CN103665430B - The thermolysis separation method of resin and carbon fiber in a kind of waste carbon fibre composite - Google Patents
The thermolysis separation method of resin and carbon fiber in a kind of waste carbon fibre composite Download PDFInfo
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- CN103665430B CN103665430B CN201310595080.5A CN201310595080A CN103665430B CN 103665430 B CN103665430 B CN 103665430B CN 201310595080 A CN201310595080 A CN 201310595080A CN 103665430 B CN103665430 B CN 103665430B
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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
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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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Abstract
The present invention relates to the thermolysis separation method of resin and carbon fiber in a kind of waste carbon fibre composite, the concrete steps of the method are: waste carbon fibre composite is put into the burner hearth of pyrolysis installation by (1), first pass into the nitrogen that oxygen content is 3-20vol% after closing fire door tight, air in burner hearth is discharged formation low-oxygen environment completely; (2) to the heating material in burner hearth to temperature to 400-650 DEG C after, keep certain hour and blowing out, make the material Temperature fall in burner hearth, there is pyrolysis in resin in burner hearth; (3) burner hearth after described cooling is opened taking-up product, due under the above-described reaction conditions, resin has decomposed completely and burner hearth is discharged in gasification, the product carbon fiber that just remaining surface is completely clean, this carbon fiber is collected and weighs, and calculate the rate of recovery.Compared with prior art, the carbon fiber rate of recovery of gained of the present invention is high, and performance damage is little, and operating procedure is simple, is applicable to suitability for industrialized production.
Description
Technical field
The present invention relates to a kind of waste carbon fibre composite, especially relate to the thermolysis separation method of resin and carbon fiber in a kind of waste carbon fibre composite.
Background technology
Carbon fiber-reinforced resin composite materials has that specific tenacity is high, specific modulus is high, the excellent properties such as thermotolerance and erosion resistance, is thus widely used in the industrial circle such as the Leisure Sport field such as aerospace field, golf club/tennis racket and automobile/wind-power electricity generation/electronic apparatus/medicine equipment.
The problem of process is all there is at carbon fiber-reinforced resin composite materials dead meals such as the scrap stock of production phase generation or the scrap products at the end of work-ing life.Carbon fiber-reinforced resin composite materials can only burning-off resin in the mode of burning, and carbon fiber still remains as residue, and therefore carbon fiber-reinforced resin composite materials waste is usually used as non-combustible solid waste, by land-fill method process.Landfill had both caused land resources to waste, and caused again the deterioration of surrounding enviroment.In addition, the carbon fiber containing high value in carbon fiber-reinforced resin composite materials, the mode of landfill can cause the huge waste of carbon fiber resource undoubtedly.
Prior art has disclosed multiplely decomposes the resin in waste carbon fiber-resin composite, and carbon fiber is wherein separated, thus realizes the method that carbon fiber reclaims.
Prior art disclosed resin decomposition method comprises thermolysis, inorganic acid decomposes, organic solvent decomposes and Asia/supercutical fluid decomposition etc.Organic solvent decomposes (CN200610151145.7, CN201010122570.X) recovery and obtains clean carbon fiber, but uses a large amount of organic solvents in removal process, may produce pollute environment; Separated from solvent (separatory, extraction, distillation etc.) operating process after using is complicated, causes recovery to cause cost height higher; And selective to the kind of the kind of carbon fiber-reinforced resin composite materials matrix resin, even solidifying agent in the method, be not applicable to all matrix resins.Due to the acid resistance that epoxy resin is lower, utilize the severe corrosive acid such as nitric acid (CN03132542.4) can to degrade to epoxy resin, the recyclable carbon fiber obtaining surface clean, but the strong acid such as nitric acid due to corrodibility strong, higher to the requirement of conversion unit, and requiring higher to the safety coefficient of operation, post-reaction treatment is more difficult; Supercritical water treatment method (MaterialsandDesign, 2010, Vol.31, p.999-1002) although have the feature of cleanliness without any pollution, but need to carry out under the reaction conditions of High Temperature High Pressure, higher to the requirement of conversion unit, and degraded after product and water mix, not easily separated; And overcritical alcohols (Ind.Eng.Chem.Res., 2010, Vol.49, p.4535-4541) although etc. fluid reaction conditions comparatively supercritical water is gentle, but still belong to high-temperature high-voltage reaction.These methods are also in laboratory stage or pilot scale stage at present, also have a segment distance from real industrialization.
