Patent Description:
More than <NUM>% of chemical raw materials come from fossil energy such as petroleum, shale gas and coal. However, fossil energy is non-renewable and will produce CO<NUM> during its use. Therefore, currently, the development of an environmentally friendly renewable energy has become one of the focuses in the energy field. For more sustainable economic and social development, there is an urgent need to replace the fossil energy with renewable biomass energies. Among them, vegetable oil has become a research focus due to its characteristics such as low price and large-scale cultivation. From <NUM> to <NUM>, a total of <NUM> million tons of major vegetable oils such as palm oil, rapeseed oil, sunflower oil and soybean oil were produced in the world. Straw is a common agricultural solid waste in rural areas in China, which is characterized by wide distribution and large resource amount. According to a report of the United Nations Environment Programme (UNEP), various grains grown in the world can provide <NUM> billion tons of straw every year, and the straw of various crops in China comes to a total output of more than <NUM> million tons, which is a huge renewable energy resource. In recent years, the rapid development of pyrolysis technology has made it one of the relatively efficient and mature biomass utilization technologies.

Ever since the <NUM>, humans have produced <NUM> billion tons of plastics, of which <NUM> billion tons have become waste. Of the <NUM> billion tons of waste plastics, <NUM>% is recycled, <NUM>% is incinerated, and the remaining <NUM>% (nearly <NUM> billion tons) is buried in landfills or accumulated in the natural environment. Humans are still accelerating the production rate of plastics. At present, the annual output of plastics has reached <NUM> million tons. It is estimated that by the year <NUM>, there will be <NUM> billion tons of waste plastics in the world. Every year, more than <NUM> million tons of plastics end up in the ocean. If no restrictions are imposed, there will be more plastic garbage in the ocean than fish by the year <NUM>. In recent years, top international publications have successively published the pollution of plastic particles to the organisms in the ocean and rivers and to drinking water, which has aroused the concern of the whole society on plastic pollution. In <NUM>, the United Nations Environment Programme focused for the first time on the issue of pollution caused by disposable plastics, and announced "Beat Plastic Pollution" as the theme of the World Environment Day, calling on the whole world to "declare war" on plastic pollution.

To solve the problem of plastic pollution, scientific researchers have made unremitting efforts. Ever since <NUM>, there has been a lot of research devoted to the preparation of plastics that are degradable in the natural environment. However, degradable plastics have important applications only in biomedicine, agricultural mulch film and garbage bags, etc., and in occasions in need of recycle, the presence of degradable plastics will seriously affect the performance of recycled plastic articles. Moreover, degradable plastics still take a relatively long time to degrade in non-ideal natural environments, thus the problem of white pollution cannot be effectively solved.

At present, mechanical recycling is the only widely-used technical solution for treating waste plastics. The main steps are successively removal of organic residues, washing, crushing, and melting and reprocessing, and in the process of melting and reprocessing, it is generally necessary to blend new materials to maintain the performance. Different plastics respond differently to the processing process, which makes the technical solution of mechanical recycling applicable to only a few types of plastics. At present, actually, only polyethylene terephthalate (PET) and polyethylene (PE) are recycled with said technology, accounting for <NUM>% and <NUM>% of the annual plastic output, respectively. Temperature-sensitive plastics, composite materials, and plastics that do not melt and flow at elevated temperatures (such as thermosetting plastics) cannot be treated by this method.

The chemical recycling method that prepares waste plastics into small molecular hydrocarbons (gas, liquid oil or solid wax) through a chemical conversion or a thermal conversion is considered to be a technical solution that can surpass mechanical recycling, and the resulting products can be used as fuels or chemical raw materials. However, this technical solution has not been widely used at present, mainly due to the high cost. On the one hand, most of the chemical recycling processes require expensive catalysts, and the selectivity of the catalyst requires that the raw material must be pure polymers, which requires time-consuming and labor-intensive sorting of waste plastics. On the other hand, the chemical recycling process consumes a lot of energy.

The microwave pyrolysis technology without catalysts has high energy efficiency and can simultaneously treat different types waste plastics that are polluted to some extent to pyrolyze them into chemical raw materials. It is expected to become the key to solving the problem of plastic pollution.

