixture of C1-3 alcohol, a base selected from a Group I hydroxide or oxide and a Group II hydroxide or oxide; and water are stored, suitably at ambient temperature.
  • the combination of pyrolysis oil and mixture of C1-3 alcohol, a base selected from a Group I hydroxide or oxide and a Group II hydroxide or oxide; and water are stored for at least one week, suitably at least two weeks, suitably at least one month.
  • the combination of pyrolysis oil and mixture of C1-3 alcohol, a base selected from a Group I hydroxide or oxide and a Group II hydroxide or oxide; and water are stored for between 1 day and 1 year, suitably between 1 week and 1 year, suitably between 1 month and 1 year.
  • the mixture/combination (essentially) consists of a C1-3 alcohol, a base selected from a Group I hydroxide or oxide and a Group II hydroxide or oxide; and water.
  • the C1-3 alcohol is methanol or ethanol.
  • the C1-3 alcohol is methanol.
  • the base is an alkali metal hydroxide, suitably selected from potassium hydroxide or sodium hydroxide, suitably potassium hydroxide.
  • the C1-3 alcohol, the base selected from a Group I hydroxide or oxide and a Group II hydroxide or oxide; and water are used as a combined solution.
  • the combined solution is added such that the mass ratio of combination of C1-3 alcohol, the base and water to pyrolysis oil is about 1 OO to about 1 :5.
  • the mass ratio of combination of C1-3 alcohol, the base and water to pyrolysis oil is about 1 :50 to about 1 :5.
  • the mass ratio of combination of C1-3 alcohol, the base and water to pyrolysis oil is about 1 :50 to about 1 :8.
  • the mass ratio of combination of C1- 3 alcohol, the base and water to pyrolysis oil is about 1 :20 to about 1 :8.
  • the mass ratio of combination of C1-3 alcohol, the base and water to pyrolysis oil is about 1 :20 to about 1 :5.
  • the mass ratio of combination of C1-3 alcohol, the base and water to pyrolysis oil is about 1 : 10 to about 1 :5.
  • the mass ratio of combination of C1-3 alcohol, the base and water to pyrolysis oil is about 1 :10 to about 1 :8.
  • the combined solution (essentially) consists of about 85% to about 90% (w/w) methanol, about 0.5% to about 3% (w/w) of potassium hydroxide and about 5% to about 15% (w/w) water. In another embodiment, the combined solution (essentially) consists of about 85% to about 90% (w/w) methanol, about 0.5% to about 1 .2% (w/w) of potassium hydroxide and about 5% to about 15% (w/w) water. In another embodiment, the combined solution (essentially) consists of about 86.5% (w/w) methanol, about 1.0% (w/w) of potassium hydroxide and about 12.5% (w/w) water.
  • the combined solution (essentially) consists of about 85% (w/w) methanol, about 1 .5% (w/w) of potassium hydroxide and about 13.5% (w/w) water.
  • the C1-3 alcohol is added in an amount such that the mass ratio of C1-3 alcohol to pyrolysis oil is about 1 OO to about 2:15.
  • the mass ratio of C1-3 alcohol to pyrolysis oil is about 1 :50 to about 2:15.
  • the mass ratio of C1-3 alcohol to pyrolysis oil is about 1 :20 to about 2:15.
  • the mass ratio of C1-3 alcohol to pyrolysis oil is about 1 :10.
  • the water is added in an amount such that the mass ratio of water to pyrolysis oil is about 1 :500 to about 1 :100.
  • the mass ratio of water to pyrolysis oil is about 1 :300 to about 1 JOO.
  • the mass ratio of water to pyrolysis oil is about 1 :200.
  • the base is added in an amount such that the mass ratio of base to pyrolysis oil is about 1 :5000 to about 1 :1000.
  • the mass ratio of base to pyrolysis oil is about 1 :3000 to about 1 :1000.
  • the mass ratio of base to pyrolysis oil is about 1 :2000.
  • the mass ratio of C1-3 alcohol to pyrolysis oil is about 1 :20 to about 2:15
  • the mass ratio of water to pyrolysis oil is about 1 :300 to about 1 :100
  • the mass ratio of alkali metal hydroxide to pyrolysis oil is about 1 :3000 to about 1 :1000.
  • the present invention relates to a mixture comprising a pyrolysis oil, a C1-3 alcohol, a base selected from a Group I hydroxide or oxide and a Group II hydroxide or oxide; and water, wherein the pyrolysis oil is derived from the pyrolysis of plastic or rubber, or a combination thereof.
  • the mixture (essentially) consists of a pyrolysis oil, a C1-3 alcohol, a base selected from a Group I hydroxide or oxide and a Group II hydroxide or oxide; and water, wherein the pyrolysis oil is derived from the pyrolysis of plastic or rubber, or a combination thereof.
  • the C1-3 alcohol is methanol or ethanol.
  • the C1-3 alcohol is methanol.
  • the base is an alkali metal hydroxide, suitably selected from potassium hydroxide or sodium hydroxide, suitably potassium hydroxide.
  • the C1-3 alcohol is present in an amount such that the mass ratio of C1-3 alcohol to pyrolysis oil is about 1 JOO to about 2:15.
  • the mass ratio of C1-3 alcohol to pyrolysis oil is about 1 :50 to about 2:15.
  • the mass ratio of C1-3 alcohol to pyrolysis oil is about 1 :20 to about 2:15.
  • the mass ratio of C1-3 alcohol to pyrolysis oil is about 1 :10.
  • the water is present in an amount such that the mass ratio of water to pyrolysis oil is about 1 :500 to about 1 : 100.
  • the mass ratio of water to pyrolysis oil is about 1 :300 to about 1 OO.
  • the mass ratio of water to pyrolysis oil is about 1 :200.
  • the base is present in an amount such that the mass ratio of the base to pyrolysis oil is about 1 :5000 to about 1 :1000.
