CN115055175B - Preparation method of defect-state zinc oxide nano-sheet catalyst for alcoholysis of PET - Google Patents
Preparation method of defect-state zinc oxide nano-sheet catalyst for alcoholysis of PET Download PDFInfo
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 140
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 70
- 239000003054 catalyst Substances 0.000 title claims abstract description 55
- 239000002135 nanosheet Substances 0.000 title claims abstract description 51
- 238000006136 alcoholysis reaction Methods 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 65
- 239000002699 waste material Substances 0.000 claims abstract description 27
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims abstract description 18
- 238000003756 stirring Methods 0.000 claims abstract description 17
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000243 solution Substances 0.000 claims abstract description 15
- 230000007547 defect Effects 0.000 claims abstract description 14
- 239000012046 mixed solvent Substances 0.000 claims abstract description 14
- 239000002243 precursor Substances 0.000 claims abstract description 12
- 239000011592 zinc chloride Substances 0.000 claims abstract description 9
- 235000005074 zinc chloride Nutrition 0.000 claims abstract description 9
- 239000004094 surface-active agent Substances 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 7
- 239000007864 aqueous solution Substances 0.000 claims abstract description 6
- 238000001291 vacuum drying Methods 0.000 claims abstract description 6
- 238000001354 calcination Methods 0.000 claims abstract description 5
- 239000007787 solid Substances 0.000 claims abstract description 4
- 239000007788 liquid Substances 0.000 claims abstract description 3
- 238000000926 separation method Methods 0.000 claims abstract description 3
- 239000000725 suspension Substances 0.000 claims abstract description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical group OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 82
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000007789 gas Substances 0.000 claims description 9
- 239000002064 nanoplatelet Substances 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical group [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 71
- 239000005020 polyethylene terephthalate Substances 0.000 description 71
- 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 24
- 230000002950 deficient Effects 0.000 description 12
- 230000000694 effects Effects 0.000 description 12
- 239000003570 air Substances 0.000 description 11
- 239000000706 filtrate Substances 0.000 description 11
- 230000003197 catalytic effect Effects 0.000 description 10
- 239000000047 product Substances 0.000 description 9
- 238000011084 recovery Methods 0.000 description 9
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 8
- 230000015556 catabolic process Effects 0.000 description 6
- 238000006731 degradation reaction Methods 0.000 description 6
- 238000004128 high performance liquid chromatography Methods 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 238000002425 crystallisation Methods 0.000 description 5
- 230000008025 crystallization Effects 0.000 description 5
- 238000003760 magnetic stirring Methods 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 238000005086 pumping Methods 0.000 description 5
- 229910021642 ultra pure water Inorganic materials 0.000 description 5
- 239000012498 ultrapure water Substances 0.000 description 5
- LLLVZDVNHNWSDS-UHFFFAOYSA-N 4-methylidene-3,5-dioxabicyclo[5.2.2]undeca-1(9),7,10-triene-2,6-dione Chemical compound C1(C2=CC=C(C(=O)OC(=C)O1)C=C2)=O LLLVZDVNHNWSDS-UHFFFAOYSA-N 0.000 description 3
- 239000007857 degradation product Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 235000013361 beverage Nutrition 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000012495 reaction gas Substances 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- -1 Polyethylene terephthalate Polymers 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical group [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000034659 glycolysis Effects 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000002055 nanoplate Substances 0.000 description 1
- 239000002073 nanorod Substances 0.000 description 1
- 238000007344 nucleophilic reaction Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
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- 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
- B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
-
- 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
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- 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
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G9/00—Compounds of zinc
- C01G9/02—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/28—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group
- C07C67/29—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group by introduction of oxygen-containing functional groups
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/01—Crystal-structural characteristics depicted by a TEM-image
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- 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
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- Chemical & Material Sciences (AREA)
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- Engineering & Computer Science (AREA)
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- Chemical Kinetics & Catalysis (AREA)
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- Catalysts (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
Abstract
The invention discloses a preparation method of a defect-state zinc oxide nano-sheet catalyst for alcoholysis of PET, which comprises the following steps: (1) Adding zinc chloride and a surfactant into a first mixed solvent, and stirring for reaction to obtain a mixed reaction solution containing Zn-CTAB; (2) Adding an aqueous solution of ethanolamine and a second mixed solvent into the mixed reaction solution containing Zn-CTAB obtained in the step (1), stirring for reaction to obtain a white suspension, carrying out solid-liquid separation to obtain a solid part, and carrying out vacuum drying to obtain a defect-state ZnO nano-sheet precursor; (3) Calcining the defect ZnO nano-sheet precursor obtained in the step (2). The defect-state zinc oxide nano-sheet prepared by the method can be used as a catalyst for alcoholysis of waste PET, the product yield is as high as 92.7%, no metal residue exists, the catalyst is easy to recycle, and the catalyst can be recycled and has potential application prospect.
