Continuous Operation Method for Microwave High-Temperature Pyrolysis of Solid Material Comprising Organic Matter

Abstract

A continuous operation method is employed for the microwave high-temperature pyrolysis of a solid material containing an organic matter. The method includes the steps of mixing a solid material containing an organic matter with a liquid organic medium; transferring the obtained mixture to a microwave field; and in the microwave field, continuously contacting the mixture with a strong wave absorption material in an inert atmosphere or in vacuum. The strong wave absorption material continuously generates a high temperature under a microwave such that the solid material containing an organic matter and the liquid organic medium are continuously pyrolyzed to implement a continuous operation.

Claims

1. Continuous operation method for the microwave high-temperature pyrolysis of a solid material comprising an organic matter, characterized in that the method comprises the following continuously performed steps: mixing the solid material comprising an organic matter with a liquid organic medium; transferring the resulting mixture to a microwave field; and in the microwave field, under an inert atmosphere or under vacuum, continuously contacting the mixture with a strongly wave-absorbing material, wherein the strongly wave-absorbing material continuously generates a high temperature in the microwave field, so that the solid material comprising an organic matter and the liquid organic medium are continuously pyrolyzed together.

2. The method according to claim 1, characterized in that the liquid organic medium refers to a medium that is liquid at a temperature of 60° C. and contains at least one carbon atom, preferably one selected from the group consisting of hydrocarbon oils, vegetable oils, silicone oils, ester oils, phosphate esters and alcohols, or a mixture thereof; and more preferably one selected from the group consisting of hydrocarbon oils and vegetable oils, or a mixture thereof; 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 selected from the group consisting of crude oil, naphtha, palm oil, rapeseed oil, sunflower oil, soybean oil, peanut oil, linseed oil and castor oil; and more preferably at least one selected from the group consisting of naphtha, palm oil, rapeseed oil, sunflower oil and soybean oil.

3. The method according to claim 1, characterized in that the solid material comprising an organic matter comprises 10%-90%, preferably 20%-80%, more preferably 30%-75% by mass of the total amount of the solid material comprising an organic matter and the liquid organic medium.

4. The method according to claim 1, characterized in that the weight ratio of the feed amount per minute of the solid material comprising an organic matter to the strongly wave-absorbing material is 1:99-99:1, preferably 1:50-50:1, and more preferably 1:30-30:1.

5. The method according to claim 1, characterized in that the microwave field is generated by a microwave device, such as household microwave oven or industrialized microwave device (such as microwave pyrolysis reactor), preferably, the microwave power of the microwave field is 200 W-100 KW, preferably 300 W-80 KW, more preferably 500 W-60 KW.

6. The method according to claim 1, characterized in that the solid material comprising an organic matter is pulverized before being mixed with the liquid organic medium, preferably, the particle size after pulverization is 0.001-10 mm, preferably 0.01-8 mm, more preferably 0.05-5 mm.

7. The method according to claim 1, characterized in that the strongly wave-absorbing material is one selected from the group consisting of activated carbon, carbon black, graphite, carbon fiber, silicon carbide, metal oxides and porous composite materials that can generate electric arcs in a microwave field, or a mixture thereof; preferably one selected from the group consisting of activated carbon, graphite, silicon carbide and porous composite materials that can generate electric arcs in a microwave field, or a mixture thereof; and more preferably a porous composite material that can generate electric arcs in a microwave field.

8. The method according to claim 7, characterized in that the porous composite material that can generate electric arcs in a microwave field comprises an inorganic porous framework, and a carbon material supported on the inorganic porous framework, wherein the average pore diameter of the inorganic porous framework is preferably 0.01-1000 μm, more preferably 0.05-1000 μm, more preferably 0.05-500 μm, more preferably 0.2-500 μm, more preferably 0.5-500 μm, and more preferably 0.5-250 μm; and preferably, the porosity of the inorganic porous framework is 1%-99.99%, preferably 10%-99.9%, and more preferably 30%-99%.

