CN116675603A - Method for catalytic recovery of waste polyester material by acetate ionic liquid - Google Patents
Method for catalytic recovery of waste polyester material by acetate ionic liquid Download PDFInfo
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- CN116675603A CN116675603A CN202310665687.XA CN202310665687A CN116675603A CN 116675603 A CN116675603 A CN 116675603A CN 202310665687 A CN202310665687 A CN 202310665687A CN 116675603 A CN116675603 A CN 116675603A
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- ionic liquid
- waste polyester
- acetate ionic
- waste
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- 229920000728 polyester Polymers 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims abstract description 40
- 239000002699 waste material Substances 0.000 title claims abstract description 28
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 title claims abstract description 24
- 239000002608 ionic liquid Substances 0.000 title claims abstract description 24
- 239000000463 material Substances 0.000 title claims abstract description 23
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 13
- 238000011084 recovery Methods 0.000 title claims description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 30
- 230000008569 process Effects 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- -1 alcohol compound Chemical class 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 239000000178 monomer Substances 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical group COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 claims description 4
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 150000001450 anions Chemical class 0.000 claims description 2
- 150000001768 cations Chemical class 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims description 2
- 150000007530 organic bases Chemical class 0.000 claims description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 claims 2
- 125000003342 alkenyl group Chemical group 0.000 claims 2
- 125000003545 alkoxy group Chemical group 0.000 claims 2
- 125000000217 alkyl group Chemical group 0.000 claims 2
- 125000000304 alkynyl group Chemical group 0.000 claims 2
- 125000003118 aryl group Chemical group 0.000 claims 2
- 125000004104 aryloxy group Chemical group 0.000 claims 2
- 125000005843 halogen group Chemical group 0.000 claims 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims 2
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 claims 1
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 claims 1
- 125000003277 amino group Chemical group 0.000 claims 1
- 125000002619 bicyclic group Chemical group 0.000 claims 1
- 239000012295 chemical reaction liquid Substances 0.000 claims 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 claims 1
- 239000005416 organic matter Substances 0.000 claims 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 16
- 238000006136 alcoholysis reaction Methods 0.000 abstract description 13
- 238000004064 recycling Methods 0.000 abstract description 9
- 239000004033 plastic Substances 0.000 abstract description 7
- 229920003023 plastic Polymers 0.000 abstract description 7
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- 230000035484 reaction time Effects 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 27
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 11
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 10
- 239000012153 distilled water Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- QPKOBORKPHRBPS-UHFFFAOYSA-N bis(2-hydroxyethyl) terephthalate Chemical compound OCCOC(=O)C1=CC=C(C(=O)OCCO)C=C1 QPKOBORKPHRBPS-UHFFFAOYSA-N 0.000 description 8
- 238000001816 cooling Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000012074 organic phase Substances 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 239000008346 aqueous phase Substances 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 5
- 238000004821 distillation Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- OEBXWWBYZJNKRK-UHFFFAOYSA-N 1-methyl-2,3,4,6,7,8-hexahydropyrimido[1,2-a]pyrimidine Chemical compound C1CCN=C2N(C)CCCN21 OEBXWWBYZJNKRK-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000002390 rotary evaporation Methods 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 238000005292 vacuum distillation Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 description 2
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 238000003818 flash chromatography Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000000053 physical method Methods 0.000 description 2
- 239000013502 plastic waste Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 229960004063 propylene glycol Drugs 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- RFDSHFWVUOCHRM-UHFFFAOYSA-N 3,4,5,6,7,8,9,10-octahydro-2h-pyrimido[1,2-a]azepin-5-ium;acetate Chemical compound CC(O)=O.C1CCCCN2CCCN=C21 RFDSHFWVUOCHRM-UHFFFAOYSA-N 0.000 description 1
- 229960000549 4-dimethylaminophenol Drugs 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229920004933 Terylene® Polymers 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000005910 alkyl carbonate group Chemical group 0.000 description 1
- 238000005915 ammonolysis reaction Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- UURSXESKOOOTOV-UHFFFAOYSA-N dec-5-ene Chemical compound CCCCC=CCCCC UURSXESKOOOTOV-UHFFFAOYSA-N 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000010793 electronic waste Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000005588 protonation Effects 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/03—Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
-
- 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
- B01J31/0282—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 aliphatic ring, e.g. morpholinium
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/01—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis
- C07C37/055—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis the substituted group being bound to oxygen, e.g. ether group
- C07C37/0555—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis the substituted group being bound to oxygen, e.g. ether group being esterified hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D317/34—Oxygen atoms
- C07D317/36—Alkylene carbonates; Substituted alkylene carbonates
- C07D317/38—Ethylene carbonate
-
- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/49—Esterification or transesterification
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a method for recycling waste polyester materials (PET, PC) by high-efficiency catalytic depolymerization of acetate ionic liquid and application of the method in recycling of polyester waste plastics. Belongs to the technology of high-value conversion of waste resources. The method solves the problems of long alcoholysis reaction time, high required temperature and metal residue caused by the metal catalyst of the existing catalyst for catalyzing polyester materials. The acetate ionic liquid catalyst provided by the invention can realize the efficient depolymerization of waste polyester under mild conditions, the conversion rate can reach 100%, and the purity can reach 99%. The method is simple to operate, low in cost and easy to obtain raw materials, environment-friendly in process, low in dosage, easy to separate and reusable, and is an economic and effective method.
