Chemical product production method, chemical product production apparatus, and granular medium

Abstract

A chemical product production method according to the present disclosure involves: introducing an inert gas into a reactor accommodating a granular medium that contains a fluid material A and an additive B having a pore volume of 0.01 cm3 / g to 10 cm3 / g, inclusive, to cause the granular medium to flow; heating the reactor; and supplying a starting material that contains a plastic to the heated reactor.

Description

Method for manufacturing chemicals, apparatus for manufacturing chemicals, and granular media

[0001] This disclosure relates to a method for producing chemicals, an apparatus for producing chemicals, and a granular medium.

[0002] One method of recycling waste plastics is chemical recycling, which involves decomposing waste plastics, monomerizing and gasifying them, or using them as blast furnace reducing agents or coke oven raw materials. For example, a fluidized bed reactor is generally used in continuous reactors that use mixed plastics containing polyolefins as raw materials to obtain basic chemicals in a single stage without going through intermediate products such as pyrolysis oils.

[0003] Patent Document 1 discloses that a plastic powder, which is a mixture of polyolefins, polystyrene, polyethylene terephthalate (PET), etc., is supplied to a fluidized bed reactor and decomposed to obtain C2 to C4 olefins, that the heating medium in the fluidized bed is a mixture of used fluid catalytic cracking (FCC) catalyst and ZSM-5, and that these catalysts may also contain binder materials such as alumina or silica.

[0004] Special table 2016-513147 publication

[0005] This disclosure aims to provide a method for producing chemicals that can efficiently obtain ethylene and propylene in high yield.

[0006] The means to solve the above problem are as follows: <1> A method for producing a chemical product, wherein the fluid material A and the pore volume are 0.01 cm ３ / g or more 10cm ３ A method for producing a chemical product, characterized by comprising: introducing an inert gas into a reaction furnace containing a granular medium containing additive B at a concentration of 1 / g or less, and causing the granular medium to flow; heating the reaction furnace; and supplying a raw material containing plastic to the heated reaction furnace. <2> The specific surface area of ​​additive B is 20 m². ２ / g or more 3,000m ２It is a method for manufacturing the chemical product according to <1>, which is below / g. <3> The method for manufacturing the chemical product according to <1> or <2>, wherein the additive B contains silica. <4> It is a method for manufacturing the chemical product according to any one of <1> to <3>, wherein the mass ratio [B / A] of the fluid material A and the additive B is 0.04 or more and 0.20 or less. <5> It is a method for manufacturing the chemical product according to any one of <1> to <4>, wherein in the heating, the temperature of the reactor is set to 500°C or more and 1,000°C or less. <6> It is a method for manufacturing the chemical product according to any one of <1> to <5>, wherein the raw material containing the plastic contains a mixed plastic containing polyethylene and polypropylene. <7> It is a method for manufacturing the chemical product according to any one of <1> to <6>, wherein the chemical product contains ethylene and propylene. <8> A manufacturing apparatus for a chemical product, comprising: a reactor containing a granular medium containing a fluid material A and an additive B having a pore volume of 0.01 cm ３ / g or more and 10 cm ３ / g or less; a plastic supply unit connected to the reactor for supplying a raw material containing plastic to the reactor; an inert gas supply unit connected to one end of the reactor and arranged to supply an inert gas to the granular medium from a direction opposite to the gravitational direction; and a heating unit for heating the reactor. It is a manufacturing apparatus for a chemical product, characterized by having these components. <9> A granular medium used for a fluidized bed for thermal decomposition of a raw material containing plastic, comprising a fluid material A and an additive B having a pore volume of 0.01 cm ３ / g or more and 10 cm ３ / g or less. It is a granular medium, characterized by containing these components. <10> The granular medium according to <9>, wherein the raw material containing the plastic contains a mixed plastic containing polyethylene and polypropylene. <11> A fluid material A and a pore volume of 0.01 cm ３ / g or more and 10 cm ３A method for using a granular medium, characterized in that a granular medium containing additive B at a concentration of 0.01 cm³ or less is used in a fluidized bed for the thermal decomposition of raw materials including plastics. <12> A method for using a granular medium used to produce chemicals by thermal decomposition of raw materials including plastics, wherein the granular medium contains a fluidizing agent A and a pore volume of 0.01 cm³. ３ / g or more 10cm ３ This is a method for using a granular medium characterized by containing additive B at a concentration of 1 / g or less.

[0007] According to embodiments of this disclosure, it is possible to provide a method for producing chemicals that can efficiently obtain ethylene and propylene in high yield.

[0008] Figure 1 is a schematic cross-sectional view showing an example of a chemical manufacturing apparatus according to the present disclosure.

[0009] The embodiments of this disclosure will be described in detail below. However, the embodiments are not limited to the following description and may be modified as appropriate without departing from the gist of this disclosure. Furthermore, in this specification, the "~" indicating a numerical range means that the values ​​described before and after it are included as the lower and upper limits, respectively, unless otherwise specified. In numerical ranges described in stages in this disclosure, the upper or lower limit described in one numerical range may be replaced with the upper or lower limit of another numerical range described in stages. Also, the upper or lower limits of numerical ranges described in this disclosure may be replaced with the values ​​shown in the examples.

