CN115286502B - Regenerated PET material and preparation method thereof - Google Patents
Regenerated PET material and preparation method thereof Download PDFInfo
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- CN115286502B CN115286502B CN202210961491.0A CN202210961491A CN115286502B CN 115286502 B CN115286502 B CN 115286502B CN 202210961491 A CN202210961491 A CN 202210961491A CN 115286502 B CN115286502 B CN 115286502B
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- 239000000463 material Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 239000003054 catalyst Substances 0.000 claims abstract description 48
- 229910052751 metal Inorganic materials 0.000 claims abstract description 42
- 239000002184 metal Substances 0.000 claims abstract description 42
- 239000005020 polyethylene terephthalate Substances 0.000 claims abstract description 38
- 239000013335 mesoporous material Substances 0.000 claims abstract description 33
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 31
- QPKOBORKPHRBPS-UHFFFAOYSA-N bis(2-hydroxyethyl) terephthalate Chemical compound OCCOC(=O)C1=CC=C(C(=O)OCCO)C=C1 QPKOBORKPHRBPS-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000005336 cracking Methods 0.000 claims abstract description 9
- 239000007787 solid Substances 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract 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 claims abstract description 4
- 239000008367 deionised water Substances 0.000 claims abstract description 4
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 4
- 238000004519 manufacturing process Methods 0.000 claims abstract description 4
- 230000009471 action Effects 0.000 claims abstract description 3
- 239000007864 aqueous solution Substances 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 23
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 7
- 238000004064 recycling Methods 0.000 claims description 7
- 239000004246 zinc acetate Substances 0.000 claims description 7
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 claims description 6
- 229940071536 silver acetate Drugs 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- YJGJRYWNNHUESM-UHFFFAOYSA-J triacetyloxystannyl acetate Chemical compound [Sn+4].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O YJGJRYWNNHUESM-UHFFFAOYSA-J 0.000 claims description 5
- 230000001172 regenerating effect Effects 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- 238000011069 regeneration method Methods 0.000 abstract description 9
- 229910021645 metal ion Inorganic materials 0.000 abstract description 4
- 230000008929 regeneration Effects 0.000 abstract description 4
- 239000002699 waste material Substances 0.000 abstract description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 36
- 238000006243 chemical reaction Methods 0.000 description 19
- 230000000694 effects Effects 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000007790 solid phase Substances 0.000 description 5
- 229960000314 zinc acetate Drugs 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- -1 polyethylene terephthalate Polymers 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 3
- 238000003776 cleavage reaction Methods 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 229910052581 Si3N4 Inorganic materials 0.000 description 2
- 235000013361 beverage Nutrition 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000007017 scission Effects 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 230000001502 supplementing effect Effects 0.000 description 2
- 206010067484 Adverse reaction Diseases 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- DTQVDTLACAAQTR-UHFFFAOYSA-M Trifluoroacetate Chemical class [O-]C(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-M 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- HRPKYGWRFPOASX-UHFFFAOYSA-N [Zn].[Ag].[Sn] Chemical compound [Zn].[Ag].[Sn] HRPKYGWRFPOASX-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000006838 adverse reaction Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229940057499 anhydrous zinc acetate Drugs 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-M benzenesulfonate Chemical class [O-]S(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-M 0.000 description 1
- 229940077388 benzenesulfonate Drugs 0.000 description 1
- 150000001558 benzoic acid derivatives Chemical class 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 238000007233 catalytic pyrolysis Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- FYIBGDKNYYMMAG-UHFFFAOYSA-N ethane-1,2-diol;terephthalic acid Chemical compound OCCO.OC(=O)C1=CC=C(C(O)=O)C=C1 FYIBGDKNYYMMAG-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000005003 food packaging material Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 239000010814 metallic waste Substances 0.000 description 1
- 238000006140 methanolysis reaction Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- YPJKMVATUPSWOH-UHFFFAOYSA-N nitrooxidanyl Chemical compound [O][N+]([O-])=O YPJKMVATUPSWOH-UHFFFAOYSA-N 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- DJWUNCQRNNEAKC-UHFFFAOYSA-L zinc acetate Chemical compound [Zn+2].CC([O-])=O.CC([O-])=O DJWUNCQRNNEAKC-UHFFFAOYSA-L 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
-
- 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)
- Catalysts (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
Abstract
The application relates to the technical field of PET regeneration, in particular to a regenerated PET material and a preparation method thereof, comprising the following steps: s1, mixing PET, ethylene glycol, mesoporous materials and a metal catalyst, and cracking the PET under the action of the metal catalyst, wherein the cracking temperature is not lower than 180 ℃; wherein the addition amount of the metal catalyst is not less than 0.05% of the mass of PET; s2, separating the separated molten system to remove solid components; s3, adding deionized water into the system, keeping the temperature at not lower than 80 ℃, and separating and removing ethylene terephthalate oligomer; s4, separating the aqueous solution to obtain BHET; wherein, after the solid component obtained in the step S2 is supplemented with the metal catalyst, the production cycle is performed again in the step S1. According to the application, the mesoporous material is used for loading the metal catalyst, so that the metal catalyst can be used for multiple times, the waste of metal ions is reduced, and the yield of BHET is improved.