Description
Technical Field
The invention belongs to the fields of macromolecule degradation, green catalysis technology and plastics, and relates to a preparation method of a defect-state zinc oxide nano-sheet catalyst for alcoholysis of PET.
Background
Polyethylene terephthalate (PET) is the polyester plastic with the greatest worldwide production, and is mainly applied to the fields of beverage, food packaging, fiber spinning and the like. Recycling of PET is attracting more and more attention because it slowly degrades in natural environments to penetrate into the soil or flow into the ocean, severely threatening the ecological environment. At present, three main PET recovery modes are available: physical recovery, biological recovery, and chemical recovery. The degradation product of the glycolysis waste PET, namely ethylene terephthalate (BHET), can be used for repolymerization into high molecular weight PET, and is a green, simple and sustainable recovery method. The waste PET ethylene glycol alcoholysis catalyst commonly used in industry is zinc acetate, but has the problems of difficult catalyst recovery, low selectivity and metal residue in degradation products, so the development of recyclable, low-cost and high-activity heterogeneous catalysts is attracting more and more attention.
Zinc oxide is used as a catalyst for the alcoholysis recovery of waste PET, which is easy to recover and low in cost, and the yield of BHET is only 67% under the conditions that the reaction temperature is 260 ℃, the reaction time is more than 80min and the reaction pressure is 5 atm. The defect zinc oxide has been widely studied in the catalytic fields of carbon dioxide reduction, methane conversion, water decomposition and the like, and the catalytic activity of the defect zinc oxide is obviously higher than that of defect-free zinc oxide because the defect zinc oxide is favorable for nucleophilic reaction.
Disclosure of Invention
The invention aims to: aiming at the defects of the prior art, the invention provides a preparation method of a defect-state zinc oxide nano-sheet catalyst for alcoholysis of PET, which can improve the selectivity and yield of a waste PET alcoholysis product BHET and realize easy recovery and recycling of the catalyst.
In order to solve the technical problems, the invention discloses a preparation method of a defect-state zinc oxide nano-sheet catalyst for alcoholysis of PET, which comprises the following steps:
(1) Adding zinc chloride and a surfactant into a first mixed solvent, and stirring for reaction to obtain a mixed reaction solution containing Zn-CTAB;
(2) Adding an aqueous solution of ethanolamine and a second mixed solvent into the mixed reaction solution containing Zn-CTAB obtained in the step (1), stirring for reaction to obtain a white suspension, carrying out solid-liquid separation to obtain a solid part, and carrying out vacuum drying to obtain a defect-state ZnO nano-sheet precursor;
(3) Calcining the defect ZnO nano-sheet precursor obtained in the step (2).
Specifically, in the step (1), the surfactant is cetyl trimethyl ammonium bromide; the mol ratio of the zinc chloride to the surfactant is 3-5: 1, a step of; the first mixed solvent comprises ethanol and water, wherein the volume ratio of the ethanol to the water is 4-8: 1, the first mixed solvent is used for dissolving zinc chloride and the surfactant.
Specifically, in the step (1), the stirring reaction is carried out for 10-60 min at 25-70 ℃.
