WO2014209117A1 - Polymer degradation - Google Patents
Polymer degradation Download PDFInfo
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- WO2014209117A1 WO2014209117A1 PCT/NL2014/050418 NL2014050418W WO2014209117A1 WO 2014209117 A1 WO2014209117 A1 WO 2014209117A1 NL 2014050418 W NL2014050418 W NL 2014050418W WO 2014209117 A1 WO2014209117 A1 WO 2014209117A1
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- WO
- WIPO (PCT)
- Prior art keywords
- catalyst
- polymer
- catalyst complex
- particles
- present
- Prior art date
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- 238000012667 polymer degradation Methods 0.000 title description 4
- 239000003054 catalyst Substances 0.000 claims abstract description 151
- 238000000034 method Methods 0.000 claims abstract description 77
- 229920000642 polymer Polymers 0.000 claims abstract description 65
- 239000002245 particle Substances 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 239000002904 solvent Substances 0.000 claims abstract description 29
- 230000000593 degrading effect Effects 0.000 claims abstract description 19
- 239000006249 magnetic particle Substances 0.000 claims abstract description 18
- 239000000178 monomer Substances 0.000 claims abstract description 16
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 33
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 32
- -1 triethoxysilylpropyl Chemical group 0.000 claims description 27
- 238000006731 degradation reaction Methods 0.000 claims description 26
- 239000002105 nanoparticle Substances 0.000 claims description 21
- 230000015556 catabolic process Effects 0.000 claims description 18
- 230000005291 magnetic effect Effects 0.000 claims description 15
- 239000000654 additive Substances 0.000 claims description 13
- 239000002699 waste material Substances 0.000 claims description 12
- 150000003839 salts Chemical class 0.000 claims description 10
- 239000000539 dimer Substances 0.000 claims description 9
- 239000000376 reactant Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- 239000008188 pellet Substances 0.000 claims description 8
- 229920000728 polyester Polymers 0.000 claims description 8
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical compound CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 claims description 7
- 239000000356 contaminant Substances 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 239000002122 magnetic nanoparticle Substances 0.000 claims description 6
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 6
- 238000004064 recycling Methods 0.000 claims description 6
- 239000013638 trimer Substances 0.000 claims description 6
- 239000008187 granular material Substances 0.000 claims description 5
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 5
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 5
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 229920000331 Polyhydroxybutyrate Polymers 0.000 claims description 4
- 230000005294 ferromagnetic effect Effects 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- CKFGINPQOCXMAZ-UHFFFAOYSA-N methanediol Chemical compound OCO CKFGINPQOCXMAZ-UHFFFAOYSA-N 0.000 claims description 4
- 229920000520 poly(3-hydroxybutyrate-co-3-hydroxyvalerate) Polymers 0.000 claims description 4
- 239000005015 poly(hydroxybutyrate) Substances 0.000 claims description 4
- 229920001610 polycaprolactone Polymers 0.000 claims description 4
- 239000004632 polycaprolactone Substances 0.000 claims description 4
- 229920000570 polyether Polymers 0.000 claims description 4
- 229920000921 polyethylene adipate Polymers 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 239000004633 polyglycolic acid Substances 0.000 claims description 4
- 229920001451 polypropylene glycol Polymers 0.000 claims description 4
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 4
- 150000001733 carboxylic acid esters Chemical class 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 claims description 3
- 230000005672 electromagnetic field Effects 0.000 claims description 3
- 229910052595 hematite Inorganic materials 0.000 claims description 3
- 239000011019 hematite Substances 0.000 claims description 3
- 229920001519 homopolymer Polymers 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 claims description 3
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 claims description 3
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 claims description 2
- KAUQJMHLAFIZDU-UHFFFAOYSA-N 6-Hydroxy-2-naphthoic acid Chemical compound C1=C(O)C=CC2=CC(C(=O)O)=CC=C21 KAUQJMHLAFIZDU-UHFFFAOYSA-N 0.000 claims description 2
- 102100024133 Coiled-coil domain-containing protein 50 Human genes 0.000 claims description 2
- 101000910772 Homo sapiens Coiled-coil domain-containing protein 50 Proteins 0.000 claims description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- 229910052779 Neodymium Inorganic materials 0.000 claims description 2
- 239000004952 Polyamide Substances 0.000 claims description 2
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 2
- 229910052772 Samarium Inorganic materials 0.000 claims description 2
- 229920000508 Vectran Polymers 0.000 claims description 2
- 239000004979 Vectran Substances 0.000 claims description 2
- 230000005290 antiferromagnetic effect Effects 0.000 claims description 2
- 150000005690 diesters Chemical class 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- 150000007524 organic acids Chemical class 0.000 claims description 2
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 claims description 2
- 230000005298 paramagnetic effect Effects 0.000 claims description 2
- 239000005014 poly(hydroxyalkanoate) Substances 0.000 claims description 2
- 229920000768 polyamine Polymers 0.000 claims description 2
- 239000011112 polyethylene naphthalate Substances 0.000 claims description 2
- 239000004626 polylactic acid Substances 0.000 claims description 2
- 229920001184 polypeptide Polymers 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 108090000765 processed proteins & peptides Proteins 0.000 claims description 2
- 102000004196 processed proteins & peptides Human genes 0.000 claims description 2
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical compound CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 claims description 2
- 229910000859 α-Fe Inorganic materials 0.000 claims description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims 3
- 229920000954 Polyglycolide Polymers 0.000 claims 2
- 150000001336 alkenes Chemical class 0.000 claims 1
- 229920002647 polyamide Polymers 0.000 claims 1
- 230000008569 process Effects 0.000 description 14
- 230000008901 benefit Effects 0.000 description 9
- 239000007857 degradation product Substances 0.000 description 6
- 239000002608 ionic liquid Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 230000006872 improvement Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000005293 ferrimagnetic effect Effects 0.000 description 2
- 239000011554 ferrofluid Substances 0.000 description 2
- 230000034659 glycolysis Effects 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 238000009434 installation Methods 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229950008885 polyglycolic acid Drugs 0.000 description 2
- 229920002215 polytrimethylene terephthalate Polymers 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- BJZYYSAMLOBSDY-QMMMGPOBSA-N (2s)-2-butoxybutan-1-ol Chemical compound CCCCO[C@@H](CC)CO BJZYYSAMLOBSDY-QMMMGPOBSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- 241001137251 Corvidae Species 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229920013724 bio-based polymer Polymers 0.000 description 1
- 239000004621 biodegradable polymer Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
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- 239000002803 fossil fuel Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 150000004693 imidazolium salts Chemical class 0.000 description 1
- 239000011553 magnetic fluid Substances 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 235000015108 pies Nutrition 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
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- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000002520 smart material Substances 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0281—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member
- B01J31/0284—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member of an aromatic ring, e.g. pyridinium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0292—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature immobilised on a substrate
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0203—Impregnation the impregnation liquid containing organic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0209—Impregnation involving a reaction between the support and a fluid
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J11/00—Recovery or working-up of waste materials
- C08J11/04—Recovery or working-up of waste materials of polymers
- C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
- C08J11/18—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material
- C08J11/28—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material by treatment with organic compounds containing nitrogen, sulfur or phosphorus
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
Definitions
- the present invention is in the field of a method of degrading a polymer into oligomers and/or monomers in a solvent, using a catalyst, and a functionalized magnetic particle comprising a catalyst being capable of degrading the polymer into oligomers and/or monomers.
- the present method and particle provide a high selectivity and a high conversion ratio.
- Magnetic Fluids are a class of smart materials that change their properties reversibly and relatively fast (milli- seconds) under presence of an external magnetic field. These fluids can show changes in apparent viscosity of several orders of magnitude when a magnetic field is applied, such as a magnetic flux density in the order of around 1 T. Below two sub-classes are identified.
- a ferrofluid relates to a liquid which becomes strongly magnetized in the presence of a magnetic field.
- ferrofluids are colloidal liquids made of nanoscale ferromagnetic, or ferrimagnetic, particles suspended in a carrier fluid (usually an organic solvent or water) .
- a carrier fluid usually an organic solvent or water
- each tiny particle is thoroughly coated with a surfactant to inhibit clumping.
- a disadvantage is that larger particles can be removed from an otherwise homogeneous colloidal mixture, forming a separate clump of magnetic dust e.g. when exposed to strong magnetic fields.
- A further issue is that if a separation is (partly) successful, degradation into smaller building units still is difficult. Many methods or processes are not selective enough, that is a discrimination, shown by a reagent in competitive attack on two or more substrates or on two or more positions in the same substrate, is relatively low. It is typically quantitatively expressed by ratios of rate constants of the competing reactions, or by the decadic logarithms of such ratios. Further a conversion is too low; efficient conversion of reactants (polymers) to desired products (monomers or oligomers) without much wastage production in terms of side products is an issue. As a consequence a yield, being regarded as a product of selectivity times conversion, is too low as well.
