CN111995796A - Electrical degradation recovery method of carbon fiber reinforced composite material - Google Patents
Electrical degradation recovery method of carbon fiber reinforced composite material Download PDFInfo
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- 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
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Abstract
The invention discloses an electric degradation recovery method of a carbon fiber reinforced composite material, which adopts electrocatalytic oxidation to oxidize thermosetting resin into low molecular weight thermoplastic polymer and quickly dissolve the low molecular weight thermoplastic polymer in a mixed solvent, thereby separating and recovering carbon fiber and realizing resource recycling. The mixed solvent has good conductivity and high polymer solubility, can obviously improve the catalytic oxidation efficiency of the fiber reinforced material, the fiber recovery rate can reach more than 95 percent, and the thermosetting cross-linked epoxy resin can be dissolved in the mixed solvent for separation, recovery and reuse after being subjected to electrocatalytic oxidation degradation into a low molecular weight thermoplastic polymer; after the electrocatalytic oxidation, water and the organic solvent can be directly distilled and recovered from the electrolysis degradation liquid, and the electrolysis degradation liquid recovered by reduced pressure distillation and the water washing liquid are mixed to be used as the electrolysis degradation liquid for reuse. The electric degradation recovery method has the advantages of mild degradation conditions, simple process operation, no corrosion, less three wastes, environment optimization and the like.
Description
Technical Field
The invention relates to the field of electrolytic recovery of carbon fiber reinforced composite materials, in particular to an electric degradation recovery method of a carbon fiber reinforced composite material.
Background
The carbon fiber belongs to high and new technology and high value-added products, has incomparable excellent performance of other materials, has gradually permeated from the initial aerospace and military departments to the civil field since the commercialization, and is expanded to various fields of the whole industry and the civil at present.
Carbon fiber composite waste is a generic term for carbon fibers, carbon fiber prepregs, and carbon fiber composite waste. With the increasing depth of carbon fiber composite materials into the lives of people, carbon fiber products are gradually increased, and the treatment of carbon fiber composite material waste is an inevitable problem. The existing processing technology of the carbon fiber composite material is a thermosetting molding technology, and once all carbon fiber products are scrapped, the carbon fiber products cannot be recycled like other thermoplastic composite materials. In the future, waste treatment and recycling of carbon fiber composite materials will also become a main direction for research in the carbon fiber industry. At present, the research on the recycling method of the fiber reinforced composite materials at home and abroad mainly aims at non-degradable thermosetting resin matrix composite material garbage wastes and comprises a landfill method, an incineration method, a crushing method, a heat treatment method and a chemical method.
Landfill and incineration will be increasingly prohibited. The crushing method is to crush the composite garbage waste into reclaimed materials with different particle sizes by means of cutting and grinding, and the reclaimed materials are used as low-value fillers.
Heat treatment processes include incineration, thermal cracking, fluidized bed and cement kiln processes, which have in common: gasifying the organic matter component (30-40%) in the composite material garbage waste at the high temperature of 500-950 ℃ and simultaneously recovering energy. Wherein, the cement kiln method can also convert inorganic components (60-70%) into raw materials required by cement manufacture; the thermal cracking method and the fluidized bed method can separate and recover fiber materials, the recovered glass fiber is used for manufacturing glass, coke often remains on the surface of the recovered carbon fiber, the mechanical property is reduced, and only 70-80% of the original carbon fiber is left, so that the recycling value of the carbon fiber is greatly influenced. The chemical methods comprise a solvent hydrolysis method, an acid digestion method, an alkali hydrolysis method, a catalytic depolymerization method, an oxidative degradation method and the like, and the methods are characterized in that: the high-crosslinking organic polymer components are degraded by chemical reaction by using high-temperature and high-pressure solvents (supercritical, subcritical or near-critical water, methanol, ethanol, propanol and the like), high-concentration strong oxidizing acids (8-12N concentrated nitric acid), strong alkali, strong corrosive reagents (phenol) or strong oxidants and the like, so that the separation and recovery of the fiber reinforced material are realized. The current solvent decomposition method is also in a laboratory test stage, needs high-temperature and high-pressure conditions, has extremely high equipment requirements, and is difficult to realize industrial scale operation; other chemical methods require the use of highly corrosive chemical hazardous materials, have harsh requirements on equipment and operating environments, generate a large number of secondary pollution sources, and are not suitable for industrial operation. It can be seen that the above recovery methods all have the disadvantage of being unavoidable, and there are many problems from the industrial requirement.
