CN101698150A - Ester exchange catalyst for glycol to degrade polyethylene glycol terephthalate and preparation method thereof - Google Patents
Ester exchange catalyst for glycol to degrade polyethylene glycol terephthalate and preparation method thereof Download PDFInfo
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- CN101698150A CN101698150A CN200910272515A CN200910272515A CN101698150A CN 101698150 A CN101698150 A CN 101698150A CN 200910272515 A CN200910272515 A CN 200910272515A CN 200910272515 A CN200910272515 A CN 200910272515A CN 101698150 A CN101698150 A CN 101698150A
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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
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Y02P20/584—Recycling of catalysts
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Abstract
The invention relates to an ester exchange catalyst, in particular to an ester exchange catalyst for glycol to degrade polyethylene glycol terephthalate, belonging to the chemical field. The catalyst is composed of the following components in percentage by weight: 20-70% of ZnO, 10-50% of Al2O3 and 10-30% of Mo, wherein, Mo represents metallic oxide comprising one of CuO, CeO and NiO. The catalyst uses a co-precipitation method to obtain the precursor of the catalyst, then, the precursor of the catalyst is calcined at high temperature to obtain the ester exchange catalyst. The invention has the advantages of simple manufacture, high catalyst activity and the like, can be recycled and is convenient to recover. After recycled three times, the catalyst still keeps high activity, i.e. the degradation productivity of waste polyester can reach more than 70%, product recovery rate is greatly improved, and degradation time can be shortened to 40 minutes; and energy consumption and cost can be greatly lowered, which is favourable for industrial production.
Description
Technical field
The present invention relates to ester exchange catalyst, particularly relate to when a kind of PETG and ethylene glycol carry out the ester exchange degraded and use catalyst, belong to chemical field.
Background technology
Polyester (PET) carries out the polycondensation reaction preparation by dimethyl terephthalate (DMT) and ethylene glycol, and it is the raw material of polyster fibre, polyester film, Sofe drink bottle, engineering plastics etc.The polyester waste material source mainly contains two aspects: 1) the polyester profiled member is at the waste material of life cycle intact back recovery, as waste PET bottle, polyester disused cloth, useless PET film etc.; 2) substandard products, waste material and the leftover pieces in production of polyester and the process.According to incompletely statistics, the annual all kinds of polyester waste materials that produce of China because petroleum resources are very in short supply in recent years, just seem particularly important so the resource of waste PET material is utilized again simultaneously more than millions of tons at present.
The resource of waste PET material is utilized again generally following two kinds of approach: 1) physics absorption method: use earlier pulverizer; cutters etc. are the polyester waste material fragmentation; polyester fragment after sorting is through a series of cleanings; remove surface attachments; dry back extruding pelletization or directly as raw material for standby, these waste materials can make various products through certain moulding process.This method by simple physical recovery polyester waste material is simple to operate, with low cost, but its material mechanical performance decline should not be made expensive goods, and its wholesomeness can not get guaranteeing simultaneously; 2) chemical recycling is exactly with solid-state polymeric material depolymerization, makes it be converted into less molecule, intermediate raw material or is converted into monomer.For polyester, chemical recycling can make polyester chain fragment into ethylene glycol terephthalate (BHET) intermediate of low relative molecular mass or be degraded to p-phthalic acid (PTA) fully or dimethyl terephthalate (DMT) (DMT) and ethylene glycol (EG).The chemical degradation absorption method mainly comprises: Hydrolyze method, alcoholysis method, overcritical edman degradation Edman etc.
Alcoholysis method does not cause the accessory substance of secondary pollution and consersion unit is required relatively the alcoholysis methods that adopt so present waste PET is degraded more environment owing to not producing.The oligoester alcoholysis generally adopts zinc acetate as catalyst, but its catalytic activity deficiency, reaction temperature is under 198 ℃, reaction time is when being 3h, the degraded productive rate only is about 60-70%, and zinc acetate and reactant are homogeneous system, and causing reaction to finish the back zinc acetate catalyst can not effectively separate, and may have a negative impact to subsequent reactions.
