CN101906218B - Method for recycling polyester waste by normal-pressure alcoholysis - Google Patents
Method for recycling polyester waste by normal-pressure alcoholysis Download PDFInfo
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- CN101906218B CN101906218B CN2010102363707A CN201010236370A CN101906218B CN 101906218 B CN101906218 B CN 101906218B CN 2010102363707 A CN2010102363707 A CN 2010102363707A CN 201010236370 A CN201010236370 A CN 201010236370A CN 101906218 B CN101906218 B CN 101906218B
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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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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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Abstract
The invention discloses a method for recycling polyester waste by normal-pressure alcoholysis, which comprises the following steps: 1) preparing polyester waste, glycol and zinc acetate; 2) adding the prepared materials into a reactor, introducing inertia gas for protection, heating to 180 to 197.5 DEG C with stirring, and keeping the temperature for 5 to 9 hours; 3) after keeping the temperature, cooling to 90 to 105 DEG C, and filtering the hot materials under vacuum to remove non-degraded polyester waste; 4) refrigerating the filtrate at 5 DEG C for 5 to 10 hours to allow the degradation products to precipitate in form of crystals, and filtering under vacuum; and 5) drying the crystallization product under vacuum to obtain a recycled product. The method shortens flow, reduces production cost, protects environment, realizes chemical recycling, changes waste into valuable material and saves resources. The method has the advantages of simple reaction conditions, easy implementation, normal-pressure operation, low equipment requirements and low recycling cost.
Description
Technical field
The present invention relates to a kind of reclamation of waste materials method, particularly a kind of polyester waste material carries out recoverying and utilizing method through alcoholysis process under normal pressure.
Background technology
Polyethylene terephthalate (PET; Be called for short polyester) be important industrial raw materials; Its main goods comprise carafe, fiber, film, sheet base, electrical apparatus insulation material and engineering plastics etc.; Polyethylene terephthalate is by the ethylene glycol terephthalate homopolymerization, or makes through terephthalic acid, terepthaloyl moietie polyreaction.Along with the rapid rising of polyester article YO, the polyester waste material that is brought by polyester article also rapidly increases, and in addition, in the forming process of polyester article, often also can produce various scrap and tailing.Because polyethylene terephthalate has very strong unreactiveness, deposit very difficult degraded naturally or, not only cause the huge wasting of resources, and produce the serious environmental pollution by microbiological degradation.Therefore, through producing, process, recycle to realize the resource benign cycle, improve environmental quality, become the important topic of current polyester industrial, this not only has important economic benefit, also has the important social benefit.
Recycle mainly contains the physics utilization and utilizes two big classes with chemistry to polyester waste material (comprise useless PET polyester and useless goods) thereof at present.Physical use of the waste PET polyester and its products through direct mixing, blending, granulation, and other simple physical treatment made renewable slice profile products can be used as a secondary spinning Ji, film and engineering plastics, etc., to achieve the second use.Because hygienic reason directly is not used for packaging material for food at present as yet, having only after the depolymerization again, the PET polyester of polycondensation just can meet the hygienic requirements of grocery trade to material through the PET of physical treatment.In addition, waste PET directly reclaims the secondary slugs that processing produces, and crosses reason such as low because of inherent viscosity and should not directly use again, can only realize its recycle through chemical depolymerization.
The PET chemical cycle utilizes method to mainly contain hydrolysis method (comprising sour water solution, alkaline water solution and neutral water solution), methyl alcohol depolymerization, terepthaloyl moietie depolymerization and overcritical terepthaloyl moietie depolymerization; Though these methods can access the brand-new chemical feedstocks that is used for polymerization PET; Realize the processing of various level polyester articles, but also there are various defectives in they.The weak point of sour water solution is: a large amount of concentrated acids and the highly basic of reaction consumes, be difficult to recycle, and be prone to cause environmental pollution, and the also difficult recovery of the terepthaloyl moietie that generates.The alkaline water solution has salkali waste to discharge equally, and contaminate environment need be carried out suitable environmental protection treatment.The neutral water solution need be carried out under high temperature, high pressure, perhaps needs alkali as a catalyst, and contains a large amount of impurity in the depolymerization product, can not directly utilize, and subsequent disposal is cumbersome.Methyl alcohol depolymerization technology is fairly simple, the complicacy but product is purified, and the finished product quality is low.Because the methyl alcohol DeR time under the usual terms is longer, decompose not thoroughly, the methyl alcohol depolymerization PET that has realized is that the degradation rate of DMT is no more than 90%, is unfavorable for industrialized continuous production.Terepthaloyl moietie depolymerization technology more complicated.Overcritical terepthaloyl moietie depolymerization severe reaction conditions needs high temperature, high pressure, and technology realizes high than difficulty and cost.