- catalysts are used for synthesis of molecules and the like, not for degradation.
- catalysts, and especially catalyst complexes, and function of a catalyst are sensitive to contaminants being present; in other words they function only properly under relative pure and clean conditions.
- contamination catalysts need to be replaced regularly, and extreme care is typically taken not to introduce contaminants. That may also a reason why catalyst are typically not considered for degradation processes, as these processes almost inherently introduce contaminants.
- metal catalysts are directly attached to a nanoparticle .
- Such catalysts are typically used for synthesis, but not for degradation, and certainly not for a reaction with at least one solid reactant.
- a reaction between two or more components is executed, wherein the two or more components are in close contact, such as in a solvent.
- the nature and relevant parameters of a synthesis reaction is considered to be quite different from degradation reactions; for instance relative low amounts of catalyst may be used and relatively high yield may be obtainable under optimal conditions.
- Various articles such as Zhang in Applied Catalysis A: General, Elsevier Science, Vol. 366, Nr. 1, pp. 141-147, Pang Wang in Catalysis Letters, Kluwer Academic Publishers-Plenum Publishers, NE, Vol. 135,
- the present invention provides a method and catalyst for degrading polymers which overcomes one or more of the above disadvantages, without jeopardizing functionality and advantages .
- the present invention relates in a first aspect to an improved reusable ionic catalyst complex for degradation of a homo or copolymer according to claim 1, and in a second aspect to a method according to claim 6, showing partly ma- jor improvements over the prior art, e.g. in terms of selectivity (93% versus 59.2%), conversion, yield, a very low amount of catalyst used per amount of product degraded/obtained (0.5-2 wt . % versus 17-80 wt . % [weight catalyst/weight polymer]), use of energy (1 hour versus 4 hours; so also much quicker), insensitivity to contaminants, insensitivity to composition of raw material to be degraded, etc.
- the present invention provides a conversion of about 100%, a selectivity of significantly more than 90% (versus some 59.2% prior art), reuse of catalyst (over 50 times, being absent in prior art deg- radation processes), allowing any mixture of waste polymers (not known in the prior art, typically well cleaned, well separated, having one type/source of material, is needed for prior art processes) , a relatively modest temperature and pressure may be used (200 °C versus e.g. 500 °C) , etc.
- the present catalyst complex shows an improved localized action.
- typically improvement in one aspect involves a deterioration in another aspect (parameter) ; the present range of improvements in various aspects together is already in that sense surprising.
- the present catalyst complex comprises three distinguishable elements: a nanoparticle, a bridging moiety attached, such as by a covalent bond, to the nanoparticle and a catalyst entity (chemically) attached to the bridging moiety.
- the bridging moiety is solely in between the catalyst and the nanoparticle, respectively.
- the present complex is for instance different from a complex having a bridging moiety fully covering a nanoparticle, such as in a core-shell particle.
- the present nanoparticle is of a magnetic nature.
- nanoparticles comprising a magnetic material are included, as well as particles that can be magnetized sufficiently under relative modest magnetic fields, such as being applied in the present method.
- the nanoparticle should be sufficiently small for the catalyst complex to function as a catalyst, therewith degrading the present polymer into smaller units, wherein the yield of these smaller units, and specifically the monomers thereof, is high enough for commercial reasons.
- a value of polymers to be degraded is relatively small, i.e. a costs of degrading should be small as well.
- the nanoparticle should be sufficiently large in order to be able to reuse the present complex by recovering the present catalyst complex. It is economically unfavorable to have catalyst complex being removed with either waste or degradation product obtained .
- the present nanoparticle is not considered to be a support.
- a prior art support in general relates to much larger entities, typically in the order of mm or larger. It is noted that for the present process a catalyst on a support is considered unsuited, in particular as a yield of degradation products is too low (or likewise time and/or temperature to obtain such a yield are unfavorable) .
- the present catalyst entity comprises at least two moieties. Such has been found to contribute to at least some of the present advantages.
- a first relates to an aro- matic moiety having a positive charge.
- a second relates to a moiety, typically a salt complex, having a negative charge.
- the negative and positive charge typically balance one and another. It has been found that the positively and negatively charged moieties have a synergistic and enhanc- ing effect on the degradation process of the polymer in terms of conversion and selectivity, especially in view of degrading polyesters and polyethers .
- the aromatic moiety preferably comprises a hetero- cycle, having at least one, preferably at least two nitro- gen atoms.
- the aromatic moiety preferably stabilizes a positive charge.
- the heterocycle may have 5 or 6 atoms, preferably 5 atoms.
- the negatively charged moiety may relate to a salt complex, preferably a metal salt complex having a two- or three-plus charged metal ion, such as Fe 3+ , Al 3+ , Ca 2+ , and Cu 2+ , and negatively charged counter-ions, such as halogen- ides, e.g. Cl ⁇ , F ⁇ , Br " , wherein one
- the present catalyst entity and nanoparticle are combined by a bridging moiety.
- a catalyst entity such as one according to the invention
- the present bridging molecule in combination with the nanoparticle provides a catalyst com- plex which functions almost as good as or better than the catalyst entity itself. It is noted that it is somewhat complicated to combine (or coat) the present nanoparticle with a bridging moiety, at least in terms of functionality obtained.
- bridging moieties or a combination thereof
- a size (diameter) of the present nanoparticle is important.
- the magnetic particles have an average diameter of 2 nm - 500 nm, preferably from 3 nm -100 nm, more preferably from 4 nm -50 nm, such as from 5-10 nm.
- the particles are preferably not too large and not too small. It has been found that e.g. in terms of yield and recovery of catalyst complex a rather small size of particles of 5-10 nm is optimal. It is noted that the term "size" relates to an average diameter of particles, wherein an actual diameter of a parti- cle may vary somewhat due to characteristics thereof.
- the bridging moiety is provided in an amount of (mole bridging moiety/gr magnetic particle) 5*10 ⁇ 6 -0.1, preferably 1*10 ⁇ 5 - 0.01, more preferably 2*10 ⁇ -10 ⁇ 3 , such as 4*10 ⁇ 5 -10 ⁇ 4 . It is preferred to have a relatively large amount available in terms of e.g. yield, energy consumption, etc., whereas in terms of amount of catalyst and costs thereof a somewhat smaller amount is available, especially as the magnetic nanoparticles are considered as a relatively cheap part of the catalyst complex. Surprisingly the present method can be performed with very low amounts of catalyst (complex), compared to prior art methods.
- the solid polymer is provided in a suitable solvent.
- the present method may be considered as a solid-liquid degradation process sup- ported by addition of a recoverable catalyst complex.
- the solvent is preferably a mono- or di-alcohol.
- the solvent also functions as a reactant.
- Some solvents form a 5 stable "dispersion" with the catalyst complex; in such a case in the step of recovery a second solvent, e.g. functioning as washing agent, may be provided and the catalyst may then be recovered using an electromagnetic field.
- the method may be carried out batch-wise, continuity ous, semi-continuous, and combinations thereof.
- the present method has a less selective feedstock, as from virgin polymer (such as PET) to various other recovered sources may be provided. Also it provides a relatively low energy process. As a consequence polymer pro-
- the present method can be considered to relate to a one-phase system for degradation, comprising a solvent, a polymer to be degraded, and a catalyst complex.
- a one-phase system for degradation comprising a solvent, a polymer to be degraded, and a catalyst complex.
- Such a system may 0 also be referred to as a dispersion in that particles (polymer and catalyst complex) are present in a solvent.
- the present method distinguishes itself from a reaction with a catalyst on a support, which ef- 5 fectively relates to a two-phase system, not being suitable for polymer degradation.
- the temperature and pressure of the method may be adjusted. Typically a somewhat higher temperature is preferred in terms of reaction velocity; a lower temperature 0 is preferred in terms of energy consumption. Likewise a
- a relatively low temperature may be 5 used, without jeopardizing yield.
- a relatively mild temperature and pressure conditions the present degradation can be carried out in a relative short time. Such provides e.g. a relative high throughput, a relatively smaller installation, and lower consumption of materi- 0 als and energy.
- the method is relatively insensitive (e.g. in terms of yield) for mixed polymers being provided.
- Mixed polymers can relate to a combination of two or more different types of polymers, such as different polyesters, such as PET, polyethylene furanoate (PEF) , and polybutylene terephthalate (PBT), to a combination of one type of polymer having different properties, such as color, thickness, origin, and combinations thereof.
- PET polyethylene furanoate
- PBT polybutylene terephthalate
- the method is relatively insensitive to contami- nants, like additives, such as pigments, fillers, filters, etc. As such the present method is considered robust, to be used under relatively sub-optimal conditions, such as in a plant .
- a characteristic of the present method is that the catalyst complex is recovered. It is preferred to use the present catalyst complex in the present method.
- the present invention relates in a first aspect to a catalyst complex according to claim 1.
