阅读说明：本技术 微波高温裂解包含有机物的固体材料的连续操作方法 (Continuous operation method for microwave pyrolysis of solid material containing organic matter ) 是由 蒋海斌 乔金樑 张晓红 刘文璐 高建明 戚桂村 宋志海 赖金梅 蔡传伦 李秉海 于 2019-09-27 设计创作，主要内容包括：一种微波高温裂解包含有机物的固体材料的连续操作方法,该方法包括连续进行的以下步骤：将包含有机物的固体材料与液态有机介质混合；将所得混合物输送至微波场；在微波场中,在惰性气氛下或在真空下,将混合物连续地与强吸波材料接触,其中强吸波材料在微波下持续产生高温而使得包含有机物的固体材料与液态有机介质一起连续地裂解,实现了连续操作,过程连续、高效,可工业化,产物组成附加值高。(A continuously operating process for microwave pyrolysis of solid material comprising organic matter, the process comprising the following steps carried out continuously: mixing a solid material comprising organic matter with a liquid organic medium; feeding the resulting mixture to a microwave field; in a microwave field, the mixture is continuously contacted with a strong wave absorption material under inert atmosphere or vacuum, wherein the strong wave absorption material continuously generates high temperature under microwave so that a solid material containing organic matters and a liquid organic medium are continuously cracked together, continuous operation is realized, the process is continuous and efficient, industrialization is realized, and the added value of the composition of products is high.)

A continuously operating process for microwave pyrolysis of solid material containing organic matter, characterized in that the process comprises the following steps carried out continuously:

mixing a solid material comprising organic matter with a liquid organic medium;

feeding the resulting mixture to a microwave field;

continuously contacting the mixture with a strongly absorbing material in a microwave field under an inert atmosphere or under vacuum, wherein the strongly absorbing material continuously generates high temperatures in the microwave field such that the solid material comprising organic matter is continuously cracked together with the liquid organic medium.

The process according to claim 1, characterized in that the liquid organic medium is a medium which is liquid at a temperature of 60 ℃ and contains at least one carbon atom, preferably selected from one or a mixture of hydrocarbon oils, vegetable oils, silicone oils, ester oils, phosphates, alcohols; more preferably one or a mixture of hydrocarbon oil and vegetable oil; preferably, the liquid organic medium is selected from the group consisting of liquid petroleum hydrocarbons and mixtures thereof and vegetable oils and mixtures thereof; preferably at least one of crude oil, naphtha, palm oil, rapeseed oil, sunflower oil, soybean oil, peanut oil, linseed oil and castor oil; more preferably at least one of naphtha, palm oil, rapeseed oil, sunflower seed oil and soybean oil.

Method according to claim 1 or 2, characterized in that the mass percentage of the solid material comprising organic matter in relation to the total amount of solid material comprising organic matter and liquid organic medium is 10% to 90%, preferably 20% to 80%, more preferably 30% to 75%.

A method according to any of claims 1-3, characterised in that the feed rate per minute of the solid material comprising organic matter to the strong wave absorbing material is in the range of 1:99 to 99:1, preferably 1:50 to 50:1, more preferably 1:30 to 30:1 by weight.

Process according to any one of claims 1 to 4, characterized in that the microwave field is generated by a microwave device, such as a domestic microwave oven or an industrial microwave device (e.g. a microwave thermal cracking reactor), preferably the microwave field has a microwave power of 200W to 100KW, preferably 300W to 80KW, more preferably 500W to 60 KW.

A method according to any of claims 1 to 5, characterized in that the solid material comprising organic matter is comminuted, preferably with a particle size of 0.001 to 10mm, preferably 0.01 to 8mm, more preferably 0.05 to 5mm, before mixing with the liquid organic medium.

A method according to any of claims 1-6, characterized in that the strong absorbing material is selected from one or a mixture of activated carbon, carbon black, graphite, carbon fiber, silicon carbide, metal oxides, porous composite materials capable of generating electric arcs in a microwave field; preferably one or a mixture of activated carbon, graphite, silicon carbide, porous composite material capable of generating electric arc in microwave field; more preferably a porous composite material capable of arcing in a microwave field.