Specifically, in the step (2), the concentration of the ethanolamine aqueous solution is 99wt%; the mol ratio of the ethanolamine aqueous solution to the zinc chloride is 4-20: 1, a step of; the second mixed solvent comprises ethanol and water, wherein the volume ratio of the ethanol to the water is 2-8: 1, the dosage of the second mixed solvent ensures that the solid of the reaction system is completely dissolved.
Specifically, in the step (2), stirring and reacting for 1-4 hours at 25-70 ℃; and the vacuum drying is carried out at the drying temperature of 70 ℃ for 12-24 hours.
Specifically, in the step (3), the defective ZnO nano-sheet precursor is calcined under the gas atmosphere, and is heated from room temperature to 200-500 ℃, preferably 350 ℃ at a rate of 2 ℃/min, and then is kept for 90-180 min.
Specifically, in the step (3), the gas atmosphere is any one of oxygen, nitrogen and air, and is preferably air.
The defect-state zinc oxide nano-sheet catalyst of the alcoholysis PET prepared by the preparation method is also within the protection scope of the invention.
The application of the defect-state zinc oxide nano-sheet catalyst for alcoholysis of PET in waste PET alcoholysis is also within the protection scope of the invention.
The specific application method is that PET and a defect zinc oxide nano-sheet catalyst are dissolved in an organic solvent under the atmosphere of gas, heating is carried out, preferably, after the reaction is finished, water is added into a reaction system, suction filtration is carried out, ethylene terephthalate (BHET) is left in filtrate, analysis is carried out on the ethylene terephthalate (BHET) by High Performance Liquid Chromatography (HPLC), and the yield is measured.
Preferably, the gas atmosphere is any one of oxygen, nitrogen and air, and is preferably air; the PET source is a beverage bottle collected by a garbage field; the mass of the defect-state zinc oxide nano-sheet catalyst accounts for 0.1-10.0 percent of the mass of PET, preferably 1.0-5.0 percent; the organic solvent is ethylene glycol; the mass ratio of the organic solvent to PET is 1:1 to 8; the heating reaction is carried out at a temperature of 140-190 ℃, preferably 160-190 ℃ for 15-180 min, preferably 60-180 min.
The reaction equation of the present invention is as follows:
wherein the conversion rate of PET and the yield of BHET are calculated according to formulas (1) and (2), respectively:
the beneficial effects are that:
the invention has the characteristics of easy recovery of catalyst, low cost, recycling, high PET conversion rate, high target product selectivity, green and pollution-free reaction process, mild reaction condition, no need of decoloring of degradation products and the like, and has low requirements on raw materials, and the alcoholysis products are easy to separate and purify.
Drawings
FIG. 1 is a transmission electron microscope image of a defect state zinc oxide nanoplate catalyst.
Fig. 2 is a schematic flow chart of the catalytic alcoholysis of waste PET glycol by a defect zinc oxide nano-sheet catalyst in an air atmosphere: (a) discarding the snowplow bottle, (b) before the alcoholysis reaction, (c) after the alcoholysis reaction, (d) alcoholysis product BHET;
Detailed Description
The present invention is described with reference to the following examples, but the present invention is not limited to the following examples, and modifications are included in the technical scope of the present invention without departing from the spirit and scope of the present invention.
Example 1 Synthesis method of defective Zinc oxide nanosheet catalyst
Firstly, adding 50mL of ethanol/water mixed solvent (v/v=4/1) into a 100mL beaker, adding 2.720g of zinc chloride and 2.420g of cetyltrimethylammonium bromide into the mixed solution, and stirring and reacting for 10min at 25 ℃ to obtain a mixed reaction solution containing Zn-CTAB; then, 5mL of an aqueous ethanolamine solution (99 wt%) and 5mL of an ethanol/water mixed solvent (v/v=2/1) were added to the mixed reaction solution, and the reaction was continued with stirring at 25 ℃ for 1 hour; after the reaction is finished, the mixture is centrifuged for three times by using water and ethanol, and the collected precipitate is transferred into a vacuum drying oven at 70 ℃ to be dried for 12 hours, so that the defect ZnO nanosheet precursor is obtained. Uniformly spreading the defect-state ZnO nano-sheet precursor in a magnetic boat, transferring the precursor into a tube furnace, heating the precursor to 350 ℃ at a heating rate of 2 ℃/min in the presence of air in the calcining atmosphere, and preserving the heat for 90min to finally obtain the defect-state ZnO nano-sheet catalyst, as shown in figure 1.
