WO2024115134A1 - 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 Download PDFInfo
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- WO2024115134A1 WO2024115134A1 PCT/EP2023/082175 EP2023082175W WO2024115134A1 WO 2024115134 A1 WO2024115134 A1 WO 2024115134A1 EP 2023082175 W EP2023082175 W EP 2023082175W WO 2024115134 A1 WO2024115134 A1 WO 2024115134A1
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- composition
- polymers
- tetramethyl
- bis
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- 239000000203 mixture Substances 0.000 title claims abstract description 84
- 238000000034 method Methods 0.000 title claims abstract description 74
- 229920000642 polymer Polymers 0.000 title claims abstract description 66
- 239000000126 substance Substances 0.000 title claims abstract description 35
- 238000004064 recycling Methods 0.000 title claims abstract description 21
- 229910052757 nitrogen Inorganic materials 0.000 title claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title description 2
- 229910052760 oxygen Inorganic materials 0.000 title description 2
- 239000001301 oxygen Substances 0.000 title description 2
- 150000001875 compounds Chemical class 0.000 claims abstract description 33
- 230000006641 stabilisation Effects 0.000 claims abstract description 29
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 21
- 125000004430 oxygen atom Chemical group O* 0.000 claims abstract description 20
- 238000004230 steam cracking Methods 0.000 claims abstract description 20
- 238000000197 pyrolysis Methods 0.000 claims abstract description 18
- 238000007669 thermal treatment Methods 0.000 claims abstract description 10
- 238000005979 thermal decomposition reaction Methods 0.000 claims abstract description 8
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000005977 Ethylene Substances 0.000 claims abstract description 5
- 238000005260 corrosion Methods 0.000 claims abstract description 5
- 230000007797 corrosion Effects 0.000 claims abstract description 5
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 5
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 5
- 239000003054 catalyst Substances 0.000 claims description 35
- -1 bis(1 ,2,2,6, 6-pentamethyl-4-piperidyl) 2-(3,5-di-tert-butyl-4- hydroxybenzyl)-2-butyl Chemical group 0.000 claims description 20
- 229920003023 plastic Polymers 0.000 claims description 16
- 239000004033 plastic Substances 0.000 claims description 16
- 239000002699 waste material Substances 0.000 claims description 16
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 12
- 229920000098 polyolefin Polymers 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 5
- 239000010817 post-consumer waste Substances 0.000 claims description 5
- NWPIOULNZLJZHU-UHFFFAOYSA-N (1,2,2,6,6-pentamethylpiperidin-4-yl) 2-methylprop-2-enoate Chemical compound CN1C(C)(C)CC(OC(=O)C(C)=C)CC1(C)C NWPIOULNZLJZHU-UHFFFAOYSA-N 0.000 claims description 4
- ROIMNSWDOJCBFR-UHFFFAOYSA-N 2-iodothiophene Chemical compound IC1=CC=CS1 ROIMNSWDOJCBFR-UHFFFAOYSA-N 0.000 claims description 4
- YKVAWSVTEWXJGJ-UHFFFAOYSA-N 4-chloro-2-methylsulfanylthieno[3,2-d]pyrimidine Chemical compound CSC1=NC(Cl)=C2SC=CC2=N1 YKVAWSVTEWXJGJ-UHFFFAOYSA-N 0.000 claims description 4
- RSOILICUEWXSLA-UHFFFAOYSA-N bis(1,2,2,6,6-pentamethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)N(C)C(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)N(C)C(C)(C)C1 RSOILICUEWXSLA-UHFFFAOYSA-N 0.000 claims description 4
- OSIVCXJNIBEGCL-UHFFFAOYSA-N bis(2,2,6,6-tetramethyl-1-octoxypiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)N(OCCCCCCCC)C(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)N(OCCCCCCCC)C(C)(C)C1 OSIVCXJNIBEGCL-UHFFFAOYSA-N 0.000 claims description 4
- XITRBUPOXXBIJN-UHFFFAOYSA-N bis(2,2,6,6-tetramethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)NC(C)(C)C1 XITRBUPOXXBIJN-UHFFFAOYSA-N 0.000 claims description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 230000003197 catalytic effect Effects 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 claims description 4
- WUPCFMITFBVJMS-UHFFFAOYSA-N tetrakis(1,2,2,6,6-pentamethylpiperidin-4-yl) butane-1,2,3,4-tetracarboxylate Chemical compound C1C(C)(C)N(C)C(C)(C)CC1OC(=O)CC(C(=O)OC1CC(C)(C)N(C)C(C)(C)C1)C(C(=O)OC1CC(C)(C)N(C)C(C)(C)C1)CC(=O)OC1CC(C)(C)N(C)C(C)(C)C1 WUPCFMITFBVJMS-UHFFFAOYSA-N 0.000 claims description 4
- NZNAAUDJKMURFU-UHFFFAOYSA-N tetrakis(2,2,6,6-tetramethylpiperidin-4-yl) butane-1,2,3,4-tetracarboxylate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)CC(C(=O)OC1CC(C)(C)NC(C)(C)C1)C(C(=O)OC1CC(C)(C)NC(C)(C)C1)CC(=O)OC1CC(C)(C)NC(C)(C)C1 NZNAAUDJKMURFU-UHFFFAOYSA-N 0.000 claims description 4
- YEYCMBWKTZNPDH-UHFFFAOYSA-N (2,2,6,6-tetramethylpiperidin-4-yl) benzoate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)C1=CC=CC=C1 YEYCMBWKTZNPDH-UHFFFAOYSA-N 0.000 claims description 3
- SXPLGYBFGPYAHS-UHFFFAOYSA-N bis(1-hydroxy-2,2,6,6-tetramethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)N(O)C(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)N(O)C(C)(C)C1 SXPLGYBFGPYAHS-UHFFFAOYSA-N 0.000 claims description 3
- 238000004523 catalytic cracking Methods 0.000 claims description 3
- WHDPTDWLEKQKKX-UHFFFAOYSA-N cobalt molybdenum Chemical compound [Co].[Co].[Mo] WHDPTDWLEKQKKX-UHFFFAOYSA-N 0.000 claims description 3
- PTISTKLWEJDJID-UHFFFAOYSA-N sulfanylidenemolybdenum Chemical compound [Mo]=S PTISTKLWEJDJID-UHFFFAOYSA-N 0.000 claims description 3
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 claims description 3
- 229910021536 Zeolite Inorganic materials 0.000 claims description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 2
- MGRWKWACZDFZJT-UHFFFAOYSA-N molybdenum tungsten Chemical compound [Mo].[W] MGRWKWACZDFZJT-UHFFFAOYSA-N 0.000 claims description 2
- MRDDPVFURQTAIS-UHFFFAOYSA-N molybdenum;sulfanylidenenickel Chemical compound [Ni].[Mo]=S MRDDPVFURQTAIS-UHFFFAOYSA-N 0.000 claims description 2
