CN111100322B - Method for microwave pyrolysis of carbon fiber composite material - Google Patents
Method for microwave pyrolysis of carbon fiber composite material Download PDFInfo
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- CN111100322B CN111100322B CN201811264420.5A CN201811264420A CN111100322B CN 111100322 B CN111100322 B CN 111100322B CN 201811264420 A CN201811264420 A CN 201811264420A CN 111100322 B CN111100322 B CN 111100322B
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Abstract
The invention discloses a method for microwave pyrolysis of a carbon fiber composite material. The method comprises the following steps: contacting a carbon fiber composite material with a porous composite material, applying a microwave field to the carbon fiber composite material and the porous composite material in an inert atmosphere or vacuum, and generating an electric arc in the porous composite material under the microwave, so that the high temperature is quickly reached, a polymer matrix in the carbon fiber composite material is cracked, and carbon fibers are reserved and recycled; the method of the invention utilizes the porous composite material which generates the electric arc in the microwave to generate the electric arc in the microwave, thereby quickly generating high temperature, leading the polymer matrix in the carbon fiber composite material to be cracked, reserving the carbon fiber and recycling, having high process efficiency and high added value of the composition of the product.
Description
Technical Field
The invention relates to the technical field of waste plastic resource utilization, in particular to a method for microwave pyrolysis of a carbon fiber composite material.
Background
The carbon fiber composite material has excellent performances of light weight, high strength, good corrosion resistance and the like, and is widely applied to high and new technical fields of aerospace, new energy, automobile industry, sports goods and the like. With the wide application of carbon fiber composite materials, the waste and old carbon fiber composite materials are increased day by day, and a large amount of carbon fiber composite material waste attracts people's attention, which has great influence on environmental protection and economic benefit. With increasing attention on environmental protection and energy and resource crisis caused by international situation, and high price and excellent comprehensive performance of carbon fiber in the carbon fiber composite material, research on carbon fiber recovery technology is an important development trend in the future.
The existing carbon fiber recovery technical method mainly comprises a physical recovery method and a chemical recovery method. The physical recovery method is to crush or melt the carbon fiber composite waste to use as a raw material of a new material. However, the method can cause damage to the properties of each component of the composite material, and particularly, carbon fibers cannot be obtained from the composite material and cannot be recycled. Chemical recovery is the recovery of carbon fibers from carbon fiber composite waste by thermal decomposition or organic solvent decomposition. The organic solvent is decomposed and recovered to obtain clean carbon fibers, but the recovery process uses a large amount of organic solvent, which may pollute the environment, the solvent separation (liquid separation, extraction, distillation, etc.) after use is complicated, which results in high recovery cost, and the method is selective to the types of matrix resins of the carbon fiber reinforced resin composite material and even the types of curing agents, and is not suitable for all matrix resins. The prior art has disclosed that it is most industrially feasible to treat carbon fiber composites by thermal decomposition, but the traditional forms of heating are generally inefficient, making energy costs too high.
Microwave refers to electromagnetic wave with wavelength between infrared ray and Ultra High Frequency (UHF) radio wave, and has very strong penetration ability, and its wavelength is between lm and l mm, and the corresponding frequency is 300 GHz-300 MHz. The magnetron of the microwave generator receives power supply power to generate microwaves, the microwaves are transmitted to the microwave heater through the waveguide, and materials to be heated are heated under the action of the microwave field. The heating mode of microwave is different from the common heat transfer, the high-frequency electric field changes the external electric field and direction periodically at the speed of hundreds of millions of levels per second, so that the polar molecules in the material vibrate with the electric field at high frequency, and the material is heated rapidly under the action of friction and extrusion among molecules, thereby the internal and surface temperatures of the material are raised rapidly. Many patents have disclosed thermal cracking technology using the characteristic of microwave, such as patent CN102585860, patent CN103252226, patent CN106520176, etc., but all use common microwave sensitive materials such as silicon carbide to generate heat in microwave field and transfer the heat to the thermal cracking material, so as to achieve the purpose of thermal cracking. In addition, CN105199139 also cracks the carbon fiber composite material directly in a microwave oven, and the carbon fiber in the carbon fiber composite material can generate heat in a microwave field, but the efficiency is low.
Therefore, how to develop a method for recovering carbon fibers by efficiently cracking the carbon fiber composite material at high temperature by microwave is still a difficult problem, and the development of the method has huge application prospect.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a method for microwave pyrolysis of a carbon fiber composite material. The invention utilizes the porous composite material which generates electric arc in the microwave to generate electric arc in the microwave, thereby quickly generating high temperature, cracking the carbon fiber composite material and recycling the carbon fiber. The method has high efficiency and high added value of the product composition.
The invention aims to provide a method for microwave pyrolysis of a carbon fiber composite material.
The method of the invention comprises the following steps:
contacting a carbon fiber composite material with a porous composite material, applying a microwave field to the carbon fiber composite material and the porous composite material in an inert atmosphere or vacuum, and generating an electric arc in the porous composite material under the microwave, so that the high temperature is quickly reached, a polymer matrix in the carbon fiber composite material is cracked, and carbon fibers are reserved and recycled; the weight ratio of the carbon fiber composite material to the porous composite material is 1: 99-99: 1, preferably 1: 50-50: 1, and more preferably 1: 30-30: 1.
The inert gas atmosphere is an inert gas atmosphere commonly used in the art, such as nitrogen, helium, neon, argon, krypton, or xenon, preferably nitrogen.
The carbon fiber composite material and the porous composite material can be contacted in various ways as long as the carbon fiber composite material and the porous composite material are contacted. Preferably: the carbon fiber composite material is placed on the porous composite material, placed in a cavity formed by the porous composite material, or covered on the lower part by the porous composite material, and the like.
The microwave power of the microwave field is 1W-100 KW; preferably 100W to 80KW, most preferably 200W to 60 KW; the microwave time is 0.1-200 min; preferably 0.5-180 min, most preferably 1-150 min; the microwave generates electric arc, which can reach 700-3000 ℃, preferably 800-2500 ℃, and more preferably 800-2000 ℃, so that the polymer matrix in the carbon fiber composite material is cracked.
The porous composite material comprises: an inorganic porous skeleton and a carbon material supported on the inorganic porous skeleton. The loading refers to that the carbon material is fixed on the surface or in the structure of the inorganic porous framework through a certain binding force.
The carbon material accounts for 0.001-99%, preferably 0.01-90%, more preferably 0.1-80% of the total mass of the porous composite material;
the inorganic porous skeleton is an inorganic material having a porous structure; the average pore diameter of the inorganic porous skeleton is 0.01 to 1000. mu.m, preferably 0.05 to 500. mu.m, more preferably 0.2 to 250. mu.m; the porosity is 1% -99.99%; preferably 10% to 99.9%, more preferably 30% to 99%. The pore diameter of an individual pore is derived from the shortest value in the distance between the intersection points of the straight line through the center of the pore and the pore profile in the SEM picture.
