阅读说明：本技术 能在微波场中产生电弧的多孔复合材料及其制备方法和用途 (Porous composite material capable of generating electric arc in microwave field and preparation method and application thereof ) 是由 蒋海斌 乔金樑 张晓红 刘文璐 宋志海 戚桂村 高建明 蔡传伦 李秉海 王湘 赖 于 2019-09-27 设计创作，主要内容包括：一种能在微波场中产生电弧的多孔复合材料及其制备方法和用途。所述多孔复合材料包含无机多孔骨架和负载于所述无机多孔骨架上的碳材料,其中所述无机多孔骨架的平均孔径为0.2-1000μm。所述多孔复合材料具有优异的机械性能,并能够在微波场中产生电弧从而迅速产生高温,由此可以用于微波高温加热、生物质裂解、植物油处理、废旧高分子材料裂解、石油化工裂解、碳纤维复合材料回收、垃圾处理、VOC废气治理、COD污水治理、高温催化、废电路板全组分回收利用以及制备氢气等领域。(A porous composite material capable of generating electric arc in microwave field, its preparation method and application are disclosed. The porous composite material comprises an inorganic porous skeleton and a carbon material supported on the inorganic porous skeleton, wherein the average pore diameter of the inorganic porous skeleton is 0.2-1000 μm. The porous composite material has excellent mechanical property, can generate electric arc in a microwave field to quickly generate high temperature, and can be used in the fields of microwave high-temperature heating, biomass cracking, vegetable oil treatment, waste high polymer material cracking, petrochemical cracking, carbon fiber composite material recovery, garbage treatment, VOC waste gas treatment, COD sewage treatment, high-temperature catalysis, all-component recycling of waste circuit boards, hydrogen preparation and the like.)

A porous composite material capable of generating an arc in a microwave field, comprising an inorganic porous skeleton and a carbon material supported on the inorganic porous skeleton, wherein the inorganic porous skeleton has an average pore diameter of 0.2 to 1000 μm.

Porous composite material according to claim 1, characterized in that the average pore size of the inorganic porous framework is between 0.2 and 500 μm, preferably between 0.5 and 500 μm, more preferably between 0.5 and 250 μm;

and/or

The porosity of the inorganic porous framework is 1% to 99.99%, preferably 10% to 99.9%, more preferably 30% to 99%.

Porous composite material according to claim 1 or 2, characterized in that the proportion of carbon material is 0.001% to 99%, preferably 0.01% to 90%, more preferably 0.1% to 80% based on the total mass of the porous composite material.

The porous composite material according to any of claims 1 to 3, characterized in that the electric arc generated in the microwave field causes the porous composite material to reach a temperature above 1000 ℃.

Porous composite material according to any one of claims 1 to 4, characterized in that the carbon material is selected from graphene, carbon nanotubes, carbon nanofibers, graphite, carbon black, carbon fibers, carbon dots, carbon nanowires, products resulting from the carbonization of a carbonizable organic substance or of a mixture comprising carbonizable organic substances, and combinations thereof, preferably from graphene, carbon nanotubes, products resulting from the carbonization of a carbonizable organic substance or of a mixture comprising carbonizable organic substances, and combinations thereof;

preferably, the carbonizable organic substance is an organic polymer compound, including synthetic organic polymer compounds, preferably rubber, or plastics, including thermosetting plastics and thermoplastic plastics, more preferably selected from epoxy resins, phenolic resins, furan resins, polystyrene, styrene-divinylbenzene copolymers, polyacrylonitrile, polyaniline, polypyrrole, polythiophene, styrene butadiene rubber, polyurethane rubber, and combinations thereof; and a natural organic high molecular compound, preferably at least one of starch, viscose, lignin and cellulose;

preferably, the mixture containing the carbonizable organic substance is a mixture of the carbonizable organic substance with other metal-free organic substances and/or metal-free inorganic substances; more preferably selected from coal, natural asphalt, petroleum asphalt or coal tar asphalt and combinations thereof.