Disclosure of Invention
The technical problems to be solved by the invention are as follows: the invention provides an electrolytic recovery method of a fiber reinforced composite material, which aims to solve various problems in the high-efficiency and environment-friendly recovery process of the existing carbon fiber reinforced composite material.
In order to solve the technical problems, the invention provides the following technical scheme:
an electric degradation recovery method of carbon fiber reinforced composite material comprises the following steps:
step 1: adding a mixed solvent obtained by mixing an organic solvent, water and an ionic compound in proportion into an electric degradation tank to be used as an electrolyte;
step 2: the carbon fiber reinforced composite material is taken as an anode, and the conductive material is taken as a cathode and is respectively arranged in the electric degradation tank and connected with a direct current power supply;
and step 3: starting a power supply to cause the resin base in the carbon fiber reinforced composite material as the anode to be electrochemically oxidized and degraded into a low-molecular-weight thermoplastic polymer to be dissolved in the mixed solvent;
and 4, step 4: and (3) after the resin base in the carbon fiber reinforced composite material is completely oxidized, washing and drying the fiber material obtained in the step (3) to obtain recycled carbon fibers, and distilling the degraded mixed solvent obtained in the step (3) under reduced pressure, washing with water and drying to obtain the low-molecular-weight thermoplastic polymer.
And 5: the distillate fraction obtained by the reduced pressure distillation and the water washing solution are mixed and used again as the electrolyte.
Preferably, the carbon fiber-reinforced composite material contains at least one of glycidyl ether epoxy resin, glycidyl ester epoxy resin, glycidyl amine epoxy resin, linear aliphatic epoxy resin, and alicyclic epoxy resin.
Preferably, the constant voltage across the electrical degradation tank is 10-36V.
Preferably, the mass ratio of the ionic compound, the organic solvent and the water in the mixed solvent is 1: 5-100: 5 to 100.
Preferably, the organic solvent is one or more of 1-methyl-2-pyrrolidone, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, tetrahydrofuran, methyl ethyl ketone, cyclohexanone, ethyl acetate, chloroform, dioxane, acetonitrile, benzene, toluene, xylene, methanol, ethanol, ethylene glycol, N-butanol, tert-butanol, formic acid and acetic acid.
Preferably, the ionic compound is an acid or an alkali or a salt, and the acid comprises one or more of hydrochloric acid, sulfuric acid, nitric acid, formic acid, acetic acid, benzoic acid, oxalic acid and malonic acid.
Preferably, the alkali comprises one or more of sodium hydroxide, potassium hydroxide, calcium hydroxide and ammonia water.
Preferably, the salts include one or more of sodium chloride, potassium chloride, magnesium chloride, calcium chloride, ammonium chloride, ferric chloride, cobalt chloride, nickel chloride, copper chloride, zinc chloride, sodium sulfate, potassium sulfate, ammonium sulfate, ferric sulfate, cobalt sulfate, nickel sulfate, copper sulfate, zinc sulfate, sodium nitrate, potassium nitrate, magnesium nitrate, calcium nitrate, ammonium nitrate, ferric nitrate, cobalt nitrate, nickel nitrate, copper nitrate, zinc nitrate, sodium formate, potassium formate, ammonium formate, sodium acetate, potassium acetate, ammonium acetate, sodium benzoate, potassium benzoate, ammonium benzoate, disodium oxalate, dipotassium oxalate, diammonium oxalate, disodium malonate, dipotassium malonate, and diammonium malonate.
Preferably, the temperature of the carbon fiber reinforced composite material for electric degradation is 5-140 ℃.