9. The method according to claim 8, characterized in that the proportion of the carbon material is 0.001%-99%, preferably 0.01%-90%, and more preferably 0.1%-80% based on the total mass of the porous composite material; and/or the electric arcs generated by the porous composite material in a microwave field make the temperature of the porous composite material reach above 1000° C.; and/or the carbon material is selected from the group consisting of graphene, carbon nanotubes, carbon nanofibers, graphite, carbon black, carbon fibers, carbon dots, carbon nanowires, products obtained by carbonization of an carbonizable organic matter or a mixture comprising a carbonizable organic matter, and combinations thereof, and is preferably selected from the group consisting of graphene, carbon nanotubes, products obtained by carbonization of an carbonizable organic matter or a mixture comprising a carbonizable organic matter, and combinations thereof; preferably, the carbonizable organic matter is an organic polymer compound, comprising synthetic organic polymer compounds, which are preferably rubbers, or plastics, including thermosetting plastics and thermoplastics, and are more preferably selected from the group consisting of epoxy resin, phenolic resin, furan resin, polystyrene, styrene-divinylbenzene copolymer, polyacrylonitrile, polyaniline, polypyrrole, polythiophene, styrene butadiene rubber, polyurethane rubber and combinations thereof; and natural organic polymer compounds, which are preferably at least one selected from the group consisting of starch, viscose fiber, lignin and cellulose; preferably, the mixture comprising a carbonizable organic matter is the mixture of a carbonizable organic matter and other metal-free organic matter and/or metal-free inorganic matter; more preferably is selected from the group consisting of coal, natural pitch, petroleum pitch or coal tar pitch and combinations thereof; and/or the inorganic porous framework is an inorganic material having a porous structure, which is selected from the group consisting of carbon, silicate, aluminate, borate, phosphate, germanate, titanate, oxide, nitride, carbide, boride, sulfide, silicide, and halide and combinations thereof; preferably is selected from the group consisting of carbon, silicate, titanate, oxide, carbide, nitride, and boride and combinations thereof; wherein the oxide is preferably selected from the group consisting of aluminum oxide, silicon oxide, zirconium oxide, magnesium oxide, cerium oxide, and titanium oxide 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; and the boride is preferably selected from the group consisting of zirconium boride, hafnium boride, and tantalum boride and combinations thereof; preferably, the inorganic porous framework is at least one of the following: a carbon framework obtained after carbonization of a polymer sponge, a porous framework constituted by inorganic fibers, an inorganic sponge framework, a framework constituted by packing of inorganic particles, a ceramic porous framework obtained after baking a ceramic porous framework precursor, a ceramic fiber framework obtained after baking a ceramic fiber framework precursor; preferably a framework after carbonization of melamine sponge, a framework after carbonization of 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 magnesium oxide 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 after baking a ceramic fiber framework precursor.

10. The method according to claim 8, characterized in that the method comprises preparation of the porous composite material by a method comprising the following steps: (1) immersing the inorganic porous framework or inorganic porous framework precursor into the solution or dispersion of the carbon material and/or carbon material precursor, so that the pores of the inorganic porous framework or inorganic porous framework precursor are filled with the solution or dispersion; (2) heating and drying the porous material obtained in step (1), so that the carbon material or the carbon material precursor is precipitated or solidified and supported on the inorganic porous framework or the inorganic porous framework precursor; (3) further performing the following step if at least one of the carbon material precursor or the inorganic porous framework precursor is used as a starting material: heating the porous material obtained in step (2) under an inert gas atmosphere to convert the inorganic porous framework precursor into an inorganic porous framework, and/or reduce or carbonize the carbon material precursor.

11. The method according to claim 10, characterized in that the solution or dispersion of the carbon material or its precursor in step (1) comprises a solvent selected from the group consisting of benzene, toluene, xylene, trichlorobenzene, chloroform, cyclohexane, ethyl caproate, butyl acetate, carbon disulfide, ketone, acetone, cyclohexanone, tetrahydrofuran, dimethylformamide, water and alcohol, 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; a solvent comprising water and/or ethanol is more preferred; water and/or ethanol are further preferred; and/or the concentration of the solution or dispersion in step (1) is 0.001-1 g/mL, preferably 0.002-0.8 g/mL, and more preferably 0.003 g-0.5 g/mL; and/or in step (1), the carbon material and/or carbon material precursor comprises 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 the carbon material precursor;

12. The method according to claim 10, characterized in that the heating and drying in step (2) is carried out at a temperature of 50-250° C., preferably 60-200° C., and more preferably 80-180° C.; microwave heating is preferred, wherein the power of the microwave is preferably 1 W-100 KW, and more preferably 500 W-10 KW, and the microwave heating time is preferably 2-200 min, and more preferably 20-200 min.

13. The method according to claim 10, characterized in that the inorganic porous framework precursor is selected from the group consisting of ceramic precursors, porous materials composed of a carbonizable organic matter or porous materials composed of a mixture comprising a carbonizable organic matter, and combinations thereof; and/or the carbon material precursor is graphene oxide, modified carbon nanotubes, modified carbon nanofibers, modified graphite, modified carbon black, modified carbon fibers, carbonizable organic matters or mixtures comprising a carbonizable organic matter and combinations thereof; and/or the heating of step (3) is carried out at a temperature of 400-1800° C., preferably 600-1500° C., and more preferably 800-1200° C.; microwave heating is preferred, wherein the microwave power is preferably 100 W-100 KW, and more preferably 700 W-20 KW; and the microwave heating time is preferably 0.5-200 min, and more preferably 1-100 min.

14. The method according to claim 1, characterized in that the solid material comprising an organic matter is a waste synthetic polymer material or a waste natural polymer material, particularly one of waste plastics, waste rubbers, waste fibers and waste biomasses or a mixture thereof; wherein the plastic is preferably at least one selected from the group consisting of polyolefins, polyesters, polyamides, acrylonitrile-butadiene-styrene terpolymer, polycarbonate, polylactic acid, polyurethane, polymethyl methacrylate, polyoxymethylene, polyphenylene ether and polyphenylene sulfide; more preferably at least one selected from the group consisting of polyethylene, polypropylene, polyvinyl chloride, polyethylene terephthalate, polystyrene, polyamide, acrylonitrile-butadiene-styrene terpolymer, polycarbonate, polylactic acid, polymethyl methacrylate and polyoxymethylene; and more preferably at least one selected from the group consisting of polyethylene, polypropylene, polyvinyl chloride, polyethylene terephthalate, polystyrene, polycarbonate and polyamide; the rubber is preferably at least one selected from the group consisting of natural rubber, butadiene rubber, styrene butadiene rubber, nitrile rubber, isoprene rubber, ethylene propylene rubber, butyl rubber, chloroprene rubber, styrenic block copolymer and silicone rubber; and more preferably at least one selected from the group consisting of natural rubber, butadiene rubber, styrene butadiene rubber, isoprene rubber and ethylene propylene rubber; the fiber is preferably at least one selected from the group consisting of polypropylene fiber, acrylic fiber, vinylon, nylon, polyester fiber, polyvinyl chloride fiber and spandex, and more preferably at least one selected from the group consisting of polypropylene fiber, polyester fiber and spandex; the biomass is preferably at least one selected from the group consisting of straw, bagasse, tree branches, leaves, wood chips, rice husk, rice straw, peanut shells, coconut shells, palm seed shells and corn cobs.