- the magnetic particles are one or more of ferromagnetic particles, anti-ferromagnetic particles, ferrimagnetic particles, synthetic magnetic particles, paramagnetic particles, superpara- magnetic particles, such as particles comprising one or more of Fe, Co, Ni, Gd, Dy, Mn, Nd, Sm, and preferably one or more of 0, B, C, N, such as iron oxide, such as ferrite, such as magnetite, hematite, and maghemite.
- magnetite and maghemite are preferred magnetic parti- cles .
- relatively cheap particles are preferred, such as particles comprising Fe .
- the bridging moiety is one or more of a weak organic acid, si- lanol, silyl comprising groups, such as silylethers, such as triethoxysilylpropyl, and silanol. It has been found that de- spite negative expectations these bridging groups do not result in a non-acceptable reduced performance of the catalyst entity .
- the ar ⁇ omatic moiety has at least one tail, the at least one tail preferably having a length of Ci-C 6 , such as C 2 -C 4 , the at least one tail being attached to the at least one nitrogen atom. It has been found that for an optimal degradation a somewhat higher yield is obtained when the present tail is somewhat longer. In terms of mass of catalyst complex provided it has been found that a somewhat shorter tail is preferred.
- the magnetic nanoparticle comprises (per particle) at least one bridging moiety and catalyst entity, preferably 2-10 4 bridging moieties and catalyst entities, more preferably 10-10 3 bridg- ing moieties and catalyst entities.
- bridging moiety and catalyst entity preferably 2-10 4 bridging moieties and catalyst entities, more preferably 10-10 3 bridg- ing moieties and catalyst entities.
- the amount of catalyst entities and there functioning is in view of e.g. degradation efficiency somewhat smaller than an amount that could be achieved.
- a larger particle is selected somewhat more catalyst entities may be present.
- the amount of bridging moiety and catalyst attached thereto is 0.03-99 wt.%, preferably 0.1-75 wt.%, more preferably 0.2-25 wt.%, even more preferably 0.3-10 wt.%, relative to a total weight of catalyst complex.
- a relative low amount of 0.5-5 wt.% of catalyst entity has been found to be optimal, such as 0.6-3 wt.%, within further boundary conditions such as applied temperature.
- the pre- sent catalyst and bridging moiety may form a single (mono-) layer, a double (bi-) layer, a oligolayer, and combinations thereof. Before applying the present catalyst complex in the present method it may be washed. The above weight percentages are relative to a total weight of catalyst complex.
- the present invention relates to a method according to claim 6.
- a polymer is provided in solid form.
- the polymer is fragmented into smaller pieces .
- the polymer is a mixture of waste polymers, the mixture optionally comprising one or more of coloured polymers.
- the present method is capable of handling waste polymers, and even further a mixture of polymers, e.g. having different characteristics, such as a different colour.
- the yield of degradation has been found not to be influenced noticeably. It is noted that prior art methods at the most can only handle relatively pure waste polymer, and even then results are discouraging.
- the constituents such as solvent, catalyst complex and polymer, form a one- phase system.
- Such has been found advantageous, especially in terms of yield obtained. Also in terms of reactor design such is advantageous.
- the polymer may selected from natural polymers, biobased polymers, biodegrada- ble polymers, polymers formed (directly or indirectly) from fossil fuels, and combinations thereof.
- the polymer is one or more of a polyester, a polyether, such as poly- oxymehtylene (POM), polyethyleneglycol (PEG), polypropyl- eneglycol (PPG) , polytetramethyleneglycol
- POM poly- oxymehtylene
- PEG polyethyleneglycol
- PPG polypropyl- eneglycol
- PTMG polyethyleneoxide
- POE polypropyleneoxide
- PPO polypropyleneoxide
- PTHF polypropyleneoxide
- PTMEG polytetramethyleneetherglycol
- a polyalkene a polyalkane, a polypeptide, a polyam- ide, a polyamine, a polycondensate
- a polyester such as poly carboxylic ester
- the poly carboxylic es- ter is preferably selected from polyethylene terephthalate (PET), polyethylene furanoate (PEF), polybutylene terephthalate (PBT) , polytrimethylene terephthalate (PTT) , polygly- colic acid (PGA) , polylactic acid (PLA) , polycaprolactone (PCL), polyethylene adipate (PEA), polyhydroxyalkanoate (PHA) , polyhydroxybutyrate (PHB) , polyethylene
- the solvent is a reactant, the reactant being capable of reacting with the polymer being degraded, and preferably forming a mono- or di- ester with the monomer, such as an alkanol and alkanediol, preferably methanediol, ethanediol, and propanediol, water, and amino comprising reactants.
- a reactant being capable of reacting with the polymer being degraded, and preferably forming a mono- or di- ester with the monomer, such as an alkanol and alkanediol, preferably methanediol, ethanediol, and propanediol, water, and amino comprising reactants.
- a product obtained can e.g. in case of degradation of PET be directly used as feed-stock for PET production.
- the degrading is performed during a period of 0.1 minutes-168 hours, preferably 1 minutes-48 hours, more preferably 5 minutes-24 hours, even more preferably 15 minutes-12 hours, such as 1 hours-3 hours.
- the shorter periods possible are considered relative short, especially as compared to prior art processes.
- reactor size and boundary conditions longer or shorter periods may be used.
- a high pressure (500-3000 kPa) process at a temperature of 150 °C-350 °C leads to very short degrading times, in the order of minutes. Such indicates that the present method, and catalyst complex used therein, provide a large amount of design freedom.
- the degrading is performed at a temperature of 50 °C-500 °C, preferably 90 °C- 350 °C, more preferably 150 °C-250 °C, even more preferably 170 °C-200 °C, such as 180 °C-190 °C.
- the preferred range is considered to relate to a relative mild temperature, especial- ly as compared to prior art processes which are performed at temperatures above 300 °C. Even further, as the temperature applied is relatively mild, waste energy of an adjacent plant may be used for the present process. It is noted that the present catalyst complex has been found to be stable (enough) un- der the conditions mentioned, such as the above temperature.
- the present complex does not volatilize under the present conditions .
- the amount of catalyst is 0.1-35 wt.%, preferably 0.5-20 wt.%, more prefera- bly 1-10 wt.%, even more preferably 2-5 wt.%, relative to a total weight of polymer provided. If the amount of catalyst is higher a shorter reaction time was obtained, whereas at a lower amount longer reaction times were obtained. Depending on further boundary conditions one may vary the amount of cata- lyst.
- the amount of catalyst relates to the catalyst entity and bridging moiety, i.e. without nanoparticle .
- the pressure is from 90 kPa-10.000 kPa, preferably 100 kPa-8.000 kPa, more preferably 200 kPa-2.000 kPa.
- Mild pressures in an example are an advantage over some prior art processes,, which need to be performed at relatively high pressures, of e.g. 1000 kPa, often in combination with a high temperature.
- a range of [T, P] from [180°C, 60 kPa] to [450°C, 8.200kPa] may be chosen, preferably from [250°C, 420 kPa] to [400°C, 4.960kPa], such as from [280°C, 790 kPa] to [350°C, 2.560kPa].
- the degradation time is found to be from 1.5 hours @[180°C, 60 kPa] to about 20 seconds @[450°C, 8.250kPa].
- the degradation is best carried out at a temperature below 350°C and below a pressure of 6.000 kPa, depending on the solvent.
- the polymer is provided as small particles, such as pellets, particles, and granules, having a volume of less than 100 cm 3 , preferably 1*10 ⁇ 6 mm 3 -64 cm 3 , more preferably 0.001 mm 3 -27 cm 3 , even more preferably 0.01 mm 3 -8 cm 3 , such as 0.03 mm 3 -1 cm 3 .
- Such may require an extra process step of reducing a size of polymer provided, e.g. shredding PET-bottles and grinding. It may be somewhat costly to pelletize or granulize polymer; in view thereof somewhat larger pellets or granules are preferred. In view of e.g.
- pellets or granules are preferred. However, in view of environmental and health issued pellets or granules are preferably not too small. A size of 0.03 mm 3 -1 cm 3 has been found to be optimal, especially for PET. It is noted that also polymer bottles as such may be provided, possibly shredded to some extent.
- the present method further comprises the step of recovering the catalyst attached to the magnetic particle using an electro-magnetic field gradient, preferably in a magnetic field of 0.1-5 T, preferably from 0.3-2 T, more preferably from 0.5 - 1.5 T, such as 0.8-1.3 T, e.g. 1 T.
- an electro-magnetic field gradient preferably in a magnetic field of 0.1-5 T, preferably from 0.3-2 T, more preferably from 0.5 - 1.5 T, such as 0.8-1.3 T, e.g. 1 T.
- a relatively small magnetic field is found to be sufficient to recover the present catalyst complex.
- reactor design such is advantageous.
- water is provided, in order to separate the present complex from the present solvent. It has been found that it is much easier to remove the present complex from a water phase, than from the present solvent phase.