The invention has the following beneficial effects:
compared with the prior art, the invention provides an electric degradation recovery method of a carbon fiber reinforced composite material, which adopts electrocatalytic oxidation to oxidize thermosetting resin into low molecular weight thermoplastic polymer and quickly dissolve the low molecular weight thermoplastic polymer in a mixed solvent, thereby separating and recovering carbon fiber and realizing resource recycling. The method specifically comprises the following steps:
(1) the mixed solvent has good conductivity and high polymer solubility, can obviously improve the catalytic oxidation efficiency of the fiber reinforced material, and can realize the complete degradation of the resin matrix within 12 to 48 hours;
(2) the recovery rate of the fiber can reach more than 95 percent, and the recovered fiber has basically no defect and no residual impurity on the surface and can be reused;
(3) the thermosetting cross-linked epoxy resin is electrically catalyzed, oxidized and degraded into a low molecular weight thermoplastic polymer, then dissolved in a mixed solvent, and can be reused as a high molecular material additive and the like after being separated;
(4) after electrocatalytic oxidation, water and the organic solvent can be directly distilled and recovered from the electrolysis solution;
(5) the electrolyte recovered by reduced pressure distillation and the water washing liquid are mixed to be used as the electrolyte for reuse.
In addition, the electric degradation recovery method of the carbon fiber reinforced composite material has the advantages of mild degradation conditions, simple process operation, no corrosion, less three wastes, environment optimization and the like, and is a method for environment-friendly recovery of the carbon fiber reinforced composite material.
Detailed Description
The following examples are included to provide further detailed description of the present invention and to provide those skilled in the art with a more complete, concise, and exact understanding of the principles and spirit of the invention.
Example 1:
the resin raw material in the carbon fiber reinforced composite material is glycidyl ether epoxy resin.
In this embodiment, the ionic compound is a salt, specifically sodium chloride, and the organic solvent is acetic acid.
Respectively weighing 10 g of sodium chloride, 100 g of deionized water and 150 g of acetic acid, mixing and adding into an electric degradation tank; weighing 2 g of complete carbon fiber reinforced composite material as an anode, and placing stainless steel sheets as cathodes in an electrical degradation tank and connecting with a direct current power supply respectively; and heating to 50 ℃, starting a power supply, keeping the constant voltage of 10V at two ends of the electrical degradation tank and keeping the temperature of the electrical degradation tank constant at 50 ℃, so that the resin matrix in the carbon fiber reinforced composite material serving as the anode is subjected to electrochemical oxidation. After 40 hours, filtering the electrolytic solution, washing and drying the fiber material to obtain the recycled carbon fiber, wherein the recovery rate of the carbon fiber is 97 percent. Distilling the filtrate under reduced pressure, washing with water, drying to obtain low molecular weight thermoplastic polymer, mixing the distillate of reduced pressure distillation with water washing solution, adjusting the concentrations of ionic compound and organic solvent, and reusing as electrolyte.
Example 2:
the resin raw material in the carbon fiber reinforced composite material is glycidyl ester epoxy resin.
In this embodiment, the ionic compound is an acid, specifically hydrochloric acid, and an organic solvent ethylene glycol.
Respectively weighing 10 g of hydrochloric acid with the concentration of 37%, 100 g of deionized water and 150 g of ethylene glycol, mixing and adding into an electric degradation tank; weighing 2 g of complete carbon fiber reinforced composite material as an anode, and placing stainless steel sheets as cathodes in an electrical degradation tank and connecting with a direct current power supply respectively; and (3) heating to 80 ℃, starting a power supply, keeping the constant voltage at two ends of the electrical degradation tank at 36V, keeping the temperature of the electrical degradation at constant 80 ℃, and carrying out electrochemical oxidation on the resin matrix in the carbon fiber reinforced composite material serving as the anode. And after 36 hours, filtering the electrolytic solution, washing and drying the fiber material to obtain the recovered carbon fiber, wherein the recovery rate of the carbon fiber is 98%. And distilling the filtrate under reduced pressure, washing with water and drying to obtain the low molecular weight thermoplastic polymer. Mixing the distillate fraction obtained by reduced pressure distillation with water washing solution, adjusting the concentrations of ionic compound and organic solvent, and reusing as the electrolyte.
Example 3:
the resin raw material in the carbon fiber reinforced composite material is glycidyl amine epoxy resin.
In this embodiment, the ionic compound is an acid, specifically hydrochloric acid, and the organic solvent is formic acid.
