CN103665430A - Thermolysis separation method for resin and carbon fibers in waste carbon fiber composite material - Google Patents
Thermolysis separation method for resin and carbon fibers in waste carbon fiber composite material Download PDFInfo
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- CN103665430A CN103665430A CN201310595080.5A CN201310595080A CN103665430A CN 103665430 A CN103665430 A CN 103665430A CN 201310595080 A CN201310595080 A CN 201310595080A CN 103665430 A CN103665430 A CN 103665430A
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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
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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
Abstract
The invention relates to a thermolysis separation method for resin and carbon fibers in a waste carbon fiber composite material. The method comprises the specific steps of (1) putting the waste carbon fiber composite material into a hearth of a thermolysis device, feeding nitrogen with the oxygen content of 3-20 vol percent into the hearth after a furnace door is closed, and completely discharging air in the hearth to form a low-oxygen environment; (2) heating the material in the hearth to 400-650 DEG C, keeping the temperature for certain time, and then switching off the furnace to naturally cool the material in the hearth, wherein the resin is subjected to thermolysis reaction in the hearth; (3) opening the cooled hearth and taking out products, wherein under the reaction condition, the resin is completely decomposed and is gasified and discharged out of the hearth, and the remained products are the carbon fibers of which the surfaces are completely clean; collecting and weighing the carbon fibers, and calculating the recycling rate. Compared with the prior art, the thermolysis separation method has the advantages that the carbon fiber recycling rate is high, the performance loss is low, and the operation technology is simple; the thermolysis separation method is suitable for industrial production.
Description
Technical field
The present invention relates to a kind of discarded carbon-fibre composite, especially relate to the thermolysis separation method of resin and carbon fiber in a kind of discarded carbon-fibre composite.
Background technology
The excellent properties such as carbon fiber-reinforced resin composite materials has that specific tenacity is high, specific modulus is high, thermotolerance and erosion resistance, thereby be widely used in the industrial circles such as the Leisure Sport fields such as aerospace field, golf club/tennis racket and automobile/wind-power electricity generation/electronic apparatus/medicine equipment.
All there is the problem of processing in the scrap stock that produce in production phase or the carbon fiber-reinforced resin composite materials dead meals such as scrap products while finishing work-ing life.Carbon fiber-reinforced resin composite materials can only burning-off resin in the mode of burning, and carbon fiber is still residual as residue, so carbon fiber-reinforced resin composite materials waste is usually used as non-combustible solid waste, by land-fill method, processes.Landfill had both caused land resources waste, caused again the deterioration of surrounding enviroment.In addition, contain the carbon fiber of 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 discloses multiplely decomposes the resin in discarded carbon fiber-reinforced resin composite materials, carbon fiber is wherein separated, thereby realizes the method that carbon fiber reclaims.
The prior art decomposition method of disclosed resin comprises thermolysis, inorganic acid decomposition, organic solvent decomposition and the decomposition of Asia/supercutical fluid etc.Organic solvent decomposes (CN200610151145.7, CN201010122570.X) recovery and obtains clean carbon fiber, but in removal process, uses a large amount of organic solvents, may environment be produced and be polluted; Separated from solvent after use (separatory, extraction, distillation etc.) operating process is complicated, causes reclaiming causing cost height higher; And to the kind of carbon fiber-reinforced resin composite materials matrix resin, even the kind of solidifying agent is selective, be not applicable to all matrix resins in the method.Due to the lower acid resistance of epoxy resin, utilize the severe corrosive acid such as nitric acid (CN03132542.4) to degrade to epoxy resin, the recyclable carbon fiber that obtains surface clean, but the strong acid such as nitric acid are because corrodibility is strong, to having relatively high expectations of conversion unit, and the safety coefficient to operation is had relatively high expectations, and post-reaction treatment is more difficult; Supercritical water treatment method (Materials and Design, 2010, Vol.31, p.999-1002) although there is the feature of cleanliness without any pollution, but need under the reaction conditions of High Temperature High Pressure, carry out, to having relatively high expectations 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 gentle compared with supercritical water, but still belong to high-temperature high-voltage reaction.These methods also in laboratory stage or pilot scale stage, also have a segment distance from real industrialization at present.