The carbon material is at least one of graphene, carbon nanotubes, carbon nanofibers, graphite, carbon black, carbon fibers, carbon dots, carbon nanowires, a product obtained by carbonizing a carbonizable organic substance or a product obtained by carbonizing a mixture of carbonizable organic substances, and preferably at least one of graphene, carbon nanotubes, a product obtained by carbonizing a carbonizable organic substance and a product obtained by carbonizing a mixture of carbonizable organic substances.
The mixture of the carbonizable organic matter is a mixture of the carbonizable organic matter, inorganic matters of non-metal and non-metal compounds, and other organic matters of non-metal compounds.
The carbonization is that: treating organic matter at certain temperature and atmosphere condition to volatilize most or all of hydrogen, oxygen, nitrogen, sulfur and other components in the organic matter and obtain one kind of carbon containing synthetic material.
The organic matter capable of being carbonized is preferably an organic high molecular compound, and the organic high molecular compound comprises a synthetic high molecular compound and a natural organic high molecular compound; the synthetic polymer compound is preferably rubber or plastic; including thermosets and thermoplastics.
The natural organic polymer compound is preferably at least one of starch, viscose, lignin and cellulose.
The synthetic polymer compound is preferably at least one selected from epoxy resin, phenolic resin, furan resin, polystyrene, styrene-divinylbenzene copolymer, polyacrylonitrile, polyaniline, polypyrrole, polythiophene, styrene butadiene rubber and polyurethane rubber.
The mixture of carbonizable organic substances is preferably at least one of coal, natural asphalt, petroleum asphalt, or coal tar asphalt.
The inorganic material of the inorganic porous framework is one or a combination of more of carbon, silicate, aluminate, borate, phosphate, germanate, titanate, oxide, nitride, carbide, boride, sulfide, silicide and halide; wherein the oxide is preferably at least one of alumina, silica, zirconia, magnesia, ceria and titania; the nitride is preferably at least one of silicon nitride, boron nitride, zirconium nitride, hafnium nitride and tantalum nitride; the carbide is preferably at least one of silicon carbide, zirconium carbide, hafnium carbide and tantalum carbide; the boride is preferably at least one of zirconium boride, hafnium boride and tantalum boride.
The inorganic material of the inorganic porous skeleton is more preferably at least one of carbon, silicate, alumina, magnesia, zirconia, silicon carbide, boron nitride, and potassium titanate.
The inorganic porous framework is preferably at least one of the following specific frameworks: a carbon skeleton obtained after carbonization of the polymer sponge, a porous skeleton formed by inorganic fibers, an inorganic sponge skeleton, a skeleton formed by accumulation of inorganic particles, a ceramic sponge skeleton obtained after roasting of a ceramic precursor sponge and a ceramic fiber skeleton obtained after roasting of ceramic precursor fibers; preferred are a skeleton obtained by carbonizing a melamine sponge, a skeleton obtained by carbonizing a phenol resin sponge, a porous skeleton of aluminum silicate fiber (e.g., aluminum silicate rock wool), a porous skeleton of mullite fiber, a porous skeleton of alumina fiber (e.g., alumina fiber board), a porous skeleton of zirconia fiber, a porous skeleton of magnesia fiber, a porous skeleton of boron nitride fiber, a porous skeleton of boron carbide fiber, a porous skeleton of silicon carbide fiber, a porous skeleton of potassium titanate fiber, and a ceramic fiber skeleton obtained by firing a ceramic precursor fiber.
The porous structure of the inorganic porous framework may be derived from the pore structure of the framework material itself, for example in the form of a sponge-like structure; or from a pore structure formed by the accumulation of fibrous materials, such as the structural forms of cellucotton, fibrofelt, fiberboard and the like; it may also come from a pore structure formed by the accumulation of particulate material, for example in the form of a sand heap; but also from a combination of the above forms. Preferably from a pore structure of a pile of fibrous material. In particular, the porous skeleton made of the inorganic fibers described above is a porous structure made of a skeleton in which fibrous materials are stacked, and does not mean that the fibers themselves have porosity.
The porous composite material can generate high-temperature electric arcs in microwaves, for example, electric arcs which enable the porous composite material to be heated to more than 1000 ℃ in a 900w microwave field can be generated, and the material can resist high temperature, and can resist the high temperature of 3000 ℃ at most. The porous composite material for generating electric arc in microwave is a novel and efficient microwave heating material.
The microwave pyrolysis method for the carbon fiber composite material can comprise the preparation of the porous composite material. Specifically, the preparation method of the porous composite material preferably includes the steps of:
a. preparing a carbon material for loading or a carbon material precursor solution or dispersion liquid;
b. b, immersing an inorganic porous framework or an inorganic porous framework precursor into the solution or the dispersion liquid obtained in the step a to fill the pores of the inorganic porous framework or the inorganic porous framework precursor with the solution or the dispersion liquid; the carbon material and/or the carbon material precursor accounts for 0.001-99.999 percent of the total mass of the inorganic porous framework material or the inorganic porous framework material precursor and the carbon material and/or the carbon material precursor, preferably 0.01-99.99 percent, and more preferably 0.1-99.9 percent;
c. taking out the porous material obtained in the step b, heating, drying, separating out or curing a carbon material or a carbon material precursor, and loading the carbon material or the carbon material precursor on an inorganic porous framework or an inorganic porous framework precursor; the heating and drying temperature is 50-250 ℃, preferably 60-200 ℃, and more preferably 80-180 ℃;
if the raw materials adopt carbon materials and inorganic porous frameworks, the porous composite material for generating the electric arc in the microwave is obtained after the step c; if the raw material adopts at least one of a carbon material precursor or an inorganic porous skeleton precursor, the following step d is required to be continued:
d. c, heating the porous material obtained in the step c in an inert gas atmosphere, converting an inorganic porous skeleton precursor into an inorganic porous skeleton, and/or reducing or carbonizing a carbon material precursor to obtain a porous composite material for generating electric arcs in the microwaves; the heating temperature is 400-1800 ℃, preferably 600-1500 ℃, and more preferably 800-1200 ℃.
Among them, preferred are:
the precursor of the inorganic porous framework is a porous material which can be converted into the inorganic porous framework; at least one selected from a ceramic precursor, a porous material of a carbonizable organic substance, or a porous material of a mixture of carbonizable organic substances.
The carbon material precursor is at least one of graphene oxide, modified carbon nanotubes, modified carbon nanofibers, modified graphite, modified carbon black, modified carbon fibers and a carbonizable organic substance or a carbonizable organic substance mixture. The modified carbon nanotube, modified carbon nanofiber, modified graphite, modified carbon black and modified carbon fiber refer to carbon materials that are pretreated, for example, pretreated by using a dispersant or a surfactant or pretreated by grafting a hydrophilic group, in order to improve the dispersibility of the carbon materials in water or an organic solvent to obtain a stable dispersion liquid; these pretreatment means are those of the prior art which improve dispersibility. Carbon materials subjected to the above pretreatment, such as graphene aqueous dispersion, graphene ethanol dispersion, graphene aqueous slurry, graphene oil-based slurry, graphene oxide aqueous dispersion, graphene oxide ethanol dispersion, graphene oxide N-methylpyrrolidone dispersion, carbon nanotube aqueous dispersion, carboxylated carbon nanotube aqueous dispersion, carbon nanotube ethanol dispersion, carbon nanotube dimethylformamide dispersion, carbon nanotube N-methylpyrrolidone slurry, and the like, can also be commercially available.