Description
Technical Field
The application relates to the technical field of PET regeneration, in particular to a regenerated PET material and a preparation method thereof.
Background
PET, polyethylene terephthalate, is a widely used plastic material in the fields of food packaging materials, textiles, construction and the like, and is also a main material causing plastic pollution at present. Since degradation of PET material is difficult, its recycling and reuse have become an important research topic in the current society.
At present, the methods for regenerating PET mainly comprise a physical regeneration method and a chemical regeneration method, wherein the physical regeneration method is to pack food made of PET materials, such as a plastic bottle, and then prepare PET short fibers again after crushing. Because the granules need to be chopped and melted in the physical treatment process, on one hand, the whole PET material can be more crushed, and meanwhile, in the melting process, the PET aging is inevitably caused, and adverse reactions such as molecular fracture, side chain oxidation and the like occur. Therefore, the prepared regenerated PET has poor general properties and can only be used for preparing filling or low-strength materials.
The chemical method is a reaction method for obtaining monomers by re-cleavage of ester bonds in PET through chemical reaction. The existing methods developed at present include hydrolysis, methanolysis, ethylene glycol, etc., and the intermediate products prepared by the method are terephthalic acid or alcohol ester thereof, which can be used for preparing terephthalic acid by re-catalysis.
In the chemical regeneration method, the ethylene glycol terephthalate (BHET) obtained after the regeneration of ethylene glycol can be directly polymerized under the catalysis to prepare the PET, so that the method has excellent application prospect in industry. In the prior art, acetate (mainly zinc acetate) or titanate of metal is required for glycol degradation of PET as a catalyst, and cracking is difficult to occur in a catalyst-free state, a large amount of heavy metal waste liquid can be generated in the state, and meanwhile, more oligomer residues are also generated, so that the yield of BHET and popularization of a preparation process are influenced.
Disclosure of Invention
The invention relates to a regenerated PET material and a preparation method thereof, which have the advantages of reducing the content of metal ions in wastes, improving the environmental protection effect, simultaneously having better catalytic effect,
The PET regeneration method mainly comprises the following steps:
S1, mixing PET, glycol, mesoporous material and a metal catalyst, and cracking the PET under the action of the metal catalyst, wherein the cracking temperature is not lower than 180 ℃, and is preferably 180-200 ℃; wherein the addition amount of the metal catalyst is not less than 0.05% of the mass of PET, and is preferably 0.1-0.12% of the mass of PET;
S2, separating the separated molten system to remove solid components;
S3, adding deionized water into the system, keeping the temperature at not lower than 80 ℃, and separating and removing ethylene terephthalate oligomer;
S4, separating the aqueous solution to obtain BHET;
after the solid component obtained in step S2 is supplemented with the metal catalyst, the production cycle is performed again in step S1. Preferably, the mass of the metal catalyst to be replenished each time is 15 to 30% of the mass of the initial metal catalyst.
Preferably, the mass of the mesoporous material is 1-200 times that of the metal catalyst, and the whole regeneration process is carried out in an oxygen-free environment.
Optionally, the mesoporous material is mesoporous alumina, and the particle size of the mesoporous alumina is preferably 1-100 μm.
The metal catalyst is preferably a combination of zinc acetate, tin acetate and silver acetate, wherein the mass fraction of zinc acetate is not less than 60% and the mass fraction of silver acetate is not more than 5%. Further preferably, the mass fraction of tin acetate is 20 to 30%, and the mass fraction of silver acetate is 1 to 2%.
According to the technical scheme, the reaction efficiency is improved by adding the mesoporous material, the catalytic efficiency is improved by the mesoporous effect, meanwhile, the mesoporous material can be used as a load of a metal catalyst, and the mesoporous material can adsorb the metal catalyst in the mesoporous material in the separation process, so that after the mesoporous material is separated, the solid component can be dried and then added into an initial PET system again, the recycling of the metal catalyst is realized, the heavy metal residue in generated waste is reduced, and great progress is made in the aspects of economy and environmental protection.
Detailed Description
The technical scheme of the application is further described below with reference to the specific embodiments.