- the catalyst (complex) may be recovered.
- the present method further comprises the step of recycling the catalyst complex.
- the present complex can be recycled to the present degradation process, or removed and e.g. stored for later use.
- the present method further comprises the step of removing additives from the solvent, the additives being added to the polymer when these where produced.
- the additives may for instance be removed after adding water and applying a magnetic field; in that case additives are effectively separated from a phase wherein further the present catalyst, oligomers, trimefs and dimers may be present.
- Such is advantages as in principle these additives are at this stage not reused, whereas the degradation products are reused, possibly formed into novel polymer.
- the present method further comprises the step of retrieving trimers, dimers, and/or monomers, preferably free of additives and contaminants, such as by chemical and/or physical separation, in one step, or in a combination of steps.
- a first step of retrieving e.g. water may be added. Monomers and solvent may dissolve in water, whereas catalyst complex, additives, oligomers, trimers and dimers, especially under influence of an external magnetic field, will form a separate phase.
- the catalyst complex, additives, oligomers, trimers and dimers may be reintroduced in a first reaction step, wherein the polymer is degraded.
- the monomers can be retrieved by providing e.g. water, and then "crystallizing". As such the degradation products are ready to be reused, in fact without a further need to e.g. purify these products.
- the polymer is polyethylene terephthalate (PET) or PEF
- the solvent is ethanediol
- the catalyst comprises butylmethylimidazolium (bmim + ) and FeCl 4 ⁇
- the bridging moiety is triethoxysilylpro- pyl
- the nanoparticle is magnetite and/or maghemite.
- the nanoparticles preferably have a size of 5-10 nm.
- the bridging moiety preferably is present in an amount of 10 ⁇ 4 -10 ⁇ 2 mole bridging moiety/gr nanoparticle, such as 2*10 ⁇ 4 -10 -3 . Such is especially a preferred embodiment in view of the abundant amount of waste PET being available, being in excess of hun- dreds of thousand tons per year.
- the present method further comprises the step of adjusting an amount of partly negative charged molecules, such as by adding a salt, preferably a Fe 3+ comprising salt, such as an halogenide, such as by adding FeCl 3 .
- a salt preferably a Fe 3+ comprising salt, such as an halogenide, such as by adding FeCl 3 .
- the yield of the present method and the functioning of the catalyst complex can be maintained at a high level by adjusting an amount of the partly negatively charged molecules used.
- Such is step is relatively simple to carry out, and costs thereof are considered minimal.
- the present method further comprises the step of providing oligomers to the solvent, preferably oligomers produced by the method.
- the oligomers may be degraded further, into dimers and monomers, in a subsequent step.
- the subsequent step may be carried out in the same place as an initial step, e.g. in the same reactor.
- Fig. la-c shows chemical reactions and catalyst complexes.
- Fig. 2 shows selectivity percentages of BHET .
- Fig. la shows chemical reactions. Therein poly (ethylene ter- ephthalate) is degraded by using (bmim) FeCl in 1,2- ethanediol. As a result Terephtalic Acid Bis (2-Hydroxyethyl) ester (BHET) is formed. Further, it is shown that BHET can be converted into dimers and oligomers .
- Fig. lb shows a schematic representation of the present catalyst complex.
- A represents a nanoparticle
- B a bridging moiety
- C a catalyst entity with CI being a positive catalyst moiety and C2 being a negative catalyst moiety.
- Fig. lc shows a nanoparticle A surrounded by a number of bridging moieties and catalyst entities.
- Fig. 2 shows selectivity percentages of BHET (vertical axis), obtained from depolymerization of colored PET, as function of reaction time and amount of di-alcohol (1,2- ethanediol) (horizontal axes) .
- the PET provided was cut into pieces of about 2x2 cm 2 . In another example pieces of about 0.3x0.3 cm 2 , and in a further example as small particles having an average diameter of 50 ⁇ . The size of the pieces was found to be not particularly relevant for the outcome.
- a reaction temperature was about 197 °C. Results were obtained by varying a reaction time and amount of di-alcohol.
- the corresponding PET conversion rates obtained are close to 100% (typically 99-99.99%, as no PET-pieces could be observed anymore in the solvent) , which are considered to be very high.
- the selectivity rates (>90%, in a best case scenario so far >93%) are considered to be very high as well.
- the yield is as a result also > 90%, and up to 93%. Even further the rates are obtained in a relatively short time frame.
- the selectivities are obtained with 2 wt . % catalyst (including bridging moiety and catalyst) relative to a total amount of polymer, respectively. So a small amount of catalyst is already sufficient.
- PET raw
- PET polyester clothing, PET carpet, PET material from automotive industry, recycled PET, multi-layered PET trays containing other polymers, such as PE and PP.
- the results thereof are in the same order of magnitude for both conversion and selectivity, and thus for yield.
- the process is highly insensitive to different raw (PET) material and robust as well.
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Abstract
The present invention is in the field of a method of degrading a polymer into oligomers and/or monomers in a solvent, using a catalyst, and a functionalized magnetic particle comprising a catalyst being capable of degrading the polymer into oligomers and/or monomers. The present method and particle provide a high selectivity and a high conversion ratio.
Description
Title Polymer degradation
FIELD OF THE INVENTION
The present invention is in the field of a method of degrading a polymer into oligomers and/or monomers in a solvent, using a catalyst, and a functionalized magnetic particle comprising a catalyst being capable of degrading the polymer into oligomers and/or monomers. The present method and particle provide a high selectivity and a high conversion ratio.
BACKGROUND OF THE INVENTION
Various patent documents and scientific documents recite fluids comprising magnetic particles.
Magnetic Fluids are a class of smart materials that change their properties reversibly and relatively fast (milli- seconds) under presence of an external magnetic field. These fluids can show changes in apparent viscosity of several orders of magnitude when a magnetic field is applied, such as a magnetic flux density in the order of around 1 T. Below two sub-classes are identified.
A ferrofluid relates to a liquid which becomes strongly magnetized in the presence of a magnetic field. Typically ferrofluids are colloidal liquids made of nanoscale ferromagnetic, or ferrimagnetic, particles suspended in a carrier fluid (usually an organic solvent or water) . Typically each tiny particle is thoroughly coated with a surfactant to inhibit clumping. A disadvantage is that larger particles can be removed from an otherwise homogeneous colloidal mixture, forming a separate clump of magnetic dust e.g. when exposed to strong magnetic fields.
With respect to degradation of used polymers (or plastics) it is noted that in general this is hindered by lack of separation methods (e.g. separation of a first polymer from a second polymer, such as polyethylene (PE) and polypropylene (PP) ) . As a consequence a significant amount of used polymers is used as a fuel, which is burned.
It is noted that chemical recycling of polymers such as Polyethylene terephthalate (PET) is considered cost- efficient only applying relatively high capacity recycling lines of e.g. more than 50 ktons/year. Most likely such lines will only be combined with production sites of very large pol-
ymer producers. Several attempts of industrial magnitude to establish such chemical recycling plants have been made in the past but without resounding success. Even the promising chemical recycling in e.g. Japan has not become an industrial break through so far; there seem to be two main reasons therefore: first, a difficulty of consistent and continuous waste bottles sourcing in a required huge amount at one single site, and, at second, the steadily increased prices and price volatility of collected bottles. So despite huge amounts of PET produced on a yearly basis (> 50.000 ktons) forming similar amounts of waste no economically feasible process has been introduced.
A, further issue is that if a separation is (partly) successful, degradation into smaller building units still is difficult. Many methods or processes are not selective enough, that is a discrimination, shown by a reagent in competitive attack on two or more substrates or on two or more positions in the same substrate, is relatively low. It is typically quantitatively expressed by ratios of rate constants of the competing reactions, or by the decadic logarithms of such ratios. Further a conversion is too low; efficient conversion of reactants (polymers) to desired products (monomers or oligomers) without much wastage production in terms of side products is an issue. As a consequence a yield, being regarded as a product of selectivity times conversion, is too low as well.
A problem with a use of catalysts, especially catalysts in a solvent, is that it is virtually impossible to recover the catalyst after a first usage. As catalysts are typically quite expensive, one would like to recover a catalyst, at least largely, and reuse the catalyst a second time and preferably many more times. A small waste of catalyst would be acceptable, if a waste is in the order of a few percent or less. In this respect Wang (in Wang et al, "Fe-containing magnetic ionic liquid as an effective catalyst for glycolysis of poly (ethylene terephthalate) ", Cat. Comm. 11 (2010), pp. 763- 767, and in Eur. Pol. J., Pergamon Press Oxford, vol. 45, no. 5, 1 may 2009, pp. 1535-1544), and Xueyuan Zhou et al . (in Pure and Applied Chemistry, Vol. 84, No. 3, 1 January 2012, pp. 789-801) mention degradation of PET using a catalyst, without reusing the catalyst and with moderate results. The amount of catalyst used in these processes is relatively high
(17-80 wt% . catalyst per weight PET) and results are far from optimal .