The solvent of the carbon material or the precursor solution or dispersion thereof in the step a can be selected from one or a combination of benzene, toluene, xylene, trichlorobenzene, chloroform, cyclohexane, ethyl hexanoate, butyl acetate, carbon disulfide, ketone, acetone, cyclohexanone, tetrahydrofuran, dimethylformamide, water or alcohols;
wherein the alcohol is preferably at least one selected from propanol, n-butanol, isobutanol, ethylene glycol, propylene glycol, 1, 4-butanediol, isopropanol and ethanol;
the precursor of the carbon material for loading in the preparation method of the invention is preferably a precursor which can be dissolved or dispersed in a solvent which is friendly to human body and environment before loading, so that the preparation process is 'green'. The solvent friendly to human body and environment is at least one selected from ethanol, water and mixture of the two. I.e. the solvent in step a is more preferably a solvent comprising water and/or ethanol; further preferably water and/or ethanol.
The solution or dispersion liquid in step a can be used to fully dissolve or fully disperse the carbon material and/or carbon material precursor in the solvent, and the concentration of the solution or dispersion liquid is usually 0.001-1 g/mL, preferably 0.002-0.8 g/mL, and more preferably 0.003-0.5 g/mL.
More specifically:
when the carbon material supported on the inorganic porous skeleton in the preparation method of the present invention is graphene, the graphene oxide aqueous solution is preferably used in step a.
When the carbon material loaded on the inorganic porous framework in the preparation method of the present invention is a carbon nanotube, the carbon nanotube dispersion liquid is preferably used in step a.
When the carbon material precursor for loading in the preparation method is selected from thermosetting plastics, a proper curing system is prepared according to a curing formula commonly used in the prior art of the selected thermosetting plastics in the step a; optionally, one or more additives selected from the group consisting of: cure accelerators, dyes, pigments, colorants, antioxidants, stabilizers, plasticizers, lubricants, flow modifiers or adjuvants, flame retardants, drip retardants, antiblock agents, adhesion promoters, conductive agents, polyvalent metal ions, impact modifiers, mold release aids, nucleating agents, and the like; the dosage of the used additives is conventional dosage or is adjusted according to the requirements of actual conditions. And c, when the carbon material precursor for loading is selected from thermosetting plastics, the thermosetting resin serving as the carbon material precursor is cured after being heated in the subsequent step c, and is loaded on the inorganic porous framework.
When the carbon material precursor for loading in the preparation method is thermosetting plastic, a good solvent corresponding to the prior art is selected in the step a to dissolve the thermosetting plastic and the curing system thereof, so as to obtain the carbon material precursor solution for loading.
When the carbon material precursor for loading in the preparation method of the invention is thermoplastic plastic, common additives in the prior art in the plastic processing process, such as antioxidant, antioxidant aid, heat stabilizer, light stabilizer, ozone stabilizer, processing aid, plasticizer, softener, anti-blocking agent, foaming agent, dye, pigment, wax, extender, organic acid, flame retardant, coupling agent and the like, can be added into the solution of the carbon material precursor for loading. The dosage of the used auxiliary agent is conventional dosage or is adjusted according to the requirements of actual conditions.
In the step b of the preparation method of the present invention, the pores of the inorganic porous skeleton may be filled with the carbon material for loading or the carbon material precursor solution or dispersion by pressing several times or without pressing at all.
After the porous material obtained in step b is taken out in step c of the preparation method of the present invention, the excess solution or dispersion of the carbon material or carbon material precursor for loading in the porous material obtained in step b may be removed with or without measures, including but not limited to one or both of squeezing and centrifuging.
The heating in steps c and d of the preparation method of the present invention may preferably be microwave heating, which is not only efficient but also uniformly heated, specifically:
the power of the microwave in the step c is 1W-100 KW, preferably 500W-10 KW, and the microwave time is 2-200 min, preferably 20-200 min.
The microwave power of the step d is changed into 100W-100 KW, preferably 700W-20 KW; the microwave time is 0.5-200 min, preferably 1-100 min.
The heating in step d of the preparation method of the present invention is desirably carried out under an inert gas atmosphere selected from those commonly used in the art, preferably nitrogen.
The equipment adopted in the preparation method of the invention is common equipment.
As mentioned above, the preparation method of the porous composite material combines the inorganic porous framework and the carbon material, the prepared porous composite material has excellent mechanical property, can generate electric arc in a microwave field to quickly generate high temperature, for example, the electric arc which can heat the porous composite material to more than 1000 ℃ can be generated in a 900w microwave field, the material is high temperature resistant, the process flow is simple and easy, and the large-scale preparation is easy to realize.
The carbon fiber composite material of the present invention is preferably a carbon fiber reinforced polymer composite material in the prior art, and the polymer compounded with the carbon fiber includes, but is not limited to, at least one of polyethylene, polypropylene, nylon, phenolic resin and epoxy resin.
The microwave field in the method of the present invention can be applied to various microwave devices in the prior art, such as household microwave ovens, industrial microwave devices (such as microwave thermal cracking reactors), etc.
The device for placing or carrying the carbon fiber composite material and the porous composite material in the method can be selected from various containers or pipelines which can be penetrated by microwaves and can resist the high temperature of more than 1200 ℃ in the prior art, such as quartz crucibles, quartz reactors, quartz tubes, alumina crucibles, alumina reactors, alumina tubes and the like.
According to the method, a polymer matrix in the carbon fiber composite material is cracked and gasified, and gas obtained after cracking is collected and can be subjected to subsequent treatment, for example, the gas is separated and then used as fuel or used as a chemical industrial raw material to perform subsequent reaction and production; the cracked residue is mainly carbon fiber, and the impurities are removed after collection and reuse.
The gas collection is a method common in the art, preferably under an inert atmosphere. For example, if a household microwave oven is used as the microwave field, the gas collection mode is as follows: putting a quartz crucible bearing waste plastics and porous composite materials into a vacuum bag in a glove box protected by nitrogen, sealing, twisting the crucible through the vacuum bag after reaction under microwave, and pricking the vacuum bag into a needle cylinder for sampling; the gas collection method adopts an industrial microwave oven (such as a microwave thermal cracking reactor and the like) with a gas inlet and a gas outlet, and comprises the following steps: the reaction process is purged by nitrogen, and the gas outlet is sampled and collected by a gas collection bag.
The method of the invention utilizes the porous composite material which generates the electric arc in the microwave to generate the electric arc in the microwave, thereby quickly generating high temperature, leading the polymer matrix in the carbon fiber composite material to be cracked, reserving the carbon fiber and recycling, having high process efficiency and high added value of the composition of the product.