15. System for implementing the continuous operation method for the microwave high-temperature pyrolysis of a solid material comprising an organic matter according to claim 1, comprising a) a mixing device, which is used to mix the solid material comprising an organic matter with a liquid organic medium; b) a transferring device, which is used to continuously transfer the resulting mixture from the mixing device a) to a microwave field; and c) a device for generating a microwave field, which is used to continuously contact the mixture from the transferring device b) with a strongly wave-absorbing material under an inert atmosphere or under vacuum, where the strongly wave-absorbing material continuously generates a high temperature in the microwave field, so that the solid material comprising an organic matter and the liquid organic medium are continuously pyrolyzed together.

16. The system according to claim 15, characterized in that the mixing device a) is a mixer with a stirring mechanism; and/or the transferring device b) is a pump, for example, a peristaltic pump, a diaphragm pump, a plunger pump and a screw pump, preferably, a peristaltic pump and a screw pump; and/or the device for generating a microwave field is a microwave device, for example, a microwave oven and a microwave pyrolysis reactor.

Description

DESCRIPTION OF THE DRAWINGS

[0101] FIG. 1 shows a schematic diagram of one embodiment of the system according to the present invention.

EXAMPLES

[0102] The present invention is further illustrated with reference to the following examples, but it is not intended to be limited by these examples.

[0103] The experimental data in the examples were measured using the following instruments and measurement methods:

[0104] 1. Determination of the mass percentage of the carbon material supported in the porous composite material obtained in the examples: [0105] 1) In the case that in the starting materials, inorganic porous framework material was used, the weight of inorganic porous framework material as the starting material was first measured, and the weight of the obtained porous composite material was measured after the end of the experiment; the weight difference between the two was the weight of the supported carbon material, thereby the mass percentage of the supported carbon material in the porous composite material was determined. [0106] 2) In the case that in the starting materials, inorganic porous framework precursor was used, two inorganic porous framework precursor samples of the same weight were used. One of them was used in the example according to the present invention; and the other was used in the reference example, wherein only the steps c and d of the preparation method as described above were carried out. After the end of the experiment, the weight of the porous composite material obtained in the example according to the present invention was weighed, and the final weight of the sample obtained in the reference example was weighed; the weight difference between the two was the weight of the supported carbon material, thereby the mass percentage of the supported carbon material in the porous composite material was determined.

[0107] 2. Unless otherwise specified, the chromatographic analysis of the gas pyrolyzed in the following examples and comparative examples was carried out using the Agilent 6890N gas chromatograph manufactured by the company Agilent, USA as follows.

[0108] The Agilent 6890N gas chromatograph used was equipped with an FID detector; involved HP-PLOT AL.sub.2O.sub.3 capillary column (50 m×0.53 mm×15 μm) as the chromatograph column; He as the carrier gas, with an average linear velocity of 41 cm/s; the inlet temperature of 200° C.; the detector temperature of 250° C.; the split ratio of 15:1; the injected sample volume of 0.25 ml (gaseous); and the temperature-increasing program, wherein the initial temperature was 55° C. and maintained for 3 min; then increased to 120° C. at 4° C./min and maintained for 4 min; further increased to 170° C. at 20° C./min and maintained for 10 minutes.

[0109] 3. The average pore diameter of the inorganic porous framework and the porous composite material was determined in the following manner: the pore diameter of a individual pore was determined by the smallest value among the distances between the two intersection points of the straight line passing through the center of the individual pore and the outline of the pore in the scanning electron microscope (SEM) photograph, then the average pore diameter was determined by the number-averaged value of the pore diameter values of all the pores shown in the SEM photograph. The SEM used was Hitachi S-4800 (Hitachi, Japan) with a magnification factor of 200.

[0110] 4. Method for measuring porosity: The porosity was determined with reference to GB/T 23561.4-2009.

[0111] 5. Method for measuring particle size: The particle size was measured by an optical microscope (model BX53M, Olympus). The particle size of a individual particle was determined by the largest value among the distances between the two intersection points of a straight line passing through the center of the individual particle and the outline of the particle in the optical microphotograph (magnification factor of 200); and the average particle size was determined by the number-averaged value of the particle size values of all the particles shown in the optical microphotograph.

[0112] The starting materials used in the examples were all commercially available.

