CN117069999A - Method for catalytic degradation of carbon fiber reinforced resin matrix composite - Google Patents
Method for catalytic degradation of carbon fiber reinforced resin matrix composite Download PDFInfo
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- CN117069999A CN117069999A CN202311041955.7A CN202311041955A CN117069999A CN 117069999 A CN117069999 A CN 117069999A CN 202311041955 A CN202311041955 A CN 202311041955A CN 117069999 A CN117069999 A CN 117069999A
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- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 116
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 116
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 105
- 229920005989 resin Polymers 0.000 title claims abstract description 73
- 239000011347 resin Substances 0.000 title claims abstract description 73
- 239000011159 matrix material Substances 0.000 title claims abstract description 55
- 239000002131 composite material Substances 0.000 title claims abstract description 54
- 238000000034 method Methods 0.000 title claims abstract description 52
- 230000015556 catabolic process Effects 0.000 title claims description 18
- 238000006731 degradation reaction Methods 0.000 title claims description 18
- 230000003197 catalytic effect Effects 0.000 title claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000000835 fiber Substances 0.000 claims abstract description 51
- 239000003054 catalyst Substances 0.000 claims abstract description 26
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims abstract description 10
- 238000004321 preservation Methods 0.000 claims abstract description 10
- 238000004140 cleaning Methods 0.000 claims abstract description 6
- 235000003891 ferrous sulphate Nutrition 0.000 claims abstract description 6
- 239000011790 ferrous sulphate Substances 0.000 claims abstract description 6
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims abstract description 6
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims abstract description 6
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 claims abstract description 6
- ONIKNECPXCLUHT-UHFFFAOYSA-N 2-chlorobenzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1Cl ONIKNECPXCLUHT-UHFFFAOYSA-N 0.000 claims abstract description 5
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000012346 acetyl chloride Substances 0.000 claims abstract description 5
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims abstract description 5
- 235000019341 magnesium sulphate Nutrition 0.000 claims abstract description 5
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims abstract description 5
- 229960001763 zinc sulfate Drugs 0.000 claims abstract description 5
- 229910000368 zinc sulfate Inorganic materials 0.000 claims abstract description 5
- 230000000593 degrading effect Effects 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims abstract description 3
- 239000000463 material Substances 0.000 claims description 26
- 239000000805 composite resin Substances 0.000 claims description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 9
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 229920002302 Nylon 6,6 Polymers 0.000 claims description 4
- 229920005992 thermoplastic resin Polymers 0.000 claims description 4
- 229920001187 thermosetting polymer Polymers 0.000 claims description 4
- 229920002292 Nylon 6 Polymers 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 2
- 239000004695 Polyether sulfone Substances 0.000 claims description 2
- 239000011304 carbon pitch Substances 0.000 claims description 2
- 239000003822 epoxy resin Substances 0.000 claims description 2
- 239000005007 epoxy-phenolic resin Substances 0.000 claims description 2
- 239000004744 fabric Substances 0.000 claims description 2
- 229920001568 phenolic resin Polymers 0.000 claims description 2
- 229920000647 polyepoxide Polymers 0.000 claims description 2
- 229920006393 polyether sulfone Polymers 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 229920006305 unsaturated polyester Polymers 0.000 claims description 2
- 238000011084 recovery Methods 0.000 abstract description 32
- 238000004064 recycling Methods 0.000 abstract description 10
- 239000000126 substance Substances 0.000 abstract description 6
- 239000002699 waste material Substances 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 230000014759 maintenance of location Effects 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 238000005265 energy consumption Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000003912 environmental pollution Methods 0.000 description 3
- 238000000197 pyrolysis Methods 0.000 description 3
- 238000009864 tensile test Methods 0.000 description 3
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical group C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 230000002427 irreversible effect Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000002352 steam pyrolysis Methods 0.000 description 2
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical group C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/06—Elements
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
Abstract
The invention relates to a method for catalytically degrading a carbon fiber reinforced resin matrix composite, which solves the technical problems of long treatment time, complex procedures, serious fiber damage and the like of the traditional chemical recovery method and comprises the following steps: s1, cutting a carbon fiber resin matrix composite material to be degraded, then placing the cut carbon fiber resin matrix composite material into a first group of catalysts, and carrying out heat preservation treatment under normal pressure; the first group of catalysts are one or more of ferrous sulfate, magnesium sulfate and zinc sulfate; s2, taking out the carbon fiber resin matrix composite material treated in the step S1, cleaning, drying, putting into a second group of catalysts, and carrying out heat preservation treatment at normal temperature; the second group of catalysts are one or more of acetyl chloride, o-chlorobenzoyl chloride and terephthaloyl chloride; and S3, taking out the product, and cleaning the product with ethanol to obtain the regenerated carbon fiber with a clean surface. The invention can be used for recycling the carbon fiber reinforced resin matrix composite material.