Prior art is disclosed, and what have industrialization feasibility most is the method for the discarded carbon fiber-reinforced resin composite materials of thermal decomposition process, and thermolysis process comprises fluidized bed process and cracking process.Fluidized bed process (Plastics wherein, Rubber and Composites, 2002, Vol.31No.6, p278-282) be discarded carbon fiber-reinforced resin composite materials to be placed in to warm air decompose, the method is better to processing the heterogeneous carbon fiber-reinforced resin composite materials waste effects such as doping metals, and can operate continuously, but reclaim the carbon fiber obtain because of oxidizing reaction serious, and because clashing in reactor, separator Deng Zhong strenuous exercise, so mechanical properties decrease is more serious, and the method operation is comparatively complicated.Cracking process is that discarded carbon fiber-reinforced resin composite materials is placed in to the method for the atmosphere of inert gases thermolysiss such as N2, technological operation is simple, but reclaim the carbon fiber surface obtaining and easily tie carbon, be block and nondispersive fibrous, have a strong impact on the recycling performance that reclaims the carbon fiber later stage.
Summary of the invention
Object of the present invention is exactly to provide a kind of carbon fiber that can realize effective Separation and Recovery high value from discarded carbon fiber-reinforced resin composite materials in order to overcome the defect of above-mentioned prior art existence; thereby improve the decline of the rate of recovery and the reduction carbon fiber mechanical property of carbon fiber; reduce treating processes cost, realize the thermolysis separation method of resin and carbon fiber in the discarded carbon-fibre composite of 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 discarded carbon-fibre composite, it is characterized in that, it is to process in the nitrogen atmosphere of 3-20vol%, temperature 400-650 ℃ that discarded carbon fiber-reinforced resin composite materials is placed on to oxygen concentration, resin is heated and decomposes, gasify, thereby sub-argument goes out carbon fiber to be reclaimed, and concrete steps are:
(1) discarded carbon-fibre composite is put into the burner hearth of pyrolysis installation, first passed into the nitrogen that oxygen content is 3-20vol% after closing fire door tight, air in burner hearth is discharged to formation low-oxygen environment completely;
(2) after the heating material in burner hearth to temperature is arrived to 400-650 ℃, (this time changes along with the difference of matrix resin to keep certain hour blowing out, to decide according to prior thermal weight loss experiment, furnace outage time equated with the thermal weight loss time), material in burner hearth is lowered the temperature naturally, there is pyrolysis in resin in burner hearth;
(3) burner hearth after described cooling is opened to taking-up product, due under above-mentioned reaction conditions, resin has decomposed completely and burner hearth is discharged in gasification, and product is just left surface clean carbon fiber completely, and this carbon fiber is collected and weighed, and calculate recovery rate.
Matrix resin in described discarded 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 discarded carbon-fibre composite is one or both in PAN base carbon fibre, asphalt base carbon fiber.
The form of the carbon fiber in described discarded 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 discarded carbon-fibre composite of putting thermal decomposer into, can, according to the relative size of thermal decomposer size, determine whether to need in advance fragmentation.If the size of thermal decomposer is enough large in principle, discarded carbon fiber-reinforced resin composite materials is without pulverizing, and pyrolysis directly puts in.Also can be crushed in advance the fragment of 1-50cm, then carry out thermolysis.After discarded carbon fiber-reinforced resin composite materials is broken into fritter, be easy to be heated evenly, thereby it is consistent to be conducive to pyrolysis degree, so carry out again thermolysis after being preferably broken into fritter.
Preferably, oxygen content is 3-20vol% in described thermal decomposer, if oxygen content lower than 3vol%, carbon fiber surface knot carbon phenomenon is serious, cannot obtain the carbon fiber of surface clean.If oxygen content higher than 20vol%, easily causes carbon fiber-reinforced resin composite materials burning, 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 that is caused blast by igniting.So preferably oxygen volume content is at 3-20vol%.
