Methods for decomposing organic raw materials, and methods for producing liquid fuels, solid fuels, or activated carbon using the same.

Abstract

The present invention pertains to an organic feedstock decomposition method comprising: a feedstock supply step for supplying, to a fluidized bed decomposition device, artificial carbon particles and an organic feedstock containing biomass and / or organic polymer waste; and a decomposition step for, while introducing a carrier gas into the fluidized bed decomposition device and fluidizing the artificial carbon particles, decomposing the organic feedstock and discharging the result with the carrier gas as a non-solid-state decomposition component, whereas solid residue generated by said decomposition is discharged separate from the non-solid decomposition component.

Description

[Technical Field] 【0001】 This invention relates to a method for decomposing organic raw materials such as biomass and organic polymer waste. [Background technology] 【0002】 As a measure to combat global warming, efforts are being made to reduce greenhouse gases. For example, attempts are being made to convert biomass, organic polymer waste, and other materials into liquid fuels and carbon materials. For example, Patent Document 1 describes a method of gasifying biomass by heating it at a temperature of 600 to 1000°C at a pressure of 1 to 5 MPa to produce carbon monoxide and hydrogen, and then using a catalytic reaction to convert the resulting carbon monoxide and hydrogen into methanol, dimethyl ether (DME), or hydrocarbon liquid fuel (FT synthetic oil). Patent Document 2 describes a method of reacting biomass with pressurized hot water, supercritical water, or subcritical water at a temperature of 200 to 500°C and a pressure of 100 to 400 atm in the presence of sodium hydroxide and a catalyst to produce gaseous or liquefied gases such as methane, hydrogen, and carbon monoxide, which are then supplied inside to power generation systems such as gas turbines or diesel generators as fuel for power generation. However, these methods are not suitable for producing liquid fuels because their main purpose is to decompose biomass into C1 components such as methane and carbon monoxide or liquefied gases. They are also disadvantageous because they require high temperature and high pressure conditions. 【0003】 Patent Document 3 describes the production of petroleum substitute liquid fuel by pressurized co-thermal decomposition of woody biomass and plastics in an autoclave in the presence of mineral oil as a solvent and a catalyst (NaY-type zeolite) used as needed. Patent Document 4 describes the production of bio-oil by liquefying and thermally decomposing a mixed raw material of biomass and waste plastics in an autoclave in the presence of a solvent such as ethylene glycol. According to these methods, liquid fuels and bio-oils can be produced without decomposing them down to the C1 component. However, these methods are disadvantageous because the solvent is mixed into the decomposition products, and it is necessary to separate the solvent when extracting useful components (liquid fuels, bio-oils, etc.) from the decomposition products. They are also disadvantageous because they require high temperature and high pressure conditions. 【0004】 Patent document 5 describes the production of C2-C5 olefins, furans, aromatic compounds, etc., by thermally decomposing biomass in a fluidized bed reactor in the presence of a catalyst containing zeolite. Patent document 6 describes a method for producing bio-oil by rapidly thermally decomposing lignocellulosic biomass and thermoplastic plastics in atmospheric pressure and an inert gas stream. 【0005】 Although it concerns a method for producing fuel gas rather than liquid fuel, Patent Document 7 describes the production of fuel gas from biomass in the presence of activated carbon. [Prior art documents] [Patent Documents] 【0006】 [Patent Document 1] Japanese Patent Publication No. 2008-189704 [Patent Document 2] Japanese Patent Publication No. 2001-065364 [Patent Document 3] Japanese Patent Publication No. 2013-170224 [Patent Document 4] Japanese Patent Publication No. 2016-079325 [Patent Document 5] Special Publication No. 2016-517344 [Patent Document 6] Japanese Patent Publication No. 2017-080662 [Patent Document 7] Japanese Patent Publication No. 2009-046644 [Overview of the Initiative] [Problems that the invention aims to solve] 【0007】 However, our investigations revealed that there was room for improvement in the methods described in Patent Documents 5 and 6. Specifically, it was possible to increase the efficiency of liquid fuel production without requiring the use of a catalyst containing zeolite as shown in Patent Document 5. Furthermore, it was possible to increase the efficiency of bio-oil production compared to the method in Patent Document 6. The method in Patent Document 7 is not a method for producing liquid fuel. Moreover, it was found that even when producing liquid fuel, it is possible to efficiently produce it without using materials that require activation treatment, such as activated carbon. Therefore, the object of the present invention is to produce useful components, including liquid fuel, from organic raw materials in good yield, without requiring the use of a catalyst containing zeolite, nor without requiring the use of materials that require a complicated manufacturing process such as activated carbon. [Means for solving the problem] 【0008】 The present invention, which has achieved the above objective, employs the following configuration. [1] A raw material supply process for supplying organic raw materials, including biomass and / or organic polymer waste, and artificial carbon particles (but not activated carbon) to a fluidized bed decomposition unit, and A decomposition process in which a carrier gas is introduced into the fluidized bed decomposition apparatus to fluidize the artificial carbon particles, while the organic raw material is decomposed and discharged together with the carrier gas as a non-solid decomposition component, and the solid residue generated by the decomposition is discharged separately from the non-solid decomposition component, A method for decomposing organic raw materials having the following properties. [2] A reuse process in which at least a portion of the solid residue discharged in the decomposition process is returned to the raw material supply process as artificial carbon particles before it is cooled to room temperature. The method according to [1] having the following. [3] The method according to [1] or [2], wherein at least a part of the solid residue discharged in the decomposition step is returned to the raw material supply step as artificial carbon particles after adjusting the particle size or without adjusting the particle size. [4] The specific surface area of the artificial carbon particles is 500 m 2 / g or less, and the method according to any one of [1] to [3]. [5] The content of metal atoms in the artificial carbon particles is 20% by mass or less, and the method according to any one of [1] to [4]. [6] In the raw material supply step, the organic raw material is subjected to at least one pretreatment selected from impurity removal, moisture removal, particle size adjustment, and raw material blending, and then supplied to the fluidized bed decomposition apparatus. The method according to any one of [1] to [5]. [7] In the raw material supply step, at least one selected from the organic raw material, the artificial carbon particles, and a mixture thereof is continuously charged into the fluidized bed decomposition apparatus. The method according to any one of [1] to [6]. [8] The biomass is at least one selected from lignocellulosic biomass and oil and fat plant biomass, and the organic polymer waste is at least one waste selected from synthetic resin, synthetic rubber, and synthetic fiber. The method according to any one of [1] to [7]. [9] In the raw material supply step, organic acids are supplied to the fluidized bed decomposition apparatus together with the organic raw material and the artificial carbon particles. The method according to any one of [1] to [8].

[10] The method according to [9], wherein the organic acids are mixed with the organic raw material and the artificial carbon particles and then supplied to the fluidized bed decomposition apparatus. [[ID=二十]]

[11] The organic acids are fatty acids derived from oil and fat or salts of the fatty acids, and the method according to [9] or

[10] .

[12] The carrier gas is nitrogen with an oxygen concentration of 3% by volume or less, and the method according to any one of [1] to

[11] .

[13] A method according to any one of [1] to

[12] , further comprising a gas-liquid separation step of cooling the non-solid decomposition components discharged from the fluidized bed decomposition apparatus and separating them into off-gas components and decomposition oil, and a heat recovery step of heating the carrier gas before being introduced into the fluidized bed decomposition apparatus by combustion of the off-gas components.

[14] In addition to the steps of the decomposition method according to any one of [1] to

[12] , A method for producing decomposition oil, further comprising a gas-liquid separation step of cooling the non-solid decomposition components discharged from the fluidized bed decomposition apparatus and separating them into off-gas components and decomposition oil.

[15] In addition to the steps of the method for producing decomposition oil according to

[14] , A method for producing reformed oil, further comprising a step of performing at least one reforming treatment selected from dehydrogenation, conversion, isomerization, hydrogenation, hydrocracking, and hydrorefining in the presence of a catalyst.

[16] In addition to the steps of the method for producing reformed oil according to

[15] , A method for producing liquid fuel, further comprising a step of distilling the reformed oil.

[17] In addition to the steps of the decomposition method according to any one of [1] to

[12] , A gas-liquid separation step of cooling the non-solid decomposition components discharged from the fluidized bed decomposition apparatus and separating them into off-gas components and decomposition oil, and A decomposition oil separation step of separating the decomposition oil obtained in the gas-liquid separation step into light decomposition oil and heavy decomposition oil by utilizing the boiling point difference and / or solubility difference, and A method for producing liquid fuel, further comprising a liquid fuel production step of distilling the light decomposition oil obtained in the decomposition oil separation step.

[18] The production method according to

[17] , in which in the liquid fuel production step, at least one reforming treatment selected from dehydrogenation, conversion, isomerization, hydrogenation, hydrocracking, and hydrorefining is performed on the light decomposition oil before the distillation and / or the distillate after the distillation in the presence of a catalyst.

[19] The production method according to

[17] or

[18] , in which in the liquid fuel production step, at least one kind selected from naphtha, aviation fuel, kerosene, and gas oil is produced.

[20] The manufacturing method according to any one of

[17] to

[19] , wherein the naphtha is bionaphtha, the aviation fuel is SAF, the kerosene is biokerosene, and the diesel fuel is biodiesel.