Microwave refers to an electromagnetic wave having a wavelength between infrared ray and ultrahigh frequency (UHF) radio wave, has a very strong penetrating ability, a wavelength between <NUM> and <NUM>, and a corresponding frequency of <NUM>-<NUM>. The magnetron of the microwave generator receives the power of the power source to generate microwaves, which are transferred to the microwave heater via the waveguide, and the material to be heated is heated under the action of the microwave field. The microwave heating mode is quite different from an ordinary heat transfer. The high-frequency electric field periodically changes the applied electric field and direction at a speed of hundreds of millions per second, so that the polar molecules in the material vibrate at a high frequency with the electric field, and by the friction and squeeze action between molecules, the material heats up rapidly, thereby the internal temperature and surface temperature of the material simultaneously rise rapidly.

Many patents have disclosed the technology of pyrolysis using this characteristic of the microwave, such as the patent application <CIT>, the patent application <CIT>, the patent application <CIT>, etc., which use strongly wave-absorbing materials such as carbon particles and silicon carbide to generate heat in the microwave field and transfer it to the materials to be pyrolyzed, thereby achieving the purpose of pyrolysis. However, waste synthetic polymer materials or waste natural polymer materials are solid at room temperature, thus are quite difficult to be transferred continuously during the pyrolysis. Usually, their microwave pyrolysis can only be done in batch operation, which makes continuous production difficult, and greatly affects the production efficiency. <CIT> discloses a continuous operation method for the microwave high-temperature pyrolysis of an organic material comprising solid and/or liquid components with active coal.

Therefore, how to develop a highly efficient method for the continuous operation of a process of microwave high-temperature pyrolysis of a solid material comprising an organic matter, especially a waste synthetic polymer material or a waste natural polymer material is still a difficult problem. The development of this method has huge application prospects.

In view of the problems in the prior art, the object of the present invention is to provide a continuous operation method for the microwave high-temperature pyrolysis of a solid material comprising an organic matter. The method according to the present invention can realize continuous, highly efficient, and industrializable operation, and the obtained product can comprise a high proportion of light components (especially gas phase products), and is high value-added.

According to the present invention, by means of such characteristics that a liquid organic medium can be used both as a medium for transferring a solid material comprising an organic matter and jointly as starting materials for pyrolysis, the solid material comprising an organic matter is mixed with the liquid organic medium for transferring, and under an inert atmosphere or vacuum, they are continuously contacted with a strongly wave-absorbing material under a microwave field, said strongly wave-absorbing material generates a high temperature rapidly and continuously under the microwave, so as to continuously pyrolyze the solid material comprising an organic matter and the liquid organic medium together into a fuel (such as hydrogen gas) or a chemical raw material, thereby achieving the continuous operation and further achieving the object. Since the pyrolyzed product comprises hydrogen gas, the method according to the present invention can also be used to prepare hydrogen gas.

Specifically, the present invention provides a continuous operation method for the microwave high-temperature pyrolysis of a solid material comprising an organic matter, defined in claim <NUM>.

Preferably, the solid material comprising an organic matter is pulverized before bein mixed with the liquid organic medium. The particle size after pulverization may b <NUM>-<NUM>, preferably <NUM>-<NUM>, more preferably <NUM>-<NUM>.

The particle size described herein is measured by an optical microscope. The particle size of an individual particle is determined by the largest value of the distance betwee 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; and the averag particle size is determined by the number-averaged value of the particle size values of all the particles shown in the optical microphotograph.

In one embodiment, the method of the present invention comprises:
pulverizing the solid material comprising an organic matter, followed by mixing it with a liquid organic medium for transferring, continuously contacting the resulting mixture with a strongly wave-absorbing material under a microwave field under an inert atmosphere or vacuum, which strongly wave-absorbing material rapidly and continuously generates a high temperature under the microwave, so as to continuously pyrolyze the solid material comprising an organic matter and the liquid organic medium together into a fuel or chemical raw material.

Herein, the liquid organic medium refers to a medium that is liquid at a temperature of <NUM> and comprises 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.