Description
Technical Field
The invention relates to a method for recovering waste polyester materials by acetate ionic liquid catalysis and application of the method in alcoholysis recovery of waste polyester materials.
Background
Over the last 60 years, plastics have accumulated in the natural environment. The amount of plastic emissions is increasing and will continue to increase even in the event that the most aggressive measures are taken in the future to reduce plastic waste. It is estimated that the global emissions of plastic waste to rivers, lakes and oceans is 900 to 2300 tens of thousands of tons per year, and similar emissions into the terrestrial environment are 1300 to 2500 tens of thousands of tons by 2016. In particular, the yield of polyester textiles, electronic waste and the like continues to increase. However, at the end of their life, more than 80% of post consumer are discarded in landfills without recycling due to lack of effective recycling technology. This not only creates serious environmental problems, but also results in a great waste of valuable resources. From the standpoint of protection of resources and sustainable development, how to recycle waste polyester materials is a great challenge. At the same time, it is necessary to establish a scheme for recycling polyester resources.
Besides high cost, the traditional landfill and incineration strategies have great influence on the environment. Its adverse effect on the environment limits the sustainability of the method. At present, recycling of waste plastics mainly includes physical and chemical methods. Physical methods, such as mechanical treatment, result in secondary products, i.e. corresponding products with degraded performance. This degradation in performance is undesirable for reuse of the plastic. Chemical recovery is more advantageous than physical methods. Some chemical looping methods have been reported, such as pyrolysis, hydrolysis, ammonolysis, and alcoholysis. Pyrolysis generally requires high temperature and high pressure, has high energy loss, and the obtained product has complex components and is mostly a compound which cannot be directly applied. For example, hydrolysis may yield bisphenol A (BPA), but with low selectivity. At the same time, the reaction conditions of the process are severe, and important by-products thereof are greenhouse gases (CO 2 ). In contrast, the alcoholysis of waste plastics can result in not only valuable polyester monomers, but also chemicals such as alkyl carbonates, ethylene glycol, and the like. Thus, chemical recovery based on alcoholysis shows the absolute necessity of advanced research.
With regard to the alcoholysis chemical recovery of polyester materials, several organic catalysts have been successfully utilized, particularly organic bases including NaOH, TBD, DBU, DMAP, and the like. Although these catalysts can degrade polyesters with high efficiency, they doThermal stability limits its reuse and widespread use. Even the most desirable TBD requires at least 190 ℃ to ensure high activity recovery of PET. In addition, ionic Liquids (ILs), eutectic solvents (des) have been reported in recent years as promising green catalysts and reaction media, which exhibit enhanced thermal stability, for depolymerization of polyesters to recover the corresponding products. Still has the problems of complicated synthesis, higher cost, difficult separation and recovery, and the like. Heterogeneous catalyst (ZnO-NPs/NBu) 4 Cl nano particles and CeO 2 Nanocrystals, caO (SrO, baO)/SBA-15, caO-CeO 2 SBA 15) overcomes the problem of catalyst separation due to the heterogeneous catalysis advantage, and has obvious potential for industrial application. However, the process has the problems of high reaction temperature, participation of volatile organic solvent (THF) and transition metal, difficulty in separating impurities from plastics and the like, and the subsequent treatment of the product is complicated. Most importantly, the reaction system has the problems of high reaction temperature, long time, large catalyst dosage and the like, and limits the large-scale application of the catalyst. It is therefore highly desirable to provide a catalytic system for the rapid, high volume, green alcoholysis recovery of waste polyester materials under milder, metal-free, solvent-free conditions.
Disclosure of Invention
The invention provides a method for recycling waste polyester materials by acetate ionic liquid catalysis, which aims at the problems of long reaction time, high reaction temperature, high catalyst consumption and metal residues caused by metal catalysts in the prior art.