Summary of the invention
At above-mentioned deficiency, the objective of the invention is to propose employed ester exchange catalyst of a kind of degradation of ethylene glycol PETG and preparation method thereof, its technical solution is:
The employed ester exchange catalyst of a kind of degradation of ethylene glycol PETG, each component of catalyst and weight percentage are respectively:
ZnO 20～70％
Al
2O
3 10～50％
MO 1O～30％
Wherein, MO represents metal oxide, comprises one of CuO, CeO, three kinds of compositions of NiO.
Preparation method's step of the employed ester exchange catalyst of degradation of ethylene glycol PETG is as follows:
1. aluminium salt, zinc salt and M slaine are dissolved in respectively in the distilled water, are mixed with 20% mixed salt solution; Obtain 10% ammonia spirit with distilled water and ammoniacal liquor preparation,
2. ammonia spirit slowly being added dropwise in the mixed salt solution, stirring simultaneously and make it uniform deposition, is to stop in 8～10 o'clock to the metal salt solution pH value, leave standstill behind the 5h at the vacuum drying chamber inner drying,
3. above-mentioned sample is placed Muffle furnace, calcine 2～5h down, obtain required catalyst after the taking-up at 500～800 ℃.
Described optimum calcinating temperature is 600 ℃.
Described best calcination time is 3h.
Described ammoniacal liquor drops to catalytic effect the best that the metal salt solution pH value is the catalyst that obtained at 9 o'clock.
Described aluminium salt is aluminum nitrate, aluminum acetate etc., and zinc salt is zinc nitrate, zinc acetate etc., and the M slaine is nitric acid M, acetic acid M etc.
Owing to adopted above technical scheme, the employed ester exchange catalyst of degradation of ethylene glycol PETG of the present invention mainly contains following advantage:
1, this catalyst is a kind of ternary metal oxide type catalyst, and wherein ZnO is a major catalyst, and MO is a co-catalyst, Al
2O
3Be carrier.Because this catalyst is insoluble to ethylene glycol, so make it can make reaction system become the heterogeneous reaction system by the homogeneous reaction system that uses zinc acetate, not only be convenient to reclaim, reuse catalyst (repeat usage of catalyst can reach more than 90% under the experiment condition at present), avoided the adverse effect of catalyst simultaneously subsequent reactions;
2, this ester exchange catalyst has high reaction activity and high, and the conversion ratio that makes polyester is by often using about 65% of zinc acetate to bring up to more than 90% at present; After catalyst was reused 3 times, conversion ratio was still more than 70%; 3h when the alcoholysis time is by the use zinc acetate catalyst during same conversion is reduced to 40min, has reduced energy consumption of reaction, and production cost is reduced greatly, and industrial realization becomes possibility.
3, in this ester exchange catalyst preparation, because keeping the ammonia spirit titration end-point is pH value 8～10, slaine all has been converted into metal hydroxides with this understanding, to keep calcining heat simultaneously be 500～800 ℃, when calcination time is 2～5h, so metal hydroxides all is decomposed into its corresponding oxide.And aluminium oxide crystal formation major part is the γ type under the calcining heat, does not get transformed into not possess the catalytic Alpha-alumina, so the good catalytic activity of Zhi Bei catalyst with this understanding.
The specific embodiment
Embodiment 1:
The nitrate (weight content ratio according to its corresponding oxide is 1: 7: 2) of pro rata copper, zinc and aluminium is dissolved in the distilled water, be mixed with 20% hybrid metal nitrate solution, to obtain 10% ammonia spirit dropwise to the metal nitrate mixed solution by the preparation of distilled water and ammoniacal liquor, and accompanied by intense stirs, to the solution pH value is to stop in 10 o'clock, leaves standstill crystallization 5h, dries in 80 ℃ of vacuum drying chambers, and in 500 ℃ of following Muffle furnaces, calcine 2h, get required catalyst;
Above-mentioned catalyst is added in the mixture of bottle level PET fragment and 1: 5 weight ratio of ethylene glycol according to 3% of PET weight, in temperature is 190 ℃ of reaction 40min down, obtain BHET after crystallization after filtration,, the washing, on filter paper, obtain simultaneously reacted solid catalyst and the unreacted PET powder of small part, after separating, obtain catalyst, and reuse under the same conditions 3 times
The PET degradation rate is as follows respectively: the first time 91.2%; The second time 80.7%; For the third time 78.6%;
Embodiment 2:
Ammonia spirit with 10% is to the mixed solution of copper, zinc and aluminium acetate 20% (weight content ratio of its corresponding oxide is 3: 2: 5) dropwise, and accompanied by intense stirs, to pH value is to stop in 8 o'clock, in 50 ℃ of vacuum drying chambers, dry after leaving standstill 5h, the back is calcined 5h down at 700 ℃ in Muffle furnace, get required catalyst;
Waste PET polyster fibre and ethylene glycol is by the mixing of 1: 5 weight ratio, and above-mentioned catalyst is added according to 0.5% of PET weight, is 190 ℃ of reaction 2h down in temperature, and after filtration, obtain BHET after the crystallization, washing, the PET degradation rate is 83.2%.