Example 2 Effect of different reactive gas atmospheres on the catalytic degradation of waste PET ethylene glycol by defective Zinc oxide nanoplatelet catalysts
Examples 2a to 2c
Under different reaction gas atmospheres, waste PET, a defect-state ZnO nano-sheet catalyst (accounting for 1.0 percent of the mass of the PET, prepared in the example 1) and ethylene glycol (the mass ratio of the ethylene glycol to the PET is 1:4) are put into a single-neck flask, and the temperature is raised to 180 ℃ for magnetic stirring reaction for 60min. After the reaction is finished, 400mL of ultrapure water is added for vigorous stirring, so that the crystallization of the monomer is prevented; collecting the insoluble PET and the oligomer and filtrate which are filtered by pumping, and taking a proper amount of solution for standby after the volume of the filtrate is fixed to 1L; after the reaction was completed, the product BHET was analyzed by HPLC, and the yield of the obtained BHET and the conversion rate of PET were calculated. The BHET yield and PET conversion data of the waste PET glycol alcoholysis catalyzed by the defective zinc oxide nano-sheet catalyst under different reaction gas atmospheres are shown in table 1, and the flow chart of the waste PET glycol alcoholysis catalyzed by the defective zinc oxide nano-sheet catalyst under the air atmosphere is shown in fig. 2.
TABLE 1 Effect of different reactive gas atmospheres on the catalytic degradation of waste PET ethylene glycol by defective Zinc oxide nanoplatelet catalysts
| Examples | Catalyst | Reaction atmosphere | PET conversion/% | BHET yield/% | |
| 2a | ZnO nano-sheet | Air- |
100 | 92.6 | |
| 2b | ZnO nano- | Oxygen gas | 100 | 92.4 | |
| 2c | ZnO nano-sheet | Nitrogen gas | 28.3 | 8.7 |
Example 3. Effect of different sizes of Zinc oxide catalysts on the catalytic alcoholysis of waste PET ethylene glycol
Examples 3a to 3e
Under the air atmosphere, waste PET and ethylene glycol (the mass ratio of the ethylene glycol to the PET is 1:4) and ZnO catalyst nanorods (50 nm, 90nm, 200nm and 2 μm, which are commercially purchased and account for 1.0% of the PET mass) or defect-state ZnO nano-sheet catalyst (prepared in example 1) with different sizes are sequentially added into a 25mL single-neck flask, and the temperature is raised to 180 ℃ for magnetic stirring reaction for 60min. After the reaction is finished, 400mL of ultrapure water is added for vigorous stirring, so that the crystallization of the monomer is prevented; collecting the insoluble PET and the oligomer and filtrate which are filtered by pumping, and taking a proper amount of solution for standby after the volume of the filtrate is fixed to 1L; after the reaction was completed, the product BHET was analyzed by HPLC, and the yield of the obtained BHET and the conversion rate of PET were calculated. The effect of different sizes of zinc oxide catalysts on the catalysis of PET glycol alcoholysis is shown in Table 2 with the numbers 3a-3e.