[21] A manufacturing method according to any one of

[17] to

[20] , wherein at least one selected from the heavy cracked oil obtained in the cracked oil separation step and the oil remaining after distillation in the liquid fuel manufacturing step without being distilled as liquid fuel is returned to the cracking step for reprocessing.

[22] In addition to the steps of the disassembly method described in any of [1] to

[12] , A gas-liquid separation step in which the non-solid decomposition components discharged from the fluidized bed decomposition apparatus are cooled to separate them into off-gas components and decomposition oil, A cracked oil separation step is performed to separate the cracked oil obtained in the gas-liquid separation step into light cracked oil and heavy cracked oil using the difference in boiling point and / or solubility, A method for producing a solid fuel, further comprising a solid fuel production step of performing one or more processes selected from mixing, kneading, and mixing on the solid residue discharged in the aforementioned decomposition step and the heavy decomposition oil obtained in the aforementioned decomposition oil separation step, and then molding and / or firing as necessary.

[23] The method for manufacturing according to

[22] , wherein the solid fuel is biocoal or biocoke.

[24] The manufacturing method according to

[22] or

[23] , wherein a portion of the heavy cracked oil obtained in the cracked oil separation step is returned to the cracked step for reprocessing.

[25] In addition to the steps of the disassembly method described in any of [1] to

[12] , A method for producing activated carbon, further comprising an activated carbon production step of activating the solid residue discharged in the aforementioned decomposition step and then purifying it as necessary.

[26] The manufacturing method according to

[25] , wherein the activated carbon is bio-activated carbon.

[27] A fluidized bed decomposition apparatus that decomposes organic raw materials, including biomass and / or organic polymer waste, by fluidizing artificial carbon particles (but not activated carbon) with a carrier gas, to obtain non-solid decomposition components and solid residues, The fluidized bed decomposition apparatus is provided with one or more raw material supply ports for supplying the organic raw material and artificial carbon particles (however, not activated carbon), A carrier gas line that supplies the carrier gas to the fluidized bed decomposition apparatus, A gas discharge line for discharging the aforementioned non-solid decomposition components together with a carrier gas from the fluidized bed decomposition apparatus, A decomposition facility for organic raw materials that has [a certain feature].

[28] The solid residue outlet provided in the fluidized bed decomposition apparatus, A reuse system that returns the discharged solid residue to the raw material supply port, The disassembly equipment described in

[27] further comprises the following:

[29] The decomposition apparatus according to

[27] or

[28] , further comprising a gas-liquid separation tank 32 for separating the decomposition oil contained in the non-solid decomposition components discharged from the fluidized bed decomposition apparatus from the off-gas.

[30] A decomposition facility according to any one of

[27] to

[29] , comprising a reforming furnace for reforming the decomposed oil.

[31] The cracking facility according to any one of

[27] to

[30] , further comprising a distillation column for separating and recovering at least one liquid fuel selected from naphtha, aviation fuel, kerosene, and diesel fuel.

[32] A decomposition apparatus for separating the decomposition oil contained in the non-solid decomposition components discharged from the fluidized bed decomposition apparatus into light decomposition oil and heavy decomposition oil using the difference in boiling point and / or solubility, The system further includes a distillation column for distilling the aforementioned light cracked oil, The cracking apparatus according to any one of