Respectively weighing 10 g of hydrochloric acid with the concentration of 37%, 50 g of deionized water and 200 g of formic acid, mixing and adding into an electric degradation tank; weighing 2 g of complete carbon fiber reinforced composite material as an anode, and placing stainless steel sheets as cathodes in an electrical degradation tank and connecting with a direct current power supply respectively; and (3) heating to 80 ℃, starting a power supply, keeping the constant voltage at two ends of the electrical degradation tank at 23V, keeping the temperature of the electrical degradation at constant 80 ℃, and carrying out electrochemical oxidation on the resin matrix in the carbon fiber reinforced composite material serving as the anode. And filtering the electrolytic solution after 42 hours, washing and drying the fiber material to obtain the recovered carbon fiber, wherein the recovery rate of the carbon fiber is 98%. And distilling the filtrate under reduced pressure, washing with water and drying to obtain the low molecular weight thermoplastic polymer. Mixing the distillate fraction obtained by reduced pressure distillation with water washing solution, adjusting the concentrations of ionic compound and organic solvent, and reusing as the electrolyte.
Example 4:
the resin raw material in the carbon fiber reinforced composite material is linear aliphatic epoxy resin.
In the embodiment, the ionic compound adopts alkalies, specifically sodium hydroxide, and the organic solvent adopts n-butanol.
Respectively weighing 10 g of sodium hydroxide, 100 g of deionized water and 150 g of n-butanol, mixing and adding into an electric degradation tank; weighing 2 g of complete carbon fiber reinforced composite material as an anode, and placing stainless steel sheets as cathodes in an electrical degradation tank and connecting with a direct current power supply respectively; and (3) heating to 60 ℃, starting a power supply, keeping the constant voltage at two ends of the electrical degradation tank at 30V, keeping the temperature of the electrical degradation at constant 60 ℃, and carrying out electrochemical oxidation on the resin matrix in the carbon fiber reinforced composite material serving as the anode. And after 48 hours, filtering the electrolytic solution, washing and drying the fiber material to obtain the recovered carbon fiber, wherein the recovery rate of the carbon fiber is 97 percent. And distilling the filtrate under reduced pressure, washing with water and drying to obtain the low molecular weight thermoplastic polymer. Mixing the distillate fraction obtained by reduced pressure distillation with water washing solution, adjusting the concentrations of ionic compound and organic solvent, and reusing as the electrolyte.
Example 5:
the resin raw material in the carbon fiber reinforced composite material is alicyclic epoxy resin.
In this embodiment, the ionic compound is a salt, specifically sodium sulfate, and the organic solvent is 1-methyl-2-pyrrolidone.
Respectively weighing 10 g of sodium sulfate, 100 g of deionized water and 150 g of 1-methyl-2-pyrrolidone, mixing and adding into an electric degradation tank; weighing 2 g of complete carbon fiber reinforced composite material as an anode, and placing stainless steel sheets as cathodes in an electrical degradation tank and connecting with a direct current power supply respectively; and (3) heating to 140 ℃, starting a power supply, keeping the constant voltage at two ends of the electrical degradation tank at 15V, keeping the temperature of the electrical degradation at constant 140 ℃, and carrying out electrochemical oxidation on the resin matrix in the carbon fiber reinforced composite material serving as the anode. After 18 hours, filtering the electrolytic solution, washing and drying the fiber material to obtain the recycled carbon fiber, wherein the recovery rate of the carbon fiber is 98%. And distilling the filtrate under reduced pressure, washing with water and drying to obtain the low molecular weight thermoplastic polymer. Mixing the distillate fraction obtained by reduced pressure distillation with water washing solution, adjusting the concentrations of ionic compound and organic solvent, and reusing as the electrolyte.
Example 6:
the resin raw materials in the carbon fiber reinforced composite material are glycidyl ether epoxy resin and glycidyl ester epoxy resin.
In this embodiment, the ionic compound is a salt, specifically potassium nitrate, and the organic solvent is tetrahydrofuran.