TABLE 2 Effect of different size Zinc oxide catalysts on catalyzing the alcoholysis of waste PET ethylene glycol
Continuous table 2
Example 4 Effect of the amount of defective Zinc oxide nanoplatelet catalyst on the alcoholysis of waste PET ethylene glycol
Examples 4a to 4e
Under the air atmosphere, the waste PET, glycol (the mass ratio of glycol to PET is 1:4) and the defect-state ZnO nano-sheet catalyst (prepared in example 1) with different catalyst amounts are sequentially added into a 25mL single-neck flask, and the temperature is raised to 180 ℃ for magnetic stirring reaction for 60min. After the reaction is finished, 400mL of ultrapure water is added for vigorous stirring, so that the crystallization of the monomer is prevented; collecting the insoluble PET and the oligomer and filtrate which are filtered by pumping, and taking a proper amount of solution for standby after the volume of the filtrate is fixed to 1L; after the reaction was completed, the product BHET was analyzed by HPLC, and the yield of the obtained BHET and the conversion rate of PET were calculated. The effect of different amounts of the defect zinc oxide nano-sheet catalyst on catalyzing the alcoholysis of PET ethylene glycol is shown in the sequence numbers 4a-4e in Table 3.
TABLE 3 Effect of the amount of defective Zinc oxide nanoplatelet catalyst on the alcoholysis of waste PET ethylene glycol
| Examples | Catalyst (%) | PET conversion/% | BHET yield/% |
| 4a | 0.1 | 85.4 | 72.8 |
| 4b | 0.2 | 95.2 | 79.7 |
| 4c | 1 | 100 | 92.6 |
| 4d | 2 | 100 | 92.7 |
| 4e | 5 | 100 | 91.2 |
Example 5 Effect of different reaction temperatures on the catalytic degradation of waste PET ethylene glycol by defective Zinc oxide nanoplatelet catalysts
Examples 5a to 5d
Under the air atmosphere, waste PET, a defect-state ZnO nano-sheet catalyst (accounting for 1.0 percent of the mass of the PET and prepared in the example 1) and ethylene glycol (the mass ratio of the ethylene glycol to the PET is 1:4) are put into a single-neck flask, and the mixture is heated to different temperatures for magnetic stirring reaction for 60 minutes. After the reaction is finished, 400mL of ultrapure water is added for vigorous stirring, so that the crystallization of the monomer is prevented; collecting the insoluble PET and the oligomer and filtrate which are filtered by pumping, and taking a proper amount of solution for standby after the volume of the filtrate is fixed to 1L; after the reaction was completed, the product BHET was analyzed by HPLC, and the yield of the obtained BHET and the conversion rate of PET were calculated. BHET yield and PET conversion data of the defect zinc oxide nano-sheet catalyst for catalyzing the alcoholysis of waste PET glycol at different reaction temperatures are shown in the sequence numbers 5a-5d in Table 4.
TABLE 4 Effect of different reaction temperatures on the catalytic degradation of waste PET ethylene glycol by defective Zinc oxide nanoplatelet catalysts
| Examples | Catalyst | Reaction temperature/. Degree.C | PET conversion/% | BHET yield/% |
| 5a | ZnO nano-sheet | 160 | 70.2 | 50.8 |
| 5b | ZnO nano-sheet | 170 | 85.2 | 66.2 |
| 5c | ZnO nano-sheet | 180 | 100 | 92.6 |
| 5d | ZnO nano-sheet | 190 | 100 | 92.3 |
Example 6 Effect of different reaction times on the catalytic degradation of waste PET ethylene glycol by defective Zinc oxide nanoplatelet catalysts
Examples 6a to 6e
Under the air atmosphere, waste PET, a defect-state ZnO nano-sheet catalyst (accounting for 1.0 percent of the mass of the PET and prepared in the example 1) and ethylene glycol (the mass ratio of the ethylene glycol to the PET is 1:4) are put into a single-neck flask, and the temperature is raised to 180 ℃ and the magnetic stirring is carried out for different reaction times. After the reaction is finished, 400mL of ultrapure water is added for vigorous stirring, so that the crystallization of the monomer is prevented; collecting the insoluble PET and the oligomer and filtrate which are filtered by pumping, and taking a proper amount of solution for standby after the volume of the filtrate is fixed to 1L; after the reaction was completed, the product BHET was analyzed by HPLC, and the yield of the obtained BHET and the conversion rate of PET were calculated. The BHET yield and PET conversion data of the defect zinc oxide nano-sheet catalyst catalyzed waste PET glycol alcoholysis for different reaction times are shown in table 5 with serial numbers 6a-6e.