[0010] (Method for manufacturing chemical products) The method for manufacturing chemical products according to this disclosure involves a fluid material A and a pore volume of 0.01 cm³. ３ / g or more 10cm ３ The method for producing a chemical product of this disclosure includes introducing an inert gas into a reactor containing a granular medium containing additive B at a concentration of 1 / g or less, causing the granular medium to flow, heating the reactor, and supplying a raw material containing plastic to the heated reactor. The method for producing a chemical product of this disclosure may further include other treatments as necessary.

[0011] The method disclosed in Patent Document 1 primarily uses a mixture of FCC (Fluid Catalytic Cracking) catalyst and ZSM-5 for the decomposition of plastics, and does not optimize the conditions of the fluidized bed reaction in the thermal decomposition of plastics.

[0012] Mixed plastics, especially those containing polyethylene terephthalate (PET), tend to generate liquid products such as benzene and styrene during decomposition. In fluidized bed reactions, this can hinder the fluidization of the fluidized bed, leading to poor decomposition efficiency of the plastics.

[0013] In response, the inventors conducted diligent studies and found that the fluid material A and the pore volume are 0.01 cm³. ３ / g or more 10cm ３ We found that ethylene and propylene can be efficiently obtained in high yield by fluidizing a granular medium containing additive B at a concentration of less than / g.

[0014] -Chemicals- The chemicals produced by the chemical manufacturing method of this disclosure are not particularly limited as long as they are chemicals obtained by decomposing raw materials including plastics, and can be appropriately selected according to the purpose. However, they are preferably chemicals containing ethylene and propylene, and more preferably chemicals containing an olefin having 4 carbon atoms in addition to ethylene and propylene.

[0015] Furthermore, the chemicals produced by the chemical manufacturing method of this disclosure may contain aromatic hydrocarbons.

[0016] Therefore, in this disclosure, “useful component” means at least one chemical selected from the group consisting of olefins having 2 to 4 carbon atoms and aromatic hydrocarbons.

[0017] --Olefins having 2 to 4 carbon atoms-- In this disclosure, olefins having 2 to 4 carbon atoms may be referred to as "lower olefins". The olefin having 2 to 4 carbon atoms is preferably at least one selected from the group consisting of alkenes having 2 to 4 carbon atoms and dienes having 2 to 4 carbon atoms, and alkenes having 2 to 4 carbon atoms are more preferred.

[0018] Examples of olefins having four carbon atoms include trans-2-butene, 1-butene, 2-methylpropene, cis-2-butene, 1,3-butadiene, and isobutene.

[0019] Among these, the method for producing the chemicals described herein has the advantage of high yields of ethylene and propylene. There are no particular restrictions on the total yield (mass%) of ethylene and propylene, and it can be appropriately selected depending on the purpose, but it is preferably 30% by mass or more, more preferably 32% by mass or more, and even more preferably 34% by mass or more, relative to the raw materials including plastics. A higher total yield (mass%) of ethylene and propylene is preferable, and there are no particular restrictions on its upper limit; for example, it may be 70% by mass or less, 60% by mass or less, or 45% by mass or less.

[0020] In this disclosure, the "yield" for each component and the "total yield" refer to the mass percentage (mass%) of each component relative to the raw material containing the plastic.

[0021] There are no particular restrictions on the total yield (mass%) of olefins having 2 to 4 carbon atoms, and it can be appropriately selected depending on the purpose. However, relative to the raw materials containing plastic, it is preferably 30% by mass or more, more preferably 35% by mass or more, even more preferably 40% by mass or more, and particularly preferably 45% by mass or more. A higher total yield (mass%) of olefins having 2 to 4 carbon atoms is preferable, and there are no particular restrictions on its upper limit. For example, it may be 90% by mass or less, 85% by mass or less, or 80% by mass or less.

[0022] Olefins with 2 to 4 carbon atoms can be used as basic chemicals suitable for chemical recycling and can serve as raw materials for polyolefins. Polyolefins can be suitably used in a variety of fields, such as shopping bags, plastic wrap, straws, medical devices, home appliance casings, erasers, hoses, tires, tubes, CD cases, food trays, food containers, plastic bottles, and fibers.

[0023] --Aromatic hydrocarbons-- There are no particular restrictions on aromatic hydrocarbons, but benzene, toluene, ethylbenzene, and the three positional isomers of xylene (p-xylene, m-xylene, and o-xylene), and styrene are preferred, and the three positional isomers of benzene, toluene, and xylene are more preferred.

[0024] In this disclosure, benzene, toluene, ethylbenzene, and the three positional isomers of xylene (p-xylene, m-xylene, and o-xylene), as well as styrene, may be referred to as "useful aromatic hydrocarbons."

[0025] There are no particular restrictions on the total yield (mass%) of useful aromatic hydrocarbons, and it can be appropriately selected depending on the purpose. However, relative to the raw material containing plastic, it is preferably 3% to 50% by mass, more preferably 4% to 40% by mass, and even more preferably 5% to 30% by mass.

[0026] --By-products-- Chemicals obtained by the chemical manufacturing methods of the present disclosure may contain by-products. Examples of by-products include paraffin, carbon, and hydrogen gas. Note that carbon as a by-product refers to components consisting only of carbon atoms, such as soot, graphite, and diamond.

