CN101735061A - Method for catalysis and alcoholysis of polyethylene terephthalate by ferromagnetic substance - Google Patents
Method for catalysis and alcoholysis of polyethylene terephthalate by ferromagnetic substance Download PDFInfo
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- CN101735061A CN101735061A CN200910243347A CN200910243347A CN101735061A CN 101735061 A CN101735061 A CN 101735061A CN 200910243347 A CN200910243347 A CN 200910243347A CN 200910243347 A CN200910243347 A CN 200910243347A CN 101735061 A CN101735061 A CN 101735061A
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- polyethylene terephthalate
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- ferromagnetic material
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
Abstract
The invention relates to a method for catalysis and alcoholysis of polyethylene terephthalate (PET) by a ferromagnetic substance, which is characterized in that: the ferromagnetic substance is taken as a catalyst; one or a mixture of more of glycol, diethylene glycol, propanediol and butanediol is taken as a solvent; and the PET polyester is subjected to alcoholysis under the conditions that the dosage of the catalyst accounts for 0.5 to 5 mass percent of the PET, the reaction temperature is between 140 and 230 DEG C, the pressure is 1atm and the reaction time is 1 to 12 hours. The method has the advantages that the catalyst can be recycled and has high catalytic activity and quick reaction; reaction conditions are mild; the products are easy to separate and have high selectivity, and the like.
Description
Technical field:
The present invention relates to green, clean catalysis technical field, specifically refer to the method for ferromagnetic material catalyzed alcoholysis polyethylene terephthalate.
Background technology:
Along with science and technology development, plastics, rubber, fiber three big synthetic materials have obtained widespread use, and these class superpolymer goods are closely related with daily life.Increasing waste or used plastics is used as rubbish by people and is thrown away, and according to statistics, the waste plastic product that the whole world abandons every year has reached 8,000 ten thousand tons.These can not natural degradation plastic garbage serious environment pollution not only, and cause the great wasting of resources.Polyethylene terephthalate (PET) as main raw material in the polyester is a kind of line style thermoplastic polymer.PET can keep good physicals and mechanical property in wide temperature range, its resistance to fatigue, rub resistance and ageing resistance excellence, electrical insulating property is outstanding, stable to most of organic solvents and mineral acid, and production energy consumption is low, processibility is good, thus be widely used as packing plastic bottle always, film, medicine, sensitive film, finishing material and synthon etc.The PET bottle has relative constant volume, and used PET bottle is easily classified, and its waste recovery is worth high, and this makes the recovery of PET have feasibility.The high consumption amount of PET bottle is its main drive that increases the rate of recovery day by day.The regeneration of waste PET beverage bottle not only can reduce environmental pollution, and can become " giving up " and be " treasured ", and its recycling is significant.
The recovery method of PET polyester has physics to reclaim and two kinds of chemical recovery.The physics absorption method is that useless PET bottle is carried out process for granulating again through separation, fragmentation, washing and drying treatment.The physical method technical process is simple, and cost is lower, but still can contain a certain amount of impurity with the PET polyester that physical method was handled, and understands the deterioration product performance in removal process, makes it can not be directly used in food product pack.Chemical recovery is with solid-state polymer materials depolymerization, is converted into less molecule, intermediate raw material or is converted into monomeric process.Di-alcohols organic solvent alcoholysis PET polyester is one of important method of its chemical recovery, the temperature of reaction of this reaction is generally 180～250 ℃, pressure is 0.1～0.6MPa, dibasic alcohol and PET repeating unit mol ratio are 4: 1, reaction times is 6～8h, and the monomer that obtains can be directly used in fiber-grade polyester and production of polyurethane.Be fast reaction speed, need to add catalyzer in the reaction process.The catalyzer of at present used alcoholysis PET polyester has acetate, solid super-strong acid, titanate etc.The present invention develop a kind of novel, reaction conditions is gentle, catalytic activity is high, monomer selectivity is high, can be recycled, eco-friendly catalyzer.
Summary of the invention
The present invention's research is catalyzer with the ferromagnetic material, is solvent with the dibasic alcohol, under the reaction conditions of gentleness, realizes quick, efficient, highly selective degraded PET polyester.
Reaction expression of the present invention is (is example as solvent with ethylene glycol):
The molecular weight of used polyethylene terephthalate is 1.8～7.5 * 10
4G/mol.
Alcoholysis polyethylene terephthalate solvent for use is one or more the mixture in ethylene glycol, Diethylene Glycol, propylene glycol or the butyleneglycol.
Used ferromagnetic material can be oxide compound, the muriate of iron, the nitrate of iron, carbonate, vitriol; Liquid can be, also solid can be; It can be the mixture of two or more compounds.
The add-on of catalyzer is 0.5%～5% of a PET quality during ferromagnetic material catalyzed alcoholysis polyethylene terephthalate.