Prior art disclosed in what have commercial viability most is the method for thermal decomposition process waste carbon fiber-resin composite, thermolysis process comprises fluidized bed process and cracking process.Fluidized bed process (Plastics wherein, RubberandComposites, 2002, Vol.31No.6, p278-282) be waste carbon fiber-resin composite is placed in warm air decompose, the method is better to heterogeneous carbon fiber-reinforced resin composite materials waste effects such as process doping metals, and can operate continuously, but reclaim the carbon fiber that obtains because of oxidizing reaction serious, and because clashing in reactor, separator Deng Zhong strenuous exercise, so mechanical properties decrease is relatively more serious, and the method operation is comparatively complicated.Cracking process is method waste carbon fiber-resin composite being placed in the atmosphere of inert gases thermolysiss such as N2, technological operation is simple, but reclaim the carbon fiber surface obtained and easily tie carbon, the nondispersive threadiness in bulk, have a strong impact on the recycling performance reclaiming the carbon fiber later stage.
Summary of the invention
Object of the present invention be exactly in order to overcome above-mentioned prior art exist defect and a kind of carbon fiber that can realize effective Separation and Recovery high value from waste carbon fiber-resin composite is provided; thus improve the rate of recovery of carbon fiber and reduce the decline of carbon fiber mechanical property; reduce treating processes cost, realize the thermolysis separation method of resin and carbon fiber in the waste carbon fibre composite of the object of resources conservation and environment protection.
Object of the present invention can be achieved through the following technical solutions: the thermolysis separation method of resin and carbon fiber in a kind of waste carbon fibre composite, it is characterized in that, waste carbon fiber-resin composite being placed on oxygen concentration is process in the nitrogen atmosphere of 3-20vol%, temperature 400-650 DEG C, resin is heated decompose, gasifies, thus sub-argument goes out carbon fiber is reclaimed, concrete steps are:
(1) waste carbon fibre composite is put into the burner hearth of pyrolysis installation, first pass into the nitrogen that oxygen content is 3-20vol% after closing fire door tight, air in burner hearth is discharged formation low-oxygen environment completely;
(2) to the heating material in burner hearth to temperature to 400-650 DEG C after, (this time changes along with the difference of matrix resin to keep certain hour blowing out, to decide according to the experiment of prior thermal weight loss, furnace outage time is equal with the thermal weight loss time), make the material Temperature fall in burner hearth, there is pyrolysis in resin in burner hearth;
(3) burner hearth after described cooling is opened taking-up product, due under the above-described reaction conditions, resin has decomposed completely and burner hearth is discharged in gasification, the product carbon fiber that just remaining surface is completely clean, this carbon fiber is collected and weighs, and calculate the rate of recovery.
Matrix resin in described waste carbon fibre composite is one or more in thermosetting resin or thermoplastic resin; Wherein thermosetting resin comprises epoxy resin, unsaturated polyester, resol or Vinylite, and described thermoplastic resin comprises polyolefine, nylon or polyester.
Carbon fiber in described waste carbon fibre composite is one or both in PAN base carbon fibre, asphalt base carbon fiber.
The form of the carbon fiber in described waste carbon fibre composite is one or more in continuous fibre, macrofiber, staple fibre, powder fiber, carbon fibre fabric.
Described pyrolysis installation comprises various forms of process furnace or pyrolyzer.