Preparation of the Porous Composite Material

Example 1

[0113] (1) 500 ml of an aqueous dispersion of the graphene oxide (JCGO-95-1-2.6-W, 10 mg/ml, Nanjing Ji Cang Nano Tech Co., LTD.) was measured out and placed in a beaker; [0114] (2) 2 g of a porous framework composed of a phenolic resin (a phenolic foam, an average pore diameter of 300 μm, a porosity of 99%, Changshu Smithers-Oasis Floral Foam Co., Ltd) was immersed into the aqueous dispersion of the graphene oxide, so that the dispersion sufficiently entered into the pore channels of the porous framework; [0115] (3) the immersed porous material was withdrawn and placed on a stainless steel tray, which was placed in an oven at 180° C. and heated for 1 hour, thereby the material was dried and pre-reduced; and [0116] (4) the dried porous material was placed in a household microwave oven (700 w, model M1-L213B, Midea) for microwave treatment under a high power for 2 minutes to reduce the pre-reduced graphene oxide to graphene and carbonize the phenolic resin framework into carbon framework (an average pore diameter of 200 μm, and a porosity of 99%), thereby a porous composite material with the graphene supported on the carbon porous framework that can generate electric arcs in a microwave field was obtained, wherein the graphene comprised 10% of the total mass of the porous composite material.

Example 2

[0117] (1) 500 ml of a dispersion of the carbon nanotubes (XFWDM, 100 mg/ml, Nanjing XFNANO Materials Tech Co., Ltd.) was measured out and placed in a beaker; [0118] (2) 2 g of a porous framework composed of a phenolic resin (a phenolic foam, an average pore diameter of 200 μm, a porosity of 99%, Changshu Smithers-Oasis Floral Foam Co., Ltd) was immersed into the dispersion of the carbon nanotubes, so that the dispersion of the carbon nanotubes sufficiently entered into the pore channels of the porous framework; [0119] (3) the immersed porous material was withdrawn and placed on a stainless steel tray, which was placed in an oven at 80° C. and heated for 5 hours, thereby the material was dried; and [0120] (4) the dried porous material was placed in a tube furnace and carbonized at 800° C. for 1 hour under a nitrogen atmosphere, and a porous composite material with the carbon nanotubes supported on the carbon porous framework that can generate electric arcs in a microwave field (wherein the carbon framework had an average pore diameter of 140 μm and a porosity of 99%) was obtained, wherein the carbon nanotubes comprised 30% of the total mass of the porous composite material.

Example 3

[0121] (1) 500 ml of a dispersion of the carbon nanotubes (XFWDM, 100 mg/ml, Nanjing XFNANO Materials Tech Co., Ltd.) was measured out and placed in a beaker; [0122] (2) 5 g of a fibrous cotton-like porous framework composed of a silicate (an average pore diameter of 150 μm, and a porosity of 90%, Shandong Luyang Energy-saving Materials Co., Ltd.) was immersed into the dispersion of the carbon nanotubes and squeezed several times so that the dispersion sufficiently entered into the pore channels of the porous framework; and [0123] (3) the immersed porous material was withdrawn and placed on a stainless steel tray, which was placed in an oven at 150° C. and heated for 2 hours, thereby the material was dried and a porous composite material with the carbon nanotubes supported on the silicate fiber porous framework that can generate electric arcs in a microwave field was obtained, wherein the carbon nanotubes comprised 10% of the total mass of the porous composite material.

Example 4

[0124] (1) 30 g of a powdered phenolic resin (2123, Xinxiang Bomafengfan Industry Co., Ltd.) and 3.6 g of hexamethylenetetramine curing agent were weighed and placed in a beaker, to which 500 ml of ethanol was poured, and the mixture was stirred with a magnetic rotor for 1 hour until the components were all dissolved; [0125] (2) 5 g of a fibrous cotton-like porous framework composed of a silicate (an average pore diameter of 150 μm, and a porosity of 90%, Shandong Luyang Energy-saving Materials Co., Ltd.) was immersed into the formulated solution and squeezed several times, so that the solution sufficiently entered into the pore channels of the porous framework; [0126] (3) the immersed porous material was withdrawn and placed on a stainless steel tray, which was placed in an oven at 180° C. and heated for 2 hours, thereby the material was dried to remove the solvent so that the phenolic resin was cured; and [0127] (4) the dried and cured porous material was placed in a tube furnace and carbonized at 1000° C. for 1 hour under a nitrogen atmosphere to carbonize the phenolic resin, thereby a porous composite material with the phenolic resin carbonized product supported on the silicate fiber porous framework that can generate electric arcs in a microwave field was obtained, wherein the carbon material comprised 5% of the total mass of the porous composite material.

Example 5

[0128] (1) 50 g of a liquid phenolic resin (2152, Jining Baiyi Chemicals) was weighed and placed in a beaker, to which 500 ml of ethanol was poured, followed by stirring with a magnetic rotor for 1 hour until the component was all dissolved; [0129] (2) 8 g of a fiberboard-like porous framework composed of alumina (an average pore diameter of 100 μm, and a porosity of 85%, Shandong Luyang Energy-saving Materials Co., Ltd.) was immersed into the formulated solution, so that the solution sufficiently entered into the pore channels of the porous framework; [0130] (3) the immersed porous material was withdrawn and placed on a stainless steel tray, which was placed in an oven at 180° C. and heated for 2 hours, thereby the material was dried to remove the solvent so that the phenolic resin was cured; and [0131] (4) the dried and cured porous material was placed in a tube furnace and carbonized at 900° C. for 1 hour under a nitrogen atmosphere to carbonize the phenolic resin, thereby a porous composite material with the phenolic resin carbonized product supported on the alumina fiber porous framework that can generate electric arcs in a microwave field was obtained, wherein the carbon material comprised 6% of the total mass of the porous composite material.