Described pyrolysis temperature is 400-650 ℃.Temperature is during lower than 400 ℃, and depending on the difference of matrix resin kind, pyrolysis occurs resin pyrolysis speed slowly or not.If resin decomposition rate is slow, will cause treatment time prolongation, processing cost to increase; If pyrolysis does not occur resin, carbon fiber cannot obtain Separation and Recovery.Temperature is during higher than 650 ℃, and pyrolysis is too fierce, and 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 prior thermal weight loss experiment.Thermal decomposition time is too short, and resin decomposes not exclusively, causes carbon fiber and the resin can not be completely separated.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, adopt method of the present invention to have the following advantages: be first that equipment is simple, technological process is simple, and processing cost is low, has industrialization feasibility.Secondly, the thermal decomposition process method that the present invention proposes, can realize the abundant decomposition of resin in discarded carbon fiber-reinforced resin composite materials, and degradation production can not remain in carbon fiber surface formation knot carbon, the carbon fiber surface obtaining is clean, and this has just improved recycling performance and the field of reclaiming carbon fiber greatly.In addition, the thermal decomposition process method that the present invention proposes, can avoid carbon fiber surface generation oxidizing reaction, can either improve like this rate of recovery of carbon fiber, the degree that the carbon fiber performance that can make again to reclaim suffers damage is minimum, thereby has greatly improved the value that reclaims carbon fiber.
Embodiment
The thermolysis separation method of resin and carbon fiber in a kind of discarded carbon-fibre composite provided by the present invention, it is to process in the nitrogen atmosphere of 3-20vol%, temperature 400-650 ℃ that discarded carbon fiber-reinforced resin composite materials is placed on to oxygen concentration, resin is heated and decomposes, gasify, thereby sub-argument goes out carbon fiber, reclaimed.Specifically comprise:
Step (1), puts into discarded carbon-fibre composite in the burner hearth of pyrolysis installation, first passes into the nitrogen number minute that oxygen content is 3-20vol% after closing fire door tight, so that air in burner hearth is discharged to formation low-oxygen environment completely;
Step (2), after the heating material in burner hearth to temperature is arrived to 400-650 ℃, keeps certain hour blowing out, and the material in burner hearth is lowered the temperature naturally.In burner hearth, there is pyrolysis in resin.
Step (3), opens taking-up product by the burner hearth after described cooling.Due under above-mentioned reaction conditions, resin has decomposed completely and burner hearth is discharged in gasification, and product is just left surface clean carbon fiber completely.This carbon fiber is collected and weighed, and calculate recovery rate.
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 discarded carbon-fibre composite of putting thermal decomposer into, can, according to the relative size of thermal decomposer size, determine whether to need in advance fragmentation.If the size of thermal decomposer is enough large in principle, discarded carbon fiber-reinforced resin composite materials is without pulverizing, and pyrolysis directly puts in.Also can be crushed in advance the fragment of 1-50cm, then carry out thermolysis.After discarded carbon fiber-reinforced resin composite materials is broken into fritter, be easy to be heated evenly, thereby it is consistent to be conducive to pyrolysis degree, so carry out again thermolysis after being preferably broken into fritter.
Preferably, oxygen content is 3-20vol% in described thermal decomposer, if oxygen content lower than 3vol%, carbon fiber surface knot carbon phenomenon is serious, cannot obtain the carbon fiber of surface clean.If oxygen content higher than 20vol%, easily causes carbon fiber-reinforced resin composite materials burning, 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 that is caused blast by igniting.So preferably oxygen volume content is at 3-20vol%.