In the present application, the partial terms concerned are explained as follows:
mesoporous material refers to a mesoporous material whose surface or through which the surface is connected to the interior of the material, and the mesoporous is generally a void with a diameter of 1-100 nm. The common mesoporous material can be prepared by a method such as an organic matter template method, and can also be obtained by rusting the complete material after the preparation of the complete material is completed. In general, mesoporous materials have a specific surface area exceeding that of similar common materials, and the mesoporous materials can be plate-shaped, granular or powdery, and when the mesoporous materials are powdery, the mesoporous materials can be generally distributed in the micrometer to nanometer level in particle size.
The metal catalyst refers to a catalyst which can be used for catalyzing PET to be cracked and can be an organic salt or an inorganic salt of metal according to the prior art, wherein metal ions can be zinc, copper, cobalt, nickel, tin, rhodium, palladium, platinum, silver, cadmium, iridium, lead and the like, and counter ions can be sulfate radical, nitrate radical, halogen ions, acetate, formate, optionally substituted benzene sulfonate, optionally substituted benzoate, trifluoroacetate and the like organic acid radical or inorganic acid radical.
In the application, the solid-liquid two-phase separation method can adopt methods such as filtration, suction filtration, centrifugation and the like, and can reduce the temperature to precipitate PET and separate when the PET which is not cracked in a melting system is separated, wherein the separation temperature depends on the precipitation temperature of the PET.
Embodiment 1, a method for regenerating a PET material, wherein zinc acetate (the mass is calculated by anhydrous zinc acetate) is used as a metal catalyst and different mesoporous materials are used for finding the best mesoporous material, specifically comprising the following steps:
if the reaction is the first reaction, step S1 is as follows:
S1, adding 100gPET recovered crushed materials into a reaction kettle, wherein the recovered crushed materials are obtained from a colorless PET beverage bottle, and adding ethylene glycol, a medium material and a metal catalyst into the crushed fragrance, wherein the adding amount of the ethylene glycol is 200g, the adding amount of the mesoporous material is 5g, and the adding amount of the metal catalyst is 0.2g. Heating the components to 195 ℃ under the protection of nitrogen to react for 1h to obtain a first mixed system;
If the reaction is not the first reaction, step S1 is as follows:
S1, adding 100gPET recovered crushed materials into a reaction kettle, wherein the recovered crushed materials are obtained from a colorless PET beverage bottle, adding ethylene glycol into crushed aroma, wherein the adding amount of the ethylene glycol is 200g, adding the first solid phase component separated in the step S2 in the previous reaction cycle, and supplementing 30% (namely 0.06 g) of the mass of the metal catalyst which is added for the first time. The components react for 1h at 195 ℃ under the protection of nitrogen to obtain a first mixed system;
The rest reaction steps are as follows:
s2, cooling the first mixed system to 160 ℃ under the protection of nitrogen, and filtering to obtain a second mixed system and a first solid phase component;
S3, adding excessive deionized water into the second mixed system under the protection of nitrogen, keeping the temperature above 80 ℃, and then filtering to obtain an ethylene terephthalate oligomer (solid phase) and a third mixed system;
s4, crystallizing the third mixed system by adopting a recrystallization method under the protection of nitrogen, wherein the specific method comprises the following steps: after the system was concentrated to 100mL, it was allowed to stand at 4℃for 24 hours, followed by filtration, with BHET as the solid phase and a mixed system of ethylene glycol, water and a part of the metal catalyst as the liquid phase.
Five cycles of the above reaction steps were performed, and the following reaction data of the five cycles were evaluated.
Bhet yield: the ratio of the mass of the final BHET to the theoretical mass of BHET.
PET decomposition amount: for each reaction, the first solid phase component separated in step S2 is weighed, and then the mass of the mesoporous material added in advance is subtracted, and the value is taken as the undegraded value, and it should be noted that the calculation is not additionally performed in consideration of the fact that the amount of the metal catalyst is small, and the calculation is omitted here as an error, so that the actual PET degradation rate should be higher than that calculated in the present application.
In example 1, the experimental results using different mesoporous materials are shown in table 1.
TABLE 1 influence of mesoporous materials on reaction System
The above particle sizes are all average particle sizes, and it is found from the above data that alumina has a good ability to maintain a catalytic effect when the particle size is controlled within 1 μm as compared with mesoporous silica, mesoporous silicon nitride and mesoporous aluminum silicate. Meanwhile, the efficiency of the silicon dioxide obviously slips down after the third cycle, and the silicon nitride also has certain slip down in the fifth cycle, which proves the application effect of the aluminum oxide system in the scheme.
Example 2, a method for regenerating PET material, wherein mesoporous alumina of 100nm magnitude is used as mesoporous material to replace different metal catalysts, other reaction conditions are the same as in example 1, and experimental results are shown in Table 2.