Respectively weighing 10 g of potassium nitrate, 100 g of deionized water and 150 g of tetrahydrofuran, mixing and adding into an electric degradation tank; weighing 2 g of complete carbon fiber reinforced composite material as an anode, and placing stainless steel sheets as cathodes in an electrical degradation tank and connecting with a direct current power supply respectively; and cooling to 5 ℃ in an ice bath, starting a power supply, keeping the constant voltage of 10V at two ends of the electrical degradation tank and keeping the temperature of the electrical degradation at constant 5 ℃, so that the resin matrix in the carbon fiber reinforced composite material serving as the anode is subjected to electrochemical oxidation. And after 48 hours, filtering the electrolytic solution, washing and drying the fiber material to obtain the recovered carbon fiber, wherein the recovery rate of the carbon fiber is 96%. And distilling the filtrate under reduced pressure, washing with water and drying to obtain the low molecular weight thermoplastic polymer. Mixing the distillate fraction obtained by reduced pressure distillation with water washing solution, adjusting the concentrations of ionic compound and organic solvent, and reusing as the electrolyte.
Example 7:
the resin raw materials in the carbon fiber reinforced composite material are glycidyl ether epoxy resin and linear aliphatic epoxy resin.
In the embodiment, the ionic compound is salt, specifically sodium acetate, and the organic solvent is cyclohexanone.
Respectively weighing 10 g of sodium acetate, 50 g of deionized water and 200 g of cyclohexanone, mixing and adding into an electric degradation tank; weighing 2 g of complete carbon fiber reinforced composite material as an anode, and placing stainless steel sheets as cathodes in an electrical degradation tank and connecting with a direct current power supply respectively; and (3) heating to 75 ℃, starting a power supply, keeping the constant voltage at two ends of the electrical degradation tank at 33V, keeping the temperature of the electrical degradation at 75 ℃, and carrying out electrochemical oxidation on the resin matrix in the carbon fiber reinforced composite material serving as the anode. And after 48 hours, filtering the electrolytic solution, washing and drying the fiber material to obtain the recycled carbon fiber, wherein the recovery rate of the carbon fiber is 98%. And distilling the filtrate under reduced pressure, washing with water and drying to obtain the low molecular weight thermoplastic polymer. Mixing the distillate fraction obtained by reduced pressure distillation with water washing solution, adjusting the concentrations of ionic compound and organic solvent, and reusing as the electrolyte.
Example 8:
the resin raw materials in the carbon fiber reinforced composite material are glycidyl amine epoxy resin and alicyclic epoxy resin.
In this embodiment, the ionic compound is a salt, specifically disodium oxalate, and the organic solvent is xylene.
Respectively weighing 10 g of disodium oxalate, 50 g of deionized water and 200 g of dimethylbenzene, mixing and adding into an electric degradation tank; weighing 2 g of complete carbon fiber reinforced composite material as an anode, and placing stainless steel sheets as cathodes in an electrical degradation tank and connecting with a direct current power supply respectively; and (3) heating to 40 ℃, starting a power supply, keeping the constant voltage of two ends of the electrical degradation tank at 25V, keeping the temperature of the electrical degradation at constant 40 ℃, and carrying out electrochemical oxidation on the resin matrix in the carbon fiber reinforced composite material serving as the anode. And after 48 hours, filtering the electrolytic solution, washing and drying the fiber material to obtain the recycled carbon fiber, wherein the recovery rate of the carbon fiber is 98%. And distilling the filtrate under reduced pressure, washing with water and drying to obtain the low molecular weight thermoplastic polymer. Mixing the distillate fraction obtained by reduced pressure distillation with water washing solution, adjusting the concentrations of ionic compound and organic solvent, and reusing as the electrolyte.
The acids used in the above examples may be replaced by one or more of hydrochloric acid, sulfuric acid, nitric acid, formic acid, acetic acid, benzoic acid, oxalic acid, and malonic acid.
The alkalis used in the above embodiments may be replaced with one or more of sodium hydroxide, potassium hydroxide, calcium hydroxide, and ammonia water.