Preferably, described pyrolysis temperature is 400-650 ℃.Temperature is during lower than 400 ℃, and depending on the difference of matrix resin kind, pyrolysis occurs resin pyrolysis speed slowly or not.If resin decomposition rate is slow, will cause treatment time prolongation, processing cost to increase; If pyrolysis does not occur resin, carbon fiber cannot obtain Separation and Recovery.Temperature is during higher than 650 ℃, and pyrolysis is too fierce, and 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 prior thermal weight loss experiment.Thermal decomposition time is too short, and resin decomposes not exclusively, causes carbon fiber and the resin can not be completely separated.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 further to understand the present invention, 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 is 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%.The sheet material that is 4.0mm by thickness is broken into the fragment of 5-50cm, and taking quality is that 1000g puts into thermal decomposition furnace, passes into the nitrogen that oxygen content is 12vol% in stove.Thermal decomposition furnace is warming up to 400 ℃, makes the resin in carbon fiber-reinforced resin composite materials issue solution estranged in this temperature, degradation production is discharged burner hearth with air-flow.Stop heating, treat that thermal decomposition furnace temperature is down to after normal temperature to take out and decompose bottom product, it is fibrous that product is, and the carbon fiber for surface clean, is weighed as 634g, and the rate of recovery of calculating carbon fiber is 634g/ (1000g * 0.65)=97.5%.
Embodiment 2
Selected discarded carbon-fibre composite plate is 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%.The sheet material that is 4.0mm by thickness is broken into the fragment of 5-50cm, and taking quality is that 1000g puts into thermal decomposition furnace, passes into the nitrogen that oxygen content is 12vol% in stove.Thermal decomposition furnace is warming up to 500 ℃, makes the resin in carbon fiber-reinforced resin composite materials issue solution estranged in this temperature, degradation production is discharged burner hearth with air-flow.Stop heating, treat that thermal decomposition furnace temperature is down to after normal temperature to take out and decompose bottom product, it is fibrous that product is, and the carbon fiber for surface clean, is weighed as 625g, and the rate of recovery of calculating carbon fiber is 625g/ (1000g * 0.65)=96.2%.
Embodiment 3
Selected discarded carbon-fibre composite plate is 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%.The sheet material that is 4.0mm by thickness is broken into the fragment of 5-50cm, and taking quality is that 1000g puts into thermal decomposition furnace, passes into the nitrogen that oxygen content is 12vol% in stove.Thermal decomposition furnace is warming up to 650 ℃, makes the resin in carbon fiber-reinforced resin composite materials issue solution estranged in this temperature, degradation production is discharged burner hearth with air-flow.Stop heating, treat that thermal decomposition furnace temperature is down to after normal temperature to take out and decompose bottom product, it is fibrous that product is, and the carbon fiber for surface clean, is weighed as 527g, and the rate of recovery of calculating carbon fiber is 527g/ (1000g * 0.65)=81.1%.
Embodiment 4
Selected discarded carbon-fibre composite plate is 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%.The sheet material that is 4.0mm by thickness is broken into the fragment of 5-50cm, and taking quality is that 1000g puts into thermal decomposition furnace, passes into the nitrogen that oxygen content is 3.0vol% in stove.Thermal decomposition furnace is warming up to 500 ℃, makes the resin in carbon fiber-reinforced resin composite materials issue solution estranged in this temperature, degradation production is discharged burner hearth with air-flow.Stop heating, treat that thermal decomposition furnace temperature is down to after normal temperature to take out and decompose bottom product, it is fibrous that product is, and the carbon fiber for surface clean, is weighed as 638g, and the rate of recovery of calculating carbon fiber is 638g/ (1000g * 0.65)=98.2%.
Embodiment 5
Selected discarded carbon-fibre composite plate is 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%.The sheet material that is 4.0mm by thickness is broken into the fragment of 5-50cm, and taking quality is that 1000g puts into thermal decomposition furnace, passes into the nitrogen that oxygen content is 20.0vol% in stove.Thermal decomposition furnace is warming up to 500 ℃, makes the resin in carbon fiber-reinforced resin composite materials issue solution estranged in this temperature, degradation production is discharged burner hearth with air-flow.Stop heating, treat that thermal decomposition furnace temperature is down to after normal temperature to take out and decompose bottom product, it is fibrous that product is, and the carbon fiber for surface clean, is weighed as 586g, and the rate of recovery of calculating carbon fiber is 586g/ (1000g * 0.65)=90.1%.