The porous composite material according to any of claims 1 to 5, characterized in that the inorganic porous framework is an inorganic material having a porous structure selected from the group consisting of carbon, silicates, aluminates, borates, phosphates, germanates, titanates, oxides, nitrides, carbides, borides, sulfides, silicides and halides and combinations thereof; preferably selected from the group consisting of carbon, silicates, titanates, oxides, carbides, nitrides, borides, and combinations thereof; wherein the oxide is preferably selected from the group consisting of alumina, silica, zirconia, magnesia, ceria and titania and combinations thereof; the nitride is preferably selected from the group consisting of silicon nitride, boron nitride, zirconium nitride, hafnium nitride, and tantalum nitride, and combinations thereof; the carbide is preferably selected from the group consisting of silicon carbide, zirconium carbide, hafnium carbide and tantalum carbide and combinations thereof; the boride is preferably selected from zirconium boride, hafnium boride and tantalum boride and combinations thereof;

preferably, the inorganic porous framework is at least one selected from the group consisting of: 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; preferably, the matrix is a matrix obtained by carbonizing melamine sponge, a matrix obtained by carbonizing phenolic resin sponge, a porous matrix of aluminum silicate fiber, a porous matrix of mullite fiber, a porous matrix of alumina fiber, a porous matrix of zirconia fiber, a porous matrix of magnesia fiber, a porous matrix of boron nitride fiber, a porous matrix of boron carbide fiber, a porous matrix of silicon carbide fiber, a porous matrix of potassium titanate fiber, or a ceramic fiber matrix obtained by baking a ceramic precursor fiber.

Method for preparing a porous composite according to any one of claims 1 to 6, characterized in that it comprises the following steps:

(1) immersing the inorganic porous framework or the precursor of the inorganic porous framework into the solution or the dispersion of the carbon material and/or the precursor of the carbon material to fill the pores of the inorganic porous framework or the precursor of the inorganic porous framework with the solution or the dispersion;

(2) heating and drying the porous material obtained in the step (1) to separate out or solidify a carbon material or a carbon material precursor and load the carbon material or the carbon material precursor on an inorganic porous framework or an inorganic porous framework precursor;

(3) if at least one of the carbon material precursor or the inorganic porous skeleton precursor is used as the raw material, the following steps are further performed: and (3) heating the porous material obtained in the step (2) in an inert gas atmosphere to convert the inorganic porous skeleton precursor into an inorganic porous skeleton, and/or reducing or carbonizing the carbon material precursor.

The method according to claim 7,

the solution or dispersion of the carbon material or precursor thereof in step (1) comprises a solvent selected from the group consisting of: benzene, toluene, xylene, trichlorobenzene, chloroform, cyclohexane, ethyl hexanoate, butyl acetate, carbon disulfide, ketone, acetone, cyclohexanone, tetrahydrofuran, dimethylformamide, water and alcohols, and combinations thereof; wherein the alcohol is preferably selected from the group consisting of propanol, n-butanol, isobutanol, ethylene glycol, propylene glycol, 1, 4-butanediol, isopropanol, ethanol, and combinations thereof; more preferably a solvent comprising water and/or ethanol; further preferably water and/or ethanol; and/or

The concentration of the solution or dispersion of step (1) is 0.001-1g/mL, preferably 0.002-0.8g/mL, more preferably 0.003-0.5 g/mL; and/or

The carbon material and/or carbon material precursor in the step (1) accounts for 0.001-99.999%, preferably 0.01-99.99%, and more preferably 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.

The method according to claim 7 or 8,

the heat drying in the step (2) is carried out at a temperature of 50 to 250 ℃, preferably 60 to 200 ℃, more preferably 80 to 180 ℃; preferably by microwave heating, wherein the power of the microwave is preferably 1W to 100KW, more preferably 500W to 10KW, and the microwave heating time is preferably 2 to 200min, more preferably 20 to 200 min.

The method according to any one of claims 7 to 9,

the inorganic porous framework precursor is selected from a ceramic precursor, a porous material of a carbonizable organic matter or a porous material containing a mixture of carbonizable organic matters and a combination thereof; and/or

The carbon material precursor is graphene oxide, a modified carbon nanotube, modified carbon nanofiber, modified graphite, modified carbon black, modified carbon fiber and a carbonizable organic substance or a mixture containing the carbonizable organic substance and a combination thereof; and/or

The heating in the step (3) is carried out at the temperature of 400-1800 ℃, preferably 600-1500 ℃, and more preferably 800-1200 ℃; preferably by microwave heating, wherein the power of the microwave is preferably 100W-100 KW, more preferably 700W-20 KW; the time for microwave heating is preferably 0.5-200min, more preferably 1-100 min.

