CN104592546B - A kind of method for recycling waste and old carbon fiber/epoxy resin composite material - Google Patents
A kind of method for recycling waste and old carbon fiber/epoxy resin composite material Download PDFInfo
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- CN104592546B CN104592546B CN201410834413.XA CN201410834413A CN104592546B CN 104592546 B CN104592546 B CN 104592546B CN 201410834413 A CN201410834413 A CN 201410834413A CN 104592546 B CN104592546 B CN 104592546B
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- epoxy resin
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J11/00—Recovery or working-up of waste materials
- C08J11/04—Recovery or working-up of waste materials of polymers
- C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
- C08J11/16—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with inorganic material
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2300/00—Characterised by the use of unspecified polymers
- C08J2300/24—Thermosetting resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
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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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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
Abstract
The method of the waste and old carbon fiber/epoxy resin composite material of recycling provided by the invention, it is that one kind recycles waste and old carbon fiber/epoxy resin composite material using solvent method combination pressure method, overall process only needs a step, with inorganic acid and the composite acid of organic acid, the combination solvent of organic solvent and combine oxidant and handle waste and old carbon fiber/epoxy resin composite material at high temperature under high pressure, the few carbon fiber of the cull of isolated surface no significant defect.The method of the present invention step is succinct efficiently, clean environment firendly.
Description
Technical field
The invention belongs to macromolecule recovery technology field, is related to a kind of method for recycling same with thermosetting compound material, especially relates to
And be a kind of method that solvent method combination pressure method recycles waste and old carbon fiber/epoxy resin composite material.
Background technology
Carbon fiber/epoxy resin composite material be widely used in national defence, military project, aerospace, building, communications and transportation with
The multiple fields such as the energy, and emerging field is constantly extended to, such as：In hydrogen storage method, the full wound composite of high pressure
Cylinder is to apply most common selection at present.As application of such composite material in these high frontiers increases rapidly, institute
The junk of generation is growing day by day, but the recycling and reuse present situation to carbon fiber epoxy based composites is not allowed to find pleasure in
See, if without recycling huge pollution will be brought to environment.In addition, containing big in carbon fiber/epoxy resin composite material
Expensive carbon fiber is measured, the recycling work for carrying out waste and old CF/EP composite materials has larger economic implications, its time
Renewable resources are received gradually to attract attention.
At present, domestic and international traditional processing same with thermosetting compound material has following three kinds of approach：
(1) Material Physics crushes, its waste material recycled is included into the composite material of a new generation；
(2) then chemical recovery (such as passing through pyrolysis), the wherein recycling of polymer can use as organic compound
As a kind of chemical raw material；
(3) energy regenerating, is effectively utilized the calorie in composite material by way of burning.It is wherein traditional
The main method of Treatment of Carbon reinforced epoxy discarded object is burial and burning, mechanical crushing absorption method.Attempt pyrolysismethod,
Degrading solvent method (such as：Solidified resin can be dissolved in organic solvent by acid treatment, and Dang et al. has found Bisphenol F epoxy
Resin can decompose in salpeter solution completely, and the product of decomposition polymerize generation regenerating resin again with epoxy resin and curing agent)
Deng.
Above-mentioned three kinds of methods are cumbersome there are technique, and return period is longer, high energy consumption, the carbon fiber of recycling there are length compared with
Small, the shortcomings of surface residue is more, performance loss is larger.
The content of the invention
The technical problems to be solved by the invention are：A kind of solvent method combination pressure method is provided and recycles waste and old carbon fiber/ring
The method of epoxy resin composite material, one step of this method are completed, and can overcome above-mentioned the deficiencies in the prior art.
The present invention solves its technical problem and uses following technical solution：
The method of the waste and old carbon fiber/epoxy resin composite material of recycling provided by the invention, is that one kind utilizes solvent method group
Combined pressure force method receives waste and old carbon fiber/epoxy resin composite material back and forth, and overall process only needs a step, with the group of inorganic acid and organic acid
It is compound that conjunction acid, the combination solvent of organic solvent and combination oxidant handle waste and old carbon fiber/epoxy resin at high temperature under high pressure
Material, obtains separable carbon fiber and degradation solution.
The method of the waste and old carbon fiber/epoxy resin composite material of recycling, comprises the following steps：
(1) waste and old carbon fiber/epoxy resin composite material is cut into suitable size, it is spare；
(2) it is put into reaction kettle, adds inorganic acid and the composite acid of organic acid, the combination solvent of organic solvent and combine
Oxidant, 1.0-2.5h is heated in the case where temperature is 80-180 DEG C, pressure is 1.0-1.4Mp；
(3) centrifuge separation carbon fiber and solution are utilized；
(4) carbon fiber washed, be dried to obtain recovery product.
In step (1), in the waste and old carbon fiber/epoxy resin composite material, reinforcement carbon fiber is fine for PAN bases carbon
One kind in dimension, viscose base carbon fibre, asphalt base carbon fiber.