Detailed Description
The present invention will be further described with reference to the following examples; however, the present invention is not limited to these examples.
The experimental data in the examples were determined using the following instruments and methods:
1. determination of the mass percentage content of the carbon material loaded in the porous composite material obtained in the examples:
1) under the condition that the inorganic porous framework material is adopted in the raw materials, firstly, the weight of the inorganic porous framework material is measured, the weight of the obtained porous composite material is measured after the experiment is finished, and the weight difference between the weight of the inorganic porous framework material and the weight of the obtained porous composite material is the weight of the loaded carbon material, so that the mass percentage content of the loaded carbon material in the porous composite material is measured;
2) under the condition that the inorganic porous framework precursor is adopted in the raw materials, taking two parts of inorganic porous framework precursors with the same weight, wherein one part is taken as an embodiment, and the other part is taken as a blank sample to only carry out the step c and the step d of the preparation method; after the experiment is finished, weighing the weight of the porous composite material obtained in the embodiment, weighing the final weight of the blank sample, and determining the weight difference between the two weights as the weight of the loaded carbon material, thereby determining the mass percentage content of the loaded carbon material in the porous composite material.
2. The gas thus decomposed was analyzed by gas chromatography using Agilent 6890N, manufactured by Agilent Corp.
The raw materials of the examples of the present invention are all commercially available.
Preparation of porous composite materials：
Example 1
(1) Measuring 500ml of graphene oxide aqueous dispersion (JCGO-95-1-2.6-W, 10mg/ml, Nanjing Jicang nanometer technology Co., Ltd.) in a beaker;
(2) soaking 2g of a porous skeleton (phenolic foam, average pore diameter of 300 mu m, porosity of 99%, Uyghur oasis flower foam Co., Ltd.) made of phenolic resin into graphene oxide aqueous dispersion, and making the solution fully enter the pore channels of the porous skeleton;
(3) taking out the soaked porous material, placing the porous material in a stainless steel tray, placing the stainless steel tray in a 180 ℃ oven for heating for 1 hour, drying and pre-reducing;
(4) and (3) placing the dried porous material into a household microwave oven (700w) for high-fire microwave treatment for 2min, reducing the pre-reduced graphene oxide into graphene, carbonizing a phenolic resin framework into a carbon framework (the average pore diameter is 200 mu m, the porosity is 99%), and obtaining the graphene-loaded carbon porous framework porous composite material generating electric arcs in the microwave, wherein the graphene accounts for 10% of the total mass of the porous composite material.
Example 2
(1) Measuring 500ml of carbon nanotube dispersion (XWDM, 100mg/ml, Nanjing Xiancheng nanomaterial science and technology Co., Ltd.) in a beaker;
(2) soaking 2g of a porous skeleton (phenolic foam, average pore diameter 200 μm, porosity 99%, perennial oasis flower foam limited) made of phenolic resin into the carbon nanotube dispersion liquid, so that the carbon nanotube dispersion liquid fully enters the pore channels of the porous skeleton;
(3) taking out the soaked porous material, placing the porous material in a stainless steel tray, placing the stainless steel tray in an oven at 80 ℃ for heating for 5 hours, and drying;
(4) and putting the dried porous material into a tube furnace, and carbonizing for 1h at 800 ℃ in a nitrogen atmosphere to obtain the carbon nanotube-supported carbon porous skeleton porous composite material (the average pore diameter of the carbon skeleton is 140 microns, the porosity is 99%) which generates electric arcs in the microwave, wherein the carbon nanotube accounts for 30% of the total mass of the porous composite material.
Example 3
(1) Measuring 500ml of carbon nanotube dispersion (XWDM, 100mg/ml, Nanjing Xiancheng nanomaterial science and technology Co., Ltd.) in a beaker;
(2) soaking 5g of fibrous cotton-shaped porous skeleton (average pore diameter 150 μm, porosity 90%, Shandong Luyang energy-saving material Co., Ltd.) made of silicate into the carbon nanotube dispersion liquid, and extruding for several times to make the dispersion liquid fully enter the pore channels of the porous skeleton;
(3) and taking out the soaked porous material, putting the porous material into a stainless steel tray, heating the stainless steel tray in a drying oven at 150 ℃ for 2 hours, and drying to obtain the porous composite material of the carbon nano tube-supported silicate fiber porous framework, which generates electric arcs in microwaves, wherein the carbon nano tube accounts for 10 percent of the total mass of the porous composite material.
Example 4
(1) Weighing 30g of powdered phenolic resin (2123, bermajafan industries, ltd. in new county) and 3.6g of hexamethylenetetramine curing agent in a beaker, pouring 500ml of ethanol, and stirring for 1 hour by using a magnetic rotor until the mixture is dissolved;
(2) soaking 5g of fibrous cotton-shaped porous skeleton (average pore diameter 150 μm, porosity 90%, Shandong Luyang energy-saving material Co., Ltd.) with silicate into the prepared solution, and extruding for several times to make the solution fully enter the pore channel of the porous skeleton;
(3) taking out the soaked porous material, placing the porous material in a stainless steel tray, placing the stainless steel tray in an oven at 180 ℃ for heating for 2 hours, drying the solution, and curing the phenolic resin;
(4) and putting the dried and cured porous material into a tubular furnace, carbonizing for 1h at 1000 ℃ in a nitrogen atmosphere, and carbonizing phenolic resin to obtain the porous composite material of the silicate fiber porous framework loaded by the phenolic resin carbonized product which generates electric arc in microwave, wherein the carbon material accounts for 5 percent of the total mass of the porous composite material.
Example 5
(1) Weighing 50g of liquid phenolic resin (2152, Jining Bai Yi chemical) in a beaker, pouring 500ml of ethanol, and stirring for 1 hour by using a magnetic rotor until the ethanol is dissolved;
(2) soaking 8g of a fiber plate-shaped porous framework (average pore diameter of 100 μm, porosity of 85%, Shandong Luyang energy-saving material Co., Ltd.) made of alumina into the prepared solution, and making the solution fully enter the pore channels of the porous framework;
(3) taking out the soaked porous material, placing the porous material in a stainless steel tray, placing the stainless steel tray in an oven at 180 ℃ for heating for 2 hours, drying the solution, and curing the phenolic resin;
(4) and putting the dried and cured porous material into a tubular furnace, carbonizing at 900 ℃ for 1h in a nitrogen atmosphere, and carbonizing phenolic resin to obtain the porous composite material of the alumina fiber porous skeleton loaded with the phenolic resin carbonization product generating electric arc in microwave, wherein the carbon material accounts for 6 percent of the total mass of the porous composite material.
