CN1035515A - The recovery processing method of waste polyester sort materials - Google Patents
The recovery processing method of waste polyester sort materials Download PDFInfo
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- CN1035515A CN1035515A CN88100610A CN88100610A CN1035515A CN 1035515 A CN1035515 A CN 1035515A CN 88100610 A CN88100610 A CN 88100610A CN 88100610 A CN88100610 A CN 88100610A CN 1035515 A CN1035515 A CN 1035515A
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- polyester
- depolymerization
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- cotton fibre
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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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- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
Abstract
A kind of recovery processing method of waste polyester sort materials comprises:
(1) waste polyester sort materials is positioned in the reactor, in the presence of the depolymerization catalyzer, polyester components is carried out low depth, depolymerization fast with mixing depolymerizing agent;
(2) depolymerization condition: temperature is 175～215 ℃, and pressure is normal pressure, and the time is 0.3～2 hour;
(3) oligopolymer after the depolymerization is separated with cotton fibre.
Cotton fibre after washing, drying can be used for cotton fibre goods industry such as papermaking; Polyester components can be directly used in the synthesis modification polyester product.
Description
The present invention relates to a kind of recovery processing method of linear polyester class waste, particularly relate to the recovery processing method of the useless fabric of a kind of cotton-polyester blend.Promptly under certain process conditions, in the presence of the depolymerization catalyzer, the polyester in the waste polyester sort materials is degraded, obtain oligopolymer and the cotton fibre that directly to recycle with depolymerizing agent.
Because polyester has good physicochemical property, and it is applied in extensive fields.World today's polyester annual production has reached nearly ten million ton, and wherein the polyester more than 80% is used for textile industry as polyster fibre, and small part is used to produce plastics.As packing bottle, cinefilm, X-ray sheet, audiotape, video-tape, engineering plastic product and film article etc.Polyester is put on market the laws of use of back according to product with various goods forms, and it can become waste sooner or later and be excluded from outside the social consumption field.In the production of polyester and the course of processing, also to unavoidably produce some wastes in addition, produce as 5～10% offal is arranged in producing polyester slice and drawing process approximately; 30% leftover bits generation is arranged when producing polyester film; Apparel industry also has 7% corner blanking generation in the cutting process.
For the recycling of waste polyester sort materials abroad from the sixties, domestic from the seventies just the someone study.They overwhelming majority is conceived to produce the purified waste material that produces in the offal that produces in the polyester process and the processed polyesters process.But, to the recycling of bigger some the polyester waste products such as polyester-cotton blend yarn fabric of quantity in the waste polyester sort materials but few people dabble.Therefore, the situation that waste polyester sort materials such as the useless chemical ﹠ blended fabric of basic rejection terylene have appearred in industry is reclaimed in the whole nation at present, has to let alone to discard, and has caused very big pressure for the system of socio-ecological environment.Constantly develop in social production, polyester and today that cotton fibre goods industrial raw material is in short supply, social environment goes from bad to worse, need the processing method of rationally and effectively recycling waste polyester sort materials badly.
The recoverying and utilizing method of waste polyester sort materials can be divided into physics method and chemical method two big classes.It is greatly and inadequately economical that chemical method generally is considered to difficulty.The present invention then reclaims a kind of economy, the simple method of providing for the chemical method of waste polyester sort materials.
In the waste polyester sort materials some discarded goods etc. at present shortage utilize approach preferably, and in waste product, quantity maximum and recycling difficulty with the useless chemical fibre of cotton-polyester blend are also bigger, in other words, if can work out a kind of method of utilizing that is applicable to the useless fabric of cotton-polyester blend, then this method will be applicable to the recycling of multiple polyester wastes such as pure polyester.
According to United States Patent (USP) 1,500, No. 857 and 4,118, No. 187 patent reports, the cotton-polyester blend fabric can be by adopting the naphthalene equal solvent, polyester components is carried out physical dissolution, realize that cotton one washs the separation of component, and then carry out the recycling of polyester components by methods such as chemical degradations.But this class methods flow process is longer, and equipment requirements is high and complicated, is difficult for realizing suitability for industrialized production, and all not mentioned solvent of the method for this class physical dissolution is to the problem of utilizing of the influence of cotton fibre and cotton fibre.
The present invention is directed to the intrinsiccharacteristic of polyester wastes such as cotton-polyester blend fabric, by adopting the polyester components direct chemical is degraded, once realize cotton, wash the separation of component and the depolymerization of polyester components, make cotton, wash composition and all become the component that can directly utilize, thereby realize the purpose of comprehensive utilization.