In step (1), in the waste and old carbon fiber/epoxy resin composite material, matrix epoxy resin is sweet using shrinking
Oily ether type epoxy resins, glycidyl ester epoxy resin, glycidyl amine epoxy resin, linear aliphatic same clan asphalt mixtures modified by epoxy resin
One kind in fat, finger ring same clan epoxy resin.
In step (1), in the waste and old carbon fiber/epoxy resin composite material, using curing agent to matrix asphalt mixtures modified by epoxy resin
Fat carry out crosslinking curing, the curing agent using diethylenetriamine, triethylene tetramine, polyethylene polyamine, N, N- diethylaminopropylamines,
One kind in polyetheramine, polyamide, or several mixtures.
In step (2), the inorganic acid is using one kind in nitric acid, phosphoric acid, hydrochloric acid, sulfuric acid.
In step (2), the organic acid is using one kind in carboxylic acid, sulfonic acid, sulfinic acid, thionothiolic acid.
In step (2), the combination solvent of the organic solvent is using in toluene, dimethylbenzene, acetone, ethers, alcohols
Two or more.
In step (2), the combination oxidant is using in hydrogen peroxide, nitrate, more nitro compounds, potassium permanganate
Two or more.
The obtained recovery product of the method for the present invention, the degradation rate of its epoxy resin is >=90%.
The method that the present invention recycles waste and old carbon fiber/epoxy resin composite material using solvent method combination pressure method, with biography
System other methods, which are compared, to be had the advantage that：
1. it is the waste and old carbon fiber/epoxy resin composite material processing time is short of recycling, efficient, before there are industrial applications
Scape.
2. one-step method is completed, technique is simple.
3. the degradation rate of resin is high (up to more than 90%).
4. recycling obtained carbon fiber strength retains high, surface no significant defect.
In short, the method for the present invention step is succinct efficiently, clean environment firendly, it is ensured that isolated surface no significant defect
The few carbon fiber of cull.
Embodiment
The present invention uses solvent method combination pressure method, it is with the combination of inorganic acid and the composite acid, organic solvent of organic acid
Solvent and combination oxidant handle waste and old carbon fiber/epoxy resin composite material at high temperature under high pressure, obtain separable carbon
Fiber and degradation solution.The method adds high pressure on the basis of degrading solvent method, reduces the reaction time, improves degraded effect
Fruit, it is possible to increase the treating capacity of waste and old composite material, recycles more complete carbon fiber (the surface resin drop for the carbon fiber that recycling obtains
Solution rate can reach more than 90%, and fibre strength is more than the 90% of pristine fibre, can be compound again with epoxy resin).
With reference to example, the present invention is further elaborated, but present disclosure is not limited solely to following implementation and shows
Example.
Embodiment 1：
Composite material is cut into and is about 9cm, wide about 1.5cm, the square bar of thickness about 2mm is spare；It is put into 200ml reaction kettles
In, 20ml volume fractions are added as 70% aqueous acetic acid, 20ml concentrated phosphoric acids, 20ml acetone, 20ml benzene, 20ml30% peroxidating
Hydrogen, 20g dibastic sodium phosphates；Degrade 2.5h under 180 DEG C, 1.4Mp；Carbon fiber and solution are separated by filtration, by solid product acetone
Wash, be then placed in the carbon fiber that dry 12h is recycled at 80 DEG C of baking oven.By test, the degradation rate of epoxy resin is
93.13%.
Embodiment 2：
Composite material is cut into and is about 9cm, wide about 1.5cm, the square bar of thickness about 2mm is spare；It is put into 200ml reaction kettles
In, 20ml volume fractions are added as 70% aqueous acetic acid, 20m concentrated phosphoric acids, 20ml dimethyl ether, 20ml benzene, 20ml30% peroxides
Change hydrogen, 20g sodium nitrate；Degrade 2.5h under 180 DEG C, 1.4Mp；Carbon fiber and solution are separated by filtration, by solid product acetone
Wash, be then placed in the carbon fiber that dry 12h is recycled at 80 DEG C of baking oven.By test, the degradation rate of epoxy resin is
90.78%.
Embodiment 3：
Composite material is cut into and is about 9cm, wide about 1.5cm, the square bar of thickness about 2mm is spare；It is put into 200ml reaction kettles
In, 20ml volume fractions are added as 70% aqueous acetic acid, the 20ml concentrated sulfuric acids, 20ml acetone, 20ml benzene, 20ml30% peroxidating
Hydrogen, 20g sodium nitrate；Degrade 2h under 120 DEG C, 1.0Mp；Carbon fiber and solution are separated by filtration, solid product is washed with acetone,
It is then placed in the carbon fiber that dry 12h is recycled at 80 DEG C of baking oven.By test, the degradation rate of epoxy resin is 88.34%.
Embodiment 4：
Composite material is cut into and is about 9cm, wide about 1.5cm, the square bar of thickness about 2mm is spare；It is put into 200ml reaction kettles
In, add 20ml concentrated nitric acids, 20ml mass fractions are 37% hydrochloric acid, 20ml acetone, 20ml benzene, 20ml30% hydrogen peroxide, 20g
Dibastic sodium phosphate；Degrade 1.5h under 180 DEG C, 1.0Mp；Carbon fiber and solution are separated by filtration, solid product is washed with acetone, so
The carbon fiber that dry 12h is recycled at 80 DEG C of baking oven is put into afterwards.By test, the degradation rate of epoxy resin is 83.89%.