Further it is in general considered a disadvantage to combine a catalyst to a support. Amongst others selectivity and conversion, as well as available catalyst are jeopardized. As such compared to non-combined catalyst typically more catalyst needs to be used in order to obtain similar results, and even then selectivity and conversion still worse. In this respect Valkenberg et al . in "Immobilisation of ionic liquids on solid supports", Green Chemistry, 2002 (4), pp. 88-93, shows ionic liquids attached to solid supports, e.g. a metal oxide, such as Ti02, S1O2, A1203, etc. Lee in "Functionalized imidazo- lium salts for task-specific ionic liquids and their applications", Chem. Commun., 2006, pp. 1049-1063 mentions similar catalysts. Such relate to a two-phase system. The results of the catalytic activity tested are considered rather poor, apart from some exceptions, especially in terms of conversion and selectivity. In other words the catalysts would not be considered to be used.
In general most catalysts are used for synthesis of molecules and the like, not for degradation. Typically catalysts, and especially catalyst complexes, and function of a catalyst are sensitive to contaminants being present; in other words they function only properly under relative pure and clean conditions. As a result of contamination catalysts need to be replaced regularly, and extreme care is typically taken not to introduce contaminants. That may also a reason why catalyst are typically not considered for degradation processes, as these processes almost inherently introduce contaminants.
In some instances metal catalysts are directly attached to a nanoparticle . Such catalysts are typically used for synthesis, but not for degradation, and certainly not for a reaction with at least one solid reactant. In this respect it is noted that for synthesis a reaction between two or more components is executed, wherein the two or more components are in close contact, such as in a solvent. The nature and relevant parameters of a synthesis reaction is considered to be quite different from degradation reactions; for instance relative low amounts of catalyst may be used and relatively high yield may be obtainable under optimal conditions. One can
therefore not expect the teachings of synthesis reactions to be applicable to degradation reactions. Various articles, such as Zhang in Applied Catalysis A: General, Elsevier Science, Vol. 366, Nr. 1, pp. 141-147, Pang Wang in Catalysis Letters, Kluwer Academic Publishers-Plenum Publishers, NE, Vol. 135,
Nr. -12, pp. 159-164, Raed Abu-Reziq in J. Am. Chem. Soc, ACS publications, Vol. 128, Nr. 15, pp.5279-5282, Zhang in J. Mol . Cat. A: Chemical, Elsevier, Vol. 306, Nr. 1-2, pp.107-112, 0 Dalaigh in Angewandte Chemie, Vol. 119, pp. 4407-4410,
Oliveira in J. Phys . Chem. C, Vol. 113, Nr. 20, pp. 8566-8572 and Zhang in Green Chem., Vol. 14, pp.201-208, relate to recoverable catalysts complex. However comparative data between catalyst per se and catalyst complex are absent. In other words, no improvement is shown and in fact a deterioration in respect of e.g. yield, amount used, efficiency, energy consumption, etc. is to be expected. Further some of the above catalyst complexes are not recovered magnetically, some relate to core-shell particles, some relate to conglomerates, Flavia does not show a complex, and some do not relate to an ionic liquid. Such is considered far from optimal.
The present invention provides a method and catalyst for degrading polymers which overcomes one or more of the above disadvantages, without jeopardizing functionality and advantages .
SUMMARY OF THE INVENTION
The present invention relates in a first aspect to an improved reusable ionic catalyst complex for degradation of a homo or copolymer according to claim 1, and in a second aspect to a method according to claim 6, showing partly ma- jor improvements over the prior art, e.g. in terms of selectivity (93% versus 59.2%), conversion, yield, a very low amount of catalyst used per amount of product degraded/obtained (0.5-2 wt . % versus 17-80 wt . % [weight catalyst/weight polymer]), use of energy (1 hour versus 4 hours; so also much quicker), insensitivity to contaminants, insensitivity to composition of raw material to be degraded, etc. Put in numbers the present invention provides a conversion of about 100%, a selectivity of significantly more than 90% (versus some 59.2% prior art), reuse of catalyst (over 50 times, being absent in prior art deg-
radation processes), allowing any mixture of waste polymers (not known in the prior art, typically well cleaned, well separated, having one type/source of material, is needed for prior art processes) , a relatively modest temperature and pressure may be used (200 °C versus e.g. 500 °C) , etc. It is noted that the present catalyst complex shows an improved localized action. It is also noted that typically improvement in one aspect (parameter) involves a deterioration in another aspect (parameter) ; the present range of improvements in various aspects together is already in that sense surprising.
The present catalyst complex comprises three distinguishable elements: a nanoparticle, a bridging moiety attached, such as by a covalent bond, to the nanoparticle and a catalyst entity (chemically) attached to the bridging moiety. The bridging moiety is solely in between the catalyst and the nanoparticle, respectively. The present complex is for instance different from a complex having a bridging moiety fully covering a nanoparticle, such as in a core-shell particle.
The present nanoparticle is of a magnetic nature. As such nanoparticles comprising a magnetic material are included, as well as particles that can be magnetized sufficiently under relative modest magnetic fields, such as being applied in the present method. It has been found that the nanoparticle should be sufficiently small for the catalyst complex to function as a catalyst, therewith degrading the present polymer into smaller units, wherein the yield of these smaller units, and specifically the monomers thereof, is high enough for commercial reasons. It is noted in this respect that a value of polymers to be degraded is relatively small, i.e. a costs of degrading should be small as well. It has also been found that the nanoparticle should be sufficiently large in order to be able to reuse the present complex by recovering the present catalyst complex. It is economically unfavorable to have catalyst complex being removed with either waste or degradation product obtained .
It is noted that the present nanoparticle is not considered to be a support. A prior art support in general
relates to much larger entities, typically in the order of mm or larger. It is noted that for the present process a catalyst on a support is considered unsuited, in particular as a yield of degradation products is too low (or likewise time and/or temperature to obtain such a yield are unfavorable) .
The present catalyst entity comprises at least two moieties. Such has been found to contribute to at least some of the present advantages. A first relates to an aro- matic moiety having a positive charge. A second relates to a moiety, typically a salt complex, having a negative charge. The negative and positive charge typically balance one and another. It has been found that the positively and negatively charged moieties have a synergistic and enhanc- ing effect on the degradation process of the polymer in terms of conversion and selectivity, especially in view of degrading polyesters and polyethers .
The aromatic moiety preferably comprises a hetero- cycle, having at least one, preferably at least two nitro- gen atoms. The aromatic moiety preferably stabilizes a positive charge. The heterocycle may have 5 or 6 atoms, preferably 5 atoms.
The negatively charged moiety may relate to a salt complex, preferably a metal salt complex having a two- or three-plus charged metal ion, such as Fe3+, Al3+, Ca2+, and Cu2+, and negatively charged counter-ions, such as halogen- ides, e.g. Cl~, F~, Br", wherein one
The present catalyst entity and nanoparticle are combined by a bridging moiety. The person skilled in the art would expect that binding a catalyst entity, such as one according to the invention, onto a support would jeopardize the functioning of the catalyst entity, at least to some extent. Surprisingly, the present bridging molecule in combination with the nanoparticle provides a catalyst com- plex which functions almost as good as or better than the catalyst entity itself. It is noted that it is somewhat complicated to combine (or coat) the present nanoparticle with a bridging moiety, at least in terms of functionality obtained. It is not only important to provide suitable bridging moieties (or a combination thereof) , but also to
fit a number of bridging moieties with respect to a surface area of the present magnetic nanoparticle . In this respect also a size (diameter) of the present nanoparticle is important. For purpose of providing a catalyst complex suita- ble of degrading the present polymer the above needs to be taken into account; otherwise no effective degradation is obtained, e.g. in terms of conversion, selectivity, and economical feasibility. It is noted that up to now no economically viable process for polymer degradation has been provided.
In order to provide a suitable complex, having e.g. sufficient yield, selectivity, and conversion, it has been found that a proper functionalized magnetic particle is important. Inventors have established to produce a catalyst complex according to these requirements.
In an example of the present catalyst complex the magnetic particles have an average diameter of 2 nm - 500 nm, preferably from 3 nm -100 nm, more preferably from 4 nm -50 nm, such as from 5-10 nm. As indicated above, the particles are preferably not too large and not too small. It has been found that e.g. in terms of yield and recovery of catalyst complex a rather small size of particles of 5-10 nm is optimal. It is noted that the term "size" relates to an average diameter of particles, wherein an actual diameter of a parti- cle may vary somewhat due to characteristics thereof.