The technical scheme of the invention is as follows:
the invention provides a method for recycling waste polyester materials by acetate ionic liquid catalysis. Adding polyester, acetate ionic liquid and alcohol compound with certain mass into a reaction kettle, carrying out alcoholysis reaction on the polyester at a certain temperature and under a certain pressure, filtering, rotary steaming, washing with water, crystallizing, and directly obtaining high-purity monomers such as BPA, dimethyl terephthalate and the like.
The acetate ionic liquid is used as a catalyst to catalyze alcoholysis of polyester materials, so that extremely high depolymerization efficiency can be obtained. The acetic acid anion has extremely strong electron-donating effect, can polarize the alcohol hydroxyl to form a high-performance catalytic system, thereby effectively improving carbonyl protonation on polyester molecules and promoting ester bond breakage. Therefore, the catalyst can greatly accelerate the ester bond breaking process, and realizes the rapid alcoholysis of polyester under mild conditions.
Preferably, the method specifically comprises the following steps: crushing, cleaning and impurity removing polyester, drying, sequentially adding alcohol and acetate ionic liquid into polyester, heating to 50-200 ℃ under stirring, after the polyester is completely dissolved and disappeared, and after the solution becomes clear, finishing the reaction, drying the obtained alcoholysis liquid, filtering and cleaning, and crystallizing to obtain high-purity monomer.
Preferably, the catalyst anion is acetic acid anion and the cation is 1, 8-diazabicyclo [5.4.0] undec-7-ene (DBU), 1, 5-triazabicyclo (4.4.0) dec-5-ene (TBD), 7-methyl-1, 5, 7-triazabicyclo [4.4.0] dec-5-ene (MTBD).
Preferably, the PET is derived from terylene and composite materials thereof, clothes, PET bottles and other solvents, and the PC is derived from optical discs, films, computer housings, medical packages and electronic equipment parts.
Preferably, the alcohol small molecules are methanol, ethanol, ethylene glycol, n-propanol, isopropanol, propylene glycol and 1, 2-propylene glycol.
Preferably, the molar ratio of the alcohol compound to the polyester is 1-100:1.
Preferably, the solvent is dimethyl carbonate, dichloromethane, tetrahydrofuran, anisole or no solvent is added.
Preferably, the temperature is 50-200 ℃, and the depolymerization time is 1 min-24 h.
Preferably, the gases are nitrogen and argon, or no gas is added.
Preferably, the mass ratio of the catalyst to the polyester material is 0.0001-0.1:1.
Compared with the prior art, the invention has the following technical effects: compared with the conventional alcoholysis method for recycling polyester, the method is simpler, green and efficient. The acetate ionic liquid which is simple and easy to synthesize is used as the catalyst, the catalyst has low cost and is easy to synthesize, the alcoholysis reaction temperature is low, the depolymerization recovery of polyester can be carried out under the low temperature condition, the reaction time is short, the depolymerization rate is high, the applicability to raw materials is wide, the product purity is high, and the catalyst is easy to refine and purify and has obvious economic benefit.
Drawings
FIG. 1 is a catalyst 1,5, 7-triazido bicyclo (4.4.0) dec-5-enacetate [ TBDH ]][Ac]A kind of electronic device 1 HNMR spectrogram;
FIG. 2 is a schematic diagram of the product BPA 1 HNMR spectrogram;
Detailed Description
The invention is illustrated by specific examples in order to make the objects, technical solutions and advantages of the invention more apparent. It is important to note that the examples are presented to further illustrate the present invention and should not be construed as limiting the scope of the invention.
Example 1
As shown in figures 1 and 2 of the drawings,
the specific operation process of the embodiment is as follows:
to 20mL of an autoclave equipped with a magnetic stirrer and a thermometer, 2g of PC, 0.5mmol of 1,5, 7-triazido bicyclo (4.4.0) dec-5-enacetate ([ TBDH ] [ OAc ]), 6mL of methanol were successively added, and the mixture was stirred at 70℃for 8 hours. After natural cooling to room temperature, the filtrate was evaporated by rotary distillation to remove unreacted methanol and dimethyl carbonate (DMC). Then a pale yellow gum-like liquid was obtained, which was added to an equal volume of ethyl acetate and distilled water, and the layers were separated. The upper organic phase was desolventized to give a white solid, giving bpa1.7436g. The lower aqueous phase was treated by vacuum distillation to remove distilled water and dried under vacuum to recover the catalyst. The PC conversion rate is 100%, and the yield is 97.0%.