At present, existing abroad production of polyester enterprise will give up and prepare monomer and polymer raw after PET degrades, and realize commercial prodn.But as above-mentioned chemical process, this method PET that will give up is degraded into monomer, still exists process complicated, the problem that cost is high.
Summary of the invention
To the above-mentioned deficiency that prior art exists, the purpose of this invention is to provide that a kind of process is simple, cost is low, be prone to the polyester waste by normal-pressure alcoholysis recoverying and utilizing method realized.
The technique means of technical solution problem of the present invention is achieved in that
The polyester waste by normal-pressure alcoholysis recoverying and utilizing method the steps include:
1) gets the raw materials ready-polyester waste material, terepthaloyl moietie and the zinc acetate of cleaning processing are got the raw materials ready by mass ratio 1:5～12:0.01～0.5;
2) polyester waste material of getting ready, terepthaloyl moietie and zinc acetate are added in the reaction vessel, feed rare gas element (like CO
2Or N
2) protection, be heated to 180～197.5 ℃ of temperature of reaction under stirring, under this temperature, be incubated 3h～9h to carry out DeR;
3) insulation makes solution naturally cool to 90～105 ℃ after finishing, and suction filtration is removed the polyester waste material of not degrading while hot;
4) place cold storage container in refrigerating 5～10h below 5 ℃ filtrating, make the degraded product crystallization separate out vacuum filtration;
5) be drying to obtain the recycling product under 65 ℃ of following vacuum of crystallized product.
Present method is carried out alcoholysis through terepthaloyl moietie to useless PET goods, and the PET alcoholysis product is the mixture of BHET and oligopolymer, oligopolymer can be directly as the raw materials for production of PET.So not only shorten flow process, and reduced production cost, both accomplished the protection environment, accomplished the chemical cycle utilization again, turned waste into wealth, saved resource.Present method reaction conditions is simple, is prone to realize, under normal pressure, can carry out, so low for equipment requirements, cost recovery is low.
Present method PET percent alcoholysis can reach 98.9%, and the degraded product recovery can reach 98.4%.
Description of drawings
Fig. 1-EG consumption to the influence curve of degraded product limiting viscosity (PET consumption 10g, 190 ℃, 3h).
Fig. 2-catalyst acetic acid zinc consumption is to the influence curve of percent alcoholysis.
Fig. 3-reaction times is to the influence curve of percent alcoholysis.
Fig. 4-reaction times is to the influence curve of the recovery.
Fig. 5-temperature of reaction is to the influence curve of degraded product limiting viscosity.
The TG-DSC thermal analysis curve of Fig. 6-pet waste.
The TG-DSC thermal analysis curve of Fig. 7-PET degraded product.
The infrared spectrogram of Fig. 8-pet waste.
The infrared spectrogram of Fig. 9-PET degraded product.
The SEM figure (200 *) of Figure 10-alcoholysis product.
Embodiment
Below in conjunction with accompanying drawing the present invention is done further explain.
Polyester is to be formed by terephthalic acid and terepthaloyl moietie esterification, polycondensation; Can under catalyzer and terepthaloyl moietie effect, carry out monomer or low-molecular(weight)polymer that the reversed reaction alcoholysis obtains can be as the raw materials for production of unsaturated polyester; Add saturated again or unsaturated dibasic acid and terepthaloyl moietie, get unsaturated polyester resin through esterifying polycondensation.
The present invention is that raw material, terepthaloyl moietie (EG) are as degradation agents, zinc acetate (Zn (OAc) with polyester (PET) waste material (comprising its goods)
2) carry out alcoholysis as catalyzer, alcoholysis is carried out under normal pressure.
Its concrete steps are:
1) gets the raw materials ready-weighing polyester waste material m
1, and get the raw materials ready by mass ratio 1:5～12:0.01～0.5 by polyester waste material, terepthaloyl moietie and zinc acetate; Polyester waste material should carry out cleaning and handle dry again; Useless PET bottle should be broken into the flap about 3mm * 3mm;
2) polyester waste material of getting ready, terepthaloyl moietie and zinc acetate are added in the reaction vessel, feed rare gas element (like CO
2Or N
2) protection, be heated to 180～197.5 ℃ of temperature of reaction under stirring, under this temperature, be incubated 3h～9h to carry out DeR;
3) insulation makes reaction soln naturally cool to 90～105 ℃ after finishing, and suction filtration is removed the polyester waste material of not degrading while hot, and the PET weighing of not degrading is m
2
4) place cold storage container in refrigerating 5～10h below 5 ℃ filtrating, make the degraded product crystallization separate out vacuum filtration;
5) be drying to obtain the recycling product under 65 ℃ of following vacuum of crystallized product, weighing is m
3
For degraded product, can adopt phenol-tetrachloroethane (1:1) mixed solvent, measure its limiting viscosity, degraded product has been carried out infrared (IR), thermogravimetric-differential thermal (TG-DSC), sem (SEM) analysis.Calculate the percent alcoholysis and the recovery by formula (1), (2) simultaneously.