The salts used in the above embodiments may be equivalently replaced by one or more of sodium chloride, potassium chloride, magnesium chloride, calcium chloride, ammonium chloride, ferric chloride, cobalt chloride, nickel chloride, copper chloride, zinc chloride, sodium sulfate, potassium sulfate, ammonium sulfate, ferric sulfate, cobalt sulfate, nickel sulfate, copper sulfate, zinc sulfate, sodium nitrate, potassium nitrate, magnesium nitrate, calcium nitrate, ammonium nitrate, ferric nitrate, cobalt nitrate, nickel nitrate, copper nitrate, zinc nitrate, sodium formate, potassium formate, ammonium formate, sodium acetate, potassium acetate, ammonium acetate, sodium benzoate, potassium benzoate, ammonium benzoate, disodium oxalate, dipotassium oxalate, diammonium oxalate, disodium malonate, dipotassium malonate, and diammonium malonate.
In conclusion, the invention adopts electrocatalytic oxidation to oxidize the thermosetting resin into the low-molecular-weight thermoplastic polymer and quickly dissolve the low-molecular-weight thermoplastic polymer in the mixed solvent, thereby separating and recovering the carbon fiber and realizing the resource recycling. The method specifically comprises the following steps: the mixed solvent has good conductivity and high polymer solubility, and can obviously improve the catalytic oxidation efficiency of the fiber reinforced material; the recovery rate of the fiber can reach more than 95 percent, and the recovered fiber has basically no defect and no residual impurity on the surface and can be reused; the thermosetting cross-linked epoxy resin is electrically catalyzed, oxidized and degraded into a low molecular weight thermoplastic polymer, then dissolved in a mixed solvent, and can be reused as a high molecular material additive and the like after being separated; after electrocatalytic oxidation, water and the organic solvent can be directly distilled and recovered from the electrolysis solution; the electrolyte recovered by reduced pressure distillation and the water washing liquid are mixed to be used as the electrolyte for reuse. The electric degradation recovery method has the advantages of mild degradation conditions, simple process operation, no corrosion, less three wastes, environment optimization and the like, and is a method for environment-friendly recovery of the carbon fiber reinforced composite material.
The above embodiments are only for illustrating the technical idea of the present invention, and the protection scope of the present invention cannot be limited thereby, and any modification made on the basis of the technical scheme according to the technical idea proposed by the present invention falls within the protection scope of the present invention; the technology not related to the invention can be realized by the prior art.
Claims (9)
1. The electric degradation recovery method of the carbon fiber reinforced composite material is characterized by comprising the following steps:
step 1: adding a mixed solvent obtained by mixing an organic solvent, water and an ionic compound in proportion into an electric degradation tank to be used as an electric degradation liquid;
step 2: the carbon fiber reinforced composite material is taken as an anode, and the conductive material is taken as a cathode and is respectively arranged in the electric degradation tank and connected with a direct current power supply;
and step 3: starting a power supply to cause the resin base in the carbon fiber reinforced composite material as the anode to be electrochemically oxidized and degraded into a low-molecular-weight thermoplastic polymer to be dissolved in the mixed solvent;
and 4, step 4: and (3) after the resin base in the carbon fiber reinforced composite material is completely oxidized, washing and drying the fiber material obtained in the step (3) to obtain recycled carbon fibers, and distilling the degraded mixed solvent obtained in the step (3) under reduced pressure, washing with water and drying to obtain the low-molecular-weight thermoplastic polymer.
And 5: the fraction distilled under reduced pressure is mixed with a water washing solution and reused as an electrolyte.
2. The method for electrically degrading and recycling a carbon fiber-reinforced composite material according to claim 1, wherein the carbon fiber-reinforced composite material contains at least one of glycidyl ether type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, linear aliphatic epoxy resin, and alicyclic epoxy resin.
3. The method for recycling carbon fiber reinforced composite material through electrical degradation according to claim 2, wherein the constant pressure across the electrical degradation tank is 10-36V.
4. The method for recycling carbon fiber reinforced composite material through electrical degradation according to claim 1, wherein the mass ratio of the ionic compound, the organic solvent and the water in the mixed solvent is 1: 5-100: 5 to 100.