Use of the porous composite material according to any one of claims 1 to 6 or the porous composite material prepared according to the method of any one of claims 7 to 10 for microwave high temperature heating, cracking and recycling of organic compound containing substances (e.g. organic matter, mixtures containing organic matter and composite materials containing organic matter) or in the field of high temperature catalysis, for example for biomass cracking, vegetable oil treatment, cracking of waste high molecular materials, petrochemical cracking, carbon fiber composite material recovery, waste treatment, VOC waste gas remediation or COD sewage remediation.

A method for cracking and/or recycling a substance containing an organic compound, wherein the substance containing an organic compound is brought into contact with the porous composite material according to any one of claims 1 to 6 or the porous composite material prepared by the method according to any one of claims 7 to 10, and a microwave field is applied to the substance containing an organic compound and the porous composite material under an inert atmosphere or under vacuum, and the porous composite material is arc-generated in the microwave field to rapidly reach a high temperature to crack the organic compound contained in the substance;

wherein the substance comprising organic compounds is for example an organic substance, a mixture comprising organic substances and a composite material comprising organic substances, for example selected from

Waste plastics, such as polyolefins, polyesters, such as at least one of polyethylene terephthalate, polybutylene terephthalate and polyarylates, polyamides, acrylonitrile-butadiene-styrene terpolymers, polycarbonates, polylactic acid, polyurethanes, polymethyl methacrylate, polyoxymethylene, at least one of polyphenylene oxide and polyphenylene sulfide, preferably at least one of polyethylene, polypropylene, polyvinyl chloride, polyethylene terephthalate, polystyrene, polyamides, acrylonitrile-butadiene-styrene terpolymers, polycarbonate, polylactic acid, polymethyl methacrylate and polyoxymethylene, more preferably at least one of polyethylene, polypropylene, polyvinyl chloride, polyethylene terephthalate, polystyrene, polycarbonate and polyamides;

-a waste rubber, such as at least one of natural rubber, cis-butadiene rubber, styrene-butadiene rubber, nitrile-butadiene rubber, isoprene rubber, ethylene-propylene rubber, butyl rubber, neoprene rubber, styrenic block copolymer and silicone rubber, preferably at least one of natural rubber, cis-butadiene rubber, styrene-butadiene rubber, isoprene rubber and ethylene-propylene rubber;

-biomass, preferably at least one of straw, bagasse, branches, leaves, wood chips, rice hulls, rice straw, peanut shells, coconut shells, palm seed shells, walnut shells, macadamia nut shells, pistachio nut shells, wheat straw, corn cobs and corn cobs;

-a vegetable oil, preferably at least one of palm oil, rapeseed oil, sunflower oil, soybean oil, peanut oil, linseed oil and castor oil; more preferably at least one of palm oil, rapeseed oil, sunflower oil and soybean oil;

-a carbon fiber composite comprising a polymer matrix selected from: polyethylene, polypropylene, nylon, phenolic resins, and epoxy resins; and

-a circuit board.

The method of claim 12, wherein

The weight ratio of the substance comprising the organic compound to the porous composite material is 1:99 to 99:1, preferably 1:50 to 50:1, more preferably 1:30 to 30: 1; and/or the presence of a gas in the gas,

the microwave power of the microwave field is 1W-100 KW; more preferably from 100W to 50KW, most preferably from 700W to 20 KW; and/or the presence of a gas in the gas,

the microwave irradiation time is 0.1-200 min; more preferably from 0.5 to 150min, most preferably from 1 to 100 min.

The method according to claim 12, wherein the substance containing an organic compound is a carbon fiber composite material, and the remaining carbon fibers are recovered for reuse after the polymer matrix in the carbon fiber composite material is cracked.

The method according to claim 12, wherein the substance containing organic compounds is a circuit board, and a solid residue obtained by cracking the circuit board is treated to separate metals and non-metal components therein and separately recovered for reuse; and/or collecting a gas product obtained by cracking the circuit board.

The process of claim 15 wherein hydrogen is collected from the cracked product.