Percent alcoholysis=
(1)
The recovery=
(2)
Result and discussion
1.EG consumption is to the influence of degraded product limiting viscosity
The △ H=0 of calculation of thermodynamics PET DeR; Be that temperature of reaction is to the not influence of the alcoholysis equilibrium constant; It is transesterification reaction mechanism that but PET terepthaloyl moietie is separated reaction, improves the terepthaloyl moietie consumption and helps transesterification reaction and the degraded product molecular weight is significantly reduced, as EG:PET during greater than 12:1; Molecular weight reduces limited, sees Fig. 1.
2. catalyst levels is to the influence of percent alcoholysis
In the various metallic salt catalyzer, the color of the degraded product of zinc acetate is the most shallow, so present method selects zinc acetate as catalyzer.Terepthaloyl moietie 120g, pet waste 10g, 190 ℃ of temperature of reaction, reaction times 3h, catalyst acetic acid zinc consumption (PET usage percentage) is seen Fig. 2 to the influence of percent alcoholysis.When not having catalyzer to exist, PET does not degrade basically, along with the increase of catalyst levels; Percent alcoholysis increases, and catalyst levels is 2% when above, and it is very little that percent alcoholysis increases variation with catalyst levels; Catalyst levels is excessive to be easy to generate side reaction, causes the recovery to descend on the contrary.
3. temperature of reaction, reaction times are to the influence of alcoholysis reaction
The boiling point of terepthaloyl moietie is 197.5 ℃, and PET normal pressure alcoholysis temperature of reaction is near the terepthaloyl moietie boiling temperature, and alcoholysis reaction temperature and reaction times are seen Fig. 3, Fig. 4 respectively to the influence of the percent alcoholysis and the recovery.PET normal pressure alcoholysis optimum reaction condition EG:PET:Zn (OAc)
2Mass ratio is 12:1:0.02,194 ℃ of temperature of reaction, and reaction times 3h, at this moment, the PET percent alcoholysis is 98.9%, the degraded product recovery is 98.4%.
The reaction of PET glycolysis mainly is the liquid-solid state reaction of carrying out at the pet sheet face, receives diffusion control.Alcoholysis speed is very slow during the reaction beginning, and along with time lengthening, EG is penetrated in the macromolecular chain segment of pet sheet face gradually; The swell layer of pet sheet face is thickened; And then the phase interface of augmenting response, more EG small molecules is contacted with ester bond on the PET macromolecular chain, thus the final completion of accelerating degraded; Generate the increase of ethylene glycol terephthalate (BHET) amount simultaneously along with reaction, the swell layer on pet waste surface also can be thickeied, and the reacting phase interface increases gradually, and degradation rate also increases thereupon.So, along with the increase in reaction times, the trend that all is increase that the percent alcoholysis of PET and the recovery are total.The rising temperature of reaction has improved velocity of diffusion, has increased the reacting phase interface, and alcoholysis reaction speed is increased.
The alcoholysis product limiting viscosity raises with temperature of reaction and reduces (see figure 5), explains that also the rising temperature of reaction increases alcoholysis reaction speed, makes the degraded product molecular weight littler.
4. comprehensive heat is analyzed
The comprehensive hot analytical results of pet waste and degraded product is seen Fig. 6, Fig. 7 respectively.
The DSC curve of pet waste can know that waste material mother glass transition temperature is 69.4 ℃, along with temperature raises, two peaks occur, and first is the PET crystalline exotherm peak, 129.1 ℃ of peak values, and second is the fusion endotherm(ic)peak, shows 256.1 ℃ of pet waste fusing points.Can find out that from waste material sample TG curve 411.5 ℃ of pet waste initial decomposition temperatures decompose under the high temperature fully.