Comparative example 1
Selected discarded carbon-fibre composite plate is 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%.The sheet material that is 4.0mm by thickness is broken into the fragment of 5-50cm, and taking quality is that 1000g puts into thermal decomposition furnace, passes into the nitrogen that oxygen content is 12vol% in stove.Thermal decomposition furnace is warming up to 300 ℃, makes the resin in carbon fiber-reinforced resin composite materials issue solution estranged in this temperature, degradation production is discharged burner hearth with air-flow.Stop heating, treat that thermal decomposition furnace temperature is down to after normal temperature to take out and decompose bottom product, product is hard tabular while putting into, and because temperature is too low, decomposition reaction does not almost occur epoxy resin, and carbon fiber cannot Separation and Recovery, and product is weighed as 990g.
Comparative example 2
Selected discarded carbon-fibre composite plate is 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%.The sheet material that is 4.0mm by thickness is broken into the fragment of 5-50cm, and taking quality is that 1000g puts into thermal decomposition furnace, passes into the nitrogen that oxygen content is 12vol% in stove.Thermal decomposition furnace is warming up to 700 ℃, makes the resin in carbon fiber-reinforced resin composite materials issue solution estranged in this temperature, degradation production is discharged burner hearth with air-flow.Stop heating, treat that thermal decomposition furnace temperature is down to after normal temperature to take out and decompose bottom product, it is fibrous that product is, and the carbon fiber for surface clean, is weighed as 410g, and the rate of recovery of calculating carbon fiber is 410g/ (1000g * 0.65)=63.1%.Gained carbon fiber is fragility, disconnected with hand touching, illustrates due to excess Temperature, 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 is 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%.The sheet material that is 4.0mm by thickness is broken into the fragment of 5-50cm, and taking quality is that 1000g puts into thermal decomposition furnace, passes into the nitrogen that oxygen content is 0vol% in stove.Thermal decomposition furnace is warming up to 500 ℃, makes the resin in carbon fiber-reinforced resin composite materials issue solution estranged in this temperature, degradation production is discharged burner hearth with air-flow.Stop heating, treat that thermal decomposition furnace temperature is down to after normal temperature to take out and decompose bottom product, it is soft tabular that product is, and product is weighed as 790g.Explanation, because oxygen content is too low, makes carbon fiber surface knot carbon phenomenon serious, cannot obtain the carbon fiber of surface clean.
Comparative example 4
Selected discarded carbon-fibre composite plate is 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%.The sheet material that is 4.0mm by thickness is broken into the fragment of 5-50cm, and taking quality is that 1000g puts into thermal decomposition furnace, passes into the nitrogen that oxygen content is 35vol% in stove.Thermal decomposition furnace is warming up to 500 ℃, makes the resin in carbon fiber-reinforced resin composite materials issue solution estranged in this temperature, degradation production is discharged 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, and burning continues 9 minutes automatic distinguishings.After certain resolving time, stop body of heater heating, and treat that thermal decomposition furnace temperature is down to after normal temperature and take out and decompose bottom product, it is fibrous that product is, and is the carbon fiber of surface clean, be weighed as 468g, the rate of recovery of calculating carbon fiber is 468g/ (1000g * 0.65)=72.0%.Gained carbon fiber is highly brittle, disconnected with hand touching, illustrates that, because oxygen content is too high, carbon fiber is by severe oxidation, and mechanical properties decrease is serious, and the rate of recovery is low.
The explanation of above embodiment is just for helping to understand method of the present invention and core concept thereof.Be 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 improvement and modification also fall in the protection domain of the claims in the present invention.
Above-mentioned explanation to the disclosed embodiments, makes professional and technical personnel in the field can realize or use the present invention.To the multiple modification of these embodiment, will be apparent for those skilled in the art, General Principle as defined herein can, in the situation that not departing from the spirit or scope of the present invention, realize in other embodiments.Therefore, the present invention will can not be restricted to these embodiment shown in this article, but will meet the widest scope consistent with principle disclosed herein and features of novelty.