The temperature of reaction of ferromagnetic material catalyzed alcoholysis polyethylene terephthalate is 140 ℃ to 230 ℃.
The reaction times of ferromagnetic material catalyzed alcoholysis polyethylene terephthalate is 1 hour to 12 hours.
After reaction finished, the degradation rate of PET polyester and product selectivity be (1) (2) calculating by formula respectively:
Wherein, A represents to add the initial mass of PET, and B represents the not quality of depolymerization PET.
Embodiment
The present invention illustrates with following embodiment, but the present invention is not limited to following embodiment, under the scope of described aim, changes and implements to be included in the technical scope of the present invention before and after not breaking away from.
Embodiment 1
Implementation method: in the 50mL there-necked flask, add 5.0g PET particle, 20.0g ethylene glycol and 1.0g1-butyl-3-Methylimidazole titanium tetrachloride salt ([bmim] FeCl successively
4).Control reaction temperature is 150 ℃, and pressure is 1atm, and 4 hours postcooling of condensing reflux reaction are to room temperature.With this understanding, the degradation rate of PET polyester is 16.5%, and the selectivity of monomers terephthalic acid binaryglycol ester (BHET) is 76.4%.
Embodiment 2
Implementation method: in the 50mL there-necked flask, add 5.0g PET particle, 20.0g ethylene glycol and 0.5g1-butyl-3-Methylimidazole titanium tetrachloride salt ([bmim] FeCl successively
4).Control reaction temperature is 160 ℃, and pressure is 1atm, and 4 hours postcooling of condensing reflux reaction are to room temperature.With this understanding, the degradation rate of PET polyester is 26.4%, and the selectivity of monomers terephthalic acid binaryglycol ester (BHET) is 76.8%.
Embodiment 3
Implementation method: in the 50mL there-necked flask, add 5.0g PET particle, 20.0g ethylene glycol and 0.5g iron trichloride (FeCl successively
3).Control reaction temperature is 178 ℃, and pressure is 1atm, and 4 hours postcooling of condensing reflux reaction are to room temperature.With this understanding, the degradation rate of PET polyester is 79.3%, and the selectivity of monomers terephthalic acid binaryglycol ester (BHET) is 52.8%.
Embodiment 4
With embodiment 2, catalyzer [bmim] FeCl
4Add-on be 1.0g.With this understanding, the degradation rate of PET polyester is 51.9%, and the selectivity of monomers B HET is 69.5%.
Embodiment 5
With embodiment 2, catalyzer [bmim] FeCl
4Add-on be 1.5g.With this understanding, the degradation rate of PET polyester is 72.8%, and the selectivity of monomers B HET is 62.8%.
Embodiment 6
With embodiment 1, control reaction temperature is 170 ℃.With this understanding, the degradation rate of PET polyester is 88.6%, and the selectivity of monomers B HET is 62.8%.
Embodiment 7
With embodiment 1, controlling reaction time is 178 ℃.With this understanding, the degradation rate of PET polyester is 100%, and the selectivity of monomers B HET is 59.2%.
Claims (8)
1. the method for ferromagnetic material catalyzed alcoholysis polyethylene terephthalate is characterized in that with the dibasic alcohol being solvent, is the catalyst degradation polyethylene terephthalate with the ferromagnetic material.
2. method according to claim 1, the molecular weight that it is characterized in that the polyethylene terephthalate of degrading is 1.8～7.5 * 10
4G/mol.
3. method according to claim 1 is characterized in that alcoholysis polyethylene terephthalate solvent for use is one or more the mixture in ethylene glycol, Diethylene Glycol, propylene glycol or the butyleneglycol.
4. method according to claim 1 is characterized in that used ferromagnetic material can be oxide compound, the muriate of iron, the nitrate of iron, carbonate, vitriol; Liquid can be, also solid can be.
5. method according to claim 1 is characterized in that used ferromagnetic material can be the mixture of two or more compounds.
6. method according to claim 1 is characterized in that catalyst levels is 0.5%～5% of a polyethylene terephthalate quality.
7. method according to claim 1, the temperature of reaction that it is characterized in that ferromagnetic material catalyzed alcoholysis polyethylene terephthalate are 140 ℃ to 230 ℃.