The described waste carbon fibre composite putting thermal decomposer into, according to the relative size of thermal decomposer size, can determine in advance the need of fragmentation.If the size of thermal decomposer is enough large in principle, waste carbon fiber-resin composite is then without the need to pulverizing, and directly put in pyrolysis.Also can be crushed to the fragment of 1-50cm in advance, then carry out thermolysis.After waste carbon fiber-resin composite is broken into fritter, be easy to be heated evenly, thus it is consistent to be conducive to pyrolysis degree, so carry out thermolysis again after being preferably broken into fritter.
Preferably, in described thermal decomposer, oxygen content is 3-20vol%, if oxygen content is lower than 3vol%, carbon fiber surface knot carbon phenomenon is serious, cannot obtain the carbon fiber of surface clean.If oxygen content is higher than 20vol%, easily cause carbon fiber-reinforced resin composite materials to burn, carbon fiber-reinforced resin composite materials burning will cause carbon fiber surface seriously oxidized, cause mechanical property degradation, and the carbon fiber rate of recovery reduces.The inflammable gas that carbon fiber-reinforced resin composite materials burning produces also has the danger being caused by igniting exploding.So preferred oxygen volume content is at 3-20vol%.
Described pyrolysis temperature is 400-650 DEG C.When temperature is lower than 400 DEG C, depending on the difference of matrix resin kind, there is pyrolysis in resin pyrolysis speed slowly or not.If resin decomposition rate is slow, treatment time prolongation, processing cost increase will be caused; If resin pyrolysis does not occur, then carbon fiber cannot obtain Separation and Recovery.When temperature is higher than 650 DEG C, pyrolysis is too fierce, easily cause local resin to remain in carbon fiber surface, or cause part carbon fiber excessively oxidated, mechanical property degradation, and the carbon fiber rate of recovery reduces.
Preferably, the described pyrolysis time changes along with the difference of matrix resin.To decide according to the experiment of prior thermal weight loss.Thermal decomposition time is too short, and resin decomposition is incomplete, causes carbon fiber can not be separated completely with resin.Thermal decomposition time is long, and carbon fiber is excessively oxidated, causes the carbon fiber rate of recovery low, and the carbon fiber mechanical properties decrease of gained is serious simultaneously.
Preferably, the described carbon fiber rate of recovery is greater than 80%, is preferably greater than 90%.
Compared with prior art, method of the present invention is adopted to have the following advantages: be first that equipment is simple, technological process is simple, and processing cost is low, has commercial viability.Secondly, the thermal decomposition process method that the present invention proposes, the abundant decomposition of resin in waste carbon fiber-resin composite can be realized, and degradation production can not form knot carbon remaining in carbon fiber surface, namely the carbon fiber surface obtained is clean, and this just substantially increases the recycling performance and field that reclaim carbon fiber.In addition, the thermal decomposition process method that the present invention proposes, can avoid carbon fiber surface generation oxidizing reaction, can either improve the rate of recovery of carbon fiber like this, the degree that the carbon fiber performance of recovery can be made again to suffer damage is minimum, thus drastically increases the value reclaiming carbon fiber.
Embodiment
The thermolysis separation method of resin and carbon fiber in a kind of waste carbon fibre composite provided by the present invention, waste carbon fiber-resin composite being placed on oxygen concentration is process in the nitrogen atmosphere of 3-20vol%, temperature 400-650 DEG C, resin is heated decompose, gasifies, thus sub-argument goes out carbon fiber is reclaimed.Specifically comprise:
Step (1), puts into the burner hearth of pyrolysis installation by waste carbon fibre composite, first pass into the nitrogen number minute that oxygen content is 3-20vol%, so that air in burner hearth is discharged formation low-oxygen environment completely after closing fire door tight;
Step (2), to the heating material in burner hearth to temperature to 400-650 DEG C after, keep certain hour and blowing out, make the material Temperature fall in burner hearth.Pyrolysis is there is in resin in burner hearth.
Step (3), opens taking-up product by the burner hearth after described cooling.Due under the above-described reaction conditions, resin has decomposed completely and burner hearth is discharged in gasification, the product carbon fiber that just remaining surface is completely clean.This carbon fiber is collected and weighs, and calculate the rate of recovery.