Description
Technical Field
The invention relates to a recovery method of a carbon fiber reinforced resin matrix composite material, in particular to a method for catalytically degrading the carbon fiber reinforced resin matrix composite material.
Background
The carbon fiber is a light high-strength fiber, and the carbon fiber composite material prepared by the carbon fiber has the advantages of high specific strength, high specific modulus, corrosion resistance and the like, and is widely used in the fields of sports goods, rail transit, aerospace and the like.
As the amount of carbon fiber composite material increases year by year, more and more composite materials will reach life service cycle, and the carbon fiber in the carbon fiber composite material has higher value, and if the carbon fiber composite material is burnt or buried by traditional, huge waste of carbon fiber resources is undoubtedly caused, and environmental pollution is also caused. So that the recycling of these wastes is urgently required. However, since the fibers obtained by the recovery treatment generally exhibit a chopped state, have poor dispersibility, and after undergoing the recovery treatment process, the surface of the fibers has numerous surface defects, and thus have poor interfacial bonding properties with the resin matrix, resulting in a limited range of applications of the recovered fibers, the conventional recovered fibers are generally used as fillers.
At present, a plurality of methods for recycling carbon fiber composite materials exist, and the resin matrix is degraded and the fibers in the resin matrix are stripped in the recycling process, so that the purpose of recycling the carbon fibers is achieved. The degradation method mainly comprises mechanical recovery, pyrolysis recovery, chemical recovery and the like.
Mechanical recovery is currently used as a mature recovery method, and the process generally comprises the steps of crushing, cutting, grinding and other physical means for crushing and screening the composite material, and the recovered fibers can be directly used without any post-treatment process. However, the mechanical properties of the fiber are greatly damaged after the fiber is subjected to physical effects such as extrusion, cutting and the like in the mechanical recovery process, and the treated fiber is poor in morphology, so that the regenerated fiber obtained after mechanical recovery is severely limited in application field. The thermal degradation method is the most perfect recovery method developed at present and is the only successful industrialized method. The thermal degradation method comprises fluidized bed recovery, pyrolysis recovery and super-heat steam recovery. The pyrolysis recovery method mainly decomposes resin under the action of oxidation and heat, and although the recovery efficiency is high and the types of recovered fibers are various, the recovery process requires huge energy consumption, and part of liquid phase byproducts have toxic effects on the environment and human bodies.
The chemical method recovery does not need too high treatment temperature, the waste is soaked in the organic solution, and the resin molecules are cracked into soluble small molecules under the action of the solvent at a certain temperature, so that the carbon fibers are stripped. The range of the solvent which can be selected is very wide, and the solvent can be divided into a dissolution catalytic recovery method and a supercritical solvent recovery method according to the different states of the recovery solution. However, most chemical recovery methods at present need strong oxidizing agents such as strong acid, strong alkali and the like, have high requirements on recovery equipment and cause environmental pollution, and meanwhile, the problems of long recovery time, complex recovery process and the like are accompanied, part of the recovery methods need high temperature and high pressure, and after treatment, the fiber needs complex post-treatment procedures to obtain regenerated fiber with cleaner surface.
The Chinese patent publication No. 114044936B discloses a method for recovering carbon fiber resin matrix composite material by catalytic steam pyrolysis, which solves the problems of high temperature, long treatment time and serious damage of carbon fiber in the existing steam pyrolysis method and comprises the following steps: s1, placing two groups of catalysts into a reaction container according to a preset proportion; s2, cutting the carbon fiber composite material to be degraded, then putting the cut carbon fiber composite material into the catalyst in the step S1, introducing water vapor, and preserving heat under normal pressure; and S3, taking out the product, and cleaning the product by using ultrasonic waves to obtain the recovered carbon fiber with a clean surface.
The above method mainly has the following problems:
(1) The reaction temperature is too high, so that more energy consumption is easy to generate;
(2) The regenerated fiber obtained by the method has the mechanical property reduced due to the high-temperature environment, so that the application field of the regenerated fiber is severely limited;
(3) The method aims at catalytic degradation in a special gas environment, and has no universality in a common gas environment.
Disclosure of Invention
The invention aims to solve the technical problems of high reaction temperature, long treatment time, complex working procedure, serious fiber damage and the like in the prior art, and provides a method for catalyzing and degrading a carbon fiber reinforced resin matrix composite material more quickly and completely at a lower temperature.