Embodiment 3:
Adopt the nitrate of cerium, zinc and aluminium and be to be mixed with 20% mixed solution at 3: 6: 1 according to the content ratio of its corresponding oxide, ammoniacal liquor with 10% is dropwise to mixed solution, and accompanied by intense stirs, to pH value is to stop in 8 o'clock, leave standstill crystallization 5h, oven dry under 80 ℃, the back is calcined 3h down at 600 ℃, gets required catalyst;
Waste PET film and ethylene glycol is by the mixing of 1: 6 weight ratio, and above-mentioned catalyst is added according to 2% of PET weight, is 190 ℃ of reaction 1h down in temperature, and after filtration, obtain BHET after crystallization, washing and the drying, the PET degradation rate is 81.3%.
Embodiment 4:
Distilled water and ammoniacal liquor is mixed with 10% ammonia spirit, and it slowly is added drop-wise in the mixed solution of acetate 20% of nickel, zinc and aluminium, and accompanied by intense stirs, the content ratio of guaranteeing its corresponding oxide simultaneously is 2: 7: 1, titration end-point is that solution maintenance pH value is 9, leaves standstill crystallization 5h, in 50 ℃ of oven dry down, the back is calcined 4h down at 800 ℃, gets required catalyst;
Discarded bottle level PET fragment and ethylene glycol is by the mixing of 1: 3 weight ratio, and above-mentioned catalyst is added according to 3% of PET weight, is 190 ℃ of reaction 2h down in temperature, and after filtration, obtain BHET after the crystallization, washing, the PET degradation rate is 53.2%.
Embodiment 5:
The nitrate (weight content ratio according to its corresponding oxide is 1: 7: 2) of copper, zinc and aluminium is dissolved in the distilled water, be mixed with 20% mixed salt solution, to obtain 10% ammonia spirit dropwise to the metal nitrate mixed solution by the preparation of distilled water and ammoniacal liquor, and accompanied by intense stirs, to the solution pH value is to stop in 9 o'clock, leaves standstill crystallization 5h, dries in 80 ℃ of vacuum drying chambers, and in 600 ℃ of following Muffle furnaces, calcine 3h, this scheme is a preferred plan;
Discarded bottle level PET fragment and ethylene glycol is by the mixing of 1: 5 weight ratio, and above-mentioned catalyst is added according to 3% of PET weight, is 190 ℃ of reaction 40min down in temperature, and after filtration, obtain BHET after the crystallization, washing, the PET degradation rate is 93.4%.
Claims (6)
1. the employed ester exchange catalyst of degradation of ethylene glycol PETG is characterized in that, each component of catalyst and weight percentage are respectively:
ZnO 20～70％
Al
2O
3 10～50％
MO 10～30％
Wherein MO represents metal oxide, comprises one of CuO, CeO, three kinds of compositions of NiO.
2. the preparation method of the employed ester exchange catalyst of degradation of ethylene glycol PETG is characterized in that, the step of preparation ester exchange catalyst is as follows:
1. aluminium salt, zinc salt and M slaine are dissolved in respectively in the distilled water, are mixed with 20% mixed salt solution; Obtain 10% ammonia spirit with distilled water and ammoniacal liquor preparation,
2. ammonia spirit slowly being added dropwise in the mixed salt solution, stirring simultaneously and make it uniform deposition, is to stop in 8～10 o'clock to the pH value of mixed salt solution, leaves standstill 5h, at the vacuum drying chamber inner drying,
3. above-mentioned sample is placed Muffle furnace, calcine 2～5h down, obtain required catalyst after the taking-up at 500～800 ℃.