Matrix resin in described carbon fiber-reinforced resin composite materials, comprises the thermosetting resins such as epoxy resin, unsaturated polyester, resol, Vinylite, also comprises the thermoplastic resins such as polyolefine, nylon, polyester.
Carbon fiber in described carbon fiber-reinforced resin composite materials, comprises PAN base carbon fibre and asphalt base carbon fiber.
The form of the carbon fiber in described carbon fiber-reinforced resin composite materials, comprises all carbon fiber forms such as continuous fibre, macrofiber, staple fibre, powder fiber and carbon fibre fabric.
Described thermal decomposer, comprises various forms of process furnace or pyrolyzer.
The described waste carbon fibre composite putting thermal decomposer into, according to the relative size of thermal decomposer size, can determine in advance the need of fragmentation.If the size of thermal decomposer is enough large in principle, waste carbon fiber-resin composite is then without the need to pulverizing, and directly put in pyrolysis.Also can be crushed to the fragment of 1-50cm in advance, then carry out thermolysis.After waste carbon fiber-resin composite is broken into fritter, be easy to be heated evenly, thus it is consistent to be conducive to pyrolysis degree, so carry out thermolysis again after being preferably broken into fritter.
Preferably, in described thermal decomposer, oxygen content is 3-20vol%, if oxygen content is lower than 3vol%, carbon fiber surface knot carbon phenomenon is serious, cannot obtain the carbon fiber of surface clean.If oxygen content is higher than 20vol%, easily cause carbon fiber-reinforced resin composite materials to burn, carbon fiber-reinforced resin composite materials burning will cause carbon fiber surface seriously oxidized, cause mechanical property degradation, and the carbon fiber rate of recovery reduces.The inflammable gas that carbon fiber-reinforced resin composite materials burning produces also has the danger being caused by igniting exploding.So preferred oxygen volume content is at 3-20vol%.
Preferably, described pyrolysis temperature is 400-650 DEG C.When temperature is lower than 400 DEG C, depending on the difference of matrix resin kind, there is pyrolysis in resin pyrolysis speed slowly or not.If resin decomposition rate is slow, treatment time prolongation, processing cost increase will be caused; If resin pyrolysis does not occur, then carbon fiber cannot obtain Separation and Recovery.When temperature is higher than 650 DEG C, pyrolysis is too fierce, easily cause local resin to remain in carbon fiber surface, or cause part carbon fiber excessively oxidated, mechanical property degradation, and the carbon fiber rate of recovery reduces.
Preferably, the described pyrolysis time changes along with the difference of matrix resin.To decide according to the experiment of prior thermal weight loss.Thermal decomposition time is too short, and resin decomposition is incomplete, causes carbon fiber can not be separated completely with resin.Thermal decomposition time is long, and carbon fiber is excessively oxidated, causes the carbon fiber rate of recovery low, and the carbon fiber mechanical properties decrease of gained is serious simultaneously.
Preferably, the described carbon fiber rate of recovery is greater than 80%, is preferably greater than 90%.
In order to understand the present invention further, below in conjunction with embodiment, the thermolysis separation resin of carbon fiber-reinforced resin composite materials provided by the invention and the method for carbon fiber are described in detail.
Embodiment 1
Selected discarded carbon-fibre composite plate to be weaved cotton cloth by the plain weave of the T300-6K of toray company by carbon fiber and epoxy resin is composited, and wherein carbon fiber weight content is 65%.Be the fragment that the sheet material of 4.0mm is broken into 5-50cm by thickness, taking quality is that 1000g puts into thermal decomposition furnace, passes into the nitrogen that oxygen content is 12vol% in stove.Be warming up to 400 DEG C to thermal decomposition furnace, the resin in carbon fiber-reinforced resin composite materials is decomposed at such a temperature, and degradation production discharges burner hearth with air-flow.Stop heating, treat that thermal decomposition furnace temperature takes out decomposition bottom product after being down to normal temperature, product, in threadiness, is the carbon fiber of surface clean, is weighed as 634g, and the rate of recovery calculating carbon fiber is 634g/ (1000g × 0.65)=97.5%.