The method according to claim 7, characterized in that the porous composite material capable of generating an arc in a microwave field 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 preferably 0.01 to 1000 μm, more preferably 0.05 to 500 μm, more preferably 0.2 to 500 μm, more preferably 0.5 to 250 μm; preferably, the inorganic porous framework has a porosity of 1% to 99.99%, preferably 10% to 99.9%, more preferably 30% to 99%.

The method according to claim 8, characterized in that the proportion of the 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; and/or

The electric arc generated by the porous composite material in the microwave field enables the porous composite material to reach the temperature of more than 1000 ℃; and/or

The carbon material is selected from graphene, carbon nanotubes, carbon nanofibers, graphite, carbon black, carbon fibers, carbon dots, carbon nanowires, products resulting from carbonization of a carbonizable organic substance or a mixture comprising a carbonizable organic substance, and combinations thereof, preferably from graphene, carbon nanotubes, products resulting from carbonization of a carbonizable organic substance or a mixture comprising a carbonizable organic substance, 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 the group consisting of coal, natural asphalt, petroleum asphalt or coal tar asphalt, and combinations thereof; and/or

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.

The method according to claim 8 or 9, characterized in that it comprises preparing the porous composite by a method comprising the steps of:

(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 10,

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 10 or 11,

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 10 to 12,

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-100KW, more preferably 700W-20 KW; the time for microwave heating is preferably 0.5-200min, more preferably 1-100 min.

The method according to any one of claims 1 to 13, characterized in that the solid material containing organic matter is waste synthetic polymer material or waste natural polymer material, in particular one or a mixture of waste plastics, waste rubber, waste fibers, waste biomass;

wherein the plastic is preferably at least one of polyolefin, polyester, polyamide, acrylonitrile-butadiene-styrene terpolymer, polycarbonate, polylactic acid, polyurethane, polymethyl methacrylate, polyformaldehyde, polyphenyl ether and polyphenylene sulfide; more preferably at least one of polyethylene, polypropylene, polyvinyl chloride, polyethylene terephthalate, polystyrene, polyamide, acrylonitrile-butadiene-styrene terpolymer, polycarbonate, polylactic acid, polymethyl methacrylate, and polyoxymethylene; more preferably at least one of polyethylene, polypropylene, polyvinyl chloride, polyethylene terephthalate, polystyrene, polycarbonate and polyamide;

the rubber is preferably at least one of natural rubber, butadiene rubber, styrene-butadiene rubber, nitrile rubber, isoprene rubber, ethylene-propylene rubber, butyl rubber, chloroprene rubber, styrene block copolymer and silicon rubber; more preferably at least one of natural rubber, butadiene rubber, styrene-butadiene rubber, isoprene rubber and ethylene-propylene rubber;

the fiber is preferably at least one of polypropylene fiber, acrylic fiber, vinylon, chinlon, terylene, polyvinyl chloride fiber and spandex, and is preferably at least one of polypropylene fiber, terylene and spandex;

the biomass is preferably at least one of straw, bagasse, branches, leaves, sawdust, rice hulls, straws, peanut shells, coconut shells, palm seed shells and corncobs.

System for carrying out a continuously operating process for microwave pyrolysis of solid material comprising organic matter according to any one of claims 1 to 14, comprising

a) Mixing means for mixing a solid material comprising organic matter with a liquid organic medium;

b) a conveying device for continuously conveying the resulting mixture from the mixing device a) to the microwave field;

c) means for generating a microwave field for continuously contacting said mixture from the conveying means b) with a strongly absorbing material under an inert atmosphere or under vacuum, where said strongly absorbing material continuously generates high temperatures in the microwave field such that the solid material containing organic substances is continuously cracked together with the liquid organic medium.

The system of claim 15, wherein the system is characterized by

The mixing device a) is a mixer with a stirring mechanism; and/or

The conveying device b) is a pump, such as a peristaltic pump, a diaphragm pump, a plunger pump and a screw pump, preferably a peristaltic pump and a screw pump; and/or

The means for generating a microwave field are microwave devices such as microwave ovens and microwave pyrolysis reactors.