Example 6

[0132] (1) 30 g of a water-soluble starch (medicinal grade, item number: S104454, Shanghai Aladdin Bio-Chem Technology Co., LTD) was weighed and placed in a beaker, to which 500 ml of deionized water was poured, followed by stirring for 1 hour with a magnetic rotor until the component was all dissolved; [0133] (2) 8 g of a fiber mat-like porous framework composed of alumina (an average pore diameter of 100 μm, and a porosity of 85%, Shandong Luyang Energy-saving Materials Co., Ltd.) was immersed into the formulated solution, so that the solution sufficiently entered into the pore channels of the porous framework; [0134] (3) the immersed porous material was withdrawn and placed into a microwave pyrolysis reactor (XOLJ-2000N, Nanjing Atpio Instrument Manufacturing Co., Ltd) for microwave treatment at a power of 10 KW for 2 minutes to dry the porous material; and [0135] (4) the dried porous material was placed in a tube furnace and carbonized at 1200° C. for 1 hour under a nitrogen atmosphere to carbonize the water-soluble starch, thereby a porous composite material with the starch carbonized product supported on the alumina fiber porous framework that can generate electric arcs in a microwave field was obtained, wherein the carbon material comprised 0.1% of the total mass of the porous composite material.

Example 7

[0136] (1) 50 g of a water-soluble starch (medicinal grade, item number: S104454, Shanghai Aladdin Bio-Chem Technology Co., LTD) was weighed and placed in a beaker, to which 500 ml of deionized water was poured, followed by stirring for 1 hour with a magnetic rotor until the component was all dissolved; [0137] (2) 8 g of a fiber cotton-like porous framework composed of alumina (an average pore diameter of 100 μm, and a porosity of 85%, Shandong Luyang Energy-saving Materials Co., Ltd.) was immersed into the formulated solution and squeezed several times, so that the solution sufficiently entered into the pore channels of the porous framework; [0138] (3) the immersed porous material was withdrawn and placed into a microwave pyrolysis reactor (XOLJ-2000N, Nanjing Atpio Instrument Manufacturing Co., Ltd) for microwave treatment at a power of 500 W for 2 h to dry the porous material; and [0139] (4) the dried porous material was placed in a tube furnace and carbonized at 1000° C. for 1 hour under a nitrogen atmosphere to carbonize the starch, thereby a porous composite material with the starch carbonized product supported on the alumina fiber porous framework that can generate electric arcs in a microwave field was obtained, wherein the carbon material comprised 0.2% of the total mass of the porous composite material.

Example 8

[0140] (1) 2 kg of a liquid phenolic resin (2152, Jining Baiyi Chemicals) was weighed and placed in a beaker, to which 4 L of ethanol was poured, followed by stirring with a magnetic rotor for 1 hour until the component was all dissolved; [0141] (2) 2 g of a porous framework composed of a phenolic resin (a phenolic foam, an average pore diameter of 500 μm, a porosity of 99%, Changshu Smithers-Oasis Floral Foam Co., Ltd) was immersed into the formulated solution, so that the solution sufficiently entered into the pore channels of the porous framework; [0142] (3) the immersed porous material was withdrawn and placed on a stainless steel tray, which was placed in an oven at 150° C. and heated for 2 hours, thereby the material was dried; and [0143] (4) the dried porous material was placed in a microwave pyrolysis reactor (XOLJ-2000N, Nanjing Atpio Instrument Manufacturing Co., Ltd.) for microwave treatment at a power of 20 KW for 100 minutes under a nitrogen atmosphere, thereby a porous composite material with the phenolic resin carbonized product supported on the carbon porous framework that can generate electric arcs in a microwave field (wherein the carbon framework had an average pore diameter of 350 μm and a porosity of 99%) was obtained, wherein the carbon material supported on the inorganic carbon framework comprised 80% of the total mass of the porous composite material.

Example 9

[0144] (1) 0.3 g of a liquid phenolic resin (2152, Dining Baiyi Chemicals) was weighed and placed in a beaker, to which 100 ml of ethanol was poured, followed by stirring with a magnetic rotor for 1 hour until the component was all dissolved; [0145] (2) 300 g of an active alumina (an average pore diameter of 0.05 μm, and a porosity of 30%, Shandong Kaiou Chemical Technology Co., Ltd.) was immersed into the formulated solution, so that the solution sufficiently entered into the pore channels of the active alumina; [0146] (3) the immersed porous material was withdrawn and placed on a stainless steel tray, which was placed in an oven at 150° C. and heated for 2 hours, thereby the material was dried; and [0147] (4) the dried porous material was placed in a tube furnace and carbonized at 1000° C. for 1 hour under a nitrogen atmosphere to carbonize the phenolic resin, thereby a porous composite material with the phenolic resin carbonized product supported on the active alumina (porous framework) that can generate electric arcs in a microwave field was obtained, wherein the carbon material comprised 0.05% of the total mass of the porous composite material.