8. method according to claim 1, the reaction times that it is characterized in that ferromagnetic material catalyzed alcoholysis polyethylene terephthalate is 1 hour to 12 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910243347A CN101735061A (en) | 2009-12-18 | 2009-12-18 | Method for catalysis and alcoholysis of polyethylene terephthalate by ferromagnetic substance |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910243347A CN101735061A (en) | 2009-12-18 | 2009-12-18 | Method for catalysis and alcoholysis of polyethylene terephthalate by ferromagnetic substance |
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| CN101735061A true CN101735061A (en) | 2010-06-16 |
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| CN200910243347A Pending CN101735061A (en) | 2009-12-18 | 2009-12-18 | Method for catalysis and alcoholysis of polyethylene terephthalate by ferromagnetic substance |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103030564A (en) * | 2011-10-09 | 2013-04-10 | 中国科学院过程工程研究所 | Method for carrying out high-efficiency catalytic alcoholysis on polyethylene terephthalate (PET) by multi-component catalyst |
| CN105555401A (en) * | 2013-06-24 | 2016-05-04 | 爱奥尼亚技术有限责任公司 | Polymer degradation |
| CN106279756A (en) * | 2016-08-15 | 2017-01-04 | 宁波大发化纤有限公司 | The polyurethane contained in diethylene glycol alcoholysis removal Waste Polyester textile is for the method for polyester spinning melts |
| CN106279759A (en) * | 2016-08-15 | 2017-01-04 | 宁波大发化纤有限公司 | The polyurethane contained in glycolysis alcoholysis removal Waste Polyester textile is for the method for polyester spinning melts |
| CN106283228A (en) * | 2016-08-15 | 2017-01-04 | 宁波大发化纤有限公司 | The method that the polyurethane contained in Waste Polyester textile carries out Direct-spinning of PET Fiber is removed in a kind of alcoholysis |
| EP3205391A1 (en) * | 2013-03-12 | 2017-08-16 | Ioniqa Technologies B.V. | Magnetic fluid |
| CN114269714A (en) * | 2019-08-21 | 2022-04-01 | 爱奥尼亚技术有限责任公司 | Method and reactor system for depolymerizing terephthalate polymers into reusable raw materials |
| CN115340706A (en) * | 2021-05-13 | 2022-11-15 | 北京化工大学 | Method for degrading waste polyester based on magnetic recyclable nano catalyst |
| CN117447685A (en) * | 2023-12-22 | 2024-01-26 | 山东佳纳环保科技有限公司 | Waste fiber spinning and waste plastic mixed circulation recovery process |
-
2009
- 2009-12-18 CN CN200910243347A patent/CN101735061A/en active Pending
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103030564B (en) * | 2011-10-09 | 2015-04-01 | 中国科学院过程工程研究所 | Method for carrying out high-efficiency catalytic alcoholysis on polyethylene terephthalate (PET) by multi-component catalyst |
| CN103030564A (en) * | 2011-10-09 | 2013-04-10 | 中国科学院过程工程研究所 | Method for carrying out high-efficiency catalytic alcoholysis on polyethylene terephthalate (PET) by multi-component catalyst |
| US10340067B2 (en) | 2013-03-12 | 2019-07-02 | Ioniqa Technologies B.V. | Magnetic fluid |
| US10777343B2 (en) | 2013-03-12 | 2020-09-15 | Ioniqa Technologies B.V. | Magnetic fluid |
| EP3205391A1 (en) * | 2013-03-12 | 2017-08-16 | Ioniqa Technologies B.V. | Magnetic fluid |
| CN105555401A (en) * | 2013-06-24 | 2016-05-04 | 爱奥尼亚技术有限责任公司 | Polymer degradation |
| US10703703B2 (en) | 2013-06-24 | 2020-07-07 | Ioniqa Technologies B.V. | Polymer degradation |
| CN105555401B (en) * | 2013-06-24 | 2018-04-27 | 爱奥尼亚技术有限责任公司 | Depolymerization |
| US10266479B2 (en) | 2013-06-24 | 2019-04-23 | Ioniqa Technologies B.V. | Polymer degradation |
| CN106279759A (en) * | 2016-08-15 | 2017-01-04 | 宁波大发化纤有限公司 | The polyurethane contained in glycolysis alcoholysis removal Waste Polyester textile is for the method for polyester spinning melts |
| CN106283228A (en) * | 2016-08-15 | 2017-01-04 | 宁波大发化纤有限公司 | The method that the polyurethane contained in Waste Polyester textile carries out Direct-spinning of PET Fiber is removed in a kind of alcoholysis |
| CN106279756A (en) * | 2016-08-15 | 2017-01-04 | 宁波大发化纤有限公司 | The polyurethane contained in diethylene glycol alcoholysis removal Waste Polyester textile is for the method for polyester spinning melts |
| CN114269714A (en) * | 2019-08-21 | 2022-04-01 | 爱奥尼亚技术有限责任公司 | Method and reactor system for depolymerizing terephthalate polymers into reusable raw materials |
| CN115340706A (en) * | 2021-05-13 | 2022-11-15 | 北京化工大学 | Method for degrading waste polyester based on magnetic recyclable nano catalyst |
| CN117447685A (en) * | 2023-12-22 | 2024-01-26 | 山东佳纳环保科技有限公司 | Waste fiber spinning and waste plastic mixed circulation recovery process |
| CN117447685B (en) * | 2023-12-22 | 2024-03-19 | 山东佳纳环保科技有限公司 | Waste fiber spinning and waste plastic mixed circulation recovery process |
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Application publication date: 20100616 |