The fusion endotherm(ic)peak of BHET appears in PET degraded product DSC curve in the time of 112.2 ℃, and the PET melting peak do not occur, explains that pet waste degrades.TG is along with temperature raises, and whole peak demonstrates the heat release shape, about 350 ℃, begins heat absorption again.Weightlessness appears twice in degraded product TG curve, 200.1 ℃ of initial weightless temperatures, and weightlessness 34.99% is the mass loss that the BHET volatilization causes; 403.5 ℃ of initial weightless temperatures, weightlessness 56.64% for oligopolymer decomposes, explains that degraded product is the mixture of BHET and oligopolymer.
5. IR spectroscopy
The results of IR of pet waste and degradation product is seen Fig. 8, Fig. 9.
The strongest bands of a spectrum of polyethylene terephthalate are at 1730cm
-1, be the C=O stretching vibration peak, the wave number of C-O stretching vibration peak is respectively at 1265 cm
-1With 1100 cm
-1The place.The PET degraded product is at 1270 cm
-1Strong C-O stretching vibration peak appears in the place, at 4000～3000cm
-1Between O-H stretching vibration characteristic absorbance peak area greater than the peak area of pet waste, explain that PET degrades, degraded back O-H content is higher than waste material.
6. scanning electron microscope analysis
Degraded product is the white needles thing; SEM figure (Figure 10) is visible laminar structured down, and this white needles thing surface tissue is similar with the physical structure of BHET, and PET can not show stratiform; Explain that DeR has taken place polymkeric substance, product is monomer or the oligopolymer similar with BHET.
Claims (2)
1. polyester waste by normal-pressure alcoholysis recoverying and utilizing method, it is characterized in that: method step is:
1) gets the raw materials ready-polyester waste material, terepthaloyl moietie and the zinc acetate of cleaning processing are got the raw materials ready by mass ratio 1:12:0.02;
2) polyester waste material of getting ready, terepthaloyl moietie and zinc acetate are added in the reaction vessel, feed protection of inert gas, be heated to 194 ℃ of temperature of reaction under stirring, insulation 3h is to carry out DeR under this temperature;
3) insulation makes solution naturally cool to 90～105 ℃ after finishing, and suction filtration is removed the polyester waste material of not degrading while hot;
4) place cold storage container in refrigerating 5～10h below 5 ℃ filtrating, make the degraded product crystallization separate out vacuum filtration;
5) be drying to obtain the recycling product under 65 ℃ of following vacuum of crystallized product.
2. polyester waste by normal-pressure alcoholysis recoverying and utilizing method according to claim 1 is characterized in that: the 2nd) going on foot described rare gas element is CO
2Or N
2
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| CN2010102363707A CN101906218B (en) | 2010-07-26 | 2010-07-26 | Method for recycling polyester waste by normal-pressure alcoholysis |
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| CN102153443B (en) * | 2011-02-23 | 2013-07-31 | 合肥工业大学 | Method for degrading polyethylene terephthalate |
| CN102675113A (en) * | 2012-06-08 | 2012-09-19 | 沈冬杰 | Method for preparing diglycol phthalate by performing alcoholysis on polyester (PET) |
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| CN110128271A (en) * | 2019-06-10 | 2019-08-16 | 东莞博斯环保科技有限公司 | A method of dimethyl terephthalate (DMT) is prepared using waste PET polyester |
| CN111569887B (en) * | 2020-06-02 | 2021-12-03 | 江南大学 | Application of magnetic microspheres in alcoholysis recovery of colored waste polyester |
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| CN1413178A (en) * | 1999-10-22 | 2003-04-23 | 帝人株式会社 | Method for separating and recovering dimethyl terephthalate and ethylene glycol from polyester waste |
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| CN101177503A (en) * | 2006-11-10 | 2008-05-14 | 宁波市鄞州天顺塑粉厂 | Method for preparing powder paint polyesters by discarded polyester decomposing reclamation |
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2010
- 2010-07-26 CN CN2010102363707A patent/CN101906218B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN87101849A (en) * | 1987-03-10 | 1988-09-21 | 陕西省化学研究所 | The method and the catalyzer that are used for depolymerizing waste and old polyester plastics |
| CN1413178A (en) * | 1999-10-22 | 2003-04-23 | 帝人株式会社 | Method for separating and recovering dimethyl terephthalate and ethylene glycol from polyester waste |
| CN1747982A (en) * | 2001-12-15 | 2006-03-15 | 三星电子株式会社 | The recovery method and the salvage material thereof of useless polyester |
| CN101177503A (en) * | 2006-11-10 | 2008-05-14 | 宁波市鄞州天顺塑粉厂 | Method for preparing powder paint polyesters by discarded polyester decomposing reclamation |
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