Embodiment 2
Selected discarded carbon-fibre composite plate to be weaved cotton cloth by the plain weave of the T300-6K of toray company by carbon fiber and epoxy resin is composited, and wherein carbon fiber weight content is 65%.Be the fragment that the sheet material of 4.0mm is broken into 5-50cm by thickness, taking quality is that 1000g puts into thermal decomposition furnace, passes into the nitrogen that oxygen content is 12vol% in stove.Be warming up to 500 DEG C to thermal decomposition furnace, the resin in carbon fiber-reinforced resin composite materials is decomposed at such a temperature, and degradation production discharges burner hearth with air-flow.Stop heating, treat that thermal decomposition furnace temperature takes out decomposition bottom product after being down to normal temperature, product, in threadiness, is the carbon fiber of surface clean, is weighed as 625g, and the rate of recovery calculating carbon fiber is 625g/ (1000g × 0.65)=96.2%.
Embodiment 3
Selected discarded carbon-fibre composite plate to be weaved cotton cloth by the plain weave of the T300-6K of toray company by carbon fiber and epoxy resin is composited, and wherein carbon fiber weight content is 65%.Be the fragment that the sheet material of 4.0mm is broken into 5-50cm by thickness, taking quality is that 1000g puts into thermal decomposition furnace, passes into the nitrogen that oxygen content is 12vol% in stove.Be warming up to 650 DEG C to thermal decomposition furnace, the resin in carbon fiber-reinforced resin composite materials is decomposed at such a temperature, and degradation production discharges burner hearth with air-flow.Stop heating, treat that thermal decomposition furnace temperature takes out decomposition bottom product after being down to normal temperature, product, in threadiness, is the carbon fiber of surface clean, is weighed as 527g, and the rate of recovery calculating carbon fiber is 527g/ (1000g × 0.65)=81.1%.
Embodiment 4
Selected discarded carbon-fibre composite plate to be weaved cotton cloth by the plain weave of the T300-6K of toray company by carbon fiber and epoxy resin is composited, and wherein carbon fiber weight content is 65%.Be the fragment that the sheet material of 4.0mm is broken into 5-50cm by thickness, taking quality is that 1000g puts into thermal decomposition furnace, passes into the nitrogen that oxygen content is 3.0vol% in stove.Be warming up to 500 DEG C to thermal decomposition furnace, the resin in carbon fiber-reinforced resin composite materials is decomposed at such a temperature, and degradation production discharges burner hearth with air-flow.Stop heating, treat that thermal decomposition furnace temperature takes out decomposition bottom product after being down to normal temperature, product, in threadiness, is the carbon fiber of surface clean, is weighed as 638g, and the rate of recovery calculating carbon fiber is 638g/ (1000g × 0.65)=98.2%.
Embodiment 5
Selected discarded carbon-fibre composite plate to be weaved cotton cloth by the plain weave of the T300-6K of toray company by carbon fiber and epoxy resin is composited, and wherein carbon fiber weight content is 65%.Be the fragment that the sheet material of 4.0mm is broken into 5-50cm by thickness, taking quality is that 1000g puts into thermal decomposition furnace, passes into the nitrogen that oxygen content is 20.0vol% in stove.Be warming up to 500 DEG C to thermal decomposition furnace, the resin in carbon fiber-reinforced resin composite materials is decomposed at such a temperature, and degradation production discharges burner hearth with air-flow.Stop heating, treat that thermal decomposition furnace temperature takes out decomposition bottom product after being down to normal temperature, product, in threadiness, is the carbon fiber of surface clean, is weighed as 586g, and the rate of recovery calculating carbon fiber is 586g/ (1000g × 0.65)=90.1%.