[0027] There are no particular restrictions on the paraffin, but examples include aliphatic saturated hydrocarbons having 1 to 4 carbon atoms, with aliphatic saturated hydrocarbons having 2 to 4 carbon atoms being preferred. Examples of aliphatic saturated hydrocarbons having 1 to 4 carbon atoms include chain-like aliphatic saturated hydrocarbons having 1 to 4 carbon atoms.

[0028] Specific examples of paraffins include methane, ethane, propane, isobutane, and n-butane. Among these, the method for producing the chemicals described herein has a low selectivity for methane.

[0029] There are no particular restrictions on the total yield (mass%) of paraffins having 1 to 4 carbon atoms, but it is preferably 35% by mass or less, more preferably 30% by mass or less, even more preferably 20% by mass or less, and particularly preferably 10% by mass or less, relative to the raw material containing plastic. The lower limit of the total yield (mass%) of paraffins having 1 to 4 carbon atoms is preferable as it is lower, for example, 0.001% by mass or more, 0.01% by mass or more, 0.1% by mass or more, relative to the raw material containing plastic.

[0030] The yields of useful components and by-products contained in the chemical can be determined by analyzing the gaseous and liquid products obtained as products of the chemical manufacturing method of this disclosure using a gas chromatograph (GC) equipped with a flame ionization detector.

[0031] When analyzing the gaseous products as byproducts, the analysis can be performed using gas chromatography (GC) equipped with a flame ionization detector under the analytical conditions described in the examples. Each component can then be quantified using the internal standard method, based on the ratio of the peak area of ​​each component to that of the internal standard. The internal standard is not particularly limited as long as it is stable under the analytical conditions and easily separated from the analyte; for example, cyclopentane can be used.

[0032] Furthermore, when analyzing the liquid substance as a product, it can be analyzed using gas chromatography (GC) equipped with a flame ionization detector under the analytical conditions described in the examples, and each component can be quantified by the internal standard method based on the ratio of the peak area of ​​each component to that of the internal standard. The internal standard is not particularly limited as long as it is stable under the analytical conditions and easily separated from the analyte; for example, cyclopentane can be used.

[0033] <Flowing the granular medium> When flowing the granular medium, the fluid material A and the pore volume are 0.01 cm３ / g or more 10cm ３ An inert gas is introduced into a reactor containing a granular medium containing additive B at a concentration of 1 / g or less, and the granular medium is made to flow. Preferably, the inert gas is introduced into the reactor containing the granular medium from the opposite direction to gravity to the granular medium, and the granular medium is made to flow.

[0034] The reactor is a reactor capable of accommodating granular media and having a certain internal space to ensure a flow path for raw materials including plastic and inert gas, and is preferably a fluidized bed.

[0035] There are no particular restrictions on the shape, structure, and size of the reactor, and they can be appropriately selected according to the purpose. However, from the viewpoint of allowing the raw materials containing plastic and the generated chemicals to flow smoothly and ensuring sufficient contact time between the raw materials containing plastic and the fluidized bed, it is preferable that the flow direction of the raw materials containing plastic be perpendicular to the flow direction, i.e., longer than the inner diameter of the reactor.

[0036] A fluidized bed is placed inside the reactor. A fluidized bed is a reactor vessel that suspends granular media by passing an inert gas through it at a sufficient speed, causing the granular media to behave like a fluid.

[0037] -Granular media- The granular media consists of a fluid material A and a pore volume of 0.01 cm³. ３ / g or more 10cm ３ It contains additive B at a concentration of 1 / g or less. The granular medium may further contain other components besides the fluidizing agent A and additive B.

[0038] --Fluidizing agent A-- There are no particular restrictions on fluidizing agent A, and it can be appropriately selected from materials commonly used in fluidized bed reactions according to the purpose. However, it is preferable that the material is stable in the temperature range of thermal decomposition when heated, does not react with hydrocarbons, carbon, hydrogen, etc. produced by the thermal decomposition of plastics, and does not react with inert gases.

[0039] Specific examples of fluidizing agent A include silica sand, zirconium oxide, yttria-stabilized zirconium oxide, calcia-stabilized zirconium oxide, magnesium oxide, calcium oxide, silicon carbide, silicon nitride, silicon oxide, tantalum oxide, niobium oxide, beryllium oxide, lanthanum oxide, manganese(II) oxide, chromium(III) oxide, gallium oxide, forstenite, and cordierite. Furthermore, fluidizing agent A may be a surface-treated version of the above materials for purposes such as surface deactivation or improving the fluidity of raw materials containing plastics. These may be used individually or in combination of two or more. Among these, silica sand or a surface-treated version thereof is preferred as fluidizing agent A.

[0040] There are no particular restrictions on the surface-treated fluid material A, and it can be appropriately selected depending on the purpose. Examples include granular media having an oxide film on the surface and granular media having a carbon film on the surface. There are no particular restrictions on the method for surface-treating the fluid material A, and it can be appropriately selected from known methods.

[0041] The structure of surface-treated fluid material A can be confirmed, for example, by observation using a scanning electron microscope (SEM), a transmission electron microscope (TEM), X-ray photoelectron spectroscopy (XPS), or micro-Raman spectroscopy.