  • the mass ratio of the base to pyrolysis oil is about 1 :3000 to about 1 :1000.
  • the mass ratio of the base to pyrolysis oil is about 1 :2000.
  • the mass ratio of C1-3 alcohol to pyrolysis oil is about 1 :20 to about 2:15
  • the mass ratio of water to pyrolysis oil is about 1 :300 to about 1 :100
  • the mass ratio of the base to pyrolysis oil is about 1 :3000 to about 1 :1000.
  • the mass ratio of pyrolysis oil to C1-3 alcohol, the base and water combined is from about 12:1 to about 5:1 . In one embodiment, the mass ratio of pyrolysis oil to C1-3 alcohol, the base and water combined is about 11 :1 to about 8:1 , suitably about 10:1.
  • a feed stream of aqueous potassium hydroxide (502), an water stream (501) and a methanol stream (503) is delivered, suitably pumped, to a mixer tank (504).
  • the combined methanol, KOH and water solution is then transferred to a storage vessel, such as a bulk tank, a drum, an IBC or other suitable container (505) where it is combined with the pyrolysis oil derived from plastic, rubber or a combination thereof (506).
  • the storage vessel may optionally comprise an agitation means.
  • the oil and the methanol, KOH and water solution in the storage vessel (505) may be left in contact with or without agitation for extended time period up to or more than 1 year, suitably at ambient temperature, in order to inhibit accumulation and deposition of gums or solids in the storage vessel.
  • the contents of the storage vessel is transferred to a separator with heating device (507).
  • the separator (507) is suitably a column, mixer settler or centrifuge.
  • the oil, methanol, KOH and water mixture is allowed to settle under gravity for a desired time, typically 30 minutes to 24 hours and typically at a temperature of about 15°C to about 40°C.
  • the upper phase (508) comprising pyrolysis oil is recovered from the separator (507).
  • a process for producing an upgraded pyrolysis oil product comprising:
  • the ratio of the base to pyrolysis oil is 1 :50 to about 1 :200.
  • the ratio of the base to pyrolysis oil is about 1 :90 to about 1 :110.
  • step (i) the pyrolysis oil is combined with the C1-3 alcohol, the base and water at a temperature of about 10°C to about 50°C, suitably about 15°C to about 40°C.
  • step (i) the pyrolysis oil is combined with the C1-3 alcohol, the base and water at a pressure of about 101 kPa to about 160 KPa, suitably about 101 KPa to about 140 KPa.
  • step (ii) the two liquid phases are filtered before separation in step (iii).
  • sorbent is selected from zeolites, aluminosilicates, activated carbon and mixtures thereof.
  • the base is a Group I hydroxide or oxide and a Group II hydroxide or oxide from potassium hydroxide, sodium hydroxide, lithium hydroxide, potassium oxide, sodium oxide, lithium oxide, caesium hydroxide, caesium oxide, barium hydroxide, barium oxide, calcium hydroxide, calcium oxide, magnesium hydroxide and magnesium oxide
  • pyrolysis oil is derived from the pyrolysis of plastic or rubber, or a combination thereof.
  • heteroatoms are selected from one or more of sulphur, nitrogen, chlorine, oxygen and silicon.
  • the combined solution consists of: about 85% to about 90% (w/w) of C1-3 alcohol; about 8% to about 15% (w/w) of water; and about 0.5% to about 1 .2% (w/w) of the base.
  • the combined solution consists of about 86.5% (w/w) C1-3 alcohol, about 12.5% (w/w) water and about 1 % (w/w) of the base; or about 85% (w/w) C1-3 alcohol, about 13.5% (w/w) water and about 1 .5% (w/w) of the base.
  • a mixture comprising a pyrolysis oil, a C1-3 alcohol, a base selected from a Group I hydroxide or oxide and a Group II hydroxide or oxide; and water, wherein the pyrolysis oil is derived from the pyrolysis of plastic or rubber, or a combination thereof.
  • a mixture according to any one of clauses 66 to 74, wherein the mass ratio of pyrolysis oil to C1-3 alcohol, the base and water combined is from about 12:1 to about 5:1 , suitably about 11 :1 to about 8:1 , more suitably about 10:1.
  • the bottle was mixed vigorously by shaking for one minute and then placed into the water bath (if used) and allowed to separate into upper and lower phases.
  • Demineralised water is optionally warmed to the set temperature and is measured into the treated pyrolysis oil.
  • the mixture is mixed by shaking for 1 minute and the allowed to separate by gravity in the water bath (if used).
  • the lower aqueous phase is removed by syringe and weighed to determine quantity of water-soluble species present in the upgraded oil.
  • An extraction solution consisting of 85 wt.% methanol/1 .50 wt.% KOH/ 13.5 wt.% water were prepared as described above.
  • a pyrolysis oil and the extraction solution were weighed into a bottle in the desired ratio and mixed vigorously by shaking for two minutes and then placed into the water bath at 40°C and allowed to separate into upper and lower phases under gravity.
  • aprotic solvents such as dipolar NMP and polar propylene carbonate are more difficult to recover from the extract phase.
  • elevated temperatures required during recovery represent a high energy cost and carry a significant risk of deterioration and permanent loss due to instability.
  • NMP and PC suffer from ring opening at elevated temperatures which can be accelerated by the presence of extracted species.
  • methanol can be easily recovered by direct distillation at relatively low temperature offering significant energy savings.