3. ester exchange catalyst preparation method according to claim 2 is characterized in that, described optimum calcinating temperature is 600 ℃.
4. ester exchange catalyst preparation method according to claim 2 is characterized in that, its best calcination time is 3h.
5. ester exchange catalyst preparation method according to claim 2 is characterized in that, ammoniacal liquor drops to catalytic effect the best that the metal salt solution pH value is the catalyst that obtained at 9 o'clock.
6. ester exchange catalyst preparation method according to claim 2 is characterized in that, wherein aluminium salt is aluminum nitrate, aluminum acetate etc., and zinc salt is zinc nitrate, zinc acetate etc., and the M slaine is nitric acid M, acetic acid M etc.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102701985A (en) * | 2012-06-12 | 2012-10-03 | 唐海峰 | Method for preparing epoxy resin curing agent by performing alcoholysis on PET (Polyethylene Terephthalate) polyester |
| CN109289900A (en) * | 2018-10-29 | 2019-02-01 | 中国科学院过程工程研究所 | One kind is for catalytic degradation polyethylene terephthalate Engineering of Supported Metal Oxide Catalysts and its preparation method and application |
| CN114591168A (en) * | 2022-03-31 | 2022-06-07 | 南京大学 | Heteroatom-doped zinc oxide catalyzed waste PET glycolysis method |
| CN114849714A (en) * | 2022-05-27 | 2022-08-05 | 南京大学 | Preparation method of solid base catalyst for alcoholysis of PET |
| CN114904542A (en) * | 2022-04-25 | 2022-08-16 | 中国科学院青岛生物能源与过程研究所 | Composite catalyst for catalyzing and degrading polyester/polycarbonate plastics and preparation method and application thereof |
| CN115286502A (en) * | 2022-08-11 | 2022-11-04 | 浙江高乐高分子材料有限公司 | Regenerated PET material and preparation method thereof |
| CN115594708A (en) * | 2022-10-11 | 2023-01-13 | 广东电网有限责任公司（Cn） | Method for recycling waste silicon rubber insulating material by alcoholysis method |
-
2009
- 2009-10-26 CN CN200910272515A patent/CN101698150A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102701985A (en) * | 2012-06-12 | 2012-10-03 | 唐海峰 | Method for preparing epoxy resin curing agent by performing alcoholysis on PET (Polyethylene Terephthalate) polyester |
| CN109289900A (en) * | 2018-10-29 | 2019-02-01 | 中国科学院过程工程研究所 | One kind is for catalytic degradation polyethylene terephthalate Engineering of Supported Metal Oxide Catalysts and its preparation method and application |
| CN114591168A (en) * | 2022-03-31 | 2022-06-07 | 南京大学 | Heteroatom-doped zinc oxide catalyzed waste PET glycolysis method |
| CN114591168B (en) * | 2022-03-31 | 2023-06-09 | 南京大学 | Method for catalyzing waste PET glycol alcoholysis by using heteroatom doped zinc oxide |
| CN114904542A (en) * | 2022-04-25 | 2022-08-16 | 中国科学院青岛生物能源与过程研究所 | Composite catalyst for catalyzing and degrading polyester/polycarbonate plastics and preparation method and application thereof |
| CN114849714A (en) * | 2022-05-27 | 2022-08-05 | 南京大学 | Preparation method of solid base catalyst for alcoholysis of PET |
| CN115286502A (en) * | 2022-08-11 | 2022-11-04 | 浙江高乐高分子材料有限公司 | Regenerated PET material and preparation method thereof |
| CN115286502B (en) * | 2022-08-11 | 2024-04-16 | 浙江高乐高分子材料有限公司 | Regenerated PET material and preparation method thereof |
| CN115594708A (en) * | 2022-10-11 | 2023-01-13 | 广东电网有限责任公司（Cn） | Method for recycling waste silicon rubber insulating material by alcoholysis method |
| CN115594708B (en) * | 2022-10-11 | 2024-04-26 | 广东电网有限责任公司 | Method for recycling waste silicon rubber insulating material by alcoholysis method |
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Application publication date: 20100428 |