In an example of the present catalyst complex the bridging moiety is provided in an amount of (mole bridging moiety/gr magnetic particle) 5*10~6-0.1, preferably 1*10~5- 0.01, more preferably 2*10~ -10~3, such as 4*10~5-10~4. It is preferred to have a relatively large amount available in terms of e.g. yield, energy consumption, etc., whereas in terms of amount of catalyst and costs thereof a somewhat smaller amount is available, especially as the magnetic nanoparticles are considered as a relatively cheap part of the catalyst complex. Surprisingly the present method can be performed with very low amounts of catalyst (complex), compared to prior art methods.
For the present method the solid polymer is provided in a suitable solvent. As such the present method may be considered as a solid-liquid degradation process sup- ported by addition of a recoverable catalyst complex. For a
glycolysis the solvent is preferably a mono- or di-alcohol. As such the solvent also functions as a reactant. Inventors have found that in view of recovery of the present catalyst complex not all solvents are suited. Some solvents form a 5 stable "dispersion" with the catalyst complex; in such a case in the step of recovery a second solvent, e.g. functioning as washing agent, may be provided and the catalyst may then be recovered using an electromagnetic field.
The method may be carried out batch-wise, continuity ous, semi-continuous, and combinations thereof.
The present method has a less selective feedstock, as from virgin polymer (such as PET) to various other recovered sources may be provided. Also it provides a relatively low energy process. As a consequence polymer pro-
15 duced from the present degradation products is considered to be 'Green' produced, such as in a case of PET up to 25%.
The present method can be considered to relate to a one-phase system for degradation, comprising a solvent, a polymer to be degraded, and a catalyst complex. Such a system may 0 also be referred to as a dispersion in that particles (polymer and catalyst complex) are present in a solvent. It is noted that in general it is difficult to obtain a (time) stable one- phase system. In this respect the present method distinguishes itself from a reaction with a catalyst on a support, which ef- 5 fectively relates to a two-phase system, not being suitable for polymer degradation.
The temperature and pressure of the method may be adjusted. Typically a somewhat higher temperature is preferred in terms of reaction velocity; a lower temperature 0 is preferred in terms of energy consumption. Likewise a
higher pressure is somewhat preferred; in view of complexity of an installation a lower pressure is preferred, that is a pressure being about 100 kPa . It is an advantage of the present method that a relatively low temperature may be 5 used, without jeopardizing yield. It is also an advantage that using relatively mild temperature and pressure conditions the present degradation can be carried out in a relative short time. Such provides e.g. a relative high throughput, a relatively smaller installation, and lower consumption of materi- 0 als and energy.
It is a further advantage of the present method that the method is relatively insensitive (e.g. in terms of yield) for mixed polymers being provided. Mixed polymers can relate to a combination of two or more different types of polymers, such as different polyesters, such as PET, polyethylene furanoate (PEF) , and polybutylene terephthalate (PBT), to a combination of one type of polymer having different properties, such as color, thickness, origin, and combinations thereof. Also the method is relatively insensitive to contami- nants, like additives, such as pigments, fillers, filters, etc. As such the present method is considered robust, to be used under relatively sub-optimal conditions, such as in a plant .
Compared to prior art method a characteristic of the present method is that the catalyst complex is recovered. It is preferred to use the present catalyst complex in the present method.
Thereby the present invention provides a solution to one or more of the above mentioned problems. The various exam- pies and embodiments of the present invention may be combined.
Advantages of the present description are detailed throughout the description.
DETAILED DESCRIPTION OF THE INVENTION
The present invention relates in a first aspect to a catalyst complex according to claim 1.
In an example of the present catalyst complex the magnetic particles are one or more of ferromagnetic particles, anti-ferromagnetic particles, ferrimagnetic particles, synthetic magnetic particles, paramagnetic particles, superpara- magnetic particles, such as particles comprising one or more of Fe, Co, Ni, Gd, Dy, Mn, Nd, Sm, and preferably one or more of 0, B, C, N, such as iron oxide, such as ferrite, such as magnetite, hematite, and maghemite. In view of degradation yield magnetite and maghemite are preferred magnetic parti- cles . In view of costs, even when fully or largely recovering the present catalyst complex, relatively cheap particles are preferred, such as particles comprising Fe . It is noted that it is not possible to just choose a magnetic metal and/or counter-ion at random; present inventors have found that some sophisticated tailoring is required.
In an example of the present catalyst complex the bridging moiety is one or more of a weak organic acid, si- lanol, silyl comprising groups, such as silylethers, such as triethoxysilylpropyl, and silanol. It has been found that de- spite negative expectations these bridging groups do not result in a non-acceptable reduced performance of the catalyst entity .
In an example of the present catalyst complex the ar¬ omatic moiety has at least one tail, the at least one tail preferably having a length of Ci-C6, such as C2-C4, the at least one tail being attached to the at least one nitrogen atom. It has been found that for an optimal degradation a somewhat higher yield is obtained when the present tail is somewhat longer. In terms of mass of catalyst complex provided it has been found that a somewhat shorter tail is preferred.
In an example of the present catalyst complex the magnetic nanoparticle comprises (per particle) at least one bridging moiety and catalyst entity, preferably 2-104 bridging moieties and catalyst entities, more preferably 10-103 bridg- ing moieties and catalyst entities. In principle, e.g. in view of yield, as many catalyst entities as possible may be provided. However the amount of catalyst entities and there functioning is in view of e.g. degradation efficiency somewhat smaller than an amount that could be achieved. Also when a larger particle is selected somewhat more catalyst entities may be present.
In an example of the present catalyst complex the amount of bridging moiety and catalyst attached thereto is 0.03-99 wt.%, preferably 0.1-75 wt.%, more preferably 0.2-25 wt.%, even more preferably 0.3-10 wt.%, relative to a total weight of catalyst complex. Likewise as above, a relative low amount of 0.5-5 wt.% of catalyst entity has been found to be optimal, such as 0.6-3 wt.%, within further boundary conditions such as applied temperature. It is noted that the pre- sent catalyst and bridging moiety may form a single (mono-) layer, a double (bi-) layer, a oligolayer, and combinations thereof. Before applying the present catalyst complex in the present method it may be washed. The above weight percentages are relative to a total weight of catalyst complex.
In a second aspect the present invention relates to a
method according to claim 6. Therein a polymer is provided in solid form. Preferably the polymer is fragmented into smaller pieces .
In an example of the present method the polymer is a mixture of waste polymers, the mixture optionally comprising one or more of coloured polymers. The present method is capable of handling waste polymers, and even further a mixture of polymers, e.g. having different characteristics, such as a different colour. The yield of degradation has been found not to be influenced noticeably. It is noted that prior art methods at the most can only handle relatively pure waste polymer, and even then results are discouraging.
In an example of the present method the constituents such as solvent, catalyst complex and polymer, form a one- phase system. Such has been found advantageous, especially in terms of yield obtained. Also in terms of reactor design such is advantageous.
In an example of the present method the polymer may selected from natural polymers, biobased polymers, biodegrada- ble polymers, polymers formed (directly or indirectly) from fossil fuels, and combinations thereof. In an example the polymer is one or more of a polyester, a polyether, such as poly- oxymehtylene (POM), polyethyleneglycol (PEG), polypropyl- eneglycol (PPG) , polytetramethyleneglycol
(PTMG) , polyethyleneoxide (POE) , polypropyleneoxide (PPO) , pol- ytetrahydrofuran (PTHF) , and polytetramethyleneetherglycol (PTMEG) , a polyalkene, a polyalkane, a polypeptide, a polyam- ide, a polyamine, a polycondensate , preferably a polyester, such as poly carboxylic ester, wherein the poly carboxylic es- ter is preferably selected from polyethylene terephthalate (PET), polyethylene furanoate (PEF), polybutylene terephthalate (PBT) , polytrimethylene terephthalate (PTT) , polygly- colic acid (PGA) , polylactic acid (PLA) , polycaprolactone (PCL), polyethylene adipate (PEA), polyhydroxyalkanoate (PHA) , polyhydroxybutyrate (PHB) , polyethylene naphthalate (PEN) , Poly (3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) , and a polycondensate of 4-hydroxybenzoic acid and 6- hydroxynaphthalene-2-carboxylic acid (VECTRAN) . In other words a large variety of polymers may be degraded by the present method. Some adjustments may be necessary, e.g. in terms of
catalyst used, temperature applied, solvent used, etc. The present method is best suited for degradation of polyesters and polyethers .
In an example of the present method the solvent is a reactant, the reactant being capable of reacting with the polymer being degraded, and preferably forming a mono- or di- ester with the monomer, such as an alkanol and alkanediol, preferably methanediol, ethanediol, and propanediol, water, and amino comprising reactants. In terms of e.g. reactor de- sign and complexity of reaction such is an advantage. Further, a product obtained can e.g. in case of degradation of PET be directly used as feed-stock for PET production.