[27] to

[31] further comprises a re-cracking system that returns at least one of the heavy cracked oil obtained in a separation device and the oil remaining in the distillation column without being distilled as liquid fuel to the raw material supply port. In this specification, the term "artificial carbon particles" refers to artificial carbon particles excluding activated carbon. [Effects of the Invention] 【0009】 According to the present invention, useful components including liquid fuel can be produced from organic raw materials in high yield and at low cost, without requiring the use of a catalyst containing zeolite or a complicated manufacturing process such as activated carbon. [Brief explanation of the drawing] 【0010】 [Figure 1] Figure 1 is a schematic conceptual diagram illustrating an example of the disassembly equipment of the present invention. [Figure 2] Figure 2 is a schematic cross-sectional view showing an example of a disassembly device used in the disassembly facility shown in Figure 1. [Modes for carrying out the invention] 【0011】 [Raw material supply process] The present invention relates to a raw material supply process for supplying organic raw materials, including biomass and / or organic polymer waste, and artificial carbon particles to a fluidized bed decomposition device, The apparatus includes a fluidized bed decomposition unit, which introduces a carrier gas to fluidize the artificial carbon particles while decomposing the organic raw material and discharging it as a non-solid decomposition component along with the carrier gas, and a decomposition step in which the solid residue generated by the decomposition is discharged separately from the non-solid decomposition component. According to the method of the present invention, the presence of artificial carbon particles appropriately decomposes organic raw materials, improving the yield of decomposed oil (distillate) contained in the non-solid decomposition components. This decomposed oil (distillate) is useful as a raw material for liquid fuel. 【0012】 As for the biomass, any plant-derived material containing carbon components can be used, such as lignocellulosic biomass and oil-based plant biomass. Lignocellulosic biomass is a solid component containing cellulose, hemicellulose, and lignin, and includes woody biomass, herbaceous biomass, and resource plant biomass. For woody biomass, raw materials derived from coniferous trees, broad-leaved trees, etc., are used, and from the viewpoint of effective resource utilization, thinned wood, forest residues, sawmill residues, construction waste, pruned branches and leaves, and chips are preferred. For herbaceous biomass, raw materials derived from rice, wheat, pampas grass, reeds, etc., are used, and from the viewpoint of effective resource utilization, parts that do not contain edible seeds, such as rice straw, wheat straw, pampas grass, and reeds, are preferred. For resource plant biomass, by-products of sugarcane, corn, sorghum, etc. (e.g., unused parts such as bagasse and stems) are desirable. 【0013】 Oily plant biomass includes plants that can produce oils such as rapeseed oil, cottonseed oil, palm oil, coconut oil, sunflower oil, soybean oil, rice oil, corn oil, oil palm oil, coconut oil, jatropha oil, and olive oil. Oily plant biomass may be oils, presses (e.g., palm residue (PKS, EFB, OPT, etc.)), oil-containing seeds, or parts other than oil-containing seeds. From the standpoint of production efficiency of decomposed oils, oils and oil-containing seeds are preferred, while from the standpoint of efficient resource utilization, presses, parts other than oil-containing seeds, and used edible oil (UCO) are preferred. Oils and presses obtained by hydrolysis and further neutralization as needed can also be used as biomass. However, fatty acids or salts thereof obtained from oily plants are classified as organic acids, as described later in this invention. The aforementioned biomass may be used alone or as a mixture of two or more types. 【0014】 The aforementioned organic polymer waste includes at least one type of synthetic polymer waste selected from synthetic resins, synthetic fibers, and synthetic rubber; at least one type of natural polymer waste selected from natural fibers and natural rubber, and waste of recycled polymers (such as recycled fibers) and semi-synthetic polymers (such as semi-synthetic fibers) obtained by chemically treating natural polymers is also included in natural polymer waste. The aforementioned synthetic resins include thermoplastics (including resins) and thermosetting plastics (including resins), and examples of thermoplastics include polyethylene, polypropylene, polystyrene, ABS resin, AS resin, polyacrylonitrile, acrylic resin, polyvinyl chloride, polyamide, polyimide, polyacetal, polycarbonate, polybutylene terephthalate, polyethylene terephthalate, polyarylate, polyphenylene oxide, polyphenylene ether, polyamideimide, polyether, polyetherimide, and polyetheretherketone. Examples of thermosetting plastics include phenolic resin, urea resin, melamine resin, furan resin, phenol furfural resin, unsaturated polyester resin, epoxy resin, and polyurethane resin. 【0015】 The aforementioned synthetic fibers include, for example, vinylon fibers (polyvinyl alcohol fibers), nylon fibers, polyester fibers, acrylic fibers, polyethylene fibers, and polypropylene fibers. The aforementioned synthetic rubbers include, for example, styrene-butadiene rubber, butadiene rubber, acrylonitrile-butadiene rubber, isoprene rubber, butyl rubber (isobutylene-isoprene copolymer), ethylene-propylene-diene rubber, and the like. The aforementioned natural fibers include cotton fibers, hemp fibers, wool fibers, silk fibers, and the like. The aforementioned natural rubber may be raw rubber before vulcanization or vulcanized rubber. 【0016】 Among these organic polymer wastes, the organic raw material is preferably thermoplastic waste such as polyethylene, polypropylene, and polystyrene. Thermoplastic waste is preferably present in the organic polymer waste at a concentration of 50% by mass or more, more preferably 70% by mass or more. The organic polymer waste may also include rubber waste (raw rubber waste, vulcanized natural rubber waste, etc.) and textile waste (cotton waste, etc.). 【0017】 The organic raw materials may include materials other than the biomass and organic polymer waste. Examples of organic raw materials other than the biomass and organic polymer waste include waste oils (mineral oils, animal oils, lubricating oils, insulating oils, cutting oils, tar pitch, etc.). 【0018】 The total amount of biomass and organic polymer waste is, for example, 50% by mass or more, preferably 70% by mass or more, more preferably 90% by mass or more, and may be 100% by mass, in the organic raw material. The organic raw material may contain only biomass and organic polymer waste, or both. When both are included, the amount of biomass is, for example, 0.01 to 100 parts by mass, preferably 0.1 to 10 parts by mass, and more preferably 0.3 to 3 parts by mass, per 1 part by mass of organic polymer waste. 【0019】 One preferred embodiment is the use of a combination of biomass (especially woody biomass, etc.) and organic polymer waste (especially thermoplastic waste, etc.) as organic raw materials. Combining biomass and organic polymer waste produces synergistic effects in terms of improving the yield of decomposed oil and the proportion of hexane-soluble components in the decomposed oil. 【0020】 When two or more of the above-mentioned organic raw materials are used, they may be mixed before being supplied to the fluidized bed decomposition unit, or they may be supplied separately to the fluidized bed decomposition unit without being mixed. The organic raw materials may be mixed with artificial carbon particles before being supplied to the fluidized bed decomposition unit, or they may be supplied separately to the fluidized bed decomposition unit without being mixed with artificial carbon particles. 【0021】 The organic raw material may be liquid or solid, but a mixture of liquid and solid, or solid, is preferred. The organic raw material as a solid is preferably of a suitable size or smaller. For example, 90% or more by mass of the biomass is preferably passable through a sieve with a mesh size of 10 mm, preferably 7 mm, and more preferably 5 mm. Similarly, 90% or more by mass of the organic polymer waste is preferably passable through a sieve with a mesh size of 30 mm, more preferably 20 mm, even more preferably 10 mm, and particularly preferably 5 mm. There is no particular lower limit to the size of the organic raw material, but 90% or more by mass is preferably placed on a sieve with a mesh size of 0.05 mm, more preferably 0.1 mm, and even more preferably 0.2 mm. 【0022】 The artificial carbon particles are not particularly limited as long as they do not contain activated carbon and are granular carbonized material. Because they do not contain activated carbon, the artificial carbon particles of the present invention can be easily obtained. Furthermore, even without containing activated carbon, liquid fuel can be produced efficiently. Preferably, 90% by mass or more of the artificial carbon particles can pass through a sieve with a mesh size of 5.0 mm, more preferably 3.0 mm, and even more preferably 1.0 mm. Also, preferably 90% by mass or more of the artificial carbon particles rest on a sieve with a mesh size of 0.05 mm, more preferably 0.1 mm, and even more preferably 0.2 mm. 【0023】 The apparent density of artificial carbon particles is, for example, 0.1 g / cm³. 3 Preferably 0.2 g / cm³ 3 More preferably 0.3 g / cm³ 3 That's all; for example, 0.65 g / cm³ 3 The following is preferably 0.60 g / cm³ 3 More preferably, 0.55 g / cm³ 3 More preferably, 0.45 g / cm³ 3 The following applies: The apparent density can be determined by putting 20 g of artificial carbon particles dried at 120°C for 2 hours or more into a 200 mL graduated cylinder and continuing tapping until the volume reduction stops, and then using the volume at that time. 【0024】 The carbide is not particularly limited as long as it does not contain natural products (such as coal). For example, carbides industrially carbonized from coconut shells, pine, bamboo, walnut shells, apricot shells, sunflower seed shells, Jatropha seed shells, rice husks, sawdust, bark chips, rayon, acrylonitrile, etc. can be mentioned. Also, the organic raw material may be industrially carbonized. Particularly preferred is the carbide (solid residue) generated in the decomposition step of the present invention. When using the solid residue, the yield of the decomposition oil (distillate) can be significantly increased and the production cost can be reduced. 【0025】 The carbide can be obtained by heating the carbide raw material at about 300 to 900°C, preferably about 350 to 600°C, more preferably about 400 to 500°C, in an inert gas atmosphere such as nitrogen. Also, the solid residue is obtained according to the decomposition step conditions described later. From the viewpoint of simplifying the process, it is preferable that the conditions of the decomposition step at the time of obtaining the solid residue are the same as the conditions of the decomposition step when the obtained solid residue is used as artificial carbon particles in the decomposition step, but they may be different. The solid residue may be used as it is taken out from the decomposition step, or may be used after performing the pretreatment described later. 【0026】 The specific surface area of the artificial carbon particles can be measured by the BET method using nitrogen gas. For example, it is 400 m 2 / g or less, preferably 300 m 2 / g or less, more preferably 200 m 2 / g or less. As long as the effects of the present invention are achieved, the artificial carbon particles (excluding activated carbon) may be used in combination with activated carbon. The activated carbon includes those obtained by activating the solid residue. The activated carbon is, for example, about 0 to 100 parts by mass, preferably about 0 to 50 parts by mass, more preferably about 0 to 10 parts by mass, and particularly preferably 0 parts by mass, based on 100 parts by mass of the artificial carbon particles. 【0027】 The artificial carbon particles preferably have a low metal content. Using artificial carbon particles with a low metal content prevents the accumulation of metal when the solid residue recycling process described later is carried out. The metal content (metal atoms) in the artificial carbon particles is, for example, 20% by mass or less, preferably 15% by mass or less, more preferably 10% by mass or less, and particularly preferably 5% by mass or less. Within this range, metal atoms may or may not be present. The metal atoms include metalloids such as boron, silicon, arsenic, and tellurium. Silicon may be included in the artificial carbon particles as silica, for example, but it is preferable that the amount of silicon atoms is kept below the above range. 