For this purpose, the invention provides a method for catalytic degradation of carbon fiber reinforced resin matrix composite materials, comprising the following steps: s1, cutting a carbon fiber resin matrix composite material to be degraded, then placing the cut carbon fiber resin matrix composite material into a first group of catalysts, and carrying out heat preservation treatment under normal pressure; the first group of catalysts are one or more of ferrous sulfate, magnesium sulfate and zinc sulfate, and the concentration is 1-5 mol/L; s2, taking out the carbon fiber resin matrix composite material treated in the step S1, washing with ethanol, drying, putting into a second group of catalysts, and carrying out heat preservation treatment at normal temperature; the second group of catalysts are one or more of acetyl chloride, o-chlorobenzoyl chloride and terephthaloyl chloride, and the solvent is one or more of ethanol, tetrahydrofuran and N, N-dimethylformamide; the mass ratio of the solute to the solvent in the second group of catalysts is 1 (1-5); and S3, taking out the product, and cleaning the product with ethanol to obtain the regenerated carbon fiber with a clean surface.
Preferably, in the step S1, the thickness of the cut carbon fiber resin matrix composite is 1-20 mm.
Preferably, in the step S1, the carbon fiber resin matrix composite is subjected to heat preservation in the first group of catalysts at normal pressure for 30-200 min and at a temperature of 50-150 ℃. The higher the temperature, or longer the hold time, the higher the resin clearance, but too high a treatment temperature or treatment time may cause irreversible performance damage to the fiber.
Preferably, in the step S1, the resin matrix of the carbon fiber resin matrix composite material is a thermosetting resin and a thermoplastic resin, and the thermosetting resin includes epoxy resin, phenolic resin and unsaturated polyester; thermoplastic resins include polyethersulfone, nylon 6, nylon 66.
Preferably, in the step S1, the carbon fiber morphology of the carbon fiber resin matrix composite material includes chopped fibers, continuous fibers, carbon fiber cloth or powder fibers.
Preferably, in the step S1, the fibers of the carbon fiber resin matrix composite are polyacrylonitrile-based carbon fibers or pitch-based carbon fibers.
Preferably, in the step S2, the carbon fiber resin matrix composite is subjected to heat preservation for 60-300 min in the second group of catalysts under normal pressure; the temperature is 50-200 ℃. The higher the temperature, or longer the hold time, the higher the resin clearance, but too high a treatment temperature or treatment time may cause irreversible performance damage to the fiber.
The invention has the following beneficial effects:
(1) The catalyst can catalyze and degrade the resin matrix in the waste carbon fiber resin matrix composite material, so that the resin matrix can be fully degraded and the impurities are removed;
(2) According to the method provided by the invention, the composite material is degraded step by step, the selected catalyst can efficiently break specific chemical bonds in the resin system, and the first group of catalysts play roles; the second group of catalysts are specially selected catalysts, so that the resin can be effectively degraded;
(3) The method provided by the invention does not need excessive temperature in the reaction process, and has higher recovery efficiency. The retention rate of the mechanical property of the recovered carbon fiber obtained by the method can reach more than 95%, and the interface property of the fiber and the resin matrix is not obviously reduced;
(4) The fiber treated by the method can be cleaned by using ethanol, and other solvents are not needed, so that the working procedures are reduced, and the environmental pollution is also reduced.
Drawings
FIG. 1 is an SEM image of the surface of a fiber recovered with the addition of zinc sulfate and acetyl chloride/ethanol in the present invention;
FIG. 2 is an SEM image of the surface of a fiber recovered under the addition of magnesium sulfate and terephthaloyl chloride/ethanol in the present invention.
Detailed Description
The invention is further described below with reference to examples.
Example 1
The carbon fiber in the selected waste carbon fiber resin matrix composite material is DONGLIT 700, the fiber monofilament tensile strength is 4.90GPa, the resin matrix is 4, 5-epoxyhexane-1, 2-diglycidyl ester (TDE-85), the curing agent is 4, 4' -diaminodiphenylmethane (DDM), the carbon fiber is PAN-based fiber, the carbon fiber is in a form of continuous fiber, and the weight content of the carbon fiber is 60 percent.
The embodiment provides a method for recycling carbon fibers in waste carbon fiber resin matrix composite materials, which comprises the following specific steps:
1. cutting a carbon fiber resin composite material with the thickness of 10mm into a proper size, and putting the carbon fiber resin composite material into a reaction device;
2. the materials are put into 1mol/L magnesium sulfate to be treated for 60min at 100 ℃, washed by ethanol, put into acetyl chloride/N, N-dimethylformamide mixed solution, mixed mass ratio is 1:2, and kept at 200 ℃ for 150min;
3. the product was taken out and washed with ethanol by ultrasonic.