[0042] There are no particular restrictions on the particle size of fluid material A, and it can be appropriately selected according to the purpose, but it is preferably 0.05 mm to 4.75 mm, preferably 0.06 mm to 3 mm, and more preferably 0.075 mm to 2 mm. The particle size of fluid material A is measured by the dry sieving test according to ISO 2591-1:1988.

[0043] The pore volume of the fluid material is 0.01 cm³. ３ Preferably less than 0.0001 cm² / g, and 0.0001 cm². ３ / g or more 0.01cm ３ A value less than / g is more preferable. The pore volume of the fluid material is measured in accordance with ISO 15901-2:2006 and analyzed by the BET method.

[0044] There are no particular restrictions on the specific surface area of ​​the fluid material, and it can be appropriately selected depending on the purpose, but 0.1 m ２ / g or more 20m ２ Preferably less than 0.2 m ２ / g or more 15m ２ Preferably less than / g, and 0.3m ２ / g or more 10m ２ A value of less than / g is more preferable. The specific surface area of ​​the fluid material is 0.1 m². ２ / g or more 20m ２ A value of less than / g is preferable because it allows for the use of readily available materials and makes it easier to maintain a suitable flow state even during long-term operation. The specific surface area of ​​the fluid material is measured in accordance with ISO 9277:2010 using a specific surface area measuring device (e.g., BELSORP® MAX II, manufactured by Microtrac-Bell Co., Ltd.) at liquid nitrogen temperature, with nitrogen molecules as the probe.

[0045] There are no particular restrictions on the shape and structure of the fluid material A, and it can be appropriately selected according to the purpose. The shape of the granular medium may be fixed or irregular. A shape that does not easily allow molten plastic to accumulate on the granular medium is preferred, a spherical shape is preferred, and a perfectly spherical shape is more preferred.

[0046] --Additive B-- Additive B has a pore volume of 0.01 cm ３ / g or more 10cm ３ As long as the particles are less than or equal to / g, there are no particular restrictions, and they can be appropriately selected according to the purpose. However, it is preferable that the material is stable in the temperature range of thermal decomposition when heated, does not undergo reduction by by-products such as carbon and hydrogen generated by the thermal decomposition of plastics, and does not react with inert gases.

[0047] Additive B preferably contains silica. Specific examples of additive B include silica alone, as well as SiO ２ -MgO,SiO ２ - Al ２ O ３ SiO ２ -TiO ２ SiO ２ -V ２ O5, SiO ２ -Cr２ O ２ SiO ２ -TiO ２ -MgO is one example. These may be used individually. ２ You may use more than one type in combination.

[0048] Additive B may adsorb a small amount of moisture and may contain a small amount of impurities. In this disclosure, there are no particular restrictions on the content of "small amount of moisture" and "small amount of impurities" as long as ethylene and propylene can be obtained efficiently in high yield, and they can be appropriately selected depending on the purpose, but it is preferably 5% by mass or less, more preferably 3% by mass or less, and even more preferably 1% by mass or less, relative to the total mass of additive B.

[0049] Among these, additive B is preferably one that does not contain moisture and impurities. Additive B that does not contain moisture and impurities can be obtained by calcining the raw material of additive B (for example, silica) at a temperature of 100°C to 1,000°C, preferably 150°C to 700°C, under the flow of a dry gas such as air or nitrogen gas.

[0050] The pore volume of additive B is 0.01 cm³. ３ / g or more 10cm ３ Less than / g, but 0.03cm ３ / g or more 8cm ３ / g is preferred, and 0.1cm ３ / g or more 5cm ３ / g is more preferable. The pore volume of additive B is 0.01 cm³. ３ If the amount is less than 10 cm², the yield of ethylene and propylene will be poor. The pore volume of additive B is 10 cm². ３ Manufacturing a product exceeding [amount] / g is difficult and undesirable due to the high cost. The pore volume of additive B is measured in accordance with ISO 15901-2:2006 and analyzed by the BET method.

[0051] There are no particular restrictions on the specific surface area of ​​additive B, and it can be appropriately selected depending on the purpose, but 20 m ２ / g or more 3,000m ２ Preferably less than / g, and 25m ２ / g or more 2,000m ２ More preferably less than / g, and 30m ２ / g or more 1,000m ２ It is even more preferable that the amount is less than or equal to 20 m². The specific surface area of ​​additive B is 20 m². ２ When the concentration is 3,000 m² or higher, the yield of ethylene and propylene is further improved. Also, when the specific surface area of ​​additive B is 3,000 m² ２ Manufacturing additives exceeding 1 / g is difficult and costly, making it undesirable. The specific surface area of ​​additive B is measured in accordance with ISO 9277:2010 using a specific surface area measuring device (e.g., BELSORP® MAX II, manufactured by Microtrac-Bell Co., Ltd.) at liquid nitrogen temperature, with nitrogen molecules as the probe.

[0052] There are no particular restrictions on the particle size of additive B, and it can be appropriately selected according to the purpose, but it is preferably 0.045 mm to 8 mm, more preferably 0.055 mm to 6 mm, and even more preferably 0.063 mm to 5.6 mm. When the particle size of additive B is 0.045 mm to 5.6 mm, it mixes well with fluid material A. The particle size of additive B is determined by sieving using a test sieve and shaker according to ISO 3310-1:2016, creating a graph of the particle size at each sieve opening and the mass percentage calculated from the integrated mass of the sample remaining on each sieve, and setting the particle size at 50% mass percentage to be the particle size at 50% mass percentage.

