EP4627004A1 - Procédé et composition de recyclage chimique de polymères à teneur réduite en azote et en oxygène - Google Patents

Procédé et composition de recyclage chimique de polymères à teneur réduite en azote et en oxygène

Info

Publication number
EP4627004A1
EP4627004A1 EP23808784.5A EP23808784A EP4627004A1 EP 4627004 A1 EP4627004 A1 EP 4627004A1 EP 23808784 A EP23808784 A EP 23808784A EP 4627004 A1 EP4627004 A1 EP 4627004A1
Authority
EP
European Patent Office
Prior art keywords
ppm
composition
polymers
tetramethyl
bis
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
EP23808784.5A
Other languages
German (de)
English (en)
Inventor
Maria Soliman
Nicolas GOYHENEIX
Carolus WILSENS
Patrick Elisabeth Luc Voets
Johan PASTWA
Gerardus Theodorus Cornelis KWAKKENBOS
Safa FARAJZADEH BIBALAN
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.)
SABIC Global Technologies BV
Original Assignee
SABIC Global Technologies BV
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 SABIC Global Technologies BV filed Critical SABIC Global Technologies BV
Publication of EP4627004A1 publication Critical patent/EP4627004A1/fr
Pending legal-status Critical Current

Links

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
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
    • C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
    • C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G9/34—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils by direct contact with inert preheated fluids, e.g. with molten metals or salts
    • C10G9/36—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils by direct contact with inert preheated fluids, e.g. with molten metals or salts with heated gases or vapours
    • 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