Solid materials comprising an organic matter are difficult to be transferred continuously during the pyrolysis process, thus they can only be operated in batch mode. The main purpose of adding a liquid organic medium is to formulate the liquid organic medium and the powder of the solid material comprising an organic matter into a slurry that can be transferred via a pump, so as to enable the process to be carried out continuously, and at the same time the liquid organic medium can be pyrolyzed together with the solid material comprising an organic matter into a fuel or chemical raw material. The above-mentioned pumping speed only needs to ensure the residence time of the mixture of the solid material comprising an organic matter and the liquid organic medium under the microwave field.

The solid material comprising an organic matter may comprise <NUM>%-<NUM>%, preferably <NUM>%-<NUM>%, more preferably <NUM>%-<NUM>% by mass of the total amount of the solid material comprising an organic matter and the liquid organic medium.

The weight ratio of the feed amount per minute of the solid material comprising an organic matter to the strongly wave-absorbing material may be <NUM>:<NUM>-<NUM>:<NUM>, preferably <NUM>:<NUM>-<NUM>:<NUM>, and more preferably <NUM>:<NUM>-<NUM>:<NUM>.

Herein, the inert atmosphere is an inert gas atmosphere commonly used in the prior art, such as nitrogen, helium, neon, argon, krypton, or xenon, preferably nitrogen.

The microwave power of the microwave field can be 200W-100KW; preferably 300W-80KW, more preferably 500W-60KW.

Herein, the strongly wave-absorbing material refers to a material that can absorb microwaves to a large extent, and the strongly wave-absorbing material can generate high temperature in a microwave field, rapidly reaching <NUM>-<NUM>, preferably <NUM>-<NUM>, more preferably <NUM>-<NUM>, preferably <NUM>-<NUM>, and more preferably <NUM>-<NUM>, so that the solid material comprising an organic matter and the liquid organic medium are pyrolyzed together.

The porous composite material capable of generating electric arcs in a microwave field preferably comprises an inorganic porous framework and a carbon material supported on the inorganic porous framework. The term "supported" means that the carbon material is fixed to the surface or in the structure of the inorganic porous framework via specific binding force. The surface refers to all the interfaces of the porous framework that can be in contact with the gas phase. The term "fixed in the structure" refers to being inlaid or anchored inside the porous framework itself, rather than inside the pore channels.

The carbon material may comprise <NUM>%-<NUM>%, preferably <NUM>%-<NUM>%, and more preferably <NUM>%-<NUM>% of the total mass of the porous composite material.

The inorganic porous framework is an inorganic material with a porous structure. The average pore diameter of the inorganic porous framework may be <NUM>-<NUM>, preferably <NUM>-<NUM>, more preferably <NUM>-<NUM>, more preferably <NUM>-<NUM>, more preferably <NUM>-<NUM>, and more preferably <NUM>-<NUM> or <NUM>-<NUM>; and the porosity may be <NUM>%-<NUM>%; preferably <NUM>%-<NUM>%, and more preferably <NUM>%-<NUM>%.

Herein, the average pore diameter is measured by a scanning electron microscope (SEM). Firstly, the pore diameter of an individual pore is determined by the smallest value of the distance 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 SEM photograph; then, the average pore diameter is determined by the number-averaged value of the pore diameter values of all the pores shown in the SEM photograph.

The porosity is determined with reference to GBIT <NUM>-<NUM>.

The carbon material may be at least one 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 a carbonizable organic matter and products after carbonization of a mixture of a carbonizable organic matter, and is preferably at least one selected from the group consisting of graphene, carbon nanotubes, products obtained by carbonization of a carbonizable organic matter and products after carbonization of a mixture of a carbonizable organic matter.

The mixture of a carbonizable organic matter may be a mixture of a carbonizable organic matter with an inorganic substance which is not a metal or a metal compound, and other organic matter which is not a metal compound.

The carbonization means that by treating an organic matter under the conditions of a certain temperature and atmosphere, all or most of the hydrogen, oxygen, nitrogen, sulfur, etc. in the organic matter are volatilized, thereby obtaining a synthetic material with high carbon content.