Embodiment 5：
Composite material is cut into and is about 9cm, wide about 1.5cm, the square bar of thickness about 2mm is spare；It is put into 200ml reaction kettles
In, addition 20ml volume fractions are 70% aqueous acetic acid, 20ml mass fractions are 37% hydrochloric acid, 20ml acetone, 20ml diformazans
Ether, 20g sodium nitrate, 20g dibastic sodium phosphates；Degrade 2h under 120 DEG C, 1.0Mp；Carbon fiber and solution are separated by filtration, solid is produced
Thing is washed with acetone, is then placed in the carbon fiber that dry 12h is recycled at 80 DEG C of baking oven.By test, the drop of epoxy resin
Solution rate is 83.67%.
Claims (6)
- A kind of 1. method for recycling waste and old carbon fiber/epoxy resin composite material, it is characterized in that a kind of utilize solvent method combination pressure Force method recycles waste and old carbon fiber/epoxy resin composite material, and overall process only needs a step, with the combination of inorganic acid and organic acid Acid, the combination solvent of organic solvent and combination oxidant handle waste and old carbon fiber/epoxy resin composite wood at high temperature under high pressure Material, obtains separable carbon fiber and degradation solution；The combination oxidant is using hydrogen peroxide, nitrate, more nitro compounds Two or more in thing, potassium permanganate；In the waste and old carbon fiber/epoxy resin composite material, reinforcement carbon fiber is PAN base carbon fibres, viscose base carbon is fine One kind in dimension, asphalt base carbon fiber；In the waste and old carbon fiber/epoxy resin composite material, matrix epoxy resin using glycidyl ether type epoxy resin, Glycidyl ester epoxy resin, glycidyl amine epoxy resin, linear aliphatic same clan epoxy resin, alicyclic ring same clan asphalt mixtures modified by epoxy resin One kind in fat；In the waste and old carbon fiber/epoxy resin composite material, crosslinking curing is carried out to matrix epoxy resin using curing agent, The curing agent is using diethylenetriamine, triethylene tetramine, polyethylene polyamine, N, in N- diethylaminopropylamines, polyetheramine, polyamide One kind, or several mixture.
- 2. according to the method described in claim 1, it is characterized in that comprise the following steps：(1) waste and old carbon fiber/epoxy resin composite material is cut into suitable size, it is spare；(2) it is put into reaction kettle, adds inorganic acid and the composite acid of organic acid, the combination solvent of organic solvent and combine oxidation Agent, 1.0-2.5h is heated in the case where temperature is 80-180 DEG C, pressure is 1.0-1.4Mp；(3) centrifuge separation carbon fiber and solution are utilized；(4) carbon fiber washed, be dried to obtain recovery product.
- 3. according to the method described in claim 2, it is characterized in that in step (2), the inorganic acid is using nitric acid, phosphoric acid, salt One kind in acid, sulfuric acid.
- 4. according to the method described in claim 2, it is characterized in that in step (2), the organic acid is using carboxylic acid, sulfonic acid, Asia One kind in sulfonic acid, thionothiolic acid.
- 5. according to the method described in claim 2, it is characterized in that in step (2), the combination solvent of the organic solvent uses Two or more in toluene, dimethylbenzene, acetone, ethers, alcohols.
- 6. according to the method described in claim 2, it is characterized in that obtained recovery product, the degradation rate of its epoxy resin are >=90%.
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| CN107636054A (en) * | 2015-05-01 | 2018-01-26 | 艾达索高新材料无锡有限公司 | It is a kind of to degrade and reclaim cross-linked polymer or strengthen the method for composite |
| KR101801788B1 (en) * | 2015-12-11 | 2017-11-28 | 한국과학기술연구원 | Method and apparatus for recovering fiber assembly from thermosetting resin composite materials and recovered fiber assembly |
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| GB2557682A (en) * | 2016-12-15 | 2018-06-27 | saperatec GmbH | Method and apparatus for recycling packaging material |
| CN108359233A (en) * | 2017-07-28 | 2018-08-03 | 安徽旭升新材料有限公司 | A kind of waste material continuously enhances thermoplastic carbon fiber composite wood and preparation method thereof |
| CN108640699B (en) * | 2018-04-28 | 2020-10-27 | 中国人民解放军国防科技大学 | Method for preparing carbon/carbon preformed body by recycling carbon fiber reinforced resin matrix composite material |
| CN109897216B (en) * | 2019-03-15 | 2021-02-09 | 四川大学 | Recycling method of waste thermosetting resin and composite material thereof |
| CN110757682A (en) * | 2019-10-29 | 2020-02-07 | 中国科学院山西煤炭化学研究所 | Method for recycling waste circuit boards in full-component mode through two-step method |
| US20240042651A1 (en) * | 2020-12-23 | 2024-02-08 | Miraikasei Inc. | Method of producing recycled reinforcing fibers |
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