[0053] There are no particular restrictions on the average pore size of additive B, and it can be appropriately selected depending on the purpose, but it is preferably 0.1 nm to 100 nm, more preferably 0.5 nm to 50 nm, and even more preferably 1 nm to 10 nm. When the average pore size of additive B is 0.1 nm to 100 nm, the desired by-product can be adsorbed. The average pore size of additive B is measured according to ISO 15901-2:2006.

[0054] --Mass Ratio [B / A]-- There are no particular restrictions on the mass ratio [B / A] of fluid material A to additive B, and it can be appropriately selected according to the purpose, but it is preferably 0.04 or more and 0.20 or less, preferably 0.06 or more and 0.18 or less, and more preferably 0.08 or more and 0.16 or less. When the mass ratio [B / A] is 0.04 or more or 0.20 or less, the yield of ethylene and propylene is further improved.

[0055] -Inert Gas- There are no particular restrictions on the inert gas, but a gas that is stable in the heating temperature range is preferred.

[0056] Specific examples of inert gases include nitrogen gas, water vapor, carbon dioxide, and noble gases. These may be used individually or in combination of two or more. Among these, at least one of nitrogen gas and water vapor is preferred as the inert gas due to its industrial availability and low cost, with nitrogen gas being more preferred.

[0057] The flow rate of the inert gas introduced into the reactor is not particularly limited as long as it can flow the granular medium, and can be appropriately selected according to the purpose. However, the cross-sectional area of ​​the inside of the reactor at the lower end of the part containing the granular medium is 1 cm². ２ The volume flow rate per unit is 1 N mL / cm³. ２ More than 500NmL / cm ２ A flow rate of 3 N mL / cm² is preferred. ２ More than 300NmL / cm ２ A flow rate of 5 N mL / cm² is more preferable. ２ More than 50NmL / cm ２ A flow rate of the following is even more preferable: The flow rate of the inert gas is 1 N mL / cm³ per cross-sectional area. ２ More than 500NmL / cm ２ At the flow rates specified below, sufficient contact time between the raw materials containing plastic and the granular medium can be ensured, and side reactions can be suppressed, thereby enabling the efficient acquisition of useful components in high yield. The linear velocity of the inert gas can be determined by the method described in the examples. In the flow rate unit, "N" indicates the amount of gas converted to 0°C and 101.325 kPa.

[0058] <Heating> Heating involves heating the reactor. Heating may be done separately from or simultaneously with the fluidization of the granular medium.

[0059] There are no particular restrictions on the method of heating the reactor, and it can be appropriately selected according to the purpose. It may be an external heating method in which the reactor is heated by heat transfer from the outside, or an internal heating method in which the granular medium is heated by resistance heating using heat transfer wires or the like inside the reactor.

[0060] There are no particular restrictions on the heating temperature of the reactor, and it can be appropriately selected depending on the purpose, but it is preferably 1,000°C or lower, more preferably 990°C or lower, and even more preferably 980°C or lower. When the heating temperature of the reactor is 1,000°C or lower, useful components can be obtained efficiently in high yield. In addition, when the heating temperature of the reactor is 1,000°C or lower, the generation of methane, a by-product produced when plastics decompose and which is difficult to use as a basic chemical, can be suppressed.

[0061] There are no particular restrictions on the lower limit of the heating temperature for the reactor, as long as the plastic can be decomposed, and it can be appropriately selected depending on the purpose. However, a temperature of 500°C or higher is preferred, 580°C or higher is more preferred, and 650°C or higher is even more preferred. When the lower limit of the heating temperature for the reactor is 500°C or higher, useful components can be obtained efficiently in high yield.

[0062] <Supplying> In the supplying process, raw materials containing plastic are supplied to the heated fluidized bed. This causes the raw materials containing plastic to decompose thermally, and chemical products containing ethylene and propylene can be produced.

[0063] From the viewpoint of thermally decomposing the raw materials, including plastics, in a fluidized bed, it is preferable to perform the supply simultaneously with fluidizing and heating the granular medium. There are no particular restrictions on the timing of starting the supply, fluidizing the granular medium, and heating; they may be performed simultaneously or separately.

[0064] There are no particular restrictions on the method of supplying raw materials containing plastic to the fluidized bed; they may be supplied intermittently or continuously. Among these methods, continuous supply is preferred because it minimizes temperature fluctuations in the fluidized bed.

[0065] When supplying raw materials containing plastic to a fluidized bed intermittently, there are no particular restrictions on the supply time, non-supply time, or intervals between these.

[0066] When supplying raw materials containing plastic to a granular medium intermittently, there are no particular restrictions on the amount of raw materials containing plastic supplied at one time. However, when supplying raw materials containing plastic to a granular medium intermittently, it is preferable to wait until the temperature of the granular medium, which has dropped due to the previous supply, has recovered to the desired temperature before adding the raw materials containing plastic for the second and subsequent times, from the viewpoint of preventing the temperature of the granular medium from dropping too low.