Example 2
The specific operation process of the embodiment is as follows:
to 20mL of an autoclave equipped with a magnetic stirrer and a thermometer, 2g of PET, 0.5mmol of 7-methyl-1, 5, 7-triazabicyclo [4.4.0] dec-5-enacetate ([ MTBDH ] [ Ac ]), and 6mL of methanol were successively added, and the mixture was stirred at 170℃for 2 hours. After natural cooling to room temperature, the filtrate was evaporated by rotary distillation to remove unreacted methanol. Then a pale yellow gum-like liquid was obtained, which was dissolved in an equal volume of ethyl acetate and distilled water, transferred to a separatory funnel, vigorously shaken, and mixed in two stages. The upper organic phase was removed from the ethyl acetate by rotary evaporation to give a white solid, 1.9420g of dimethyl terephthalate (DMT). The lower aqueous phase was treated by vacuum distillation to remove distilled water and dried under vacuum to recover the catalyst. The PET conversion rate is 96%, and the yield is 95.5%.
Example 3
The specific operation process of the embodiment is as follows:
to 20mL of an autoclave equipped with a magnetic stirrer and a thermometer, 0.5g of PC, 0.5mmol of 1,5, 7-triazido bicyclo (4.4.0) dec-5-enacetate ([ TBDH ] [ OAc ]), 1mL of methanol, 2mL of Tetrahydrofuran (THF) were successively added, and the mixture was stirred at 70℃for 30 minutes. After natural cooling to room temperature, the filtrate was evaporated by rotary distillation to remove solvent, methanol and dimethyl carbonate (DMC). Then a pale yellow gum-like liquid was obtained, which was dissolved in an equal volume of ethyl acetate and distilled water, transferred to a separatory funnel, vigorously shaken, and mixed in two stages. The upper organic phase was freed from ethyl acetate by rotary evaporation to give a white solid, obtaining 0.4389g of the product BPA. The lower aqueous phase was treated by vacuum distillation to remove distilled water and dried under vacuum to recover the catalyst. The PC conversion rate is 100%, and the yield is 97.6%.
Example 4
The specific operation process of the embodiment is as follows:
to 20mL of an autoclave equipped with a magnetic stirrer and a thermometer, 1g of PET, 0.5mmol of 1, 8-diazabicyclo [5.4.0] undec-7-ene acetate ([ DBUH ] [ OAc ]), and 4mL of ethylene glycol were successively added, and the mixture was stirred at 170℃for 2 hours. After naturally cooling to room temperature, the reaction solution was then diluted with 1L of distilled water, and the product bishydroxyethyl terephthalate (BHET) was precipitated. Filtration, washing and drying gave a white solid, crystalline, which was BHET (0.9865 g, 97.5%). The BHET selectivity was greater than 99% as analyzed by GC-MS.
Example 5
The specific operation process of the embodiment is as follows:
to 20mL of an autoclave equipped with a magnetic stirrer and a thermometer, 0.5g of PC, 0.5mmol of 1, 3-dimethylbenzimidazole acetate and 1mL of glycerol were successively added, and the mixture was stirred at 70℃for 3 hours. After natural cooling to room temperature, the reaction was then cooled to room temperature and then dissolved in diethyl ether and water. First, the organic phase was washed 3 times with water, with MgSO 4 The organic phase was dried. The diethyl ether was then removed by rotary evaporation and washed with excess water to yield crystals of a white solid, BPA (0.3675 g, 81.78%). The combined aqueous phase is evaporated to recover the heterocycle and catalyst. 4- (hydroxymethyl) -1, 3-dioxo-2-one was purified by flash column chromatography using acetone as eluent.
Example 6
The specific operation process of the embodiment is as follows:
into a 20mL autoclave equipped with a magnetic stirrer and a thermometer, 0.5g of PC, 0.5mmol of 1,5, 7-triazido bicyclo (4.4.0) dec-5-enacetate ([ TBDH) were successively added][OAc]) 2mL of ethylene glycol was reacted at 160℃with stirring for 1 hour. After natural cooling to room temperature, the reaction was then cooled to room temperature and then dissolved in diethyl ether and water. First, the organic phase was washed 3 times with water, with MgSO 4 The organic phase was dried. The diethyl ether was then removed by rotary evaporation and washed with excess water to yield crystals of a white solid, BPA (0.4125 g, 91.79%). The combined aqueous phase is evaporated to recover the heterocycle and catalyst. The ethylene carbonate was purified by flash column chromatography using acetone as eluent.