TABLE 2 influence of Metal catalysts on the reaction System
The experimental result shows that the tin-zinc-silver composite catalytic system has obvious promotion effect on the catalytic effect, and has better effect in the catalyst. Since the PET decomposition rate was close to 100% in the above conditions, the subsequent data will not be reproduced and the BHET yield will be studied with great emphasis.
Example 3 the quality of the metal catalyst initially charged and the metal catalyst to be replenished each time was further examined on the basis of the best mode of embodiment (20% tin acetate +78% zinc acetate +2% silver acetate) in example 2, the other conditions were the same as in example 2 to investigate the effect of catalyst usage on PET material cracking, and the results were shown in table 3.
TABLE 3 influence of the amount of Metal catalyst on BHET yield
The experiment shows that the primary catalyst has better effect within the mass fraction range of 0.1-0.2%, and no obvious effect is caused by continuously increasing the reaction of the system. The amount of catalyst added each time is 15-30%, and good circulation effect can be maintained in at least five circulation. When the supplementing amount is too large, the reaction efficiency is not obviously improved, the yield is not obviously changed, and meanwhile, because the adsorption capacity of the mesoporous material is limited, more metal ions are also caused in the discharged wastewater.
Example 4 based on example 3, the mass of the mesoporous material was further adjusted by using a scheme in which the mass of the metal catalyst added for the first time was 0.2% of the mass of PET (i.e., 0.2 g), and the metal catalyst added for the subsequent time was 30% of the initial amount (i.e., 0.06 g), and the remaining conditions were unchanged, and the experimental results are shown in table 4.
TABLE 4 influence of the quality of mesoporous materials on BHET yield
The increase of the mesoporous material can reduce the yield to a certain extent, but the influence is smaller before reaching 200 times of the mass of the composite metal catalyst, but the 5g of the mesoporous material has a better effect in consideration of the convenience of process separation (for example, in the practical industry, excessive solid content can cause pipeline blockage, difficult filtration, abrasion or seizing of stirring blades).
Example 5 the effect of the cleavage temperature of step S1 on BHET yield was further studied, a scheme of adding 5g of mesoporous material was selected in example 4, the remaining conditions remained unchanged, and the experimental results are shown in Table 5.
TABLE 5 influence of cleavage temperature on BHET yield
In general, the high temperature is favorable for the catalytic pyrolysis of PET, but the high temperature is unfavorable for the adsorption of the catalyst in the porous material, so that the cycle times are reduced, and the catalyst loss is larger. Through comprehensive experiments, the method has the best circulation effect in the range of 180-200 ℃. The production enterprises can measure whether the high yield and the high energy consumption brought by the high temperature accord with the actual effect of the enterprises according to the actual conditions, and then the proper temperature is selected.
The above detailed description is intended to illustrate the present invention by way of example only and not to limit the invention to the particular embodiments disclosed, but to limit the invention to the precise embodiments disclosed, and any modifications, equivalents, improvements, etc. that fall within the spirit and scope of the invention as defined by the appended claims.
Claims (5)
1.A method for recycling PET material, comprising the steps of:
S1, mixing PET, ethylene glycol, mesoporous materials and a metal catalyst, and cracking the PET under the action of the metal catalyst, wherein the cracking temperature is not lower than 180 ℃; wherein the addition amount of the metal catalyst is not less than 0.05% of the mass of PET;
S2, separating the separated molten system to remove solid components;
S3, adding deionized water into the system, keeping the temperature at not lower than 80 ℃, and separating and removing ethylene terephthalate oligomer;
S4, separating the aqueous solution to obtain BHET;
wherein, after the solid component obtained in the step S2 is supplemented with the metal catalyst, the production cycle is carried out again in the step S1;
wherein the mesoporous material is mesoporous alumina with average grain diameter not more than 1 mu m,
The metal catalyst is a combination of zinc acetate, tin acetate and silver acetate, wherein the mass fraction of the zinc acetate is not less than 60%, the mass fraction of the tin acetate is 20-30%, and the mass fraction of the silver acetate is 1-2%.
2. The method for recycling PET material according to claim 1, wherein in step S1, the cracking temperature is 180-200 ℃.
3. The method for recycling PET material according to claim 1, wherein the mass of the supplementary metal catalyst is 15-30% of the mass of the initial metal catalyst when the recovered solid component is re-introduced into the system for the catalytic reaction.
4. The method for regenerating a PET material according to claim 1, wherein the mass of the mesoporous material is 10 to 200 times that of the metal catalyst.
5. A method of recycling PET material in accordance with claim 1, wherein recycling PET is performed in an oxygen-free environment.
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