The carbonizable organic matter is preferably an organic polymer compound, wherein the organic polymer compound includes synthetic polymer compounds and natural organic polymer compounds; the synthetic polymer compound is preferably a rubber or a plastic; and the plastic includes thermosetting plastics and thermoplastics.

The natural organic polymer compound is preferably at least one selected from the group consisting of starch, viscose fiber, lignin and cellulose.

The synthetic polymer compound is preferably at least one selected from the group consisting of epoxy resin, phenolic resin, furan resin, polystyrene, styrene-divinylbenzene copolymer, polyacrylonitrile, polyaniline, polypyrrole, polythiophene, styrene butadiene rubber and polyurethane rubber.

The mixture of a carbonizable organic matter is preferably at least one selected from the group consisting of coal, natural pitch, petroleum pitch and coal tar pitch.

The inorganic material of the inorganic porous framework may be 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 selected from the group consisting of aluminum oxide, silicon oxide, zirconium oxide, magnesium oxide, cerium oxide and titanium oxide; the nitride is preferably at least one selected from the group consisting of silicon nitride, boron nitride, zirconium nitride, hafnium nitride and tantalum nitride; the carbide is preferably at least one selected from the group consisting of silicon carbide, zirconium carbide, hafnium carbide and tantalum carbide; and the boride is preferably at least one selected from the group consisting of zirconium boride, hafnium boride and tantalum boride.

The inorganic material of the inorganic porous framework is more preferably at least one selected from the group consisting of carbon, silicate, aluminum oxide, magnesium oxide, zirconium oxide, silicon carbide, boron nitride, and potassium titanate.

The inorganic porous framework is preferably at least one of the following specific frameworks: 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 (such as aluminum silicate rock wool), a porous framework of mullite fiber, a porous framework of alumina fiber (such as alumina fiber board), 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.

The porous structure of the inorganic porous framework can be from the pore structure of the framework material itself, such as the sponge-like structural form; or from the pore structure formed by the packing of fiber materials, such as fiber cotton, fiber felt, fiberboard and other structural forms; or from the pore structure formed by the packing of granular materials, such as the sand pile structural form; or from a combination of the above various forms. It is preferably from the pore structure formed by the packing of fiber materials. It should be specially noted that for the porous framework constituted by inorganic fibers as described above, the "porous" therein refers to the pore structure in the framework formed by the packing of fiber materials, but does not mean that the fibers per se are porous.

The porous composite material can generate high-temperature electric arcs in microwaves, for example, in a 900w microwave field, the porous composite material can generate electric arcs that can raise the temperature thereof to above <NUM>, and the material per se can withstand high temperatures, which are up to <NUM>. This porous composite material that can generate electric arcs in a microwave field is a novel and efficient microwave heating material.

The continuous operation method for the microwave high-temperature pyrolysis of a solid material comprising an organic matter of the present invention can be integrated into the preparation process of the porous composite material.

Specifically, the porous composite material can be prepared by a method comprising the following steps:.

The solution or dispersion of the carbon material or its precursor in step (<NUM>) may comprise 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, <NUM>,<NUM>-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 (<NUM>) may be <NUM>-<NUM>/mL, preferably <NUM>-<NUM>/mL, and more preferably <NUM>-<NUM>/mL.

The heating and drying in step (<NUM>) can be carried out at a temperature of <NUM>-<NUM>, preferably <NUM>-<NUM>, and more preferably <NUM>-<NUM>; microwave heating is preferred, wherein the power of the microwave is preferably 1W-100KW, and more preferably 500W-10KW, and the microwave heating time is preferably <NUM>-<NUM>, and more preferably <NUM>-<NUM>.

The inorganic porous framework precursor can be selected from the group consisting of ceramic precursors, porous materials of a carbonizable organic matter or porous materials of a mixture comprising a carbonizable organic matter, and combinations thereof.

The carbon material precursor can be 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.

The heating of step (<NUM>) can be carried out at a temperature of <NUM>-<NUM>, preferably <NUM>-<NUM>, and more preferably <NUM>-<NUM>; microwave heating is preferred, wherein the microwave power is preferably 100W-100KW, and more preferably 700W-20KW; and the microwave heating time is preferably <NUM>-<NUM>, and more preferably <NUM>-<NUM>.