Example 10

[0148] (1) 30 g of a powdered phenolic resin (2123, Xinxiang Bomafengfan Industry Co., Ltd.) and 3.6 g of hexamethylenetetramine curing agent were weighed and placed in a beaker, to which 500 ml of ethanol was poured, followed by stirring with a magnetic rotor for 1 hour until dissolution; [0149] (2) 8 g of a fiberboard-like porous framework composed of magnesium oxide (an average pore diameter of 100 μm, and a porosity of 80%, Jinan Huolong Thermal Ceramics Co., Ltd.) was immersed into the formulated solution, so that the solution sufficiently entered into the pore channels of the porous framework; [0150] (3) the immersed porous material was withdrawn and placed on a stainless steel tray, which was placed in an oven at 180° C. and heated for 2 hours, thereby the material was dried to remove the solvent so that the phenolic resin was cured; and [0151] (4) the dried and cured porous material was placed in a tube furnace and carbonized at 1000° C. for 1 hour under a nitrogen atmosphere to carbonize the phenolic resin, thereby a porous composite material with the phenolic resin carbonized product supported on the magnesium oxide fiber porous framework that can generate electric arcs in a microwave field was obtained, wherein the carbon material comprised 3% of the total mass of the porous composite material.

Example 11

[0152] (1) 100 g of a water-soluble starch (medicinal grade, Shanghai Aladdin Bio-Chem Technology Co., LTD) was weighed and placed in a beaker, to which 500 ml of deionized water was poured, followed by stirring for 1 hour with a magnetic rotor until the component was all dissolved; [0153] (2) 8 g of a fiberboard-like porous framework composed of zirconia (an average pore diameter of 150 μm, and a porosity of 80%, Jinan Huolong Thermal Ceramics Co., Ltd.) was immersed into the formulated solution, so that the solution sufficiently entered into the pore channels of the porous framework; [0154] (3) the immersed porous material was withdrawn and placed into a microwave pyrolysis reactor (XOLJ-2000N, Nanjing Atpio Instrument Manufacturing Co., Ltd) for microwave treatment at a power of 3 KW for 20 minutes to dry the porous material; and [0155] (4) the dried porous material was placed in a tube furnace and carbonized at 900° C. for 2 hours under a nitrogen atmosphere to carbonize the starch, thereby a porous composite material with the starch carbonized product supported on the zirconia fiber porous framework that can generate electric arcs in a microwave field was obtained, wherein the carbon material comprised 0.5% of the total mass of the porous composite material.

Example 12

[0156] (1) 50 g of a liquid phenolic resin (2152, Jining Baiyi Chemicals) was weighed and placed in a beaker, to which 500 ml of ethanol was poured, followed by stirring with a magnetic rotor for 1 hour until the component was all dissolved; [0157] (2) 8 g of a fiberboard-like porous framework composed of boron nitride (an average pore diameter of 100 μm, and a porosity of 80%, Jinan Huolong Thermal Ceramics Co., Ltd.) was immersed into the formulated solution, so that the solution sufficiently entered into the pore channels of the porous framework; [0158] (3) the immersed porous material was withdrawn and placed on a stainless steel tray, which was placed in an oven at 180° C. and heated for 2 hours, thereby the material was dried to remove the solvent so that the phenolic resin was cured; and [0159] (4) the dried and cured porous material was placed in a tube furnace and carbonized at 900° C. for 1 hour under a nitrogen atmosphere to carbonize the phenolic resin, thereby a porous composite material with the phenolic resin carbonized product supported on the boron nitride fiber porous framework that can generate electric arcs in a microwave field was obtained, wherein the carbon material comprised 5% of the total mass of the porous composite material.

Example 13

[0160] (1) 100 g of a liquid phenolic resin (2152, Dining Baiyi Chemicals) was weighed and placed in a beaker, to which 500 ml of ethanol was poured, followed by stirring with a magnetic rotor for 1 hour until the component was all dissolved; [0161] (2) 8 g of a fiberboard-like porous framework composed of silicon carbide (an average pore diameter of 100 μm, and a porosity of 80%, Jinan Huolong Thermal Ceramics Co., Ltd.) was immersed into the formulated solution, so that the solution sufficiently entered into the pore channels of the porous framework; [0162] (3) the immersed porous material was withdrawn and placed on a stainless steel tray, which was placed in an oven at 180° C. and heated for 2 hours, thereby the material was dried to remove the solvent so that the phenolic resin was cured; and [0163] (4) the dried and cured porous material was placed in a tube furnace and carbonized at 800° C. for 1 hour under a nitrogen atmosphere to carbonize the phenolic resin, thereby a porous composite material with the phenolic resin carbonized product supported on the silicon carbide fiber porous framework that can generate electric arcs in a microwave field was obtained, wherein the carbon material comprised 10% of the total mass of the porous composite material.