【0028】 Furthermore, metal components may be actively incorporated into the artificial carbon particles. By incorporating metal components, effects such as improved reaction rate of decomposition (liquefaction) of organic raw materials, light oil selectivity, and de-heterogenetic (especially deoxygenation) efficiency can be expected. Examples of metal components that can be actively incorporated include solid bases such as calcium oxide and magnesium oxide (alkaline earth metal oxides, etc.), and solid acids such as acid clay, silica-alumina, and silica-magnesia. When incorporating the aforementioned solid bases such as alkaline earth metal oxides, the amount is, for example, 0.1 to 10 parts by mass, preferably 0.1 to 5 parts by mass, and more preferably 0.5 to 3 parts by mass, per 100 parts by mass of artificial carbon particles. The artificial carbon particles may also contain hydrogen, nitrogen, oxygen, sulfur, chlorine, and other elements in addition to carbon. 【0029】 The organic raw materials and artificial carbon particles may be pretreated as appropriate before being supplied to a fluidized bed decomposition unit. Pretreatment may include, for example, removal of impurities, removal of moisture, particle size adjustment, tar removal, and raw material blending. Particle size adjustment may include crushing, granulation, and classification. The aforementioned tar removal treatment is performed when tar is attached to artificial carbon particles, and may be performed, for example, when solid residue is used as the artificial carbon particles. Specifically, it refers to heat-treating the artificial carbon particles (such as solid residue) in an inert gas atmosphere such as nitrogen at a temperature of 450 to 900°C, preferably around 500 to 700°C, for a short period of time (for example, 5 hours or less, preferably 3 hours or less), and the tar is removed by this heat treatment. Furthermore, the yield of decomposed oil (distillate) can be accurately determined by this tar removal treatment. Raw material formulations include combining two or more different organic raw materials (e.g., biomass and organic polymer waste), combining two or more different artificial carbon particles, and combining organic raw materials with artificial carbon particles. Any known method can be used for raw material formulation, such as mixing, kneading, compounding, and granulation, with mixing being preferred. It is preferable that at least a portion (or all) of the artificial carbon particles be supplied to the fluidized bed decomposition apparatus separately from the organic raw materials in order to form a fluidized bed. 【0030】 For the removal of moisture, drying is preferred. When drying, the method is not particularly limited, but from the viewpoint of energy saving, for example, natural drying or drying by process waste heat (for example, waste heat from off-gas combustion) is desirable. The preferred moisture content is, for example, 15% by mass or less, more preferably 10% by mass or less, and even more preferably 8% by mass or less. 【0031】 The grinding method used in the aforementioned grinding is not particularly limited, and conventional coarse grinding machines such as cutter mills, vibratory mills, and hammer mills can be used. Furthermore, if necessary, organic raw materials or artificial carbon particles may be frozen before grinding. 【0032】 Before supplying organic raw materials and artificial carbon particles to a fluidized bed decomposition unit, it is preferable to create an oxygen-free atmosphere around the organic raw materials and / or artificial carbon particles. Maintaining an oxygen-free atmosphere prevents quality degradation when the organic raw materials and artificial carbon particles are supplied to the fluidized bed decomposition unit. Oxygen-free gases include inert gases such as argon, helium, and nitrogen; reducing gases such as hydrogen, carbon monoxide, and hydrocarbon gases; ammonia gas; and off-gas. Oxidizing gases other than oxygen, such as water vapor, carbon dioxide, and combustion gases (combustion gases of the off-gas), also become substantially non-reactive gases in the decomposition process of the present invention and are therefore included in the oxygen-free gases, but it is preferable not to include oxidizing gases such as water vapor, carbon dioxide, and combustion gases. Preferred oxygen-free gases are inert gases and off-gas, with nitrogen being more preferred. These oxygen-free gases may be one type or a combination of two or more types. Oxygen-free gases may contain oxygen as an impurity, but the amount of oxygen is, for example, 3% by volume or less, preferably 2% by volume or less, and more preferably 1% by volume or less. Furthermore, the amount of oxidizing gas in the oxygen-free gas is, for example, 10% by volume or less, preferably 5% by volume or less, more preferably 3% by volume or less, and most preferably 0% by volume. 【0033】 [Disassembly process] In the decomposition process, a carrier gas is introduced into the lower part (preferably the bottom) of the fluidized bed decomposition apparatus to fluidize the artificial carbon particles, while the organic raw material is decomposed and discharged together with the carrier gas as a non-solid decomposition component. The solid residue generated by the decomposition is discharged separately from the non-solid decomposition component. Depending on the type of artificial carbon particles, decomposition may occur during the decomposition process, such as thermal decomposition, catalytic decomposition, or decomposition by catalytic action. 【0034】 The fluidized bed only needs to contain artificial carbon particles, and a mixture of artificial carbon particles and organic raw materials may also form the fluidized bed. Furthermore, once the decomposition reaction has started, the solid residue also becomes a component of the fluidized bed. The carrier gas used to form the fluidized bed is preferably an oxygen-free gas. Examples of oxygen-free gases are the same as those shown as the oxygen-free gases used as the atmospheric gas for the organic raw materials and artificial carbon particles, and the preferred range is also the same. 【0035】 The fluidized bed may be formed before the start of the decomposition reaction or during the decomposition reaction, but it is preferable to form it before the decomposition reaction. When the fluidized bed is formed before the decomposition reaction, the amount of material for forming the fluidized bed (artificial carbon particles, organic raw materials, etc.) is, for example, 10 to 1000 parts by mass, preferably 50 to 500 parts by mass, and more preferably 100 to 300 parts by mass, per 1 part by mass of the material (organic raw materials, artificial carbon particles, etc.) supplied to the fluidized bed decomposition apparatus per minute. 【0036】 The carrier gas flow rate is, for example, 0.05 to 30 m³ per minute of the amount of material (organic raw materials, artificial carbon particles) supplied to the fluidized bed decomposition unit. 3 (This refers to the volume under standard conditions. The same applies hereafter unless otherwise specified), preferably 0.1 to 20 m³. 3 , more comfortable 0.15~10m 3 That is the case. 【0037】 In the decomposition process, organic raw materials are supplied into the decomposition apparatus. Artificial carbon particles may be supplied together with the organic raw materials, or they may be supplied into the decomposition apparatus as a material to form the initial fluidized bed before the reaction starts, or both. During the decomposition reaction, it is preferable to continuously feed the organic raw materials, a mixture of the organic raw materials and artificial carbon particles into the decomposition apparatus, and artificial carbon particles may be continuously fed in as needed. The organic raw materials supplied into the decomposition apparatus are decomposed (preferably by thermal decomposition, more preferably by catalytic action of the artificial carbon particles) in the presence of the artificial carbon particles, producing non-solid decomposition components, some of which remain in the decomposition apparatus as solid residue. Non-solid decomposition components are components that are gaseous or liquid (preferably gaseous) within the decomposition unit, and include, for example, components that are difficult to liquefy, such as carbon dioxide, carbon monoxide, hydrogen, and hydrocarbons having 1 to 4 carbon atoms (for example, components that are gaseous at 25°C) (referred to herein as off-gas components; carbon monoxide, hydrogen, and hydrocarbons having 1 to 4 carbon atoms are also called fuel gases), and components that are easier to liquefy than the off-gas components (for example, components that are liquid at 25°C) (hereinafter referred to as decomposition oil components). These non-solid decomposition components are discharged from the gas discharge line together with the carrier gas. 【0038】 The rate at which organic raw materials or a mixture of organic raw materials and artificial carbon particles are introduced into the decomposition unit during the decomposition process is determined by the cross-sectional area of ​​the decomposition reactor of the decomposition unit (1 m²). 2 For example, the flow rate is 0.01 to 10 kg / min, preferably 0.03 to 1 kg / min, and more preferably 0.05 to 0.5 kg / min. The temperature inside the decomposition apparatus is, for example, 300 to 700°C, preferably 350 to 650°C, and more preferably 400 to 600°C. The temperature inside the decomposition apparatus can be set to, for example, within ±200°C, preferably within ±100°C, more preferably within ±50°C, and most preferably within ±20°C, in addition to the production temperature of the artificial carbon particles. 【0039】 In the decomposition step, organic acids may be supplied to the fluidized bed decomposition apparatus in addition to the organic raw material and the artificial carbon particles. Using organic acids allows for more effective decomposition of the organic raw material. The organic acids may be supplied separately from the organic raw material and artificial carbon particles, or they may be supplied mixed with the organic raw material and / or artificial carbon particles, but it is preferable to supply them mixed with the organic raw material. Examples of organic acids include organic carboxylic acids, organic sulfonic acids, and organic phosphoric acids, with organic carboxylic acids being preferred. As organic carboxylic acids, fatty acids are preferred, such as saturated fatty acids with approximately 6 to 30 carbon atoms, including caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, stearic acid, arachidic acid, behenic acid, and lignoceric acid; monounsaturated fatty acids with approximately 10 to 30 carbon atoms, including palmitoleic acid, oleic acid, elaidic acid, paxenic acid, and erucic acid; and polyunsaturated fatty acids with approximately 15 to 30 carbon atoms, including linoleic acid, linolenic acid, arachidonic acid, eicosapentaenoic acid, and docosahexaenoic acid. Furthermore, the organic acids are preferably fatty acids derived from oils and fats, and more preferably fatty acids derived from vegetable oils. Vegetable oil-derived fatty acids are part of biomass, and using them as organic acids can result in a process with a lower environmental impact. The aforementioned organic acids may be neutralized products (salts), and fatty acids derived from oils and fats may also be neutralized products (salts) thereof. Furthermore, oils and fats readily produce fatty acids during the decomposition process (thermal decomposition and / or catalytic decomposition), and can function in a similar manner to the aforementioned organic acids. 【0040】 When using organic acids, the amount is, for example, 0.01 to 30 parts by mass, preferably 0.1 to 20 parts by mass, and more preferably 1 to 10 parts by mass, per 100 parts by mass of the organic raw material (excluding fatty acids derived from vegetable oils). 