In one embodiment, the method for preparing the porous composite material comprises the following steps:.

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 carbonizable organic matters or mixtures of a carbonizable organic matter. Modified carbon nanotubes, modified carbon nanofibers, modified graphite, modified carbon black, and modified carbon fibers refer to the carbon materials that are pretreated in order to improve the dispersibility of these carbon materials in water or organic solvents and obtain stable dispersions. For example, pretreatment is performed with dispersing agents and surfactants, or pretreatment is performed by grafting hydrophilic groups, etc. These pretreatment means all adopt the pretreatment means for improving dispersibility in the prior art. All the carbon materials subjected to the above pretreatments such as aqueous dispersion of graphene, ethanol dispersion of graphene, aqueous slurry of graphene, oily slurry of graphene, aqueous dispersion of graphene oxide, ethanol dispersion of graphene oxide, N-methylpyrrolidone dispersion of graphene oxide, aqueous dispersion of carbon nanotubes, aqueous dispersion of carboxylated carbon nanotubes, ethanol dispersion of carbon nanotubes, dimethylformamide dispersion of carbon nanotubes, N-methylpyrrolidone slurry of carbon nanotubes, etc., can also be obtained commercially.

The solvent of the solution or dispersion of the carbon material or its precursor in step a can be one selected from the group consisting of benzene, toluene, xylene, trichlorobenzene, trichloromethane, cyclohexane, ethyl caproate, butyl acetate, carbon disulfide, ketone, acetone, cyclohexanone, tetrahydrofuran, dimethylformamide, water and alcohols or a combination thereof.

The alcohols are preferably at least one selected from the group consisting of propanol, n-butanol, isobutanol, ethylene glycol, propylene glycol, <NUM>,<NUM>-butanediol, isopropanol and ethanol.

In the preparation method, the carbon material precursor for supporting is preferably a precursor that can be dissolved or dispersed in a solvent, which is friendly to the human body and the environment, prior to supporting, so that the preparation process is "green". The solvent which is friendly to the human body and the environment is at least one selected from the group consisting of ethanol, water and a mixture of the two. That is, the solvent in step a is more preferably a solvent comprising water and/or ethanol; and further preferably, water and/or ethanol.

The solution or dispersion of step a only needs to achieve the sufficient dissolution or sufficient dispersion of the carbon material and/or the carbon material precursor in the solvent. Usually, its concentration can be <NUM>-<NUM>/mL, preferably <NUM>-<NUM>/mL, and further preferably <NUM>-<NUM>/mL.

More specifically, in the preparation method, when the carbon material supported on the inorganic porous framework is graphene, an aqueous solution of graphene oxide is preferably used in step a.

In the preparation method, when the carbon material supported on the inorganic porous framework is carbon nanotubes, a dispersion of carbon nanotubes is preferably used in step a.

In the preparation method, when a thermosetting plastic is selected as the carbon material precursor for supporting, in step a, a suitable curing system needs to be formulated according to the conventional curing formulation of the selected thermosetting plastic in the prior art. In the curing system, optional one or more additives selected from the following group may be added: curing accelerators, dyes, pigments, colorants, antioxidants, stabilizers, plasticizers, lubricants, flow modifiers or aids, flame retardants, anti-dripping agents, anti-caking agents, adhesion promoters, conductive agents, polyvalent metal ions, impact modifiers, release aids, nucleating agents, etc. The amounts of the additives used are all conventional amounts, or can be adjusted according to actual conditions. When a thermosetting plastic is selected as the carbon material precursor for supporting, after heating in the subsequent step c, the thermosetting resin used as the carbon material precursor is cured and supported on the inorganic porous framework.

In the preparation method, when a thermosetting plastic is selected as the carbon material precursor for supporting, in step a, a corresponding good solvent in the prior art is selected to dissolve the above thermosetting plastic and its curing system to obtain a carbon material precursor solution for supporting.