Claims (4)
1. a thermolysis separation method for resin and carbon fiber in discarded carbon-fibre composite, is characterized in that, the concrete steps of the method are:
(1) discarded carbon-fibre composite is put into the burner hearth of pyrolysis installation, first passed into the nitrogen that oxygen content is 3-20vol% after closing fire door tight, air in burner hearth is discharged to formation low-oxygen environment completely;
(2) after the heating material in burner hearth to temperature is arrived to 400-650 ℃, keep certain hour blowing out, the material in burner hearth is lowered the temperature naturally, there is pyrolysis in resin in burner hearth;
(3) burner hearth after described cooling is opened to taking-up product, due under above-mentioned reaction conditions, resin has decomposed completely and burner hearth is discharged in gasification, and product is just left surface clean carbon fiber completely, and this carbon fiber is collected and weighed, and calculate recovery rate.
2. the thermolysis separation method of resin and carbon fiber in a kind of discarded carbon-fibre composite according to claim 1, it is characterized in that, the matrix resin in described discarded 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 discarded carbon-fibre composite according to claim 1, it is characterized in that, the carbon fiber in described discarded 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 discarded carbon-fibre composite according to claim 1, it is characterized in that, the form of the carbon fiber in described discarded carbon-fibre composite is one or more in continuous fibre, macrofiber, staple fibre, powder fiber, carbon fibre fabric.
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| CN106750506A (en) * | 2016-12-29 | 2017-05-31 | 青海大学 | A kind of method that two-step thermal processing reclaims carbon fiber |
| CN106807425A (en) * | 2017-04-01 | 2017-06-09 | 北京化工大学 | Discarded carbon fiber resin matrix composite pyrolysis catalysts and recovery carbon fiber method |
| CN106810711A (en) * | 2016-12-29 | 2017-06-09 | 青海大学 | A kind of method that carbon fiber is reclaimed from waste and old carbon fibre reinforced composite |
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| CN114589836A (en) * | 2022-03-04 | 2022-06-07 | 广东长亨石业有限公司 | Method for extracting fibers from asphalt mixture and measuring mixing amount |
| CN114908610A (en) * | 2022-04-29 | 2022-08-16 | 上海交通大学 | Regenerated carbon fiber paper and preparation method thereof |
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| CN104975378A (en) * | 2014-04-08 | 2015-10-14 | 丰田自动车株式会社 | Processing device and processing method of fiber containing resin |
| CN105216136A (en) * | 2014-06-27 | 2016-01-06 | 卡米尔工矿业协助公司 | Pulse power recirculation contains the apparatus and method of the composite of reinforce and matrix |
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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 |
| CN106810711A (en) * | 2016-12-29 | 2017-06-09 | 青海大学 | A kind of method that carbon fiber is reclaimed from waste and old carbon fibre reinforced composite |
| CN106750506B (en) * | 2016-12-29 | 2019-07-12 | 青海大学 | A kind of method of two-step thermal processing recycling carbon fiber |
| CN106750506A (en) * | 2016-12-29 | 2017-05-31 | 青海大学 | A kind of method that two-step thermal processing reclaims carbon fiber |
| 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 |
| CN106807425A (en) * | 2017-04-01 | 2017-06-09 | 北京化工大学 | Discarded carbon fiber resin matrix composite pyrolysis catalysts and recovery 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 |
| CN111518312A (en) * | 2020-05-07 | 2020-08-11 | 南通复源新材料科技有限公司 | Recovery method of thick-wall carbon fiber composite material |
| CN111518312B (en) * | 2020-05-07 | 2022-05-24 | 南通复源新材料科技有限公司 | Recovery method of thick-wall carbon fiber composite material |
| CN114589836A (en) * | 2022-03-04 | 2022-06-07 | 广东长亨石业有限公司 | Method for extracting fibers from asphalt mixture and measuring mixing amount |
| CN114908610A (en) * | 2022-04-29 | 2022-08-16 | 上海交通大学 | Regenerated carbon fiber paper and preparation method thereof |
| CN115026972A (en) * | 2022-05-16 | 2022-09-09 | 上海治实合金科技有限公司 | Method for harmless treatment and fiber recovery of fiber reinforced composite material waste |
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