TABLE 5 influence of different reaction times on the catalytic alcoholysis of waste PET ethylene glycol by defective Zinc oxide nanoplatelet catalysts
| Examples | Catalyst | Reaction time/min | PET conversion/% | BHET yield/% |
| 6a | ZnO nano-sheet | 15 | 40.6 | 38.1 |
| 6b | ZnO nano-sheet | 30 | 89.3 | 68.9 |
| 6c | ZnO nano-sheet | 60 | 100 | 92.6 |
| 6d | ZnO nano-sheet | 120 | 100 | 91.3 |
| 6e | ZnO nano-sheet | 180 | 100 | 90.8 |
The invention provides a method and a thinking of a preparation method of an alcoholysis PET defect-state zinc oxide nano-sheet catalyst, and a plurality of methods and ways for realizing the technical scheme are provided, the above is only a preferred embodiment of the invention, and it should be pointed out that a plurality of improvements and modifications can be made by a person of ordinary skill in the art without departing from the principle of the invention, and the improvements and modifications are also regarded as the protection scope of the invention. The components not explicitly described in this embodiment can be implemented by using the prior art.
Claims (9)
1. The preparation method of the defect-state zinc oxide nano-sheet catalyst for alcoholysis of PET is characterized by comprising the following steps:
(1) Adding zinc chloride and a surfactant into a first mixed solvent, and stirring for reaction to obtain a mixed reaction solution containing Zn-CTAB;
(2) Adding an aqueous solution of ethanolamine and a second mixed solvent into the mixed reaction solution containing Zn-CTAB obtained in the step (1), stirring for reaction to obtain a white suspension, carrying out solid-liquid separation to obtain a solid part, and carrying out vacuum drying to obtain a defect-state ZnO nano-sheet precursor;
(3) Calcining the defect-state ZnO nano-sheet precursor obtained in the step (2);
the first mixed solvent comprises ethanol and water, wherein the volume ratio of the ethanol to the water is 4-8: 1, a step of;
the second mixed solvent comprises ethanol and water, wherein the volume ratio of the ethanol to the water is 2-8: 1, a step of;
in the step (3), the calcination is carried out, and the defect ZnO nano-sheet precursor is calcined under the atmosphere of gas to obtain the product of the formula 2 o The C/min rate is increased from room temperature to 200-500 o C, then keeping for 90-180 min; wherein the gas atmosphere is any one of oxygen and air.
2. The method of claim 1, wherein in step (1), the surfactant is cetyltrimethylammonium bromide; the molar ratio of the zinc chloride to the surfactant is 3-5: 1.
3. the preparation method according to claim 1, wherein in the step (1), the stirring reaction is performed for 10-60 min at 25-70 ℃.
4. The method according to claim 1, wherein in the step (2), the concentration of the aqueous ethanolamine solution is 99% wt%; the mol ratio of the ethanolamine aqueous solution to the zinc chloride is 4-20: 1.
5. the preparation method of claim 1, wherein in the step (2), the stirring reaction is carried out for 1-4 hours at a reaction temperature of 25-70 ℃; the vacuum drying temperature is 70 o And C, drying for 12-24 hours.
6. The defect-state zinc oxide nano-sheet catalyst of the alcoholysis PET prepared by the preparation method of any one of claims 1-5.
7. The use of the defect-state zinc oxide nano-sheet catalyst for alcoholysis of PET as claimed in claim 6 in the alcoholysis of waste PET.
8. The use according to claim 7, wherein PET and the defect-state zinc oxide nanoplatelet catalyst are dissolved in an organic solvent under a gas atmosphere and heated for reaction.
9. The application of claim 8, wherein the defect-state zinc oxide nano-sheet catalyst accounts for 0.1-10.0% of the PET by mass; the organic solvent is ethylene glycol; the mass ratio of the organic solvent to PET is 1: 1-8; the heating reaction is carried out at the temperature of 140-190 ℃ for 15-180 min.
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