According to linear polyester can depolymerization in alcohols characteristic, present method utilizes ethylene glycol-one condensed ethandiol mixture to be depolymerizing agent, polyester esterifications such as acetate, transesterification catalyst is the depolymerization catalyzer, normal pressure is realized the collecting process of separating to polyester, this depolymerization has low depth, the characteristics of fast speed, cotton fibre form in separating collecting process is not changed, polyester components then depolymerization to become with polyester small molecules segment be the oligomer of main component, this oligopolymer can be as the basic raw material of modified poly ester products such as preparation tackiness agent, coating.The cotton fibre that obtains still is the fair raw material of cotton fibre goods industry such as papermaking.
Low depth, fast speed are that present method realizes its process economics, simple, reasonably crucial, and mixing the composition of depolymerizing agent and the use of consumption thereof is to influence this crucial principal element.
In this technology to the control of the depolymerization degree of depth of polyester with smooth realizations cotton wash separate and depolymerization product can to satisfy synthesis modification vibrin arts demand be aim, the depolymerization reaction time should be shortened as much as possible, reach the reaction process that shortens the synthesis modification polyester simultaneously, thus excessive to the depolymerization degree of depth of polyester components be unnecessary.This technology has been selected the least possible depolymerizing agent for use, and the Duan depolymerization time finishes the low depth of polyester components, separates collecting process fast as far as possible.
Ethylene glycol depolymerization to polyester has the depolymerizing agent that adds ast response that propylene glycol, a condensed ethandiol, 1,4-butyleneglycol, multicondensed ethylene glycol etc. are arranged.Consider from processing requirement and economic, practical angle, mix the mixture that depolymerizing agent is preferably a condensed ethandiol and ethylene glycol.Separate in the collecting process at polyester, during the ethylene glycol too high levels, the speed of polyester depolymerization is slower in mixing depolymerizing agent, the destruction of separating collecting process middle cotton fiber is also bigger, mix when a condensed ethandiol equal size is too high in the depolymerizing agent, temperature of reaction is too high, also easily causes the destruction of cotton fibre.In addition, the non-ethylene glycol component of mixing in the depolymerizing agent both can play the effect that improves speed of response in separating collecting process, can play the effect of chemical structure modification again in the process of subsequent preparation modified polyester resin.
Be not damaged in order to protect cotton fibre as far as possible; and raising speed of response; reduce consumption of raw and auxiliary materials and energy consumption; different requirements according to preparation modified poly ester product; in separating collecting process; 5～the 80%(that the ratio of mixing a condensed ethandiol in the depolymerizing agent suitably can be controlled at ethylene glycol weight is heavy) in the scope, 25～80%(that whole depolymerizing agent consumption accounts for polyester waste weight is heavy).The depolymerization time is 0.3～2 hour, and the depolymerization temperature is 175～215 ℃, and pressure is normal pressure.
Owing to contained the required catalyzer of a certain amount of depolymerization reaction in the polyester, thus when separating the polyester component catalyst levels can suitably to be controlled at 0.01～0.05%(heavy) in the scope.
Recovery processing method of the present invention is equally applicable to be other waste that pure linear polyester form exists.
Details are as follows for the recovery processing method of waste polyester sort materials of the present invention:
Waste polyester sort materials is positioned in the reactor, and polyester is carried out depolymerization, the depolymerization condition with mixing depolymerizing agent in the presence of the depolymerization catalyzer: temperature is 175～215 ℃, is preferably 175～200 ℃.Pressure is normal pressure, and the time is 0.3～2 hour, is preferably 0.5～1 hour, with the oligopolymer after the depolymerization or cotton fibre separation, washing, drying.
Used waste polyester sort materials comprises pure linear polyester waste and the useless chemical ﹠ blended fabric of blending terylene among the present invention.Used in the present invention mixing depolymerizing agent is the mixture of a condensed ethandiol and ethylene glycol, and 25～80%(that consumption accounts for the polyester waste is heavy), it is heavy to be preferably 30～50%().A condensed ethandiol accounts for 5～80%(weight of ethylene glycol weight in the mixing depolymerizing agent), it is heavy to be preferably 10～40%().
Depolymerization catalyzer used in the processing method of the present invention is an acetate, and as zinc acetate, Cobaltous diacetate, manganese acetate, antimony acetate, consumption are that 0.01～0.05%(of polyester waste is heavy), it is heavy to be preferably 0.02～0.03%().
After depolymerization reaction is finished, polyester is pulpous state, unreacted cotton fibre is the weaving attitude, polyester after the depolymerization is filtered, cotton fibre and polyester components are separated, cotton fibre is through cleaning, removal of impurities, after the drying, just become the basic raw material that is used to produce paper product or nonwoven material, polyester components can directly or through further modification be prepared into modified poly ester products such as some hotmelts.