Definitions

  • the present invention relates to a process for chemical recycling of polymers.
  • the invention further relates to a composition of polymers that is suitable for use in chemical recycling processes, in particular in chemical recycling processes involving pyrolysis of polymer compositions to obtain pyrolysis oils and subsequent processing of such pyrolysis oils via steam cracking or via refinery operations to obtain chemical feed streams for the production of polymers.
  • streams of polymer materials that one can access contain a wide variety of polymers of different chemical constitution, due to the fact that such streams are typically collected in a combined way; at the user level, e.g. the household, the knowledge and means that would allow the user to separate one type of polymer from the other generally is not available, nor can likely be expected to be available.
  • compositions of waste polymers of varying chemical nature can be processed via routes of desirably high value and desirably low environmental impact.
  • a particular route via which mixed streams of waste polymers can be processed that is gaining traction is via chemical recycling routes.
  • Such routes typically involve a first stage of processing waste polymer streams of certain, defined, composition to produce one or more chemical compositions of oily nature, for example compositions that would be comparable to naphtha-type compositions as one can obtain from refining fossil crude oils, which stage then may be followed by the processing of such oily compositions via thermochemical decomposition processes to obtain hydrocarbon chemical compositions comprising a slate of chemicals that can be used again for manufacturing new, or ‘virgin’, products, including ‘virgin’ polymer materials such as for example polyethylenes and polypropylenes.
  • Such chemical recycling routes can be considered as a (part of) a solution for dealing with the abundantly available waste plastics streams.
  • the composition of the waste plastics streams can affect the efficiency of the operation of such chemical recycling routes.
  • a particular element that may be detrimental to the capability of processing waste plastics via chemical recycling routes is nitrogen.
  • the presence of nitrogen may lead to disruptions in the operation of equipment that is employed in unit operations for production of chemical compositions comprising ethylene and propylene, such as in steam cracking operations.
  • processes of the art provide for separate unit operations to capture nitrogen-containing compounds at various stages of the chemical recycling process.
  • stages may include hydrotreatment stages, and polishing stages.
  • hydrotreatment stages and polishing stages.
  • polishing stages As will be understood, in view of process efficiency it is preferred to minimise additional stages that need to be used in such chemical recycling process; each stage comes at a cost, involves additional consumption of energy, and leads to reduction of the yield of the process. Therefore, it is desired to employ a process in which the least amount of unit operations or process stages have to be incorporated.
  • the inventors of the present application have now found a particularly suitable process for chemical recycling, wherein the process involves the steps of: i. supplying a composition of polymers; ii. subjecting the composition of polymers to a thermal treatment to obtain a pyrolysis oil; iii. optionally, subjecting the product obtained in step ii. to a hydrotreatment process; iv. subjecting the product obtained in step ii., or, when applied, the product obtained in step iii.
  • stabilisation compound(s) comprising both oxygen atoms and nitrogen atoms are present only to such amount that such stabilisation compound(s) attribute to at most 20 ppm of nitrogen atoms and at most 50 ppm of oxygen atoms, with regard to the total weight of the composition of polymers.
  • Such process allows for efficient chemical recycling of polymers, using a simplified process, wherein the fouling of the equipment employed in the process is reduced.
  • the chemical recycling involves steam cracking
  • such process allows for the use of an increased fraction of the product of step ii., e.g. a pyrolysis oil product, and/or the product of step iii, e.g. a hydrotreated pyrolysis oil product, without detrimental effects on the steam cracking process, such as reduction of service life of the steam cracker, or fouling.
  • the stabilisation compound(s) attribute to at most 15 ppm of nitrogen atoms, more preferably at most 10 ppm, even more preferably at most 5 ppm, in the composition of polymers, with regard to the total weight of the composition of polymers.
  • the stabilisation compound(s) attribute to > 5 ppb and ⁇ 15 ppm of nitrogen atoms, more preferably > 5 ppb and ⁇ 10 ppm, even more preferably > 5 ppb and ⁇ 5 ppm, in the composition of polymers, with regard to the total weight of the composition of polymers.
  • the stabilisation compound(s) attribute to > 5 ppb and ⁇ 40 ppm of oxygen atoms, more preferably > 5 ppb and ⁇ 30 ppm, even more preferably > 5 ppb and ⁇ 20 ppm, in the composition of polymers, with regard to the total weight of the composition of polymers.
  • the stabilisation compound(s) may attribute to
  • the stabilisation compound(s) are compounds comprising one or more moiety(ies) according to formula I:
  • the stabilisation compound(s) may be selected from bis(2, 2,6,6- tetramethyl-4-piperidinyl) sebacate, bis(1 ,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate, bis(1 , 2,2,6, 6-pentamethyl-4- piperidyl) 2-(3,5-di-tert-butyl-4-hydroxybenzyl)-2-butyl malonate, 1 ,2,2,6, 6-pentamethyl- 4-piperidyl methacrylate, 2,2,6,6-tetramethyl-4-piperidyl benzoate, 2,2,6,6-tetramethyl-4- piperidyl methacrylate, tetrakis(2,2,6,6-tetramethyl-4-piperidyl) 1 ,2,3,4- butanetetracarboxylate, bis(1-
  • the composition of polymer may comprise ⁇ 5000 ppm by weight of the stabilisation compound(s), preferably > 500 and ⁇ 5000 ppm, more preferably > 500 and ⁇ 3000 ppm, with regard to the total weight of the composition of polymers.
  • the composition of polymers comprises an amount of stabilisation compound(s) comprising both oxygen atoms and nitrogen atoms so that the composition of polymers comprises > 1 ppb by weight or oxygen atoms and > 1 ppb by weight of nitrogen atoms attributable to the stabilisation compound(s), preferably > 5 ppb by weight or oxygen atoms and > 5 ppb by weight of nitrogen atoms, with regard to the total weight of the composition of polymers.
  • the thermal treatment of step ii. may for example involve a low-severity pyrolysis process, wherein the pyrolysis of the composition of polymers is performed at a temperature of > 250°C and ⁇ 450°C, or a high-severity pyrolysis process, wherein the pyrolysis of the composition of polymers is performed at a temperature of > 450°C and ⁇ 650°C.
  • the thermal treatment may be a catalytic process, preferably wherein the thermal treatment is a process operated in the presence of a ZSM-5 zeolite catalyst and/or a spent FCC catalyst.
  • the hydrotreatment step iii. may be performed at a temperature of ⁇ 350°C, in the presence of hydrogen, preferably at a pressure of ⁇ 10.0 MPa, preferably > 1 .0 and ⁇ 10.0 MPa, more preferable at > 2.0 and ⁇ 7.0 MPa.
  • the feed composition that is supplied to the steam cracking process may for example comprise > 2.5 wt% and ⁇ 75.0 wt%, preferably > 5.0 wt% and ⁇ 50.0 wt%, more preferably > 10.0 wt% and ⁇ 50.0 wt% of the product obtained in step iii.
  • composition of polymers may for example comprise:
  • composition of polymers • at most 20 ppm of nitrogen atoms, preferably > 1 ppb and ⁇ 20 ppm; and • at most 50 ppm of oxygen atoms, preferably > 1 ppb and ⁇ 50 ppm with regard to the total weight of the composition of polymers; preferably wherein the composition is obtained as a waste plastics stream from postconsumer wastes.
  • the invention also relates to a composition of polymers comprising:
  • composition of polymers may for example comprise one or more stabilisation compound(s), wherein the stabilisation compound(s) are compounds comprising one or more moiety(ies) according to formula I:
  • composition of polymers is obtained as a waste plastics stream, for example from post-consumer or household wastes.
  • the invention also relates to the use of a composition of polymers according to the invention for the reduction of fouling and/or corrosion during steam cracking of chemical feeds comprising waste plastics-derived materials.
  • the hydrotreatment process of step iii. may for example be performed in one of more vessel(s) configured to hold a hydrotreatment catalyst.
  • the vessel may be configured to operate in gas phase, liquid phase, vapour-liquid phase, or slurry phase.
  • the vessel may include one or more beds of the hydrotreatment catalyst.
  • Such bed(s) may be fixed bed(s), fluidized bed(s), moving bed(s), slurry bed(s), or combinations thereof.
  • the vessel may be operated in adiabatic, isothermal, non-adiabatic, or nonisothermal conditions.
  • the product of step ii. may be subjected to treatment in the presence of hydrogen, wherein the volume flow ratio of hydrogen to the product of step ii. may for example be 10 to 3000, preferably 200 to 1000.
  • the hydrotreatment step iii may be performed in the presence of a catalyst.
  • the composition of polymers preferably comprises > 70.0 wt% of polyolefins.
  • polyolefins preferably comprise polyethylenes and polypropylenes.
  • the polyolefins may comprise > 80.0 wt% of polyethylenes, or > 90.0 wt% of polyethylenes.
  • the polyolefins may comprise ⁇ 20.0 wt% of polypropylenes, or ⁇ 10.0 wt% of polypropylenes.
  • Such polyethylenes may be a composition comprising low-density polyethylenes, linear low-density polyethylenes, and high-density polyethylenes.
  • the process of the present invention allows for the suitable conversion of waste plastics into new plastics of high quality, thereby creating a circular economy of material use.