In the preparation method, when a thermoplastic is selected as the carbon material precursor for supporting, the solution of the carbon material precursor for supporting can be added with antioxidants, co-antioxidants, heat stabilizers, light stabilizers, ozone stabilizers, processing aids, plasticizers, softeners, anti-blocking agents, foaming agents, dyes, pigments, waxes, extenders, organic acids, flame retardants, coupling agents and other additives commonly used in the prior art during plastic processing. The amounts of additives used are all conventional amounts or can be adjusted according to actual conditions.

In step b of the preparation method, the pores of the inorganic porous framework can be filled with the solution or dispersion of the carbon material or carbon material precursor for supporting by squeezing several times or not squeezing at all.

After the porous material obtained in step b is withdrawn in step c of the preparation method, measures can be taken or not to remove the excess solution or dispersion of the carbon material or carbon material precursor for supporting in the porous material obtained in step b. The above measures include, but are not limited to, one or two of the squeezing and centrifugal operations.

The heating in steps c and d of the preparation method may preferably be microwave heating, which not only is efficient but also can achieve uniform heating.

Specifically, in step c, the power of the microwave is 1W-100KW, preferably 500W-10KW, and the microwave time is <NUM>-<NUM>, preferably <NUM>-<NUM>.

In step d, the power of the microwave is changed to 100W-100KW, preferably 700W-20KW; and the microwave time is <NUM>-<NUM>, preferably <NUM>-<NUM>.

The heating in step d of the preparation method needs to be performed under an inert gas atmosphere, which is selected from the inert gas atmospheres commonly used in the prior art, preferably nitrogen.

The devices used in the preparation method are all common ones.

As described above, the above method for the preparation of a porous composite material combines an inorganic porous framework and a carbon material to prepare a porous composite material which has excellent mechanical properties and can generate electric arcs in a microwave field to thereby rapidly generate a high temperature, for example, in a 900w microwave field, the porous composite material can generate electric arcs that raise the temperature thereof to above <NUM>. The material per se is resistant to high temperature, the process flow is simple and easy to implement, and it is easy to realize large-scale preparation.

The solid material comprising an organic matter in the present invention can be one of waste plastics, waste rubbers, waste fibers and waste biomasses or a mixture thereof.

The waste plastic in the present invention refers to the plastic and its mixture for civilian, industrial and other purposes that have been used while eventually disused or replaced. The plastic includes, but is not limited to, at least one of polyolefins, polyesters, polyamides, acrylonitrile-butadiene-styrene terpolymer, polycarbonate, polylactic acid, polyurethane, polymethyl methacrylate, polyoxymethylene, polyphenylene ether and polyphenylene sulfide, preferably at least one of polyethylene, polypropylene, polyvinyl chloride, polyethylene terephthalate, polystyrene, polyamide, acrylonitrile-butadiene-styrene terpolymer, polycarbonate, polylactic acid, polymethyl methacrylate and polyoxymethylene, and further preferably at least one of polyethylene, polypropylene, polyvinyl chloride, polyethylene terephthalate, polystyrene, polycarbonate and polyamide.

The waste rubber in the present invention refers to the rubber and its mixture for civil, industrial and other purposes that have been used while eventually disused or replaced. 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, styrenic block copolymer and silicone rubber; more preferably at least one of natural rubber, butadiene rubber, styrene butadiene rubber, isoprene rubber and ethylene propylene rubber.

The waste fiber in the present invention refers to the fiber article and its mixture for civil, industrial and other purposes that have been used while eventually disused or replaced. The fiber is preferably at least one of polypropylene fiber, acrylic fiber, vinylon, nylon, polyester fiber, polyvinyl chloride fiber and spandex, more preferably at least one of polypropylene fiber, polyester fiber and spandex.

The waste biomass of the present invention is a variety of animals, plants and algae produced through photosynthesis, and is composed of cellulose, hemicellulose and lignin. It is preferably one of straw, bagasse, tree branches, leaves, wood chips, rice husk, rice straw, peanut shells, coconut shells, palm seed shells and corn cobs or a mixture thereof.