Example 7
The specific operation process of the embodiment is as follows:
to 20mL of an autoclave equipped with a magnetic stirrer and a thermometer, 2g of PET, 0.25mmol of 1,5, 7-triazido bicyclo (4.4.0) dec-5-enacetate ([ TBDH ] [ OAc ]), 0.25mmol of 1, 3-dimethylbenzimidazole acetate, and 6mL of ethylene glycol were successively added, and the mixture was stirred at 160℃for 1 hour. After naturally cooling to room temperature, the reaction solution was then diluted with 1L of distilled water, and the product bishydroxyethyl terephthalate (BHET) was precipitated. After filtration, washing and drying, a white solid was obtained as crystals of BHET (1.9560 g, 96.0%). The BHET selectivity was greater than 99% as analyzed by GC-MS.
Example 8
The specific operation process of the embodiment is as follows:
to a high-pressure reactor 10L equipped with a mechanical stirrer, 1kg of polyester foam (PET), 10 mmoles of 1,5, 7-triazidine bicyclo (4.4.0) dec-5-enacetate ([ TBDH ] [ OAc ]), and 4L of methanol were successively added, and the mixture was stirred at 190℃for 3 hours. Naturally cooling to room temperature, and removing methanol by distillation to obtain the mixed liquid of glycol and DMT. Adding distilled water with equal volume into the mixture, filtering to obtain DMT as white crystal with yield of 98%. The lower aqueous phase was treated by distillation under reduced pressure to remove distilled water and ethylene glycol and dried under vacuum to recover the catalyst.
Example 9
The procedure of this example was the same as in example 2, except that the catalyst was changed to the recovered catalyst, and 5 repeated experiments were conducted. The results of repeated reuse of the catalyst are shown in Table 1.
TABLE 1 repeated use results of [ TBDH ] [ OAc ]
The raw materials and equipment used in the invention are common raw materials and equipment in the field unless specified otherwise; the methods used in the present invention are conventional in the art unless otherwise specified.
The foregoing description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and any simple modification, variation and equivalent transformation of the above embodiment according to the technical substance of the present invention falls within the scope of the technical solution of the present invention.
Claims (9)
1. A method for recovering waste polyester material by acetate ionic liquid catalysis is characterized in that waste polyester is taken as a raw material, acetate ionic liquid is taken as a catalyst, and the waste polyester is alcoholyzed into a monomer capable of being polymerized again at 50-200 ℃.
2. The method for catalytic recovery of waste polyester material by acetate ionic liquid according to claim 1, wherein: adding acetate ionic liquid and alcohol compound into waste polyester, adding solvent, stirring and heating until the waste polyester completely disappears and the solution becomes clear, filtering and cleaning the obtained reaction liquid, crystallizing and drying to obtain high-purity monomer.
3. A process for the catalytic recovery of waste polyester material from acetate ionic liquids as claimed in claim 2 wherein: the structure of the acetate ionic liquid is shown as follows:
anions:
cation:
organic bases of formula (I): the nitrogen-containing polycyclic organic matter is selected from six-membered bicyclic guanidine, diazabicycloalkane and diazabicycloalkene compounds;
(II) imidazole and derivatives thereof:
R 1 ,R 2 ,R 3 ,R 4 is hydrogen atom, halogen atom, hydroxyl, alkyl, alkenyl, alkynyl, alkoxy, aryloxy, aryl, amino, independently of each other.
4. A process for the catalytic recovery of waste polyester material, according to claim 2, wherein the alcohol compound is selected from the group consisting of compounds of the general formula:
r represents a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryloxy group, an aryl group, or an amino group.
5. A process for the catalytic recovery of waste polyester material from acetate ionic liquid according to claim 4, wherein: the molar ratio of the alcohol compound to the polyester is 1-1000:1.
6. The method for catalytic recovery of waste polyester material by acetate ionic liquid according to claim 2, wherein the solvent is anisole, dimethyl carbonate, methylene chloride, chloroform, tetrahydrofuran or 2-methyl-tetrahydrofuran or no solvent is added.
7. The method for catalytic recovery of waste polyester material by acetate ionic liquid according to claim 2, wherein the temperature is heated to 50-200 ℃ and the depolymerization time is 1 min-100 h.
8. The method for catalytic recovery of waste polyester material by acetate ionic liquid according to claim 2, wherein the mass ratio of catalyst to polyester is 0.00001-0.1:1.
9. The method for catalytic recovery of waste polyester material by acetate ionic liquid according to claim 2, wherein the polyester is PET or PC material.
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