Below several embodiment are further specifying to processing method of the present invention.But scope of the present invention is not restricted to this.
Embodiment 1
To heating is housed, drop into ethylene glycol mixing depolymerizing agent, 0.06 gram zinc acetate that 120 grams contain 10% 1 condensed ethandiol in the reaction flask (500 milliliters) of stirring and reflux.Heating, stirring add the useless fabric pieces of the white cotton-polyester blend of 300 grams simultaneously continuously or in batches.Reacted 0.3 hour down at 180～200 ℃, trevira is promptly depolymerized to oligomer, and the weaving attitude of trevira is thoroughly destroyed.Adopt heat filtering (or press filtration or centrifugal) separation method with polyester components with after cotton fibre separates, the depolymerizing agent that is preheated to more than 100 ℃ with 50 grams washes 1 to 2 time, washing fluid can mix with the depolymerization mother liquor.Then isolated cotton fibre is washed with water, drying obtains cotton fibre 105 grams, and the cotton fibre of this moment is textile state.Mother liquor after the depolymerization pulpous state that is white in color, weight are 350 grams, include the polymerization degree and be 1～7 polyester components 180 grams.
Embodiment 2
To heating is housed, stir, add the ethylene glycol mixing depolymerizing agent that 300 grams contain 5% 1 condensed ethandiol in 2000 milliliters of reaction flasks of reflux, 0.2 gram antimony acetate.Heating, stirring add the useless fabric pieces of the yellow cotton-polyester blend of 1000 grams simultaneously, and reaction is 0.5 hour under 180～195 ℃ of temperature.It is light yellow that reaction solution is.Press the separating step of embodiment 1, can obtain cotton fibre 350 grams; The polymerization degree is 1～7 light yellow polyester oligomer mother liquor 1200 grams.
Embodiment 3
With 350 grams, one condensed ethandiol content is 10% ethylene glycol mixings depolymerizing agent, 0.3 gram manganese acetate, and the operation steps of press embodiment 2 can restrain white Te Liling fragment with 1000 and depolymerize to 1350 restrain white pulpous state polyester oligomer in 0.4 hour.The polymerization degree is 1～7.
Embodiment 4
With a condensed ethandiol content 30% 400 gram ethylene glycol mixing depolymerizing agents, 0.2 the gram Cobaltous diacetate is a catalyzer, press the operation steps of embodiment 2, can and produce the offal depolymerization with 1000 gram mylars or polyester film, polyester bottles fragment and other pure linear polyester goods becomes the polyester oligomer that can be directly used in the poly-vinegar products of modification such as preparation tackiness agent.The polymerization degree is 1～7.
Application examples 1
With the white that obtains among the embodiment 1 weaving attitude cotton fibre directly in the sharp knife hollander, discongest, pull an oar, when the paper pulp beating degree be 18 ° of SR, during weight in wet base 15 grams, add the 1%mf resin, adjusting concentration to 0.45% back is gone up little paper machine and is manufactured paper with pulp, drying, press polish can be made into speciality paper goods such as textile filter paper.After tested, the every index of filter paper is as shown in table 1.(table 1 vides infra)
Application examples 2
The weaving attitude cotton fibre that obtains among the embodiment 1,2 is put into the teaser shredding become fiber condition, utilize the intact type technology of two net dip bonding method non-woven fabrics can produce textile type adhesive-bonded goods.Infuse product outward appearance and every performance index all reach like product water product.
Application examples 3
Polyester components 650 grams that obtain among the embodiment 1 to embodiment 4 are put into reaction flask, add 65 gram sebacic acid or m-phthalic acids, through esterification and in the following copolycondensation of 0.5 mmhg, can make a limiting viscosity is 0.73, and softening temperature is 146 ℃ a modified polyester resin.This resin can be used to as hotmelt, or is made into the solvent cement use.
Owing to when the polyester depolymerization, added an a certain amount of about condensed ethandiol etc. as the chemical structure modification agent, and the polyester depolymerization degree of depth is less, so in esterification and copolycondensation, only need add some other diprotic acid or alcohols, can in the short reaction times, prepare modified polyester resin.
The limiting viscosity of modified poly ester, indexs such as softening temperature can become the properties-correcting agent consumption by changing according to different requirements, and composition and synthetic technological condition are suitably adjusted.
The dibasic alcohol that reclaims in copolycondensation can be reused as depolymerizing agent.