[0067] When supplying raw materials containing plastic to a fluidized bed continuously, there are no particular restrictions on the amount of raw materials containing plastic that can be supplied.

[0068] -Raw materials containing plastic- There are no particular restrictions on raw materials containing plastic, and they can be appropriately selected according to the purpose. Examples include mixed plastics containing polyolefins, aromatic plastics, and chlorine-containing plastics. These may be used individually or in combination of two or more. Furthermore, raw materials containing plastic may also contain other components as needed.

[0069] --Mixed Plastics-- There are no particular restrictions on the polyolefins included in mixed plastics, and they can be appropriately selected depending on the purpose, but it is preferable that they include polyethylene (PE) and polypropylene (PP), which are commonly used in beverage and food containers, packaging materials, molded products, films, etc. In other words, it is preferable that the mixed plastic containing polyolefins as a raw material for plastics is a mixed plastic containing polyethylene and polypropylene.

[0070] There are no particular restrictions on the polyolefin content in the raw materials containing plastics, and it can be appropriately selected depending on the purpose. However, it is preferably 50% to 90% by mass relative to the raw materials containing plastics, more preferably 55% to 87% by mass, and even more preferably 60% to 85% by mass. When the polyolefin content in the raw materials containing plastics is 50% to 90% by mass, chemical products containing ethylene and propylene can be obtained efficiently in high yield.

[0071] --Aromatic Plastics-- Aromatic plastics are plastics having an aromatic skeleton. There are no particular restrictions on aromatic plastics, and they can be appropriately selected from those commonly used for beverage and food containers, packaging materials, molded products, films, etc., depending on the purpose. Examples include polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), acrylonitrile-butadiene-styrene copolymer, polycarbonate (PC), and polystyrene (PS). These may be contained individually or in combination of two or more. Among these, aromatic plastics preferably contain polyethylene terephthalate (PET) and polystyrene (PS). In the chemical manufacturing method of this disclosure, even if the raw material plastic contains aromatic plastics such as polyethylene terephthalate (PET) and polystyrene (PS), chemicals containing ethylene and propylene can be obtained efficiently in high yield.

[0072] --Chlorine-containing plastics-- There are no particular restrictions on chlorine-containing plastics, and they can be appropriately selected depending on the purpose, but it is preferable that they contain at least one selected from the group consisting of polyvinyl chloride (PVC), polyvinylidene chloride (PVDC), and chlorinated polyethylene (CPE), which are commonly used in beverage and food containers, packaging materials, molded products, films, etc.

[0073] There are no particular restrictions on the content of at least one selected from the group consisting of aromatic plastics and chlorine-containing plastics in the plastic, and it can be appropriately selected depending on the purpose. However, it is preferably 10% by mass or more and 50% by mass or less, more preferably 13% by mass or more and 45% by mass or less, and even more preferably 15% by mass or more and 40% by mass or less, relative to the total mass of the plastic. When the content of at least one selected from the group consisting of aromatic plastics and chlorine-containing plastics in the plastic is 10% by mass or more and 50% by mass or less, chemical products containing ethylene and propylene can be obtained efficiently in high yield. Furthermore, the lower the content of at least one selected from the group consisting of aromatic plastics and chlorine-containing plastics, the better. The lower limit may be, for example, 0.1% by mass or more, 0.5% by mass or more, 5% by mass or more, or 10% by mass or more.

[0074] --Other Components-- There are no particular restrictions on other components contained in raw materials containing plastics, and they can be appropriately selected depending on the purpose. Examples include other plastics other than polyolefins, aromatic plastics, and chlorine-containing plastics; and materials that are normally found in waste plastics such as paper and metal. These may be contained individually or in combination of two or more types.

[0075] Other plastics are not particularly limited and can be selected as appropriate depending on the purpose, and examples include polyamide, polyurethane, and polymethyl methacrylate.

[0076] There are no particular restrictions on the content of other components in the raw material containing plastic, and they can be appropriately selected depending on the type of raw material containing plastic used. However, from the viewpoint of the yield of chemicals containing ethylene and propylene, it is preferable that the content be less than 30% by mass, more preferably 25% by mass or less, and even more preferably 20% by mass or less, based on the total mass of the raw material containing plastic.

[0077] From the viewpoint of reducing environmental impact, it is preferable that the raw materials containing plastic include waste plastic. When the raw materials containing plastic are waste plastic, there are no particular restrictions on the composition and composition ratio, and they can be appropriately selected according to the purpose, but it is preferable that PE is 20% to 40% by mass, PP is 20% to 40% by mass, PS is 10% to 30% by mass, and PET is 10% to 30% by mass.

[0078] As waste plastics, for example, Refuse-derived paper and plastics-densified fuel (RPF) can be used.

[0079] The structure and content of each component in raw materials containing plastics can be determined by analysis using methods such as Fourier transform infrared spectroscopy (FT-IR), gel permeation chromatography (GPC), ion chromatography (IC), nuclear magnetic resonance (NMR), liquid chromatography-mass spectrometry (LC-MS), pyrolysis gas chromatography-mass spectrometry (PyGC-MS), and matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOFMS).

[0080] In terms of supply, there are no particular restrictions on the state of the plastic in the raw materials supplied to the fluidized bed; for example, it can be crystalline, glassy, ​​rubbery, or liquid. The plastic may also be in the form of decomposed products. Among these, rubbery or liquid plastic is preferred because it is easier to control the supply amount.