【0041】 In the decomposition process, a mixed gas of oxygen (an oxygen-containing gas such as air may also be used) and a carrier gas may be introduced from the lower part (preferably the bottom) of the decomposition apparatus, either in combination with or in place of the aforementioned carrier gas. The carrier gas can be similar to the carrier gas used for forming the fluidized bed, and the preferred range is also the same. Relatively large artificial carbon particles among those introduced into the decomposition apparatus, or artificial carbon particles that have become coarse due to the deposition of carbonaceous material on their surface during the decomposition reaction, may lose fluidity and settle, forming a fixed bed at the bottom of the fluidized bed. By introducing a mixed gas of oxygen and a carrier gas, the fixed bed can be partially combusted and used as a heat source for the decomposition reaction (endothermic reaction) of the organic raw material. The oxygen concentration in the mixed gas can be appropriately set within a range that does not exceed safety limits (e.g., explosion limits), and when a mixed gas of oxygen and a carrier gas is supplied as a gas for forming the fluidized bed, it is, for example, 0.1 to 3 volume percent. In this case, it is preferable that 95 volume percent or more of the oxygen in the mixed gas is consumed by the partial combustion of the residue in the fixed bed portion. On the other hand, when only a carrier gas is supplied as the gas for forming the fluidized bed, the oxygen concentration is less than 0.1% by volume, preferably less than 0.01% by volume, and even more preferably substantially oxygen-free. 【0042】 [Reuse process] [Activated carbon manufacturing process] The solid residue generated in the decomposition process is discharged from the decomposition apparatus separately from the non-solid decomposition components. The discharged solid residue may be temporarily stored in a solid residue storage facility as needed. At least a portion of the solid residue is preferably returned to the raw material supply process as artificial carbon particles before it cools to room temperature (preferably at 50°C or higher) (reuse process). By returning the heated solid residue to the raw material supply process, heat can be utilized efficiently. To return the solid residue to the raw material supply process, particle size adjustment (crushing, granulation, classification, etc.; classification preferred) may be performed as needed. 【0043】 The solid residue may also be activated and, if necessary, purified to produce activated carbon (preferably bio-activated carbon) (activated carbon manufacturing process). Alternatively, the activated carbonized solid residue may be returned to the raw material supply process together with the artificial carbon particles. 【0044】 [Gas-liquid separation process] The non-solid components discharged along with the carrier gas in the aforementioned decomposition process are cooled and separated into off-gas components and liquid components (referred to as decomposition oil) (this process is called the gas-liquid separation process). In the cooling process, the cooling may be divided into multiple steps, and liquid components (decomposition oil) with different boiling points may be separated and recovered from each step. Separation and recovery can reduce the load on the decomposition oil separation process described later, or it may be possible to skip the decomposition oil separation process. Alternatively, the cooling may not be divided into multiple steps, or the liquid components (decomposition oil) obtained from each step may be combined after the cooling has been divided into multiple steps. 【0045】 The decomposed oil may or may not contain separated water. When water is not separated, the yield of the decomposed oil is, for example, 53-95% by mass, preferably 55-90% by mass, and more preferably 58-80% by mass. When water is separated, the yield of the decomposed oil is, for example, 30-80% by mass, preferably 40-75% by mass, and more preferably 45-70% by mass. Furthermore, the higher the proportion of organic polymer waste in the organic raw material, for example, when the proportion of organic polymer waste in the organic raw material is 30% by mass or more, and especially when it is 50% by mass or more, it becomes more difficult to separate water from the decomposed oil. On the other hand, the lower the proportion of organic polymer waste in the organic raw material, for example, when the proportion of organic polymer waste in the organic raw material is less than 30% by mass, and especially when it is 20% by mass or less, it becomes easier to separate water from the decomposed oil. 【0046】 In 100% by mass of the cracked oil, the proportion of hexane-soluble content (HS) is, for example, 70 to 99% by mass, preferably 80 to 99% by mass, and more preferably 90 to 99% by mass. In 100% by mass of the cracked oil, the proportion of hexane-insoluble - THF-soluble content (HI-THFS) is, for example, 30% by mass or less, preferably 20% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less. In 100% by mass of the cracked oil, the proportion of THF-insoluble content (THFI) is, for example, 10% by mass or less, preferably 5% by mass or less, and more preferably 1% by mass or less. Furthermore, the proportion of components with 20 or fewer carbon atoms (light oil) in the HS component is, for example, 70 to 99% by mass, preferably 75 to 95% by mass, and more preferably 78 to 90% by mass, out of 100% by mass of the HS component. The yield (yield relative to the dry base material) of the components with 20 or fewer carbon atoms (light oil) is, for example, 35 to 70% by mass. The proportion and yield of the light oil are achieved even when the cracked oil is separated. 【0047】 [Heat recovery process] On the other hand, the components that did not liquefy due to the cooling (off-gas) include carbon dioxide, carbon monoxide, hydrogen, and hydrocarbons having 1 to 4 carbon atoms. The off-gas may be burned in the presence of oxygen, and the resulting heat may be used to heat the carrier gas before it is introduced into the fluidized bed decomposition unit (heat recovery step). The off-gas or its combustion gas may be used as an atmospheric gas for the organic raw materials and / or artificial carbon particles, or as the carrier gas. The yield of the off-gas is, for example, 5 to 40% by mass, preferably 10 to 35% by mass, and more preferably 15 to 30% by mass. 【0048】 [Cracked oil separation process] The cracked oil obtained in the gas-liquid separation step is preferably separated into light cracked oil and heavy cracked oil using the difference in boiling point and / or solubility (cracked oil separation step). In this cracked oil separation step, when using the difference in boiling point, a distillation operation (referred to as the first distillation in this specification) is usually performed. When using the difference in solubility, at least one selected from naphtha, aviation fuel, kerosene, diesel fuel, and aliphatic hydrocarbons having equivalent boiling points is used as a solvent for separation. Alternatively, light cracked oil, a modified product of light cracked oil (such as a hydrogenated product) described later, or hexane-soluble components (HS) described later may be used as solvents. Light cracked oil has high solubility in the solvent, while heavy cracked oil has low solubility in the solvent. Therefore, after mixing the solvent and the cracked oil, the solvent-insoluble components can be separated by appropriate separation means (such as sedimentation, centrifugation, or filtration) to separate the light cracked oil and heavy cracked oil. Light cracked oil usually contains hexane-soluble components (HS) described later. Heavy cracked oil (residue) typically contains hexane-insoluble-THF-soluble components (HI-THFS) and THF-insoluble components (THFI), as described below. Heavy cracked oil may be stored in a storage tank if necessary. 【0049】 [Solid fuel manufacturing process] The hexane-insoluble-THF-soluble components (HI-THFS) contained in the heavy cracked oil correspond to asphaltenes and pre-asphaltenes, while the THF-insoluble components (THFI) correspond to carbonaceous precursors. By performing at least one treatment selected from mixing, kneading, and mixing the heavy cracked oil with the solid residue, and then molding and / or calcining as necessary, solid fuels (preferably biosolid fuels) such as alternative coal (preferably bio-coal) and alternative coke (preferably bio-coke) can be produced. 【0050】 [Liquid fuel manufacturing process] The light cracked oil obtained in the aforementioned cracked oil separation step may then be distilled (hereinafter referred to as the second distillation) to produce liquid fuel (liquid fuel production step). It is preferable to perform at least one reforming treatment, selected from dehydrogenation, conversion, isomerization, hydrogenation, hydrocracking, and hydrorefining, on the light cracked oil before separation in the second distillation, or on the distillate obtained in the second distillation, in the presence of a catalyst. By performing the reforming treatment, the yield (particularly the selectivity of the target liquid fuel) or quality of the liquid fuel can be improved. Furthermore, by performing fractional distillation in multiple steps during the first distillation, the first distillation may also serve as the second distillation. When the first distillation also serves as the second distillation, it is preferable to perform at least one reforming treatment selected from dehydrogenation, conversion, isomerization, hydrogenation, hydrocracking, and hydrorefining on the cracked oil before separation in the first distillation, or on the distillate obtained in the first distillation, in the presence of a catalyst. By performing the reforming treatment, the yield (particularly the selectivity of the target liquid fuel) or quality of the liquid fuel can be improved. The fuel produced by the liquid fuel manufacturing process described above is, for example, naphtha (preferably bionaphtha), aviation fuel (preferably SAF (Sustainable Aviation Fuel)), kerosene (preferably biokerosene), and diesel fuel (preferably biodiesel). 【0051】 [Re-decomposition process] The heavy cracked oil obtained in the cracked oil separation step may be used in the solid fuel manufacturing step, or it may be subjected to further cracking instead of being used in the solid fuel manufacturing step, or both may be performed. The oil remaining without distillation in the second distillation of the liquid fuel manufacturing step (distillation residue) may also be subjected to further cracking. Both the heavy cracked oil and the distillation residue may be subjected to further cracking, or one of them may be subjected to further cracking. In the further cracking step, the heavy cracked oil and / or distillation residue are supplied to the cracking step for further processing. The heavy cracked oil and / or distillation residue may be supplied directly to the cracking step, or it may be returned to the raw material supply step as part of the organic raw material and then supplied to the cracking step. 【0052】 [Disassembly equipment] The following describes disassembly equipment useful for carrying out the above manufacturing method, with reference to the illustrated examples. The disassembly equipment of the present invention is not limited to the illustrated examples and can be modified as appropriate to suit the above manufacturing method. Figure 1 is a schematic conceptual diagram showing an example of the decomposition equipment of the present invention, and Figure 2 is a schematic cross-sectional view showing an example of a decomposition device used in the decomposition equipment. The decomposition equipment in Figure 1 is equipped with a fluidized bed decomposition device 21, which is capable of decomposing organic raw materials in the presence of artificial carbon particles. The organic raw materials and artificial carbon particles are processed in a pretreatment device (impurity removal device, moisture removal device, particle size adjustment device (crushing device, granulation device, classification device, etc.), raw material blending device (mixing device, kneading device, mixing device, granulation device, etc.), etc.) 11 as needed, and then introduced into the reaction tube 25 from a raw material supply port 22 located at the top of the decomposition device 21. The introduced organic raw materials and artificial carbon particles are received by a filter 30 located at the bottom of the reaction tube 25, and a fluidized bed 29 is formed by carrier gas supplied from the bottom of the filter 30 through a carrier gas line 27. The reaction tube 25 is heated by a heating furnace 28 located on its outer circumference, and organic raw materials are introduced from the raw material supply port 22. Within the reaction tube 25, the organic raw materials are decomposed, separating into solid residue and non-solid decomposition components. The non-solid decomposition components are discharged outside the reaction tube 25 through a gas discharge line 26 located at the top of the reaction tube 25. The supply amounts of organic raw materials and artificial carbon particles can be adjusted by a supply amount adjustment unit 24 located directly below the raw material supply port 22. An oxygen-free gas replacement line 23 is connected to the raw material supply port 22, allowing for the replacement of the raw material atmosphere by supplying oxygen-free gas in the opposite direction to the raw material supply. Two or more raw material supply ports 22 may be provided for different raw materials. The carrier gas is supplied from a gas container 12, and its flow rate can be controlled by a mass flow controller (MFC) 13 located in the carrier gas line 27. 