Example 6
(1) Weighing 30g of water-soluble starch (pharmaceutical grade, Shanghai Aladdin Biotechnology Co., Ltd.) in a beaker, pouring 500ml of deionized water, and stirring with a magnetic rotor for 1 hour until dissolving;
(2) soaking 8g of fibrous felt-shaped porous framework (average pore diameter is 100 μm, porosity is 85%, Shandong Luyang energy-saving material Co., Ltd.) made of alumina into the prepared solution, and making the solution fully enter the pore channels of the porous framework;
(3) taking out the soaked porous material, placing into a microwave thermal cracking reactor (XOLJ-2000N, Nanjing Europe instruments manufacturing Co., Ltd.), performing microwave treatment with power of 10KW for 2min, and drying the porous material;
(4) and putting the dried porous material into a tubular furnace, carbonizing at 1200 ℃ for 1h in a nitrogen atmosphere, and carbonizing the water-soluble starch to obtain the porous composite material of the starch carbonization product loaded alumina fiber porous skeleton, which generates electric arc in microwave, wherein the carbon material accounts for 0.1 percent of the total mass of the porous composite material.
Example 7
(1) Weighing 50g of water-soluble starch (pharmaceutical grade, Shanghai Aladdin Biotechnology Co., Ltd.) in a beaker, pouring 500ml of deionized water, and stirring with a magnetic rotor for 1 hour until dissolving;
(2) soaking 8g of a fibrous cotton-shaped porous framework (average pore diameter of 100 μm, porosity of 85%, Shandong Luyang energy-saving material Co., Ltd.) made of alumina into the prepared solution, and extruding for several times to make the solution fully enter the pore channels of the porous framework;
(3) taking out the soaked porous material, placing into a microwave thermal cracking reactor (XOLJ-2000N, Nanjing Europe instruments manufacturing Co., Ltd.), performing microwave treatment with power of 500W for 2h, and drying the porous material;
(4) and putting the dried porous material into a tubular furnace, carbonizing for 1h at 1000 ℃ in a nitrogen atmosphere, and carbonizing starch to obtain the porous composite material of the starch carbonization product loading alumina fiber porous framework generating electric arc in microwave, wherein the carbon material accounts for 0.2 percent of the total mass of the porous composite material.
Example 8
(1) Weighing 2kg of liquid phenolic resin (2152, Jining Bai Yi chemical) in a beaker, pouring 4L of ethanol, and stirring with a magnetic rotor for 1 hour until dissolving;
(2) taking 2g of a prepared solution of a porous skeleton (phenolic foam, average pore diameter of 500 mu m, porosity of 99 percent, and evergreen flower foam Co., Ltd.) made of phenolic resin, and enabling the solution to fully enter pore channels of the porous skeleton;
(3) taking out the soaked porous material, putting the porous material in a stainless steel tray, putting the stainless steel tray in a drying oven at 150 ℃ for heating for 2 hours, and drying;
(4) the dried porous material is put into a microwave thermal cracking reactor (XOLJ-2000N, Nanjing Europe instruments manufacturing Co., Ltd.), microwave treatment is carried out for 100min under the nitrogen atmosphere with the power of 20KW, and the porous composite material (the average pore diameter of the carbon framework is 350 mu m, the porosity is 99%) of the carbon porous framework loaded with the phenolic resin carbonization product which generates electric arcs in the microwave is obtained, and the percentage of the carbon material loaded on the inorganic carbon framework in the total mass of the porous composite material is 80%.
Example 9
(1) Weighing 0.3g liquid phenolic resin (2152, JINING BAO YI CHEMICAL), placing in a beaker, adding 100ml ethanol, and stirring with magnetic rotor for 1 hr to dissolve;
(2) soaking 300g of activated alumina (average pore diameter of 0.05 μm, porosity of 30%, Shandong Kai Euro chemical engineering Co., Ltd.) in the prepared solution to make the solution fully enter the pore canal of the activated alumina;
(3) taking out the soaked porous material, putting the porous material in a stainless steel tray, putting the stainless steel tray in a drying oven at 150 ℃ for heating for 2 hours, and drying;
(4) and putting the dried porous material into a tubular furnace, carbonizing for 1h at 1000 ℃ in a nitrogen atmosphere, and carbonizing phenolic resin to obtain the phenolic resin carbonized product loaded active alumina (porous framework) porous composite material generating electric arc in microwave, wherein the carbon material accounts for 0.05 percent of the total mass of the porous composite material.
Example 10
(1) Weighing 30g of powdered phenolic resin (2123, bermajafan industries, ltd. in new county) and 3.6g of hexamethylenetetramine curing agent in a beaker, pouring 500ml of ethanol, and stirring for 1 hour by using a magnetic rotor until the mixture is dissolved;
(2) soaking 8g of a fibrous plate-shaped porous framework (average pore diameter of 100 mu m, porosity of 80%, and Jinnan Pitaya thermal ceramics Limited liability company) made of magnesium oxide into the prepared solution, and making the solution fully enter the pore channels of the porous framework;
(3) taking out the soaked porous material, placing the porous material in a stainless steel tray, placing the stainless steel tray in an oven at 180 ℃ for heating for 2 hours, drying the solution, and curing the phenolic resin;
(4) and putting the dried and cured porous material into a tubular furnace, carbonizing for 1h at 1000 ℃ in a nitrogen atmosphere, and carbonizing phenolic resin to obtain the porous composite material of the phenolic resin carbonized product loaded with the magnesium oxide fiber porous framework, wherein electric arcs are generated in microwaves, and the carbon material accounts for 3 percent of the total mass of the porous composite material.
Example 11
(1) Weighing 100g of water-soluble starch (pharmaceutical grade, Shanghai Aladdin Biotechnology Co., Ltd.) in a beaker, pouring 500ml of deionized water, and stirring with a magnetic rotor for 1 hour until dissolving;
(2) soaking 8g of a fibrous plate-shaped porous framework (with the average pore diameter of 150 mu m and the porosity of 80 percent, and Vietnam fire ceramics Limited liability company) made of zirconia into the prepared solution, and enabling the solution to fully enter pore channels of the porous framework;
(3) taking out the soaked porous material, placing into a microwave thermal cracking reactor (XOLJ-2000N, Nanjing Europe instruments manufacturing Co., Ltd.), performing microwave treatment with power of 3KW for 20min, and drying the porous material;
(4) and putting the dried porous material into a tubular furnace, carbonizing at 900 ℃ for 2h in a nitrogen atmosphere, and carbonizing starch to obtain the porous composite material of the zirconium oxide fiber porous skeleton loaded with the starch carbonization product which generates electric arc in microwave, wherein the percentage of the carbon material in the total mass of the porous composite material is 0.5%.
Example 12
(1) Weighing 50g of liquid phenolic resin (2152, Jining Bai Yi chemical) in a beaker, pouring 500ml of ethanol, and stirring for 1 hour by using a magnetic rotor until the ethanol is dissolved;
(2) soaking 8g of a fiber plate-shaped porous framework (average pore diameter is 100 mu m, porosity is 80%, and Vietnam fire ceramics Limited liability company) made of boron nitride into the prepared solution, and making the solution fully enter the pore channels of the porous framework;
(3) taking out the soaked porous material, placing the porous material in a stainless steel tray, placing the stainless steel tray in an oven at 180 ℃ for heating for 2 hours, drying the solution, and curing the phenolic resin;
(4) and putting the dried and cured porous material into a tubular furnace, carbonizing for 1h at 900 ℃ in a nitrogen atmosphere, and carbonizing phenolic resin to obtain the porous composite material of the phenolic resin carbonized product loaded boron nitride fiber porous skeleton, which generates electric arc in microwave, wherein the carbon material accounts for 5 percent of the total mass of the porous composite material.