Example 14

[0164] (1) 100 g of a liquid phenolic resin (2152, Dining Baiyi Chemicals) was weighed and placed in a beaker, to which 500 ml of ethanol was poured, followed by stirring with a magnetic rotor for 1 hour until the component was all dissolved; [0165] (2) 8 g of a fiberboard-like porous framework composed of potassium titanate (an average pore diameter of 100 μm, and a porosity of 80%, Jinan Huolong Thermal Ceramics Co., Ltd.) was immersed into the formulated solution, so that the solution sufficiently entered into the pore channels of the porous framework; [0166] (3) the immersed porous material was withdrawn and placed on a stainless steel tray, which was placed in an oven at 180° C. and heated for 2 hours, thereby the material was dried to remove the solvent so that the phenolic resin was cured; and [0167] (4) the dried and cured porous material was placed in a tube furnace and carbonized at 800° C. for 1 hour under a nitrogen atmosphere to carbonize the phenolic resin, thereby a porous composite material with the phenolic resin carbonized product supported on the potassium titanate fiber porous framework that can generate electric arcs in a microwave field was obtained, wherein the carbon material comprised 10% of the total mass of the porous composite material.

Continuous Operation of Microwave Pyrolysis of a Solid Material Comprising an Organic Matter

Example 15

[0168] 50 g of a high-density polyethylene (HDPE, 3300F, Maoming Petrochemical) was pulverized at a low temperature (the particle size after pulverization was about 100 microns), and fully stirred with 100 g of a palm oil (commercially available) in a three-necked flask. 30 g of the porous composite material obtained in Example 1 was placed in a quartz reactor, which was purged with 500 ml/min nitrogen for 10 min, followed by adjusting the flow rate to 100 ml/min, the microwave pyrolysis reactor (XOLJ-2000N, Nanjing Atpio Instrument Manufacturing Co., Ltd) was started with a power of 1000 W, the above materials were continuously added through a quartz capillary at a speed of about 2 g/min using a peristaltic pump (LongerPump BT100-2J precision peristaltic pump) to the surface of the porous composite material in the quartz reactor, and were continuously pyrolyzed into gases, which were collected with a gas collecting bag at the gas outlet. The collected gases were chromatographically analyzed, and the analysis results are shown in Table 1.

[0169] 30 g of a polypropylene (PP, F280, Shanghai Petrochemical) was pulverized at a low temperature (the particle size after pulverization was about 100 microns), and stirred with 30 g of a soybean oil (commercially available) in a three-necked flask. 50 g of the porous composite material obtained in Example 6 was placed in a quartz reactor, which was purged with 500 ml/min nitrogen for 10 min, followed by adjusting the flow rate to 100 ml/min, the microwave pyrolysis reactor (XOLJ-2000N, Nanjing Atpio Instrument Manufacturing Co., Ltd) was started with a power of 1500 W, the above materials were continuously added through a quartz capillary at a speed of about 2 g/min using a peristaltic pump (LongerPump BT100-2J precision peristaltic pump) to the surface of the porous composite material in the quartz reactor, and were continuously pyrolyzed into gases, which were collected with a gas collecting bag at the gas outlet. The collected gases were chromatographically analyzed, and the analysis results are also shown in Table 1.

TABLE-US-00001 TABLE 1 Ethane, Acetylene, 1-Butene, 1,3- Methane propane Ethylene Propylene propyne isobutene, Butadiene Others Materials vol % vol % vol % vol % vol % vol % vol % vol % HDPE + 12 4 43 15 4 6 7 9 palm oil PP + 14 6 37 20 4 7 5 7 soybean oil

Example 16

[0170] Example 15 was repeated, except that the soybean oil was replaced with a palm oil and the high-density polyethylene was replaced with a low-density polyethylene, and the collected gases were chromatographically analyzed as follows: the gas product collected after pyrolysis was analyzed using a refinery gas analyzer (HP Agilent 7890 A, configured with 3 channels, including 1 FID and 2 TCDs (thermal conductivity detector)) in accordance with the ASTM D1945-14 method. Hydrocarbons were analyzed on the FID channel. One TCD using a nitrogen carrier gas was used to determine the hydrogen content, because there was a small difference between hydrogen and helium carrier gas in conductivity. The other TCD using helium as the carrier gas was used to detect CO, CO.sub.2, N.sub.2, and O.sub.2. For quantitative analysis, the response factor was determined by using RGA (refinery gas analysis) calibration gas standards. The analysis results are shown in Table 2-1.

[0171] In addition, for comparison, the following batch experiments were performed.

[0172] PE-batch method: 50 g of a low-density polyethylene (LDPE, LD600, Yanshan Petrochemical) was pulverized at a low temperature and placed in a three-necked flask. 30 g of the porous composite material obtained in Example 1 was placed in a quartz reactor, the above material was added to the surface of the porous composite material in the quartz reactor, which was purged with 500 ml/min nitrogen for 10 min, followed by adjusting the flow rate to 100 ml/min, the microwave pyrolysis reactor (XOLJ-2000N, Nanjing Atpio Instrument Manufacturing Co., Ltd) was started with a power of 1000 W, the above material was added to the surface of the porous composite material in the quartz reactor, and was pyrolyzed into gases, which were collected with a gas collecting bag at the gas outlet. As mentioned previously in this example, the collected gases were chromatographically analyzed, and the analysis results are shown in Table 2-1.