The liquid organic medium of the present invention is preferably a liquid petroleum hydrocarbon and its mixture and/or a vegetable oil and its mixture; more preferably one of crude oil, naphtha, palm oil, rapeseed oil, sunflower oil, soybean oil, peanut oil, linseed oil and castor oil, or a mixture thereof; further preferably one of naphtha, palm oil, rapeseed oil, sunflower oil and soybean oil, or a mixture thereof.

The microwave field in the method of the present invention can be generated by various microwave devices in the prior art, such as household microwave oven, industrialized microwave device (such as microwave pyrolysis reactor) and the like.

In the method of the present invention, the device for placing or loading the solid material comprising an organic matter, the liquid organic medium and the strongly wave-absorbing material can be selected from various containers or pipes in the prior art that can be penetrated by microwaves and can withstand high temperatures of above <NUM>, such as a quartz crucible, a quartz reactor, a quartz tube, an alumina crucible, an alumina reactor, an alumina tube, etc..

In the method of the present invention, the solid material comprising an organic matter and the liquid organic medium are pyrolyzed and then gasified, and the gas obtained after pyrolysis is collected for subsequent treatment, for example, the gas is separated and then used as a fuel or as a raw material for chemical industry for subsequent reaction and production. The residue after pyrolysis is disposed as waste.

The gas collection is a common method in the prior art, and is preferably carried out under an inert atmosphere. For example, an industrial microwave oven with a gas inlet and a gas outlet (such as a microwave pyrolysis reactor, etc.) is used. The gas collection manner is purging with nitrogen during the reaction process, and sampling and collecting with a gas collecting bag at the gas outlet.

In the method of the present invention, by utilizing such characteristics of the liquid organic medium that it can be used both as a medium for transferring the solid material comprising an organic matter and jointly as starting materials for pyrolysis, the solid material comprising an organic matter is pulverized and then mixed with the liquid organic medium for transferring; under an inert atmosphere or under vacuum, the resulting mixture is continuously contacted with the strongly wave-absorbing material under a microwave field, which strongly wave-absorbing material rapidly and continuously generates a high temperature under the microwaves, thereby continuously pyrolyzing the solid material comprising an organic matter and the liquid organic medium together to realize a continuous operation. The method of the invention is continuous in process, highly-efficient and industrializable, and the product composition has high added value. In particular, it is unexpectedly discovered that in the method of the present invention, the combined use of a liquid organic medium and a solid material comprising an organic matter achieves a synergistic effect. The liquid organic medium not only acts as a transferring medium for the solid material, but also promotes the high temperature pyrolysis reaction of them together, so that the continuous operation method has higher pyrolysis efficiency and lighter products.

According to another aspect, the present invention further provides a system for implementing the continuous operation method for the microwave high-temperature pyrolysis of a solid material comprising an organic matter according to the present invention, comprising.

The mixing device a) can be any type of mixing equipment that can mix a solid material comprising an organic matter with a liquid organic medium, preferably a mixer with a stirring mechanism. Correspondingly, such a process section can also be referred to as a material mixing section or a material stirring section, and said process section refers to an operation section where a solid material comprising an organic matter is mixed with a liquid organic medium.

The device c) for generating a microwave field, as described above, may be a microwave device, such as a household microwave oven and an industrial microwave pyrolysis reactor. The process section herein can also be referred to as a microwave treatment section. The microwave treatment section refers to an operation section 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 pyrolyzed together.

The transferring device b) can be any type of transferring device that can transfer a mixture of a solid (such as a powder) and a liquid, such as pumps, including but not limited to peristaltic pumps, diaphragm pumps, plunger pumps and screw pumps, preferably peristaltic pumps and screw pumps. The rated power of the pump may be 10W-100kW, preferably 50W-50kW, and more preferably 100W-30kW.

The pump can be arranged between the material mixing section and the microwave treatment section. Through a pump (such as a peristaltic pump), a mixture of a solid material comprising an organic matter and a liquid organic medium can be continuously added to the surface of the strongly wave-absorbing material. The pumping speed can ensure the continuous contact of the mixture of the solid/liquid mixed materials and the strongly wave-absorbing material under the microwave field.

For example, the continuous operation method for the microwave high-temperature pyrolysis of a solid material comprising an organic matter according to the present invention can be performed in a system as shown in <FIG>.