Comparative example 1
Selected discarded carbon-fibre composite plate to be weaved cotton cloth by the plain weave of the T300-6K of toray company by carbon fiber and epoxy resin is composited, and wherein carbon fiber weight content is 65%.Be the fragment that the sheet material of 4.0mm is broken into 5-50cm by thickness, taking quality is that 1000g puts into thermal decomposition furnace, passes into the nitrogen that oxygen content is 12vol% in stove.Be warming up to 300 DEG C to thermal decomposition furnace, the resin in carbon fiber-reinforced resin composite materials is decomposed at such a temperature, and degradation production discharges burner hearth with air-flow.Stop heating, treat that thermal decomposition furnace temperature is taken out and decomposed bottom product after being down to normal temperature, product is in hard board when putting into, and because temperature is too low, epoxy resin almost decomposition reaction does not occur, and carbon fiber cannot Separation and Recovery, and Weighed product is 990g.
Comparative example 2
Selected discarded carbon-fibre composite plate to be weaved cotton cloth by the plain weave of the T300-6K of toray company by carbon fiber and epoxy resin is composited, and wherein carbon fiber weight content is 65%.Be the fragment that the sheet material of 4.0mm is broken into 5-50cm by thickness, taking quality is that 1000g puts into thermal decomposition furnace, passes into the nitrogen that oxygen content is 12vol% in stove.Be warming up to 700 DEG C to thermal decomposition furnace, the resin in carbon fiber-reinforced resin composite materials is decomposed at such a temperature, and degradation production discharges burner hearth with air-flow.Stop heating, treat that thermal decomposition furnace temperature takes out decomposition bottom product after being down to normal temperature, product, in threadiness, is the carbon fiber of surface clean, is weighed as 410g, and the rate of recovery calculating carbon fiber is 410g/ (1000g × 0.65)=63.1%.Gained carbon fiber is fragility, namely breaks, illustrate because temperature is too high with hand touching, and carbon fiber is by severe oxidation, and mechanical properties decrease is serious, and the rate of recovery is low.
Comparative example 3
Selected discarded carbon-fibre composite plate to be weaved cotton cloth by the plain weave of the T300-6K of toray company by carbon fiber and epoxy resin is composited, and wherein carbon fiber weight content is 65%.Be the fragment that the sheet material of 4.0mm is broken into 5-50cm by thickness, taking quality is that 1000g puts into thermal decomposition furnace, passes into the nitrogen that oxygen content is 0vol% in stove.Be warming up to 500 DEG C to thermal decomposition furnace, the resin in carbon fiber-reinforced resin composite materials is decomposed at such a temperature, and degradation production discharges burner hearth with air-flow.Stop heating, treat that thermal decomposition furnace temperature takes out decomposition bottom product after being down to normal temperature, product is soft tabular, and Weighed product is 790g.Illustrate because oxygen content is too low, make carbon fiber surface tie carbon phenomenon serious, the carbon fiber of surface clean cannot be obtained.
Comparative example 4
Selected discarded carbon-fibre composite plate to be weaved cotton cloth by the plain weave of the T300-6K of toray company by carbon fiber and epoxy resin is composited, and wherein carbon fiber weight content is 65%.Be the fragment that the sheet material of 4.0mm is broken into 5-50cm by thickness, taking quality is that 1000g puts into thermal decomposition furnace, passes into the nitrogen that oxygen content is 35vol% in stove.Be warming up to 500 DEG C to thermal decomposition furnace, the resin in carbon fiber-reinforced resin composite materials is decomposed at such a temperature, and degradation production discharges burner hearth with air-flow.Decomposition reaction has just started first minute, and in stove, carbon fiber-reinforced resin composite materials takes fire, and occurs naked light, combustion continuation 9 minutes automatic distinguishings.Stop after certain resolving time heating body of heater, and treat that thermal decomposition furnace temperature takes out decomposition bottom product after being down to normal temperature, product, in threadiness, is the carbon fiber of surface clean, be weighed as 468g, the rate of recovery calculating carbon fiber is 468g/ (1000g × 0.65)=72.0%.Gained carbon fiber is highly brittle, and namely breaks, illustrate because oxygen content is too high with hand touching, and carbon fiber is by severe oxidation, and mechanical properties decrease is serious, and the rate of recovery is low.