[0173] PP-batch method: 30 g of a polypropylene (PP, F280, Shanghai Petrochemical) was pulverized at a low temperature and placed in a three-necked flask. 50 g of the porous composite material obtained in Example 6 was placed in a quartz reactor, which was purged with 500 ml/min nitrogen for 10 min, followed by adjusting the flow rate to 100 ml/min, the microwave pyrolysis reactor (XOLJ-2000N, Nanjing Atpio Instrument Manufacturing Co., Ltd) was started with a power of 1500 W, the above material was added to the surface of the porous composite material in the quartz reactor, and was continuously pyrolyzed into gases, which were collected with a gas collecting bag at the gas outlet. As mentioned previously in this example, the collected gases were chromatographically analyzed, and the analysis results are also shown in Table 2-1.

[0174] In addition, as a reference, a similar experiment was performed using 100 g of a palm oil instead of the above low-density polyethylene, and the analysis results are shown in Table 2-1.

TABLE-US-00002 TABLE 2-1 Palm oil + Palm oil + Product/wt. % Palm oil PE PP PE PP Solid phase 22.0 8.5 3.3 14.0 5.4 Liquid phase 6.6 41.2 32.5 8.3 1.1 Gas phase 71.4 50.3 64.2 77.7 93.5 Gas Hydrogen 3.3 0.8 0.5 1.8 2.1 phase Carbon 15.5 1.4 0.8 12.9 9.7 compo- monoxide sition Carbon 12.8 0 0 10.1 7.9 dioxide Methane 24.1 19.2 8.3 16.0 20.7 Ethane 2.7 4.6 4.8 3.3 3.2 Ethylene 30.3 30.3 14.0 26.6 32.0 Propane 0.3 2.0 4.0 2.0 1.0 Propylene 4.5 22.6 52.5 15.1 16.1 Acetylene 1.8 1.6 0.2 1.2 1.0 1-Butene 0.2 1.3 1.0 1.8 0.1 1,3-Butadiene 0.6 4.2 1.7 1.4 1.1 Benzene 1.4 0.1 0.1 0.2 0.2 Others 2.5 11.9 12.1 7.6 4.9 (comprising butane, allene, 2-butene, isobutene, propyne, etc.) Diene yield 24.8 26.6 42.7 32.4 45.0

[0175] From the data in Table 2-1, it can be seen that the proportion of the gas phase products obtained by the continuous operation method of both palm oil and polyethylene was significantly higher than those of the gas phase products obtained by the batch operation method of using polyethylene alone and palm oil alone. Clearly, the combined use of palm oil and polyethylene achieved a synergistic effect. Palm oil not only functioned as a transferring medium for polyethylene but also promoted the high-temperature pyrolysis reaction of the two together, making the continuous operation method have a higher pyrolysis efficiency and lighter products.

[0176] In addition, activated carbon was used to replace the porous composite material according to Example 1 or 6 to repeat the above experiment. The analysis results are shown in Table 2-2.

TABLE-US-00003 TABLE 2-2 Palm oil + Palm oil + Product/wt. % Palm oil PE PP PE PP Solid phase 15 6.3 3.1 9.8 5.2 Liquid phase 42.1 50.3 45.7 31.7 18.8 Gas phase 42.9 43.4 51.2 58.5 76 Gas Hydrogen 2.9 0.7 0.4 1.5 1.9 phase Carbon 13.2 1.1 0.6 12.3 8.6 compo- monoxide sition Carbon 11.7 0 0 9.8 6.3 dioxide Methane 20.6 19.6 8.1 10.2 17.9 Ethane 2.9 4.4 4.5 3.5 3.5 Ethylene 32.3 28.4 14.5 29.8 35 Propane 0.4 2.3 4.3 2.5 1.1 Propylene 5.1 23.8 50.3 17.3 18.1 Acetylene 1.9 1.6 0.2 1.1 1.1 1-Butene 0.3 1.5 1.5 1.7 0.1 1,3-Butadiene 0.7 4.4 1.9 1.4 1.2 Benzene 1.6 0.1 0.1 0.2 0.2 Others 6.4 12.1 13.6 8.7 5 (comprising butane, allene, 2-butene, isobutene, propyne, etc.)

[0177] From the data in Table 2-2, it can be seen that when activated carbon was used as the strongly wave-absorbing material, a synergistic effect was also achieved. The proportion of the gas phase products obtained by the continuous operation method of both palm oil and polyethylene was significantly higher than those of the gas phase products obtained by the batch operation method of using polyethylene alone and palm oil alone. Palm oil not only functioned as a transferring medium for polyethylene but also promoted the high-temperature pyrolysis reaction of the two together, making the continuous operation method have a higher pyrolysis efficiency and lighter products as is compared with the batch method.

[0178] In addition, from the comparison of Table 2-2 and Table 2-1, it can be seen that the proportion of the gas phase products obtained in the microwave high-temperature pyrolysis performed using a specific porous composite material that can generate electric arcs in a microwave field was significantly higher than that using activated carbon, thus the method using such porous composite material had a higher pyrolysis efficiency, lighter products, and a higher added value of products.

LIST OF REFERENCE SIGNS

[0179] 1 Microwave oven [0180] 2 Quartz reactor [0181] 3 Peristaltic pump [0182] 4 Starting materials [0183] 5 Gas flow meter [0184] 6, 7 Cold trap [0185] 8 Ice water bath [0186] 9 Cotton filter