Example 13
(1) Weighing 100g of liquid phenolic resin (2152, Jining Bai Yi chemical) in a beaker, adding 500ml of ethanol, and stirring with a magnetic rotor for 1 hour until the solution is dissolved;
(2) soaking 8g of a fiber plate-shaped porous framework (average pore diameter of 100 mu m, porosity of 80%, and Vietnam fire ceramics Limited liability company) made of silicon carbide into the prepared solution, and making the solution fully enter the pore channels of the porous framework;
(3) taking out the soaked porous material, placing the porous material in a stainless steel tray, placing the stainless steel tray in an oven at 180 ℃ for heating for 2 hours, drying the solution, and curing the phenolic resin;
(4) and putting the dried and cured porous material into a tubular furnace, carbonizing at 800 ℃ for 1h in a nitrogen atmosphere, and carbonizing phenolic resin to obtain the porous composite material of the phenolic resin carbonized product loaded silicon carbide fiber porous skeleton, which generates electric arc in microwave, wherein the carbon material accounts for 10 percent of the total mass of the porous composite material.
Example 14
(1) Weighing 100g of liquid phenolic resin (2152, Jining Bai Yi chemical) in a beaker, adding 500ml of ethanol, and stirring with a magnetic rotor for 1 hour until the solution is dissolved;
(2) soaking 8g of a fibrous plate-shaped porous framework (average pore diameter is 100 mu m, porosity is 80%, and Vietnam fire ceramics Limited liability company) made of potassium titanate into the prepared solution, and making the solution fully enter pore channels of the porous framework;
(3) taking out the soaked porous material, placing the porous material in a stainless steel tray, placing the stainless steel tray in an oven at 180 ℃ for heating for 2 hours, drying the solution, and curing the phenolic resin;
(4) and putting the dried and cured porous material into a tubular furnace, carbonizing at 800 ℃ for 1h in a nitrogen atmosphere, and carbonizing phenolic resin to obtain the porous composite material of the potassium titanate fiber porous skeleton loaded by the phenolic resin carbonized product which generates electric arc in microwave, wherein the carbon material accounts for 10 percent of the total mass of the porous composite material.
Microwave pyrolysis of the carbon fiber composite material:
example 15
Placing 2g of carbon fiber reinforced epoxy resin composite material (Changzhou City carbon fiber composite Co., Ltd.) on 1g of the porous composite material which generates electric arc in microwave and is obtained in the embodiment 1, after nitrogen protection, cracking for 40s in a household microwave oven (700w) by adopting high-fire microwave, taking out the carbon fiber composite material, weighing to find weight loss, and easily stripping carbon fibers from the fabric; there is a violent arcing phenomenon in the microwave process. The porous composite material generates electric arc in microwave, so that high temperature is generated rapidly and transferred to the material to make the material cracked rapidly.
50g of carbon fiber reinforced epoxy resin composite (Changzhou City carbon fiber composite Co., Ltd.) was placed in a chamber made of 30g of the porous composite material having an arc generated in the microwave obtained in example 1, and treated with nitrogen gas and then with 1500W power for 5min in a microwave thermal cracking reactor (XOLJ-2000N, Nanjing Europe advanced instruments manufacturing Co., Ltd.). The carbon fiber composite material was removed, weighed and found to be weightless, and the carbon fibers could be easily peeled from the fabric.
The specific operation of placing the material to be cracked in a cavity formed by porous composite materials which generate electric arcs in microwaves is as follows: firstly, a part of porous composite materials which generate electric arcs in microwaves are placed at the bottom and around a quartz reactor to form a cavity with an upper opening, then materials are placed in the cavity, and finally the rest of porous composite materials cover the upper parts of the materials.
The same experiment as described above was performed on the samples obtained in examples 2 to 14, and similar experimental phenomena and results were obtained. The porous composite materials obtained in examples 2 to 14 were all arc-generated in the microwave, thereby rapidly generating high temperature and transferring the high temperature to the materials to rapidly crack the materials.
Comparative example 1
2g of carbon fiber reinforced epoxy resin composite material (Hezhou city China carbon fiber composite material Co., Ltd.) was placed on 1g of silicon carbide powder (98.5%, Beijing Co., Ltd., national drug group chemical reagent), and after protection with nitrogen gas, high-fire microwave treatment was carried out in a domestic microwave oven (700w) for 30 seconds. No spark is generated in the microwave process, the materials are not changed after the microwave treatment, and only the bottom of the quartz crucible is slightly warm.
Example 16
2g of carbon fiber reinforced epoxy resin composite material (Changzhou City carbon fiber composite Co., Ltd.) was placed on 1g of the porous composite material which generates an arc in microwave obtained in example 1, after protection with nitrogen gas, the porous composite material was cracked in a domestic microwave oven (700w) by high fire microwave for 40 seconds, and then the carbon fiber composite material was taken out, and weight loss was found by weighing to be 36%, and the carbon fiber could be easily peeled from the fabric. The resulting gas was collected for chromatographic analysis, the main components of which are shown in Table 1.
30g of carbon fiber reinforced polypropylene composite (Changzhou City carbon fiber composite Co., Ltd.) was placed in a chamber made of 30g of the porous composite material having an arc generated in the microwave obtained in example 6, and treated with 1500W power for 5min in a microwave pyrolysis reactor (XOLJ-2000N, Nanjing Europe instruments manufacturing Co., Ltd.) under protection of nitrogen gas. Weighing found a weight loss of 38%, the carbon fibers had been easily peeled from the fabric. The resulting gas was collected for chromatographic analysis, the main components of which are shown in Table 2.
50g of carbon fiber reinforced nylon composite (Wahua carbon fiber composite Co., Ltd., Changzhou) was placed in a chamber made of 30g of the porous composite material having generated an arc in the microwave obtained in example 7, and treated with a microwave thermal cracking reactor (XOLJ-2000N, Nanjing Europe advanced instruments Co., Ltd.) at a power of 2000W for 10min under protection of nitrogen gas. Weighing found 39% weight loss, the carbon fibers had been easily peeled from the fabric. The resulting gas was collected for chromatographic analysis, the main components of which are shown in Table 3.
The specific operation of placing the material in a cavity made of porous composite materials for generating electric arcs in microwave is as follows: firstly, a part of porous composite materials which generate electric arcs in microwaves are placed at the bottom and around a quartz reactor to form a cavity with an upper opening, then materials are placed in the cavity, and finally the rest of porous composite materials cover the upper parts of the materials.