By weighing the material before and after the treatment, the degradation rate of the resin was found to be about 98%. The carbon fiber was subjected to a monofilament tensile test according to ASTM-D3379, resulting in a monofilament tensile strength of 4.81GPa and a mechanical strength retention of 98.2%.
Example 2
The carbon fiber in the selected waste carbon fiber resin matrix composite material is short-cut Toli T700, the fiber tensile strength is 4.90GPa, the resin matrix is nylon 6, the carbon fiber is PAN-based fiber, the carbon fiber is in the form of short-cut fiber, and the weight content of the carbon fiber is 60 percent.
The embodiment provides a method for recycling carbon fibers in waste carbon fiber resin matrix composite materials, which comprises the following specific steps:
1. cutting the carbon fiber resin composite material with the thickness of 4mm into a proper size, and putting the carbon fiber resin composite material into a reaction device;
2. the materials are put into 2mol/L ferrous sulfate to be treated for 30min at 50 ℃, washed by ethanol and put into terephthaloyl chloride/tetrahydrofuran mixed solution, the mixing mass ratio is 1:5, and the temperature is kept for 300min at 50 ℃;
3. the product was taken out and washed with ethanol by ultrasonic.
By weighing the material before and after the treatment, the degradation rate of the resin was found to be about 96%. The recycled fibers were re-compounded with resin to make a composite according to ASTM-D790, and the flexural strength was measured to be 2.96Gpa and the mechanical strength retention was measured to be 95.7%.
Example 3
The carbon fiber in the selected waste carbon fiber resin matrix composite material is DONGLIT 800, the fiber tensile strength is 5.49GPa, the resin matrix is 4, 5-epoxyhexane-1, 2-diglycidyl ester (TDE-85), the curing agent is diaminodiphenyl sulfone (DDS), the carbon fiber is PAN-based fiber, the carbon fiber is in the form of continuous fiber, and the weight content of the carbon fiber is 60 percent.
The embodiment provides a method for recycling carbon fibers in waste carbon fiber resin matrix composite materials, which comprises the following specific steps:
1. cutting a carbon fiber resin composite material with the thickness of 20mm into a proper size, and putting the carbon fiber resin composite material into a reaction device;
2. the materials are put into 5mol/L ferrous sulfate to be treated for 200min at 50 ℃, washed by ethanol, put into terephthaloyl chloride/ethanol mixed solution, the mixing mass ratio is 1:3, and kept at 120 ℃ for 100min;
3. the product was taken out and washed with ethanol by ultrasonic.
By weighing the material before and after the treatment, the degradation rate of the resin was found to be about 96%. The carbon fiber was subjected to a monofilament tensile test according to ASTM-D3379, resulting in a monofilament tensile strength of 5.32GPa and a mechanical strength retention of 96.9%.
Example 4
The carbon fiber in the selected waste carbon fiber resin matrix composite material is short-cut east T800, the fiber tensile strength is 5.49GPa, the resin matrix nylon 66, the carbon fiber is PAN-based fiber, the carbon fiber is in the form of short-cut fiber, and the weight content of the carbon fiber is 60%.
The embodiment provides a method for recycling carbon fibers in waste carbon fiber resin matrix composite materials, which comprises the following specific steps:
1. cutting a carbon fiber resin composite material with the thickness of 20mm into a proper size, and putting the carbon fiber resin composite material into a reaction device;
2. the materials are put into 2mol/L zinc sulfate to be treated for 50min at 200 ℃, washed by ethanol and put into mixed solution of o-chlorobenzoyl chloride/N, N-dimethylformamide, the mixing mass ratio is 1:1, and the temperature is kept for 60min at 150 ℃;
3. the product was taken out and washed with ethanol by ultrasonic.
By weighing the material before and after the treatment, the degradation rate of the resin was found to be about 99%. The recycled fibers were re-compounded with resin to prepare a composite material according to ASTM-D790, and the flexural strength was measured to be 3.23Gpa and the mechanical strength retention was measured to be 97.6%.
Example 5
The carbon fiber in the selected waste carbon fiber resin matrix composite material is DONGLIT 700, the fiber tensile strength is 4.90GPa, the resin matrix nylon 66, the carbon fiber is PAN-based fiber, the carbon fiber is chopped fiber, and the weight content of the carbon fiber is 60%.