In an example of the present method wherein the degrading is performed during a period of 0.1 minutes-168 hours, preferably 1 minutes-48 hours, more preferably 5 minutes-24 hours, even more preferably 15 minutes-12 hours, such as 1 hours-3 hours. The shorter periods possible are considered relative short, especially as compared to prior art processes. Depending on e.g. reactor size and boundary conditions longer or shorter periods may be used. For instance, a high pressure (500-3000 kPa) process at a temperature of 150 °C-350 °C leads to very short degrading times, in the order of minutes. Such indicates that the present method, and catalyst complex used therein, provide a large amount of design freedom.
In an example of the present method the degrading is performed at a temperature of 50 °C-500 °C, preferably 90 °C- 350 °C, more preferably 150 °C-250 °C, even more preferably 170 °C-200 °C, such as 180 °C-190 °C. The preferred range is considered to relate to a relative mild temperature, especial- ly as compared to prior art processes which are performed at temperatures above 300 °C. Even further, as the temperature applied is relatively mild, waste energy of an adjacent plant may be used for the present process. It is noted that the present catalyst complex has been found to be stable (enough) un- der the conditions mentioned, such as the above temperature.
The present complex does not volatilize under the present conditions .
In an example of the present method the amount of catalyst is 0.1-35 wt.%, preferably 0.5-20 wt.%, more prefera- bly 1-10 wt.%, even more preferably 2-5 wt.%, relative to a
total weight of polymer provided. If the amount of catalyst is higher a shorter reaction time was obtained, whereas at a lower amount longer reaction times were obtained. Depending on further boundary conditions one may vary the amount of cata- lyst. Here the amount of catalyst relates to the catalyst entity and bridging moiety, i.e. without nanoparticle .
In an example of the present method the pressure is from 90 kPa-10.000 kPa, preferably 100 kPa-8.000 kPa, more preferably 200 kPa-2.000 kPa. Mild pressures in an example are an advantage over some prior art processes,, which need to be performed at relatively high pressures, of e.g. 1000 kPa, often in combination with a high temperature.
In a selection of a combination of temperature and pressure a range of [T, P] from [180°C, 60 kPa] to [450°C, 8.200kPa] may be chosen, preferably from [250°C, 420 kPa] to [400°C, 4.960kPa], such as from [280°C, 790 kPa] to [350°C, 2.560kPa]. For the combinations the degradation time is found to be from 1.5 hours @[180°C, 60 kPa] to about 20 seconds @[450°C, 8.250kPa]. For safety reasons the degradation is best carried out at a temperature below 350°C and below a pressure of 6.000 kPa, depending on the solvent.
In an example of the present method the polymer is provided as small particles, such as pellets, particles, and granules, having a volume of less than 100 cm3, preferably 1*10~6 mm3 -64 cm3, more preferably 0.001 mm3 -27 cm3, even more preferably 0.01 mm3 -8 cm3, such as 0.03 mm3 -1 cm3. Such may require an extra process step of reducing a size of polymer provided, e.g. shredding PET-bottles and grinding. It may be somewhat costly to pelletize or granulize polymer; in view thereof somewhat larger pellets or granules are preferred. In view of e.g. yield and size of a plant smaller pellets or granules are preferred. However, in view of environmental and health issued pellets or granules are preferably not too small. A size of 0.03 mm3 -1 cm3 has been found to be optimal, especially for PET. It is noted that also polymer bottles as such may be provided, possibly shredded to some extent.
In an example of the present method further comprises the step of recovering the catalyst attached to the magnetic particle using an electro-magnetic field gradient, preferably in a magnetic field of 0.1-5 T, preferably from 0.3-2 T, more
preferably from 0.5 - 1.5 T, such as 0.8-1.3 T, e.g. 1 T. As such a relatively small magnetic field is found to be sufficient to recover the present catalyst complex. In view of e.g. reactor design such is advantageous. In an example water is provided, in order to separate the present complex from the present solvent. It has been found that it is much easier to remove the present complex from a water phase, than from the present solvent phase. By providing a suited catalyst complex, such as the present complex, the catalyst (complex) may be recovered. It has been found that typically 95% of the catalyst complex can be recovered, and often even 98-99%. As a consequence the present catalyst complex can be reused 20-100 times, thereby e.g. saving costs. It has been found that a recovered catalyst complex functions equally well compared to a fresh (non-used) complex.
In an example of the present method further comprises the step of recycling the catalyst complex. After recovery the present complex can be recycled to the present degradation process, or removed and e.g. stored for later use.
In an example of the present method further comprises the step of removing additives from the solvent, the additives being added to the polymer when these where produced. The additives may for instance be removed after adding water and applying a magnetic field; in that case additives are effectively separated from a phase wherein further the present catalyst, oligomers, trimefs and dimers may be present. Such is advantages as in principle these additives are at this stage not reused, whereas the degradation products are reused, possibly formed into novel polymer.
In an example of the present method further comprises the step of retrieving trimers, dimers, and/or monomers, preferably free of additives and contaminants, such as by chemical and/or physical separation, in one step, or in a combination of steps. In a first step of retrieving e.g. water may be added. Monomers and solvent may dissolve in water, whereas catalyst complex, additives, oligomers, trimers and dimers, especially under influence of an external magnetic field, will form a separate phase. The catalyst complex, additives, oligomers, trimers and dimers may be reintroduced in a first reaction step, wherein the polymer is degraded. In a second step
of retrieving the monomers can be retrieved by providing e.g. water, and then "crystallizing". As such the degradation products are ready to be reused, in fact without a further need to e.g. purify these products.
In an example of the present method the polymer is polyethylene terephthalate (PET) or PEF, the solvent is ethanediol, the catalyst comprises butylmethylimidazolium (bmim+) and FeCl4 ~, the bridging moiety is triethoxysilylpro- pyl, and the nanoparticle is magnetite and/or maghemite. The nanoparticles preferably have a size of 5-10 nm. The bridging moiety preferably is present in an amount of 10~4-10~2 mole bridging moiety/gr nanoparticle, such as 2*10~4-10-3. Such is especially a preferred embodiment in view of the abundant amount of waste PET being available, being in excess of hun- dreds of thousand tons per year.
In an example of the present method further comprises the step of adjusting an amount of partly negative charged molecules, such as by adding a salt, preferably a Fe3+ comprising salt, such as an halogenide, such as by adding FeCl3. Surprisingly the yield of the present method and the functioning of the catalyst complex can be maintained at a high level by adjusting an amount of the partly negatively charged molecules used. Such is step is relatively simple to carry out, and costs thereof are considered minimal.
In an example of the present method further comprises the step of providing oligomers to the solvent, preferably oligomers produced by the method. As such the oligomers may be degraded further, into dimers and monomers, in a subsequent step. The subsequent step may be carried out in the same place as an initial step, e.g. in the same reactor.
The invention is further detailed by the accompanying figures and examples, which are exemplary and explanatory of nature and are not limiting the scope of the invention. To the person skilled in the art it may be clear that many variants, being obvious or not, may be conceivable falling within the scope of protection, defined by the present claims.
SUMMARY OF FIGURES
Fig. la-c shows chemical reactions and catalyst complexes.
Fig. 2 shows selectivity percentages of BHET .
DETAILED DESCRIPTION OF FIGURES
Fig. la shows chemical reactions. Therein poly (ethylene ter- ephthalate) is degraded by using (bmim) FeCl in 1,2- ethanediol. As a result Terephtalic Acid Bis (2-Hydroxyethyl) ester (BHET) is formed. Further, it is shown that BHET can be converted into dimers and oligomers .
Fig. lb shows a schematic representation of the present catalyst complex. Therein A represents a nanoparticle , B a bridging moiety, and C a catalyst entity with CI being a positive catalyst moiety and C2 being a negative catalyst moiety.
Fig. lc shows a nanoparticle A surrounded by a number of bridging moieties and catalyst entities.
Fig. 2 shows selectivity percentages of BHET (vertical axis), obtained from depolymerization of colored PET, as function of reaction time and amount of di-alcohol (1,2- ethanediol) (horizontal axes) . The PET provided was cut into pieces of about 2x2 cm2. In another example pieces of about 0.3x0.3 cm2, and in a further example as small particles having an average diameter of 50 μπι. The size of the pieces was found to be not particularly relevant for the outcome. A reaction temperature was about 197 °C. Results were obtained by varying a reaction time and amount of di-alcohol. For all degradation reactions performed, the corresponding PET conversion rates obtained are close to 100% (typically 99-99.99%, as no PET-pieces could be observed anymore in the solvent) , which are considered to be very high. The selectivity rates (>90%, in a best case scenario so far >93%) are considered to be very high as well. The yield is as a result also > 90%, and up to 93%. Even further the rates are obtained in a relatively short time frame. The selectivities are obtained with 2 wt . % catalyst (including bridging moiety and catalyst) relative to a total amount of polymer, respectively. So a small amount of catalyst is already sufficient.
So despite negative expectations that use of a cata- lyst complex would reduce selectivity, conversion and yield, the present method (and catalyst complex used therein) provides much better results e.g. in these respects than prior art methods (using a catalyst per se) . Losses are already reduced from about 20-40% (prior art) to less than 7%.