TABLE 1
TABLE 2
TABLE 3
Claims (29)
1. A method for microwave pyrolysis of carbon fiber composite material, characterized in that the method comprises:
contacting a carbon fiber composite material with a porous composite material, applying a microwave field to the carbon fiber composite material and the porous composite material in an inert atmosphere or vacuum, and generating an electric arc in the porous composite material under the microwave, so that the high temperature is quickly reached, a polymer matrix in the carbon fiber composite material is cracked, and carbon fibers are reserved and recycled; the weight ratio of the carbon fiber composite material to the porous composite material is 1: 99-99: 1;
the microwave power of the microwave field is 1W-100 KW; the microwave time is 0.1-200 min;
the porous composite material comprises: an inorganic porous skeleton and a carbon material supported on the inorganic porous skeleton; the carbon material accounts for 0.001% -99% of the total mass of the porous composite material;
the inorganic porous skeleton is an inorganic material having a porous structure; the average pore diameter of the inorganic porous framework is 0.01-1000 microns; the porosity is 1% -99.99%;
the inorganic porous framework is at least one of the following: a porous framework formed by inorganic fibers, an inorganic sponge framework, a framework formed by stacking inorganic particles, a ceramic sponge framework obtained after roasting a ceramic precursor sponge, a ceramic fiber framework obtained after roasting ceramic precursor fibers, a framework obtained after carbonizing melamine sponge and a framework obtained after carbonizing phenolic resin sponge;
the carbon material is at least one of graphene, carbon nanotubes, carbon nanofibers, graphite, carbon black, carbon fibers, carbon dots, carbon nanowires, a product obtained by carbonizing a carbonizable organic substance, or a product obtained by carbonizing a mixture of carbonizable organic substances.
2. The microwave pyrolysis method for carbon fiber composite material as claimed in claim 1, wherein:
the weight ratio of the carbon fiber composite material to the porous composite material is 1: 50-50: 1; and/or the presence of a gas in the gas,
the microwave power of the microwave field is 100W-80 KW; the microwave time is 0.5-180 min; and/or the presence of a gas in the gas,
the carbon material accounts for 0.01-90% of the total mass of the porous composite material; and/or the presence of a gas in the gas,
the carbon material is at least one of graphene, a carbon nanotube, a product obtained by carbonizing a carbonizable organic substance, and a product obtained by carbonizing a mixture of carbonizable organic substances.
3. The microwave pyrolysis method for carbon fiber composite material as claimed in claim 2, wherein:
the weight ratio of the carbon fiber composite material to the porous composite material is 1: 30-30: 1; and/or the presence of a gas in the gas,
the microwave power of the microwave field is 200W-60 KW; the microwave time is 1-150 min; and/or the presence of a gas in the gas,
the carbon material accounts for 0.1-80% of the total mass of the porous composite material.
4. The microwave pyrolysis method for carbon fiber composite material as claimed in claim 1, wherein:
the inorganic material is one or a combination of carbon, silicate, aluminate, borate, phosphate, germanate, titanate, oxide, nitride, carbide, boride, sulfide, silicide and halide.
5. The microwave pyrolysis method for carbon fiber composite material as claimed in claim 4, wherein:
the inorganic material is at least one of carbon, silicate, titanate, oxide, carbide, nitride and boride.
6. The microwave pyrolysis method for carbon fiber composite material as claimed in claim 5, wherein: the oxide is at least one of aluminum oxide, silicon oxide, zirconium oxide, magnesium oxide, cerium oxide and titanium oxide; the nitride is at least one of silicon nitride, boron nitride, zirconium nitride, hafnium nitride and tantalum nitride; the carbide is at least one of silicon carbide, zirconium carbide, hafnium carbide and tantalum carbide; the boride is at least one of zirconium boride, hafnium boride and tantalum boride.
7. The microwave pyrolysis method for carbon fiber composite material as claimed in claim 1, wherein:
the average pore diameter of the inorganic porous framework is 0.05-500 mu m; the porosity is 10% -99.9%.
8. The microwave pyrolysis method for carbon fiber composite material as claimed in claim 7, wherein:
the average pore diameter of the inorganic porous framework is 0.2-250 mu m; the porosity is 30% -99%.
9. The microwave pyrolysis method for carbon fiber composite material as claimed in claim 1, wherein:
the inorganic porous framework is at least one of the following: the composite material comprises a framework obtained by carbonizing melamine sponge, a framework obtained by carbonizing phenolic resin sponge, a porous framework of aluminum silicate fiber, a porous framework of mullite fiber, a porous framework of alumina fiber, a porous framework of zirconia fiber, a porous framework of magnesia fiber, a porous framework of boron nitride fiber, a porous framework of boron carbide fiber, a porous framework of silicon carbide fiber, a porous framework of potassium titanate fiber and a ceramic fiber framework obtained by roasting ceramic precursor fiber.
10. The microwave pyrolysis method for carbon fiber composite material as claimed in claim 1, wherein:
the mixture of the carbonizable organic matter is a mixture of the carbonizable organic matter, inorganic matters of non-metal and non-metal compounds, and other organic matters of non-metal compounds.
11. The method of microwave pyrolysis of carbon fiber composite materials of claim 10, wherein:
the mixture of the carbonizable organic matters is at least one of coal, natural asphalt, petroleum asphalt or coal tar asphalt.
12. The microwave pyrolysis method for carbon fiber composite material as claimed in claim 1, wherein:
the organic matter capable of being carbonized is an organic high molecular compound, and the organic high molecular compound comprises a synthetic high molecular compound and a natural organic high molecular compound.
13. The microwave pyrolysis method of carbon fiber composite materials as claimed in claim 12, wherein:
the synthetic high molecular compound is rubber or plastic; the plastics include thermosets and thermoplastics;
the natural organic high molecular compound is at least one of starch, viscose, lignin and cellulose.
14. The method of microwave pyrolysis of carbon fiber composite materials of claim 13, wherein:
the synthetic high molecular compound is at least one selected from epoxy resin, phenolic resin, furan resin, polystyrene, styrene-divinylbenzene copolymer, polyacrylonitrile, polyaniline, polypyrrole, polythiophene, styrene butadiene rubber and polyurethane rubber.
15. A method of microwave pyrolysis of carbon fiber composite material as claimed in claim 1, wherein the porous composite material is prepared by a method comprising the steps of:
a. preparing a carbon material for loading and/or a carbon material precursor solution or dispersion liquid;
b. b, immersing an inorganic porous framework or an inorganic porous framework precursor into the solution or the dispersion liquid obtained in the step a to fill the pores of the inorganic porous framework or the inorganic porous framework precursor with the solution or the dispersion liquid; the carbon material and/or the carbon material precursor accounts for 0.001-99.999% of the total mass of the inorganic porous framework material or the inorganic porous framework material precursor and the carbon material and/or the carbon material precursor;
c. taking out the porous material obtained in the step b, heating, drying, separating out or curing a carbon material or a carbon material precursor, and loading the carbon material or the carbon material precursor on an inorganic porous framework or an inorganic porous framework precursor; heating and drying at 50-250 ℃;
if the raw materials adopt carbon materials and inorganic porous frameworks, the porous composite material for generating the electric arc in the microwave is obtained after the step c; if the raw material adopts at least one of a carbon material precursor or an inorganic porous skeleton precursor, the following step d is required to be continued:
d. c, heating the porous material obtained in the step c in an inert gas atmosphere, converting an inorganic porous skeleton precursor into an inorganic porous skeleton, and/or reducing or carbonizing a carbon material precursor to obtain a porous composite material for generating electric arcs in the microwaves; the heating temperature is 400-1800 ℃.