[0081] When the plastic is crystalline or glassy, ​​there are no particular restrictions on its form, and examples include crushed plastic, pellets of crushed plastic, and chips of crushed plastic.

[0082] There are no particular restrictions on the type of plastic used for the pulverized material; it can be appropriately selected depending on the purpose, for example, in powder or flake form.

[0083] Rubber-like or liquid plastic refers to plastic that is fluid at a temperature above its melting point but below its thermal decomposition temperature. Rubber-like or liquid plastic is also called "molten plastic."

[0084] Plastic decomposition products are materials that have been broken down from plastics into smaller molecules, but their molecular weight is still larger than that of the final chemical product.

[0085] The molecular weight of rubbery or liquid plastics does not change from the molecular weight of crystalline or glassy plastics of the same composition. Therefore, plastics and their decomposition products can be distinguished by their molecular weight. As the molecular weight decreases due to decomposition, the melting point also decreases, so in practice, this can be determined by the melting temperature. The melting temperature is measured by the method specified in JIS K7121-2012.

[0086] There are no particular restrictions on the melting temperature of the plastic, and it can be appropriately selected depending on the raw materials used, but 80°C to 200°C is preferred, 85°C to 195°C is more preferred, and 90°C to 190°C is even more preferred.

[0087] These raw materials, including various forms of plastic, may be used after being processed separately from the chemical manufacturing methods of this disclosure, or after being subjected to other processing as described below.

[0088] <Other Processing> The method for producing the chemicals of this disclosure may further include, as necessary, other processing other than fluidizing and supplying the granular medium.

[0089] Other processing methods are not particularly limited and can be selected as appropriate depending on the purpose. Examples include pre-treating raw materials containing plastics, recovering chemicals obtained through supply, post-treating chemicals, separating chemicals, and reusing granular media.

[0090] <<Pre-treatment>> Pre-treatment involves pre-treating the raw materials containing plastic before they are supplied. By pre-treating the raw materials containing plastic to make them easier to decompose, the plastic can be decomposed more efficiently.

[0091] Examples of pretreatment include crushing the raw material containing plastic, pelletizing (chipping) the crushed raw material containing plastic, and melting the raw material containing plastic.

[0092] It is preferable to melt down raw materials containing plastics at a temperature of less than 300°C.

[0093] There are no particular restrictions on the pulverized raw materials containing plastic, and they can be appropriately selected depending on the purpose. Examples include powder and flake forms.

[0094] There are no particular restrictions on the method for obtaining pulverized material containing plastic, and any conventionally known method can be appropriately selected. For example, a method can be used in which the plastic-containing material is pulverized using a pulverizer to obtain powder or flakes.

[0095] Furthermore, there are no particular restrictions on the method of pelletizing (also called "chipping") the pulverized material, and any conventionally known method can be appropriately selected. For example, one method involves melting and extruding the pulverized material, and then cutting the strand-shaped melted extruded material to obtain chipped raw material.

[0096] The raw materials containing plastic can also be supplied in a molten state. There are no particular restrictions on the method of melting the raw materials containing plastic, and any conventionally known method can be appropriately selected. For example, a method of continuously supplying the materials to the decomposition process using a molten extruder can be used.

[0097] <<Recovery>> Recovery involves recovering the liquid substances and gases that are products containing the chemicals obtained through supply. There are no particular restrictions on the recovery method, and a method can be appropriately selected from known methods depending on the type of product obtained. For example, gaseous products can be separated by atmospheric pressure or pressurized distillation, and liquid hydrocarbons can be separated by atmospheric pressure or reduced pressure distillation.

[0098] <<Post-treatment of chemicals>> Post-treatment of chemicals is a process of decomposing by-products in chemicals generated by the thermal decomposition of raw materials, including plastics. It is preferable to perform post-treatment of chemicals after the recovery of the chemicals.

[0099] Post-treatment methods for chemicals include, for example, the removal of halogen compounds. Methods for removing halogen compounds include a fixed bed filled with an oxide or hydroxide of one metal selected from alkali metals and alkaline earth metals, or a method of passing an aqueous solution of the oxide or hydroxide of the said metal through the bed.

[0100] <<Separation>> Separation involves separating only the useful components from the recovered liquid substance and gas, and removing unwanted components.

[0101] The substances produced by the chemical manufacturing method of this disclosure are chemicals containing ethylene and propylene, preferably chemicals containing olefins having 2 to 4 carbon atoms and aromatic hydrocarbons, but paraffins having 2 to 4 carbon atoms may be produced as a by-component.

[0102] In terms of separation, there are no particular restrictions on the method used to separate the useful components from the minor components, and a method can be appropriately selected from known methods depending on the type of product obtained or the type of minor components.

[0103] The above chemical manufacturing method allows for the efficient production of chemicals containing ethylene and propylene in high yield. The produced chemicals can be used as basic chemicals suitable for chemical recycling.

[0104] <<Reusing Granular Media>> Regenerating granular media involves recovering granular media that has been used once or more from the reactor and reusing it. For example, granular media can be recovered by providing a granular media recovery section in the reactor, in addition to the product recovery section for removing the product. The recovered granular media can then be reused within the recovery section by supplying it back to the recovery section via a transfer furnace connected to the reactor.