【0053】 The solid residue generated in the reaction tube 25 is discharged from the outlet 71 and stored in the storage room 72 as needed. This discharged solid residue is activated in the activation device 81 and then purified in the purification device 82 as needed to produce activated carbon. The solid residue and activated carbon can also be reused as artificial carbon particles through a reuse system (transport device, etc.) 74 after adjusting the particle size in a particle size adjustment device (crusher, granulator, classifier, etc.) 73 as needed. 【0054】 The non-solid decomposition components discharged from the reaction tube 25 are cooled in a cooler 31. A gas-liquid separator 32 for storing liquefied components is connected to the cooler 31, where they are separated into decomposition oil and off-gas. The off-gas is sent to a heat exchanger 61 along with air and combusted by a catalyst. The carrier gas line 27 passes through this heat exchanger 61 to the reaction tube 25, where the heat of combustion obtained in the heat exchanger 61 heats the carrier gas before it is sent to the reaction tube 25. 【0055】 The cracked oil separated in the gas-liquid separation tank 32 is sent to a separation device (in the illustrated example, a first distillation column; the separation device may be a combination of a mixer for cracked oil and solvent, and a separator for insoluble components) 41 to separate it into light cracked oil and heavy cracked oil. The heavy cracked oil is mixed, kneaded, or mixed with solid residue in a mixer, kneader, or kneading machine 91, and then processed in a molding machine or calcination device 92 as needed to produce solid fuel. 【0056】 Meanwhile, the light cracked oil separated in the separation device 41 is reformed (dehydrogenated, converted, isomerized, hydrogenated, hydrocracked, hydrorefined, etc.) in a reforming furnace 51 equipped with a catalyst, and then rectified in a second distillation column 52 to produce liquid fuels such as naphtha, aviation fuel, kerosene, and diesel fuel. 【0057】 The heavy cracked oil separated by the separation device 41 and the distillation residue discharged from the bottom of the second distillation column 52 can be supplied to the fluidized bed cracking device 21 from the raw material supply port 22 via the return line 75 (re-cracking system). In the illustrated example, the return line 75 is connected to the pretreatment device 11, making the heavy cracked oil and distillation residue available for use as organic raw materials. 【0058】 This application claims the benefit of priority based on Japanese Patent Application No. 2021-068497, filed on April 14, 2021, and International Patent Application PCT / JP2021 / 036613, filed on October 4, 2021. The entire contents of the specification of Japanese Patent Application No. 2021-068497, filed on April 14, 2021, and the entire contents of the specification of International Patent Application PCT / JP2021 / 036613, filed on October 4, 2021, are incorporated herein by reference. [Examples] 【0059】 The present invention will be described in more detail below with reference to examples, but the present invention is not limited by the following examples, and it is certainly possible to implement it with appropriate modifications within the scope that is consistent with the spirit of the preceding and following descriptions, and all such modifications are included within the technical scope of the present invention. In the following examples, the following materials were used as biomass, organic polymer waste, and artificial carbon particles. The yields of the decomposed oil (distillate), solid residue, loss, and off-gas produced in the decomposition process, as well as the compositional distribution in the decomposed oil (distillate), were determined according to the following method. 【0060】 (1) Biomass Cedar powder: Made from domestic cedar sawdust that has been sorted through a 4mm sieve and dried overnight at 120°C. Jatropha: Seeds of Jatropha from Vietnam (provided by Revo International) were naturally dried, crushed, classified through a 4mm sieve, and then dried overnight at 120°C. The seed hulls accounted for 43.22 wt% of the sample, and the main component of the parts other than the seed hulls was oil. Neutralized oil residue: Neutralized oil residue provided by Nisshin Oillio Co., Ltd. (87.5 wt% fatty acids, 2.5 wt% moisture, 10.0 wt% crude ash, viscous liquid). Neutralized oil residue possesses the characteristics of both biomass and organic acids. Palm stearic acid: Palm oil is found in the fruit of the oil palm tree. Stearic acid is a component of palm oil and was obtained from Thailand. Used cooking oil: Used cooking oil collected from restaurants, households, etc., is obtained by washing, removing water, and filtering it. 【0061】 (2) Organic polymer waste Plastic simulated waste (abbreviated as "waste plastic"): A mixture of polyethylene (PE) (product name "Novatec LD-LJ803", manufactured by Nippon Polyethylene Co., Ltd.), polypropylene (PP) (product name "Novatec PP-MA3", manufactured by Nippon Polypropylene Co., Ltd.), and polystyrene (PS) (product name "GPPS-HF77", manufactured by PS Japan Co., Ltd.) in a mass ratio of PE:PP:PS = 49:33:18. Two-thirds of plastic waste consists of PE, PP, and PS, with a mass ratio of PE:PP:PS = 49:33:18 (Japan Plastic Recycling Association). The aforementioned simulated waste is formulated to match the actual state of this waste. The particle size of PE, PP, and PS is between 4mm sieve-below and 2mm sieve-above. 【0062】 (3) Artificial carbon particles and activated carbon AC (Activated Carbon): Granular activated carbon manufactured by UES Co., Ltd. Product name: Activated Carbon Granules (for water), Particle size: Mesh opening 0.84~0.3 mm (20~50 mesh), Apparent density: 0.51 g / cm³ 3 . R1 (artificial carbon particles): Prepared by mixing equal amounts (by mass) of the aforementioned cedar powder, jatropha, and waste plastic, and carbonizing them by heating at 500°C for 2 hours under a nitrogen atmosphere. Particle size: Mesh opening 0.6~1.6 mm, apparent density: 0.43 g / cm³ 3 . R2 (artificial carbon particles): Obtained in the same manner as R1, except that the carbonization temperature was set to 600°C and the particle size (mesh size) was set to 0.6-2.0 mm. Apparent density: 0.32 g / cm³ 3 . R2 + 2% MgO (artificial carbon particles): A mixture of 100 parts by mass of R2 and 2 parts by mass of MgO. R3 (Artificial Carbon Particles): Made by mixing equal amounts (by mass) of cedar powder and used cooking oil, and carbonizing them by heating at 450°C for 2 hours under a nitrogen atmosphere. Particle size: Mesh opening 2 mm or less, apparent density: 0.24 g / cm³ 3 . CC (Artificial Carbon Particles): Made by carbonizing rice husks (provided by Revo International) by heating them in a nitrogen atmosphere at 600°C for 2 hours. Also known as rice husk charcoal. Particle size: Mesh opening 2 mm or less, apparent density: 0.15 g / cm³ 3 ) R20 (Artificial Carbon Particles): 20g of R2 is used as artificial carbon particles. 189g of a mixture consisting of 30% by mass cedar powder, 15% by mass palm stearic acid, 10% by mass used cooking oil, 5% by mass neutralized oil residue, and 40% by mass waste plastic is added at a supply rate of 0.12g per minute. Thermal decomposition is carried out in the same manner as in Example 1, except that the temperature inside the reaction tube is 525°C and the nitrogen flow rate is 200ml per minute. The solid residue remaining in the reaction tube is the result of this process. Both the artificial carbon particles and activated carbon used were dried overnight at 120°C. 【0063】 (4) Yield of cracked oil (distillate) The yield of the cracked oil after the cracking process was determined based on the following formula. Cracked oil yield (mass%) = Cracked oil mass / Dry mass of raw materials × 100 In the formula, the mass of the cracked oil was determined from the difference in the total mass of the gas-liquid separation tank and piping before and after operation. The dry mass of the input raw materials is the total mass of the biomass and organic polymer waste added minus the moisture content. 【0064】 (5) Yield of solid residue The yield of solid residue after the decomposition process was determined based on the following formula. Solid residue yield (mass%) = Solid residue mass / Dry mass of raw materials × 100 In the formula, the dry mass of the raw materials used has the same meaning as described above. Furthermore, the mass of the solid residue produced by the reaction was determined as follows: (1) If carbon particles (artificial carbon particles or activated carbon) were not used, it was directly determined from the difference in the mass of the reaction tubes before and after operation; and (2) If carbon particles (artificial carbon particles or activated carbon) were used, it was determined based on the formula "Mass of solid residue = Total mass of reaction tubes after operation - (Mass of reaction tubes before operation + Mass of carbon particles)". 【0065】 (6) Loss percentage After the decomposition process was completed, the substance adhering to the inside and outside of the raw material input tube near the outlet of the raw material input tube at the top of the fluidized bed decomposition apparatus (reaction tube) (substance that had not yet been carbonized and had not become liquid) was defined as "loss." The loss fraction was calculated by determining the mass of the raw material input tube before the start of the decomposition process (W1) and the mass of the raw material input tube after the completion of the decomposition process (W2), and using the following formula. Loss percentage (by mass) = Loss mass / Dry mass of raw materials × 100 In the formula, the loss mass is the value obtained from W2 - W1. The dry mass of the raw materials used has the same meaning as above. 【0066】 (7) Off-gas yield The off-gas yield was calculated based on the following formula. Off-gas yield (mass%) = ([Dry mass of raw materials - (mass of cracked oil + mass of solid residue + mass of loss)] / Dry mass of raw materials) × 100 In the formula, the dry mass of the raw materials, the mass of the decomposed oil, the mass of the solid residue, and the loss mass have the same meanings as described above. 【0067】 (8) Composition distribution in the cracked oil (distillate) The cracked oil (distillate) obtained in the cracking process was subjected to solvent fractionation treatment using tetrahydrofuran (THF) and hexane (H) by solvent extraction and filtration, and was divided into three components: THF-insoluble component (THFI), hexane-insoluble - THF-soluble component (HI-THFS), and hexane-soluble component (HS). 【0068】 THFI ratio: 2g of decomposed oil and 200ml of THF were mixed, and ultrasonic waves (frequency 35kHz, energy 36kJ (60W x 10 mins)) were irradiated until the dispersion of insoluble matter was complete (until there was no visible change) to dissolve and suspend the decomposed oil. Then, the mixture was filtered through JIS P 3801 standard chemical analysis filter paper No. 2 (manufactured by ADVANTEC) to separate the insoluble matter (THFI) from the filtrate. The filtered filter paper was suction washed five times with 20ml of THF, dried at 107°C for 1 hour, weighed, and the weight of the insoluble matter (THFI mass) was determined by subtracting the weight of the filter paper. The insoluble matter ratio (THFI ratio) was calculated according to the following formula. THFI rate (mass%) = THFI mass / cracked oil mass × 100 【0069】 HI ratio: 2g of decomposed oil and 200ml of hexane were mixed, and ultrasonic waves (frequency 35kHz, energy 36kJ (60W x 10 mins)) were irradiated until the dispersion of insoluble matter was complete (until there was no visible change) to dissolve and suspend the decomposed oil. Then, the mixture was filtered through JIS P 3801 standard chemical analysis filter paper No. 2 (manufactured by ADVANTEC) to separate the insoluble matter (HI) from the filtrate. The filtered filter paper was suction washed five times with 20ml of hexane, dried at 107°C for 1 hour, weighed, and the weight of the insoluble matter (HI mass) was determined by subtracting the weight of the filter paper. The insoluble matter ratio (HI ratio) was calculated according to the following formula. HI rate (mass%) = HI mass / cracked oil mass × 100 HS ratio: Based on the calculation results of the HI ratio mentioned above, the HS ratio was calculated using the following formula. HS rate (mass%) = (cracking oil mass - HI mass) / cracking oil mass x 100 HI·THFS rate: Based on the calculation results of the THFI rate and HS rate