16. The microwave pyrolysis method of carbon fiber composite materials as claimed in claim 15, wherein:
the carbon material and/or carbon material precursor accounts for 0.01-99.99% of the total mass of the inorganic porous framework material or the inorganic porous framework material precursor and the carbon material and/or carbon material precursor in the step b; and/or the presence of a gas in the gas,
the heating and drying temperature of the step c is 60-200 ℃; and/or the presence of a gas in the gas,
and d, heating at 600-1500 ℃.
17. A method of microwave pyrolysis of carbon fiber composite materials as claimed in claim 16, wherein:
the carbon material and/or carbon material precursor accounts for 0.1-99.9% of the total mass of the inorganic porous framework material or the inorganic porous framework material precursor and the carbon material and/or carbon material precursor in the step b; and/or the presence of a gas in the gas,
the heating and drying temperature of the step c is 80-180 ℃; and/or the presence of a gas in the gas,
and d, heating at the temperature of 800-1200 ℃.
18. The microwave pyrolysis method of carbon fiber composite materials as claimed in claim 15, wherein:
the precursor of the inorganic porous framework is a porous material which can be converted into the inorganic porous framework; at least one selected from a ceramic precursor, a porous material of a carbonizable organic substance, or a porous material of a mixture of carbonizable organic substances.
19. The microwave pyrolysis method of carbon fiber composite materials as claimed in claim 15, wherein:
the carbon material precursor is at least one of graphene oxide, modified carbon nanotubes, modified carbon nanofibers, modified graphite, modified carbon black, modified carbon fibers and a carbonizable organic substance or a carbonizable organic substance mixture.
20. The microwave pyrolysis method of carbon fiber composite materials as claimed in claim 15, wherein:
the solvent of the carbon material or the precursor solution or dispersion liquid thereof in the step a is selected from one or a combination of benzene, toluene, xylene, trichlorobenzene, chloroform, cyclohexane, ethyl hexanoate, butyl acetate, carbon disulfide, ketone, acetone, cyclohexanone, tetrahydrofuran, dimethylformamide, water or alcohols.
21. A method of microwave pyrolysis of carbon fiber composite materials as claimed in claim 20, wherein:
the alcohol is selected from at least one of propanol, n-butanol, isobutanol, ethylene glycol, propylene glycol, 1, 4-butanediol, isopropanol and ethanol.
22. A method of microwave pyrolysis of carbon fiber composite materials as claimed in claim 21, wherein:
and (b) the solvent of the carbon material or the precursor solution or dispersion of the carbon material in the step (a) is a solvent containing water and/or ethanol.
23. A method of microwave pyrolysis of carbon fiber composite materials as claimed in claim 22, wherein:
and (b) the solvent of the carbon material or the precursor solution or dispersion liquid of the carbon material in the step a is water and/or ethanol.
24. The microwave pyrolysis method of carbon fiber composite materials as claimed in claim 15, wherein:
the concentration of the solution or dispersion liquid in the step a is 0.001-1 g/mL.
25. A method of microwave pyrolysis of carbon fiber composite materials as claimed in claim 24, wherein:
the concentration of the solution or dispersion liquid in the step a is 0.002-0.8 g/mL.
26. A method of microwave pyrolysis of carbon fiber composite materials as claimed in claim 25, wherein:
the concentration of the solution or the dispersion liquid in the step a is 0.003 g-0.5 g/mL.
27. The microwave pyrolysis method of carbon fiber composite materials as claimed in claim 15, wherein:
the heating in the step c and the step d is microwave heating;
the microwave power of the step c is 1W-100 KW, and the microwave time is 2-200 min;
the microwave power of the step d is 100W-100 KW; the microwave time is 0.5-200 min.
28. A method of microwave pyrolysis of carbon fiber composite materials as claimed in claim 27, wherein:
the microwave power of the step c is 500W-10 KW, and the microwave time is 20-200 min;
the microwave power of the step d is 700W-20 KW; the microwave time is 1-100 min.
29. The microwave pyrolysis method for carbon fiber composite material as claimed in any one of claims 1 to 28, wherein:
the carbon fiber composite material is a carbon fiber reinforced polymer composite material;
the polymer is at least one of polyethylene, polypropylene, nylon, phenolic resin and epoxy resin.
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| CN201811264420.5A CN111100322B (en) | 2018-10-29 | 2018-10-29 | Method for microwave pyrolysis of carbon fiber composite material |
| EP19880547.5A EP3876320A4 (en) | 2018-10-29 | 2019-09-27 | Porous composite material capable of generating electric arc in microwave field, preparation method therefor, and use thereof |
| CN201980057945.8A CN112823441B (en) | 2018-10-29 | 2019-09-27 | Porous composite material capable of generating electric arc in microwave field and preparation method and application thereof |
| PCT/CN2019/108632 WO2020088173A1 (en) | 2018-10-29 | 2019-09-27 | Porous composite material capable of generating electric arc in microwave field, preparation method therefor, and use thereof |
| AU2019373610A AU2019373610B2 (en) | 2018-10-29 | 2019-09-27 | Porous composite material capable of generating electric arc in microwave field, preparation method therefor, and use thereof |
| CA3117124A CA3117124A1 (en) | 2018-10-29 | 2019-09-27 | Porous composite material capable of generating electric arc in microwave field, preparation method therefor, and use thereof |
| JP2021523303A JP2022506131A (en) | 2018-10-29 | 2019-09-27 | Porous composites capable of generating electric arcs in microwave fields, their preparation methods, and their use |
| BR112021008076-7A BR112021008076A2 (en) | 2018-10-29 | 2019-09-27 | porous composite material, method for preparing the porous composite material, use of the porous composite material and method for pyrolysis or recycling a substance comprising an organic compound |
| KR1020217016481A KR20210089187A (en) | 2018-10-29 | 2019-09-27 | Porous composite material capable of generating an electric arc in a microwave field, manufacturing method and use thereof |
| US17/309,134 US20220008882A1 (en) | 2018-10-29 | 2019-09-27 | Porous Composite Material Capable of Generating Electric Arc in Microwave Field, Preparation Method therefor, and Use thereof |
| TW108138985A TWI732327B (en) | 2018-10-29 | 2019-10-29 | Porous composite material capable of generating electric arc in microwave field, and preparation method and application thereof |
| JP2024107304A JP2024133574A (en) | 2018-10-29 | 2024-07-03 | Porous composite material capable of generating electric arcs in a microwave field, method for preparing same and use thereof - Patents.com |
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