The embodiment provides a method for recycling carbon fibers in waste carbon fiber resin matrix composite materials, which comprises the following specific steps:
1. cutting a carbon fiber resin composite material with the thickness of 1mm into a proper size, and putting the carbon fiber resin composite material into a reaction device;
2. the materials are put into 2mol/L ferrous sulfate to be treated for 150min at 100 ℃, washed by ethanol and put into mixed solution of o-chlorobenzoyl chloride/N, N-dimethylformamide, the mixing mass ratio is 1:4, and the temperature is kept for 200min at 120 ℃;
3. the product was taken out and washed with ethanol by ultrasonic.
By weighing the material before and after the treatment, the degradation rate of the resin was found to be about 97%. The carbon fiber was subjected to a monofilament tensile test according to ASTM-D3379, resulting in a monofilament tensile strength of 4.83GPa and a mechanical strength retention of 98.6%.
Compared with the existing carbon fiber recovery technology, the method has the advantages of high recovery efficiency, low energy consumption and low treatment temperature, solves the problems of long operation time and high energy consumption of the chemical recovery process, can degrade resin more effectively compared with other traditional recovery methods of single-use catalysts, and has different effects in two steps of treatment and can recover more efficiently.
The state of the recycled fiber is kept good, no obvious defect structure appears on the surface, and the mechanical property of the fiber is reserved to a great extent. The carbon fiber also maintains the same shape after being recovered, so that the carbon fiber still has a certain utilization value.
However, the foregoing description is only illustrative of the present invention and is not intended to limit the scope of the invention, so that the substitution of equivalent elements or equivalent variations and modifications within the scope of the invention are intended to fall within the scope of the claims.
Claims (7)
1. The method for catalytically degrading the carbon fiber reinforced resin matrix composite material is characterized by comprising the following steps of:
s1, cutting a carbon fiber resin matrix composite material to be degraded, then placing the cut carbon fiber resin matrix composite material into a first group of catalysts, and carrying out heat preservation treatment under normal pressure; the first group of catalysts are one or more of ferrous sulfate, magnesium sulfate and zinc sulfate, and the concentration is 1-5 mol/L;
s2, taking out the carbon fiber resin matrix composite material treated in the step S1, cleaning, drying, putting into a second group of catalysts, and carrying out heat preservation treatment at normal temperature; the second group of catalysts are one or more of acetyl chloride, o-chlorobenzoyl chloride and terephthaloyl chloride, and the solvent is one or more of ethanol, tetrahydrofuran and N, N-dimethylformamide; the mass ratio of the solute to the solvent in the second group of catalysts is 1 (1-5);
and S3, taking out the product, and cleaning to obtain the regenerated carbon fiber with a clean surface.
2. The method for catalytic degradation of carbon fiber resin matrix composite according to claim 1, wherein in the step S1, the thickness of the cut carbon fiber resin matrix composite is 1-20 mm.
3. The method for catalytic degradation of carbon fiber resin matrix composite according to claim 1, wherein in step S1, the carbon fiber resin matrix composite is subjected to heat preservation in a first group of catalysts at normal pressure for 30-200 min and at a temperature of 50-150 ℃.
4. The method for catalytic degradation of carbon fiber resin-based composite material according to claim 1, wherein in step S1, the resin matrix of the carbon fiber resin-based composite material is a thermosetting resin, a thermoplastic resin, the thermosetting resin including epoxy resin, phenolic resin and unsaturated polyester; thermoplastic resins include polyethersulfone, nylon 6, nylon 66.
5. The method for catalytic degradation of carbon fiber resin-based composite material according to claim 1, wherein in step S1, the carbon fiber morphology of the carbon fiber resin-based composite material comprises chopped fibers, continuous fibers, carbon fiber cloth, or powder fibers.
6. The method for catalytic degradation of carbon fiber resin-based composite material according to claim 1, wherein in step S1, the fibers of the carbon fiber resin-based composite material are polyacrylonitrile-based carbon fibers or pitch-based carbon fibers.
7. The method for catalytic degradation of carbon fiber resin matrix composite according to claim 1, wherein in the step S2, the carbon fiber resin matrix composite is subjected to heat preservation in a second group of catalysts under normal pressure for 60-300 min; the temperature is 50-200 ℃.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202311041955.7A CN117069999A (en) | 2023-08-18 | 2023-08-18 | Method for catalytic degradation of carbon fiber reinforced resin matrix composite |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202311041955.7A CN117069999A (en) | 2023-08-18 | 2023-08-18 | Method for catalytic degradation of carbon fiber reinforced resin matrix composite |
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| CN117069999A true CN117069999A (en) | 2023-11-17 |
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