The explanation of above embodiment just understands method of the present invention and core concept thereof for helping.It is noted that for those skilled in the art, under the premise without departing from the principles of the invention, can also carry out some improvement and modification to the present invention, these improve and modify and also fall in the protection domain of the claims in the present invention.
To the above-mentioned explanation of the disclosed embodiments, professional and technical personnel in the field are realized or uses the present invention.To be apparent for those skilled in the art to the multiple modification of these embodiments, General Principle as defined herein can without departing from the spirit or scope of the present invention, realize in other embodiments.Therefore, the present invention can not be restricted to these embodiments shown in this article, but will meet the widest scope consistent with principle disclosed herein and features of novelty.
Claims (4)
1. the thermolysis separation method of resin and carbon fiber in waste carbon fibre composite, it is characterized in that, the concrete steps of the method are:
(1) waste carbon fibre composite is put into the burner hearth of pyrolysis installation, first pass into the nitrogen that oxygen content is 3-20vol% after closing fire door tight, air in burner hearth is discharged formation low-oxygen environment completely;
(2) to the heating material in burner hearth to temperature to 400-650 DEG C after, keep certain hour and blowing out, this time changes along with the difference of matrix resin, decide according to the experiment of prior thermal weight loss, furnace outage time is equal with the thermal weight loss time, make the material Temperature fall in burner hearth, there is pyrolysis in resin in burner hearth;
(3) burner hearth after described cooling is opened taking-up product, due under the above-described reaction conditions, resin has decomposed completely and burner hearth is discharged in gasification, the product carbon fiber that just remaining surface is completely clean, this carbon fiber is collected and weighs, and calculate the rate of recovery.
2. the thermolysis separation method of resin and carbon fiber in a kind of waste carbon fibre composite according to claim 1, it is characterized in that, the matrix resin in described waste carbon fibre composite is one or more in thermosetting resin or thermoplastic resin; Wherein thermosetting resin comprises epoxy resin, unsaturated polyester, resol or Vinylite, and described thermoplastic resin comprises polyolefine, nylon or polyester.
3. the thermolysis separation method of resin and carbon fiber in a kind of waste carbon fibre composite according to claim 1, it is characterized in that, the carbon fiber in described waste carbon fibre composite is one or both in PAN base carbon fibre, asphalt base carbon fiber.
4. the thermolysis separation method of resin and carbon fiber in a kind of waste carbon fibre composite according to claim 1, it is characterized in that, the form of the carbon fiber in described waste carbon fibre composite is one or more in continuous fibre, macrofiber, staple fibre, powder fiber, carbon fibre fabric.
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| CN106810711B (en) * | 2016-12-29 | 2019-09-20 | 青海大学 | A method of recycling carbon fiber from waste and old carbon fibre reinforced composite |
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| CN106807425B (en) * | 2017-04-01 | 2019-06-07 | 北京化工大学 | Discarded carbon fiber resin matrix composite pyrolysis catalysts and recycling carbon fiber method |
| CN107216480A (en) * | 2017-06-14 | 2017-09-29 | 昆明理工大学 | A kind of method that low-temperature microwave efficient process carbon fibre composite reclaims carbon fiber |
| CN110951244A (en) * | 2019-12-11 | 2020-04-03 | 上海大学 | Waste plastic regeneration enhanced recycled carbon fiber thermoplastic composite material and preparation method thereof |
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| CN114908610A (en) * | 2022-04-29 | 2022-08-16 | 上海交通大学 | Regenerated carbon fiber paper and preparation method thereof |
| CN115026972B (en) * | 2022-05-16 | 2024-06-28 | 上海治实合金科技有限公司 | Harmless treatment and fiber recovery method for fiber reinforced composite material waste |
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| CN1498259A (en) * | 2001-01-18 | 2004-05-19 | 科学技术振兴事业团 | Apparatus for gasifying solid fuel |
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