EXAMPLES
Similar tests as above haven been performed on non- colored PET. The results thereof are in the same order of magnitude for both conversion and selectivity. As a consequence inventors conclude that a color additive has hardly any or no impact in this respect. Even further, additives, such as pigments, can be removed from the degradation products, with ease .
Similar tests as above have been performed on a wide range of raw (PET) material, e.g. polyester clothing, PET carpet, PET material from automotive industry, recycled PET, multi-layered PET trays containing other polymers, such as PE and PP. The results thereof are in the same order of magnitude for both conversion and selectivity, and thus for yield. As a consequence inventors conclude that the process is highly insensitive to different raw (PET) material and robust as well.
Similar tests were performed on amorphous (AMP) pellets and solid state polymerization (SSP) pellets. Again PET conversion and BHET selectivity were high. Values obtained for SSP pellets were somewhat lower, relatively. It is considered that possibly due to a somewhat longer chain length of the polymer to be degraded selectivity and conversion are somewhat j eopardized .
The invention although described in detailed explanatory context may be best understood in conjunction with the accompanying examples and figures.
It should be appreciated that for commercial application it may be preferable to use one or more variations of the present system, which would similar be to the ones disclosed in the present application and are within the spirit of the invention .
Claims
1. An improved reusable ionic catalyst complex for degradation of a homo or copolymer comprising a catalyst entity, a magnetic nanoparticle, and a bridging moiety solely between the catalyst entity and the magnetic nanoparticle, the catalyst complex being capable of degrading a polymer into oligomers, trimers, dimers and/or monomers,
wherein the catalyst entity is selected from both partly positive and partly negative charged moieties,
wherein the positive charge is on an aromatic moiety, and wherein the negative charge is on a salt,
wherein the magnetic particles have an average diameter of 2 nm - 500 nm, and
wherein the bridging moiety is present in an amount of 5*10~6- 0.1 Mole bridging moiety/gr magnetic particle.
2. Catalyst complex according to claim 1,
wherein the magnetic particles are one or more of ferromagnetic particles, anti-ferromagnetic particles, ferromagnetic particles, synthetic magnetic particles, paramagnetic particles, superparamagnetic particles, such as particles com- prising one or more of Fe, Co, Ni, Gd, Dy, Mn, Nd, Sm, and preferably one or more of 0, B, C, N, such as iron oxide.
3. Catalyst complex according to any of claims 1-2, wherein the bridging moiety is one or more of a weak organic acid, silanol, silyl comprising groups, such as si- lylethers, such as triethoxysilylpropyl , and silanol.
4. Catalyst complex according to any of claims 1-3, wherein the aromatic moiety has at least one tail, the at least one tail preferably having a length of C1-C6, such as 02- C4, the at least one tail being attached to the at least one nitrogen atom.
5. Catalyst complex according to any of claims 1-4, wherein the magnetic nanoparticle comprises at least one bridging moiety and catalyst entity, preferably 2-104 bridging moieties and catalyst entities, more preferably 10-103 bridg- ing moieties and catalyst entities, and/or
wherein the amount of bridging moiety and catalyst attached thereto is 0.03-99 wt.%, preferably 0.1-75 wt.%, more prefera-
bly 0.2-25 wt.%, relative to a total weight of catalyst complex .
6. Catalyst complex according to any of claims 1-5, wherein the aromatic moiety is an aromatic heterocycle with at least one nitrogen atom, more preferably at least two nitrogen atoms, such as an imidazole, preferably butylmethylimidazolium (bmim+) ,
wherein the salt is an Fe3+ comprising salt complex, such as an halogenide, such as FeCl4 ~,
wherein the magnetic particles are one or more of ferrite, magnetite, hematite, and maghemite,
wherein the magnetic particles have an average diameter from 3 nm -100 nm, more preferably from 4 nm -50 nm, such as from 5- 10 nm.
7. Method of degrading a homo or copolymer into oligomers, trimers, dimers and/or monomers, comprising the steps of
providing the polymer in a suitable solvent, the polymer being in solid form, preferably in fragmented form,
adjusting temperature and pressure to reaction conditions,
providing a catalyst complex being capable of degrading the polymer into oligomers and/or monomers,
the polymer, solvent and catalyst complex forming one phase, and
degrading the polymer over a period sufficient to degrade a significant portion thereof,
characterized in the step of
recovering the catalyst complex, such as the catalyst complex according to any of claims 1-6.
8. Method according to claim 7,
wherein the polymer is a mixture of waste polymers, the mixture optionally comprising one or more of coloured polymers.
9. Method according to claim 7 or 8, wherein the pol- ymer is one or more of a polyester, a polyether, such as poly- oxymehtylene (POM) , polyethyleneglycol (PEG) , polypropyl- eneglycol (PPG) , polytetramethyleneglycol (PTMG) , polyeth- yleneoxide (POE) , polypropyleneoxide (PPO), polytetrahydrofu- ran (PTHF) , and polytetramethyleneetherglycol (PTMEG) , a poly- alkene, a polyalkane, a polypeptide, a polyamide, a polyamine,
a polycondensate , preferably a polyester, such as poly carboxylic ester, wherein the poly carboxylic ester is preferably selected from polyethylene terephthalate (PET), polyethylene furanoate (PEF) , polybutylene terephthalate (PBT) , polytri- methylene terephthalate (PTT), polyglycolic acid (PGA), pol- ylactic acid (PLA) , polycaprolactone (PCL) , polyethylene adipate (PEA) , polyhydroxyalkanoate (PHA) , polyhydroxybutyrate (PHB) , polyethylene naphthalate (PEN), Poly ( 3-hydroxybutyrate- co-3-hydroxyvalerate) (PHBV), and a polycondensate of 4- hydroxybenzoic acid and 6-hydroxynaphthalene-2-carboxylic acid (VECTRAN) .
10. Method according to any of claims 7-9, wherein the solvent is a reactant, the reactant being capable of reacting with the polymer being degraded, and preferably forming a mono- or di-ester with the monomer, such as an alkanol and alkanediol, preferably methanediol, ethanediol, and propanediol, water, and amino comprising reactants.
11. Method according to any of claims 7-10, wherein the degrading is performed during a period of 0.1 minutes-168 hours, preferably 1 minutes-48 hours, more preferably 5 minutes-24 hours, even more preferably 15 minutes-12 hours, such as 1 hours-3 hours, and/or
wherein the degrading is performed at a temperature of 50 °C-500 °C, and/or
wherein the amount of catalyst is 0.1-35 wt.%, preferably 0.5-20 wt.%, more preferably 1-10 wt.%, relative to a total weight of polymer provided, and/or
wherein the pressure is from 90 kPa-10.000 kPa, preferably 100 kPa-8.000 kPa, more preferably 200 kPa-2.000 kPa .
12. Method according to any of claims 7-11, wherein the polymer is provided as bottles, particles, pellets or granules, having a volume of less than 100 cm3, preferably 1*10~6 mm3 -64 cm3, more preferably 0.001 mm3 -27 cm3, even more preferably 0.01 mm3 -8 cm3, such as 0.03 mm3 -1 cm3.
13. Method according to any of claims 7-12, further comprising the step of
recovering the catalyst attached to the magnetic particle using an electro-magnetic field gradient, preferably in an magnetic field of 0.1-5 T, such as 0.3-2 T, and
recycling the catalyst complex, and
removing additives from the solvent, and retrieving trimers, dimers, and/or monomers, preferably free of additives and contaminants.
14. Method according to any of claims 7-13, wherein the polymer is polyethylene terephthalate (PET) or polyethylene furanoate (PEF) , the solvent is ethanediol, the catalyst comprises butylmethylimidazolium (bmim+) and FeCl4 ~, the bridging moiety is triethoxysilylpropyl, the amount of catalyst is 2-5 wt.%, the degrading is performed at a temperature of 90 °C-250 °C, preferably 120 °C-250 °C, more preferably 150 °C- 200 °C, such as 170 °C-185 °C, and the nanoparticle is one or more of magnetite, hematite, and maghemite.
15. Method according to claim 14, further comprising the step of adjusting an amount of partly negative charged molecules, such as by adding a salt, preferably an Fe3+ comprising salt, such as an halogenide, such as by adding FeCl3, and of providing oligomers to the solvent, preferably oligomers produced by the method.
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US20190185406A1 (en) | 2019-06-20 |
NL2011025C2 (en) | 2014-12-29 |
US20160107981A1 (en) | 2016-04-21 |
EP2838656B1 (en) | 2021-05-26 |
CN105555401B (en) | 2018-04-27 |
US10703703B2 (en) | 2020-07-07 |
EP2838656A1 (en) | 2015-02-25 |
US10266479B2 (en) | 2019-04-23 |
CN105555401A (en) | 2016-05-04 |
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