mentioned above, the HI·THFS rate was calculated using the following formula. HI THFS rate (mass%) = 100-(HS rate + THFI rate) 【0070】 (9) HS yield The HS yield (mass%) based on the input raw materials was calculated using the following formula. HS yield (mass%) = cracked oil yield (mass%) x HS rate (mass%) / 100 【0071】 (10)HS component distribution Analytical samples were prepared by dissolving 0.1 g of cracked oil in 2.0 g of THF. The HS component distribution was investigated by gas chromatography under the following conditions, and the hydrocarbons were divided into those with 8 or fewer carbon atoms (C8 or less), those with 9 to 14 carbon atoms (C9 to 14), those with 15 to 20 carbon atoms (C15 to 20), and those with 21 or more carbon atoms (C21 or more), and their ratios were determined. Since the cracked oil is liquid at room temperature, "C8 or less" does not substantially contain hydrocarbons with 4 or fewer carbon atoms, and is substantially composed of components with 5 to 8 carbon atoms. The total percentage of C8 or less, C9 to 14, and C15 to 20 was defined as the light oil percentage (%). [Gas chromatography conditions] Gas chromatograph: GC-2014, manufactured by Shimadzu Corporation. Column: DB-1 (φ0.32mm x 60m, film thickness 1μm, manufactured by Agilent Technologies) Sample injection volume: 1 μL Evaporation chamber temperature: 300℃ Oven (column chamber): 50°C → 320°C (10°C / min), hold at 320°C for 33 minutes. Detector: FID (330℃) Carrier gas: Helium Carrier gas control mode: Constant pressure (125kPa) How to calculate the composition ratio (%): Calculated by area ratio Method for identifying each component: After dividing the gas chromatography chart into four sections based on the reference peaks of n-octane, n-tetradecane, and n-eicosane (identified by retention time), the proportion of the constituent components in each section was determined using the following method and formula. C8 and below: Calculated by subtracting the THF peak area from the total peak area before n-octane. C9~C14: Calculated using the total peak area from the next peak of n-octane to n-tetradecane. C15~C20: Calculated using the total peak area from the peak following n-tetradecane to n-eicosane. C21 and above: Calculated using the total area from the next peak after n-eikosan. Percentage of each component (%) = Total peak area of ​​the corresponding component / (Total peak area - THF peak area) × 100 【0072】 (11) Light oil yield The light oil yield was calculated according to the following formula. Light oil yield (%) = Cracking oil yield (mass%) × Light oil percentage (%) / 100 【0073】 [Example 1] As the fluidized bed decomposition apparatus 21, the stainless steel reaction tube 25 (inner diameter 42.4 mm, reaction tube cross-sectional area 1.41 × 10) of the vertical electric furnace heating type shown in Figure 2 is used. -3 m2 ) was used. A 200-mesh filter 30 was attached to the bottom of the reaction tube 25, and artificial carbon particles (20 g of R1 in Example 1) were introduced in advance through the raw material input tube at the top of the reaction tube to form a packed bed of artificial carbon particles (fluidized bed 29). Next, nitrogen was supplied from the bottom of the reaction tube at a flow rate of 200 ml per minute, and the temperature inside the reaction tube was raised until it reached 450°C. After the temperature stabilized, the raw material mixture (a mixture of 18 g of cedar powder and 18 g of waste plastic in Example 1), with the atmosphere purged with nitrogen, was introduced into the packed bed of artificial carbon particles (fluidized bed 29) inside the reaction tube from the raw material supply port 22 at a supply rate of 0.12 g per minute and decomposed. After the entire amount of the above mixture was introduced, it was held at the same temperature for another 30 minutes, and then the reaction tube 25 was air-cooled. The components (distillates) discharged from the top of the reaction tube (gas discharge line 26) due to the decomposition of organic raw materials were separated into gas and liquid using a two-stage cooling trap (-10°C to -20°C), and the liquid product (decomposition oil (distillate)) in the trap was quantified and recovered after being returned to room temperature. The residue generated in the reaction tube 25 was quantified and recovered after the reaction tube was cooled to room temperature in a nitrogen stream. The results are shown in Table 1. 【0074】 [Example 2, Comparative Example 1, Reference Examples 1-4] The procedure was the same as in Example 1, except that the reaction tube temperature, nitrogen flow rate, type and amount of artificial carbon particles, and type and amount of organic raw materials were changed as shown in Table 1. In Reference Examples 1-4, AC was used instead of artificial carbon particles. The results are shown in Table 1. 【0075】 [Table 1] 【0076】 When organic raw materials are supplied to a fluidized bed decomposition unit for decomposition, separating them into decomposed oil, solid residue, off-gas, and loss, the decomposition in the presence of activated carbon (AC) or artificial carbon particles (R1) significantly improves the yield of decomposed oil (comparison of Comparative Example 1 with Example 1 and Reference Example 1). Artificial carbon particles (R1) are easier to obtain than activated carbon (AC) because they do not require activation, and can achieve decomposed oil yield, HS yield, etc., equivalent to that of activated carbon (comparison of Example 1 with Reference Example 1). In particular, when organic acids derived from neutralized oil residue are used together with artificial carbon particles, the yield of decomposed oil is further improved compared to when artificial carbon particles are used alone (comparison of Example 2 with Example 1), and it is presumed that the catalytic activity is further enhanced by using artificial carbon particles and organic acids, resulting in catalytic cracking. 【0077】 In the example using activated carbon, as shown in Reference Example 4, when the organic raw material was a mixture of cedar powder and waste plastic, the yield of decomposed oil improved, the residue decreased, and a synergistic effect was observed compared to the case using only cedar powder (Reference Example 2) or only waste plastic (Reference Example 3). More specifically, compared to the results predicted from the arithmetic mean of Reference Example 2 (cedar powder) and Reference Example 3 (waste plastic) (average of Reference Examples 2 and 3), Reference Example 4 showed a reduction in solid residue and an improvement in the yield of decomposed oil. Furthermore, the components in the decomposed oil showed a synergistic effect, with HI-THFS suppressed and the HS ratio increased. 【0078】 [Examples 3-9] The procedure was the same as in Example 1, except that the supply rate of the raw material mixture was changed to 0.15 g per minute, and the temperature inside the reaction tube, nitrogen flow rate, type and amount of artificial carbon particles, and type and amount of raw material mixture were changed as shown in Table 2. The results are shown in Table 2. [Table 2] Examples 3-6 are examples of decomposition tests using various organic acids (derived from oils and fats) and organic raw materials (woody biomass, oily biomass, waste plastics) in combination with artificial carbon particles (R2), demonstrating that thermal decomposition is possible at various temperatures. The solid residue (R20) obtained from the thermal decomposition process can also be used as artificial carbon particles (Example 7), and it is possible to perform both the production of artificial carbon particles and thermal decomposition using them within the thermal decomposition process. Rice husk charcoal (CC) can also be used as artificial carbon particles (Example 8). Even when the production temperature of the artificial carbon particles was set to 450°C and the thermal decomposition temperature of the organic raw materials using them was also set to 450°C, good thermal decomposition properties were observed (Example 9). 【0079】 [Example 10] 3.40 g of the cracked oil obtained in Example 6 was mixed with 3.40 g of nickel-based catalyst (commercial product, type: N102F, component: 61 wt% Ni / SiO2·MgO, manufactured by JGC Catalysts & Chemicals Co., Ltd.) and 30.60 g of n-heptane, and hydrogenated under the following conditions: initial hydrogen pressure of 2.6 MPa (gauge pressure at 25°C), reaction temperature of 325°C, holding time of 150 minutes, and stirring speed of 1000 rpm (equipment used: 120 mL stainless steel autoclave). Samples were taken from the cracked oil and its hydrogenated product, and the composition was examined by carbon number based on the HS component distribution measurement method described above, except that the preparation solvent for the analytical samples was changed from THF to n-heptane. The results are shown in Table 3. [Table 3] Both the cracked oil and its hydrogenated product showed a high proportion of light oil. This indicates that the method of the present invention is useful for producing light oils with 20 or fewer carbon atoms (such as naphtha, aviation fuel, kerosene, and diesel fuel). 【0080】 [Example 11] As the fluidized bed decomposition apparatus 21, the stainless steel reaction tube 25 (inner diameter 42.4 mm, reaction tube cross-sectional area 1.41 × 10) of the vertical electric furnace heating type shown in Figure 2 is used. -3 m 2) was used. A 200-mesh filter 30 was attached to the bottom of the reaction tube 25, and artificial carbon particles (8 g of R2 in Example 11) were introduced in advance through the raw material input tube at the top of the reaction tube to form a packed bed of artificial carbon particles (fluidized bed 29). Next, nitrogen was supplied from the bottom of the reaction tube at a flow rate of 200 ml per minute, and the temperature inside the reaction tube was raised until it reached 475°C. The raw material mixture (18 g of cedar powder and 18 g of used cooking oil in Example 11) and artificial carbon particles (12 g of R2 in Example 11) were mixed and the atmosphere was replaced with nitrogen (mixture A). After the temperature of the reaction tube 25 stabilized, the raw material mixture was decomposed by introducing mixture A into the packed bed of artificial carbon particles (fluidized bed 29) inside the reaction tube from the raw material supply port 22 at a supply rate of 0.20 g per minute (a supply rate of 0.15 g per minute for the raw material mixture and a supply rate of 0.05 g per minute for the artificial carbon particles). After adding the entire amount of the above mixture A, the reaction tube 25 was held at the same temperature for another 30 minutes, and then air-cooled. The components (distillates) discharged from the top of the reaction tube (gas discharge line 26) due to the decomposition of the organic raw materials were separated into gas and liquid using a two-stage cooling trap (-10°C to -20°C), and the liquid product (decomposition oil (distillate)) in the trap was quantified and recovered after being returned to room temperature. In addition, the residue generated in the reaction tube 25 was quantified and recovered after the reaction tube was cooled to room temperature in a nitrogen stream. [Examples 12-14, Comparative Example 2] The procedure was the same as in Example 11, except that the type and amount of artificial carbon particles were changed as shown in Table 4. The results are shown in Tables 4 and 5. [Table 4] [Table 5] 【0081】 In Examples 11-13 and Comparative Example 2, where the raw material mixture did not contain waste plastic, the decomposed oil and water were separated. The proportion of light oil (hydrocarbons with a carbon content of 20 or less) in the HS component and the light oil yield improved in Examples 11-13, which used artificial carbon particles, compared to Comparative Example 2, which did not use artificial carbon particles. [Industrial applicability] 【0082】 The method and equipment of the present invention are useful for producing liquid fuels, solid fuels, activated carbon, etc., and are particularly useful for producing liquid fuels. [Explanation of symbols] 【0083】 11 Preprocessing device 12 gas containers 13 Mass Flow Controller 21 Fluidized bed cracker 22 Raw material supply port 23. Oxygen-free gas replacement line 24 Supply amount adjustment section 25 reaction tubes 26 Gas discharge line 27 Carrier gas line 28 Furnace 29. Fluidized bed 30 filters 31 Cooler 32 Gas-liquid separation tank 41 Separation apparatus (illustrated example is the first distillation column) 51 Reformer 52 Second Distillation Column 61 Heat exchanger 71 Outlet 72 Storage Rooms 73 Particle size adjustment device 74 Reuse Systems 75. Return Line (Re-disassembly System) 81 Activation device 82 Purification equipment 91 Mixers, kneaders, and mixing machines 92 Molding machines, firing equipment