Claims (8)
1, a kind of recovery processing method of waste polyester sort materials comprises:
(1) waste polyester sort materials is positioned in the reactor, in the presence of the depolymerization catalyzer, polyester components is carried out low depth, depolymerization fast with mixing depolymerizing agent;
(2) depolymerization condition: temperature is 175～215 ℃, and pressure is normal pressure, and the time is 0.3～2 hour;
(3) oligopolymer after the depolymerization is separated with cotton fibre;
(4) cotton fibre after washing, drying can be used for cotton fibre goods industry such as papermaking, and polyester components can directly be used as the synthesis modification polyester product.
2, according to the processing method of claim 1, wherein waste polyester sort materials comprises cotton-polyester blend attitude terylene waste.
3, according to the processing method of claim 1, wherein waste polyester sort materials comprises pure linear polyester class waste.
4, according to the processing method of claim 1, wherein used mixing depolymerizing agent is the mixture of a condensed ethandiol and ethylene glycol, and 25～80%(that consumption accounts for waste polyester sort materials is heavy), it is heavy to be preferably 35～55%().
5, according to the processing method of claim 4, wherein a condensed ethandiol accounts for 5～80%(weight of ethylene glycol weight), it is heavy to be preferably 10～40%().
6, according to the processing method of claim 1, wherein said depolymerization catalyzer is zinc acetate, Cobaltous diacetate, manganese acetate, antimony acetate, and consumption is that 0.01～0.05%(of polyester waste is heavy), it is heavy to be preferably 0.02～0.03%().
7, according to the processing method of claim 1, the wherein preferred depolymerization time is 0.5～1 hour, and preferred depolymerization temperature is 175～200 ℃.
8, according to the processing method of claim 1, wherein reacted polyester is pulpous state, and cotton fibre form in separating collecting process does not change.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN88100610A CN1035515A (en) | 1988-03-05 | 1988-03-05 | The recovery processing method of waste polyester sort materials |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN88100610A CN1035515A (en) | 1988-03-05 | 1988-03-05 | The recovery processing method of waste polyester sort materials |
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| Publication Number | Publication Date |
|---|---|
| CN1035515A true CN1035515A (en) | 1989-09-13 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN88100610A Pending CN1035515A (en) | 1988-03-05 | 1988-03-05 | The recovery processing method of waste polyester sort materials |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102250379A (en) * | 2011-06-01 | 2011-11-23 | 中国人民解放军总后勤部军需装备研究所 | Method for separation of terylene-cotton blended fabrics and repolymerization of terylene |
| CN112403408A (en) * | 2020-08-20 | 2021-02-26 | 西安理工大学 | Magnetic micro-nano material based on PET degradation product and preparation method and application thereof |
| EP3835023A1 (en) * | 2019-12-13 | 2021-06-16 | Lenzing Aktiengesellschaft | Method for recycling components comprised of mixed textile waste |
| CN114479175A (en) * | 2017-02-20 | 2022-05-13 | 宜家供应股份公司 | Polyester textile waste recycling |
| CN114836003A (en) * | 2022-04-28 | 2022-08-02 | 江阴市沪澄绝缘材料有限公司 | Phenolic resin cotton cloth laminated board for automobile and preparation method thereof |
-
1988
- 1988-03-05 CN CN88100610A patent/CN1035515A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102250379A (en) * | 2011-06-01 | 2011-11-23 | 中国人民解放军总后勤部军需装备研究所 | Method for separation of terylene-cotton blended fabrics and repolymerization of terylene |
| CN102250379B (en) * | 2011-06-01 | 2013-01-16 | 中国人民解放军总后勤部军需装备研究所 | Method for separation of terylene-cotton blended fabrics and repolymerization of terylene |
| CN114479175A (en) * | 2017-02-20 | 2022-05-13 | 宜家供应股份公司 | Polyester textile waste recycling |
| EP3835023A1 (en) * | 2019-12-13 | 2021-06-16 | Lenzing Aktiengesellschaft | Method for recycling components comprised of mixed textile waste |
| WO2021115932A1 (en) * | 2019-12-13 | 2021-06-17 | Lenzing Aktiengesellschaft | Process for utilization of constituents of mixed textile wastes |
| CN112403408A (en) * | 2020-08-20 | 2021-02-26 | 西安理工大学 | Magnetic micro-nano material based on PET degradation product and preparation method and application thereof |
| CN112403408B (en) * | 2020-08-20 | 2022-10-14 | 西安理工大学 | Magnetic micro-nano material based on PET degradation product and preparation method and application thereof |
| CN114836003A (en) * | 2022-04-28 | 2022-08-02 | 江阴市沪澄绝缘材料有限公司 | Phenolic resin cotton cloth laminated board for automobile and preparation method thereof |
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