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  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
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Abstract

L'invention concerne un procédé de production d'un produit d'huile de pyrolyse valorisée, comprenant les opérations consistant à combiner l'huile de pyrolyse avec un alcool en C1-3, une base, choisie parmi un hydroxyde ou un oxyde du Groupe I et un hydroxyde ou un oxyde du Groupe II, et de l'eau pour fournir un mélange comprenant une phase d'extrait et une phase de raffinat, puis amener le mélange à former deux phases liquides consistant en une phase de raffinat et une phase d'extrait, et séparer la phase de raffinat de la phase d'extrait pour obtenir un produit d'huile de pyrolyse valorisée, l'huile de pyrolyse étant issue de la pyrolyse de matière plastique ou de caoutchouc ou d'une combinaison de ceux-ci. L'invention concerne également l'utilisation d'une solution comprenant un alcool en C1-3, une base choisie parmi un hydroxyde ou un oxyde du Groupe I et un hydroxyde ou un oxyde du Groupe II, et de l'eau pour diminuer la teneur en hétéroatomes d'une huile de pyrolyse, l'huile de pyrolyse étant issue de la pyrolyse de matière plastique ou de caoutchouc ou d'une combinaison de ceux-ci. Dans certains modes de réalisation, la teneur en les hétéroatomes silicium est réduite. Dans un mode de réalisation, l'huile de pyrolyse est combinée avec l'alcool en C1-3, la base et l'eau à une température d'entre environ 10°C à environ 50°C. Dans certains modes de réalisation, l'alcool en C1-3 est choisi parmi le méthanol ou l'éthanol. Dans certains modes de réalisation, la base est l'hydroxyde de potassium.
PCT/GB2024/052945 2023-11-23 2024-11-22 Procédé de production d'un produit d'huile de pyrolyse valorisée Pending WO2025109327A1 (fr)

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GBGB2317929.4A GB202317929D0 (en) 2023-11-23 2023-11-23 Process
GB2412622.9 2024-08-28
GBGB2412622.9A GB202412622D0 (en) 2024-08-28 2024-08-28 Process

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Citations (4)

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Publication number Priority date Publication date Assignee Title
WO2020178599A1 (fr) 2019-03-07 2020-09-10 Oxford Sustainable Fuels Limited Procédé de valorisation d'une huile de pyrolyse et solution de valorisation utilisée dans celui-ci
WO2022234225A1 (fr) * 2021-05-03 2022-11-10 Totalenergies Onetech Procede de purification de charge hydrocarbonee en presence d'un solvant et utilisation
WO2023037059A1 (fr) * 2021-09-08 2023-03-16 Totalenergies Onetech Procede de purification de charge hydrocarbonee en milieu aqueux et utilisation
WO2023172039A1 (fr) * 2022-03-07 2023-09-14 Sk Innovation Co., Ltd. Procédé d'élimination de chlore à partir d'huile de pyrolyse de déchets plastiques

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Publication number Priority date Publication date Assignee Title
WO2020178599A1 (fr) 2019-03-07 2020-09-10 Oxford Sustainable Fuels Limited Procédé de valorisation d'une huile de pyrolyse et solution de valorisation utilisée dans celui-ci
WO2022234225A1 (fr) * 2021-05-03 2022-11-10 Totalenergies Onetech Procede de purification de charge hydrocarbonee en presence d'un solvant et utilisation
WO2023037059A1 (fr) * 2021-09-08 2023-03-16 Totalenergies Onetech Procede de purification de charge hydrocarbonee en milieu aqueux et utilisation
WO2023172039A1 (fr) * 2022-03-07 2023-09-14 Sk Innovation Co., Ltd. Procédé d'élimination de chlore à partir d'huile de pyrolyse de déchets plastiques

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