- 239000010457 zeolite Substances 0.000 claims description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 229940116351 sebacate Drugs 0.000 claims 1
- CXMXRPHRNRROMY-UHFFFAOYSA-L sebacate(2-) Chemical compound [O-]C(=O)CCCCCCCCC([O-])=O CXMXRPHRNRROMY-UHFFFAOYSA-L 0.000 claims 1
- 230000001627 detrimental effect Effects 0.000 abstract description 3
- 239000002861 polymer material Substances 0.000 description 6
- 239000004698 Polyethylene Substances 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 229920000573 polyethylene Polymers 0.000 description 5
- 239000004743 Polypropylene Substances 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000010977 unit operation Methods 0.000 description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000004227 thermal cracking Methods 0.000 description 2
- 229940055764 triaz Drugs 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 206010011906 Death Diseases 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000010791 domestic waste Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229920004889 linear high-density polyethylene Polymers 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000010454 slate Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 238000004148 unit process Methods 0.000 description 1
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 hydrotreatment step iii. may be performed in the presence of a catalyst, wherein the catalyst is selected from a cobalt-molybdenum catalyst on alumina support, a nickel-molybdenum catalyst on alumina support, a tungsten-molybdenum catalyst on alumina support, a platinum-palladium catalyst on alumina support, a nickel sulphide catalyst, a molybdenum sulphide catalyst, or a nickel-molybdenum sulphide catalyst.
- the catalyst is selected from a cobalt-molybdenum catalyst on alumina support, a nickel-molybdenum catalyst on alumina support, a tungsten-molybdenum catalyst on alumina support, a platinum-palladium catalyst on alumina support, a nickel sulphide catalyst, a molybdenum sulphide catalyst, or a nickel-molybdenum sulphide catalyst.
- the thermal decomposition process of step iv. may be a steam cracking process, preferably wherein the steam cracking occurs in a steam cracking unit comprising heated coils, wherein the coil outlet temperature (COT) is in the range of 800°C to 870°C.
- the thermal decomposition process of step iv. may be a catalytic cracking process.
- 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 ii.
- 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:
- stabilisation compound(s) comprising both oxygen atoms and nitrogen atoms 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; preferably wherein the composition is obtained as a waste plastics stream from postconsumer wastes.
- 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:
- the stabilisation compound(s) may for example 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-oxy
- 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.
- Such process allows for efficient chemical recycling of polymers, using a simplified process, wherein the corrosion of the equipment employed in the process is reduced.
- 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.
- Such catalyst may for example be a catalyst selected from a cobalt-molybdenum catalyst on alumina support, a nickel-molybdenum catalyst on alumina support, a tungstenmolybdenum catalyst on alumina support, a platinum-palladium catalyst on alumina support, a nickel sulphide catalyst, a molybdenum sulphide catalyst, or a nickelmolybdenum sulphide catalyst.
- the catalyst that may be used in the hydrotreatment step iii. may for example be sulphided.
- 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 composition of polymers comprises a high fraction of polyolefins, such as > 70.0 wt%, or > 80.0 wt%, or > 90.0 wt%, with regard to the total weight of the composition of polymers.
- Compositions of polymers comprising such high fraction of polyolefins are particularly suitable for chemical recycling via catalytic or non-catalytic thermal treatment processes, due to the fact that their polymer structure is based on linear monomers, which are suitable for thermal cracking.
- the composition of plastics in particular a composition of waste plastics, may be converted into chemical building blocks, in particular ethylene and propylene.
- 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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- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
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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.
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Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
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US20190002664A1 (en) * | 2015-12-18 | 2019-01-03 | Solvay Sa | Process for producing waxes and liquid fuels from waste plastic |
WO2021105326A1 (fr) * | 2019-11-29 | 2021-06-03 | Neste Oyj | Procédé en deux étapes pour convertir des déchets plastiques liquéfiés en matière première de vapocraqueur |
WO2022017903A1 (fr) * | 2020-07-20 | 2022-01-27 | 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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- 2023-11-17 WO PCT/EP2023/082175 patent/WO2024115134A1/fr unknown
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20190002664A1 (en) * | 2015-12-18 | 2019-01-03 | Solvay Sa | Process for producing waxes and liquid fuels from waste plastic |
WO2021105326A1 (fr) * | 2019-11-29 | 2021-06-03 | Neste Oyj | Procédé en deux étapes pour convertir des déchets plastiques liquéfiés en matière première de vapocraqueur |
WO2022017903A1 (fr) * | 2020-07-20 | 2022-01-27 | 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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