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

Abstract

La présente invention concerne un procédé de recyclage chimique, le procédé comprenant les étapes consistant à : i. fournir une composition de polymères ; ii. soumettre la composition de polymères à un traitement thermique pour obtenir une huile de pyrolyse ; iii. éventuellement, la soumission du produit obtenu à l'étape ii. à un procédé d'hydrotraitement ; iv. soumettre le produit obtenu à l'étape ii. ou, lorsqu'il est appliqué, le produit obtenu à l'étape iii. à un procédé de décomposition thermique, pour obtenir une composition chimique comprenant de l'éthylène et du propylène ; dans la composition de polymères, un ou plusieurs composés de stabilisation comprenant à la fois des atomes d'oxygène et des atomes d'azote étant présents uniquement à une quantité telle que ledit ou lesdits composés de stabilisation attribuent au plus 50 ppm, de préférence au plus 20 ppm, d'atomes d'azote et au plus 125 ppm, de préférence au plus 50 ppm, d'atomes d'oxygène, par rapport au poids total de la composition de polymères. Un tel procédé permet un recyclage chimique efficace de polymères, à l'aide d'un procédé simplifié, la corrosion de l'équipement utilisé dans le procédé étant réduite. Par exemple dans des opérations dans lesquelles le recyclage chimique implique un craquage à la vapeur, un tel procédé permet l'utilisation d'une fraction accrue du produit de l'étape ii, par exemple un produit d'huile de pyrolyse, et/ou le produit de l'étape iii, par exemple un produit d'huile de pyrolyse hydrotraité, sans effets néfastes sur le processus de vapocraquage, tels que la corrosion, la réduction de la durée de vie du vapocraqueur, ou l'encrassement.
EP23808784.5A 2022-11-28 2023-11-17 Procédé et composition de recyclage chimique de polymères à teneur réduite en azote et en oxygène Pending EP4627004A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP22209975 2022-11-28
PCT/EP2023/082175 WO2024115134A1 (fr) 2022-11-28 2023-11-17 Procédé et composition de recyclage chimique de polymères à teneur réduite en azote et en oxygène

Publications (1)

Publication Number Publication Date
EP4627004A1 true EP4627004A1 (fr) 2025-10-08

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Application Number Title Priority Date Filing Date
EP23808784.5A Pending EP4627004A1 (fr) 2022-11-28 2023-11-17 Procédé et composition de recyclage chimique de polymères à teneur réduite en azote et en oxygène

Country Status (3)

Country Link
EP (1) EP4627004A1 (fr)
CN (1) CN120344636A (fr)
WO (1) WO2024115134A1 (fr)

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3390573A1 (fr) * 2015-12-18 2018-10-24 Solvay Sa Procédé de production de cires et de combustibles liquides à partir de déchets plastiques
FI128848B (en) * 2019-11-29 2021-01-29 Neste Oyj Two-step process for converting liquid plastic waste into steam cracking feed
EP4182410A1 (fr) * 2020-07-20 2023-05-24 SABIC Global Technologies B.V. Procédé de préparation de butènes et de butadiènes à partir de matières premières de déchets plastiques

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Publication number Publication date
CN120344636A (zh) 2025-07-18
WO2024115134A1 (fr) 2024-06-06

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