5. The method for recycling carbon fiber reinforced composite material through electrical degradation according to claim 4, wherein the organic solvent is one or more selected from the group consisting of 1-methyl-2-pyrrolidone, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, tetrahydrofuran, methyl ethyl ketone, cyclohexanone, ethyl acetate, chloroform, dioxane, acetonitrile, benzene, toluene, xylene, methanol, ethanol, ethylene glycol, N-butanol, t-butanol, formic acid and acetic acid.
6. The electrical degradation recovery method of the carbon fiber reinforced composite material as claimed in claim 5, wherein the ionic compound is an acid or an alkali or a salt, and the acid comprises one or more of hydrochloric acid, sulfuric acid, nitric acid, formic acid, acetic acid, benzoic acid, oxalic acid and malonic acid.
7. The electrical degradation recycling method of carbon fiber reinforced composite material as claimed in claim 6, wherein the alkali comprises one or more of sodium hydroxide, potassium hydroxide, calcium hydroxide and ammonia water.
8. The method for recycling carbon fiber reinforced composite material through electric degradation according to claim 7, wherein the salts include one or more of sodium chloride, potassium chloride, magnesium chloride, calcium chloride, ammonium chloride, ferric chloride, cobalt chloride, nickel chloride, cupric chloride, zinc chloride, sodium sulfate, potassium sulfate, ammonium sulfate, ferric sulfate, cobalt sulfate, nickel sulfate, copper sulfate, zinc sulfate, sodium nitrate, potassium nitrate, magnesium nitrate, calcium nitrate, ammonium nitrate, ferric nitrate, cobalt nitrate, nickel nitrate, copper nitrate, zinc nitrate, sodium formate, potassium formate, ammonium formate, sodium acetate, potassium acetate, ammonium acetate, sodium benzoate, potassium benzoate, ammonium formate, disodium oxalate, dipotassium oxalate, diammonium oxalate, disodium malonate, dipotassium malonate, and diammonium malonate.
9. The method for recycling carbon fiber reinforced composite material through electrical degradation according to claim 1, wherein the temperature of electrical degradation of the carbon fiber reinforced composite material is 5-140 ℃.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2615837A (en) * | 2022-03-15 | 2023-08-23 | Mdf Recovery Ltd | Method and apparatus for recovering fibres |
| CN117304567A (en) * | 2023-08-03 | 2023-12-29 | 深圳大学 | Composite strong alkali solution and application thereof in recycling carbon fibers |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02104767A (en) * | 1989-08-25 | 1990-04-17 | Toray Ind Inc | Production of carbon fiber for producing superhigh-strength composite material |
| JPH0544154A (en) * | 1991-08-06 | 1993-02-23 | Petoca:Kk | Surface treatment of carbon fiber |
| CN104499039A (en) * | 2014-12-09 | 2015-04-08 | 深圳大学 | Recovery method of carbon fibers |
| CN107109772A (en) * | 2014-12-26 | 2017-08-29 | 伊集院乘明 | Carbon fiber, its manufacture method and carbon-fiber reinforced resins composition |
| CN108323169A (en) * | 2018-02-09 | 2018-07-24 | 深圳大学 | The lossless fibre reinforced composites recovery method of environmental protection |
-
2020
- 2020-06-24 CN CN202010588331.7A patent/CN111995796A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02104767A (en) * | 1989-08-25 | 1990-04-17 | Toray Ind Inc | Production of carbon fiber for producing superhigh-strength composite material |
| JPH0544154A (en) * | 1991-08-06 | 1993-02-23 | Petoca:Kk | Surface treatment of carbon fiber |
| CN104499039A (en) * | 2014-12-09 | 2015-04-08 | 深圳大学 | Recovery method of carbon fibers |
| CN107109772A (en) * | 2014-12-26 | 2017-08-29 | 伊集院乘明 | Carbon fiber, its manufacture method and carbon-fiber reinforced resins composition |
| CN108323169A (en) * | 2018-02-09 | 2018-07-24 | 深圳大学 | The lossless fibre reinforced composites recovery method of environmental protection |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2615837A (en) * | 2022-03-15 | 2023-08-23 | Mdf Recovery Ltd | Method and apparatus for recovering fibres |
| CN117304567A (en) * | 2023-08-03 | 2023-12-29 | 深圳大学 | Composite strong alkali solution and application thereof in recycling carbon fibers |
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