<FIG> shows a schematic diagram of one embodiment of the system according to the present invention.

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

The experimental data in the examples were measured using the following instruments and measurement methods:.

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

<NUM> of a high-density polyethylene (HDPE, 3300F, Maoming Petrochemical) was pulverized at a low temperature (the particle size after pulverization was about <NUM> microns), and fully stirred with <NUM> of a palm oil (commercially available) in a three-necked flask. <NUM> of the porous composite material obtained in Example <NUM> was placed in a quartz reactor, which was purged with <NUM>/min nitrogen for <NUM>, followed by adjusting the flow rate to <NUM>/min, the microwave pyrolysis reactor (XOLJ-2000N, Nanjing Atpio Instrument Manufacturing Co. , Ltd) was started with a power of 1000W, the above materials were continuously added through a quartz capillary at a speed of about <NUM>/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 <NUM>.

<NUM> of a polypropylene (PP, F280, Shanghai Petrochemical) was pulverized at a low temperature (the particle size after pulverization was about <NUM> microns), and stirred with <NUM> of a soybean oil (commercially available) in a three-necked flask. <NUM> of the porous composite material obtained in Example <NUM> was placed in a quartz reactor, which was purged with <NUM>/min nitrogen for <NUM>, followed by adjusting the flow rate to <NUM>/min, the microwave pyrolysis reactor (XOLJ-2000N, Nanjing Atpio Instrument Manufacturing Co. , Ltd) was started with a power of 1500W, the above materials were continuously added through a quartz capillary at a speed of about <NUM>/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 <NUM>.

Example <NUM> 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 <NUM> A, configured with <NUM> channels, including <NUM> FID and <NUM> TCDs (thermal conductivity detector)) in accordance with the ASTM D1945-<NUM> 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<NUM>, N<NUM>, and O<NUM>. For quantitative analysis, the response factor was determined by using RGA (refinery gas analysis) calibration gas standards. The analysis results are shown in Table <NUM>-<NUM>.

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

PE-batch method: <NUM> of a low-density polyethylene (LDPE, LD600, Yanshan Petrochemical) was pulverized at a low temperature and placed in a three-necked flask. <NUM> of the porous composite material obtained in Example <NUM> 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 <NUM>/min nitrogen for <NUM>, followed by adjusting the flow rate to <NUM>/min, the microwave pyrolysis reactor (XOLJ-2000N, Nanjing Atpio Instrument Manufacturing Co. , Ltd) was started with a power of 1000W, 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 <NUM>-<NUM>.

PP-batch method: <NUM> of a polypropylene (PP, F280, Shanghai Petrochemical) was pulverized at a low temperature and placed in a three-necked flask. <NUM> of the porous composite material obtained in Example <NUM> was placed in a quartz reactor, which was purged with <NUM>/min nitrogen for <NUM>, followed by adjusting the flow rate to <NUM>/min, the microwave pyrolysis reactor (XOLJ-2000N, Nanjing Atpio Instrument Manufacturing Co. , Ltd) was started with a power of 1500W, 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 <NUM>-<NUM>.

In addition, as a reference, a similar experiment was performed using <NUM> of a palm oil instead of the above low-density polyethylene, and the analysis results are shown in Table <NUM>-<NUM>.

From the data in Table <NUM>-<NUM>, 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.

In addition, activated carbon was used to replace the porous composite material according to Example <NUM> or <NUM> to repeat the above experiment. The analysis results are shown in Table <NUM>-<NUM>.

From the data in Table <NUM>-<NUM>, 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.

Claim 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 of <NUM>-<NUM> in the microwave field, so that the solid material comprising an organic matter and the liquid organic medium are continuously pyrolyzed together
wherein the strongly wave-absorbing material is a porous composite material that can generate electric arcs in a microwave field, and
the liquid organic medium refers to a medium that is liquid at a temperature of <NUM> and contains at least one carbon atom and is one selected from the group consisting of hydrocarbon oils, vegetable oils, silicone oils, ester oils, phosphate esters and alcohols, or a mixture thereof.