Claims

[Claim 1] A raw material supply process for supplying organic raw materials, including biomass and / or organic polymer waste, and artificial carbon particles (but not activated carbon) to a fluidized bed decomposition unit, and A decomposition process in which, in the fluidized bed decomposition apparatus, an inert gas with an oxygen concentration of 3 volume% or less is introduced as a carrier gas to fluidize the artificial carbon particles, while the organic raw material is decomposed and discharged together with the carrier gas as a non-solid decomposition component, and the solid residue generated by the decomposition is discharged separately from the non-solid decomposition component, A gas-liquid separation step in which the non-solid decomposition components discharged from the fluidized bed decomposition apparatus are cooled to separate them into off-gas components and decomposition oil. A step of converting the cracked oil into a modified oil by performing at least one modification treatment selected from dehydrogenation, conversion, isomerization, hydrogenation, hydrocracking and hydrorefining in the presence of a catalyst. A method for producing liquid fuel, comprising the step of distilling the aforementioned reformed oil. [Claim 2] The manufacturing method according to claim 1, wherein the temperature of the decomposition process is 400 to 600°C. [Claim 3] The manufacturing method according to claim 1 or 2, wherein the decomposition of the organic raw material is caused by the catalytic action of artificial carbon particles. [Claim 4] A reuse process in which at least a portion of the solid residue discharged in the decomposition process is returned to the raw material supply process as artificial carbon particles before it cools to room temperature. The method according to claim 1 or 2, having the following characteristics: [Claim 5] The method according to claim 1 or 2, wherein at least a portion of the solid residue discharged in the decomposition step is returned to the raw material supply step as artificial carbon particles after particle size adjustment, or without particle size adjustment. [Claim 6] The specific surface area of ​​the aforementioned artificial carbon particles is 500 m². ２ The method according to claim 1 or 2, wherein the amount is less than or equal to / g. [Claim 7] The method according to claim 1 or 2, wherein the content of metal atoms in the artificial carbon particles is 20% by mass or less. [Claim 8] The method according to claim 1 or 2, wherein the artificial carbon particles contain a solid base or a solid acid. [Claim 9] The method according to claim 1 or 2, wherein at least a portion of the artificial carbon particles form a fluidized bed. [Claim 10] The method according to claim 1 or 2, wherein in the raw material supply step, the organic raw material is subjected to at least one pretreatment selected from impurity removal, moisture removal, particle size adjustment, and raw material blending, and then supplied to the fluidized bed decomposition apparatus. [Claim 11] The method according to claim 1 or 2, wherein in the raw material supply step, at least one selected from the organic raw material, the artificial carbon particles, and mixtures thereof is continuously fed into the fluidized bed decomposition apparatus. [Claim 12] The method according to claim 1 or 2, wherein the biomass is at least one selected from lignocellulosic biomass and oily plant biomass, and the organic polymer waste is at least one waste selected from synthetic resins, synthetic rubber, and synthetic fibers. [Claim 13] The method according to claim 1 or 2, wherein in the raw material supply step, organic acids are supplied to the fluidized bed decomposition apparatus together with the organic raw material and the artificial carbon particles. [Claim 14] The method according to claim 13, wherein the organic acids are mixed with the organic raw materials and the artificial carbon particles before being supplied to the fluidized bed decomposition apparatus. [Claim 15] The method according to claim 13, wherein the organic acids are fatty acids derived from oils and fats, or salts of said fatty acids. [Claim 16] The method according to claim 1 or 2, wherein the inert gas is nitrogen. [Claim 17] The method according to claim 1 or 2, further comprising a heat recovery step of heating the carrier gas before it is introduced into the fluidized bed decomposition apparatus by the combustion of the off-gas component. [Claim 18] In addition to the steps of the method according to claim 1 or 2, The cracked oil obtained in the gas-liquid separation step is further separated into light cracked oil and heavy cracked oil using the difference in boiling point and / or solubility, A method further comprising a liquid fuel production step of distilling a modified version of the aforementioned light cracked oil. [Claim 19] The manufacturing method according to claim 1 or 2, wherein the liquid fuel is at least one selected from naphtha, aviation fuel, kerosene, and diesel fuel. [Claim 20] The manufacturing method according to claim 19, wherein the naphtha is bionaphtha, the aviation fuel is SAF, the kerosene is biokerosene, and the diesel fuel is biodiesel. [Claim 21] The manufacturing method according to claim 18, wherein at least one of the heavy cracked oil obtained in the cracked oil separation step and the oil remaining after distillation in the liquid fuel manufacturing step without being distilled as liquid fuel is returned to the cracking step for reprocessing. [Claim 22] A fluidized bed decomposition apparatus that decomposes organic raw materials, including biomass and / or organic polymer waste, by fluidizing artificial carbon particles (but not activated carbon) with a carrier gas, into non-solid decomposition components and solid residues, The fluidized bed decomposition apparatus is provided with one or more raw material supply ports for supplying the organic raw material and artificial carbon particles (however, not activated carbon), A carrier gas line that supplies the carrier gas to the fluidized bed decomposition apparatus, A gas discharge line for discharging the aforementioned non-solid decomposition components together with a carrier gas from the fluidized bed decomposition apparatus, A gas-liquid separator separates the decomposed oil contained in the non-solid decomposed components discharged from the fluidized bed decomposition apparatus from the off-gas. A reforming furnace for reforming the aforementioned cracked oil into reformed oil, A liquid fuel manufacturing facility having a distillation column for distilling the aforementioned reformed oil. [Claim 23] The solid residue outlet provided in the fluidized bed decomposition apparatus, A reuse system that returns the discharged solid residue to the raw material supply port, The apparatus according to claim 22, further comprising: [Claim 24] The apparatus according to claim 22 or 23, wherein the distillation column is a distillation column for separating and recovering at least one liquid fuel selected from naphtha, aviation fuel, kerosene, and diesel fuel. [Claim 25] The apparatus includes a separation device that separates the cracked oil contained in the non-solid cracked components discharged from the fluidized bed cracking apparatus into light cracked oil and heavy cracked oil using the difference in boiling point and / or solubility, The distillation column is a distillation column for distilling the light cracked oil, The apparatus according to claim 22 or 23, further comprising a re-cracking system that returns at least one of the heavy cracked oil obtained in the separation device and the oil remaining in the distillation column without being distilled as liquid fuel to the raw material supply port.

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