[0105] The conveying furnace may have a granular media regeneration section in the middle. In the granular media regeneration section, the recovered granular media is calcined with air. Granular media that has been used once or more may undergo surface carbonization (sometimes referred to as "coking" in this disclosure) due to carbon in the raw materials containing plastic. This coking can reduce the decomposition efficiency of the raw materials containing plastic, and thus reduce the yield of ethylene and propylene. Therefore, by calcining the granular media with air in the granular media regeneration section to burn and remove the coking before returning it to the reactor, ethylene and propylene can be obtained continuously and efficiently in high yield over a long period of time.

[0106] The amount of coking, a by-product of chemicals, can be calculated by removing the granular medium from the reaction section inside the reactor and burning it in air, then measuring the weight change before and after air calcination.

[0107] The granular medium may be removed intermittently before or after each of the processes, such as fluidization, heating, supplying, and other treatments, or it may be removed continuously during or in conjunction with each of the processes.

[0108] (Chemical Manufacturing Apparatus) The chemical manufacturing apparatus of this disclosure comprises a fluid material A and a pore volume of 0.01 cm³. ３ / g or more 10cm ３The apparatus for producing chemical products comprises a reactor containing a granular medium containing additive B at a concentration of 1 / g or less, a plastic supply unit connected to the reactor and supplying raw materials including plastic to the reactor, an inert gas supply unit connected to one end of the reactor and arranged to supply inert gas to the granular medium from a direction opposite to the direction of gravity, and a heating unit for heating the reactor. The apparatus for producing chemical products of this disclosure may further have other components as needed.

[0109] The chemical manufacturing apparatus of the present disclosure can suitably carry out the chemical manufacturing method of the present disclosure.

[0110] Embodiments of the apparatus of this disclosure will be described below with reference to the drawings. Figure 1 is a schematic cross-sectional view showing an example of a chemical manufacturing apparatus of this disclosure. The embodiments shown below are illustrative examples of apparatus for realizing the technical concept of this disclosure and do not limit this disclosure to the following. Furthermore, the dimensions, materials, shapes, relative arrangements, etc. of the components described below are intended to be illustrative, and not to limit the scope of this disclosure unless otherwise specified. In addition, the size and positional relationships of the members shown in the drawings may be exaggerated to clarify the explanation. Furthermore, in order to avoid making the drawings excessively complex, schematic cross-sectional views use schematic diagrams in which some elements are omitted from the illustration.

[0111] The chemical manufacturing apparatus 100 (hereinafter sometimes abbreviated as "manufacturing apparatus 100") includes a reactor 1 that contains a granular medium 2 containing a fluidizing agent 2A and an additive 2B, a plastic supply unit 3, an inert gas supply unit 4, and a heating unit 5.

[0112] <Reactor 1> Reactor 1 is a component that contains a granular medium 2 containing a fluidizing agent 2A and an additive 2B. In reactor 1, the granular medium 2 placed inside reactor 1 is heated by the heating unit 5, thereby heating the raw material M (hereinafter sometimes abbreviated as "raw material M") containing plastic that is supplied inside reactor 1.

[0113] The material of the reactor 1 is not particularly limited as long as it is stable in terms of surface temperature and atmosphere on the inside of the reactor 1, that is, on the side of the reactor 1 that contains the raw materials M. For example, alumina (Al２ O ３ ), Zirconia (ZrO ３ ), silicon carbide (SiC), silicon nitride (Si ３ N ４ ), mullite (3Al ２ O ３ ・2SiO ２ Inorganic compounds such as SUS310S, Inconel (registered trademark), Hastelloy (registered trademark), and other alloys can be used.

[0114] The structure, shape, and size of the reactor 1 are not particularly limited as long as it can accommodate the granular medium 2 and allow the raw material M containing plastic to flow through it, and can be appropriately selected according to the purpose.

[0115] Examples of the shape of the reactor 1 include cylindrical, rectangular parallelepiped, conical, frustoconical, and columnar shapes in which the cross-sectional shape perpendicular to the longitudinal direction of the reactor 1 is polygonal.

[0116] In order to retain the granular medium 2 inside the reactor 1, it is preferable to plug the pipe 9 with a mesh plate that allows an inert gas G such as quartz wool and the compound R as a product to flow through it.

[0117] Furthermore, regarding the size of the reactor 1, it is preferable that the direction of flow of the raw material M is perpendicular to the flow direction, i.e., longer than the inner diameter of the reactor 1, from the viewpoint of allowing the raw material M and the generated chemical product R to flow smoothly and ensuring sufficient contact time between the raw material M and the fluidized bed of granular medium 2.

[0118] The structure, shape, material, and size of the stopper 9 are not particularly limited, as long as they do not allow the granular medium 2 to pass through, but do allow the inert gas G, raw material M, or chemical product R to pass through. They can be appropriately selected according to the purpose, and examples include quartz wool, a mesh plate, a screen, and a dispersion plate. These may be used individually or in combination of two or more types.

[0119] In Figure 1, the fluidizing agent 2A and the additive 2B are not shown separately, but the granular medium 2 contains the fluidizing agent 2A and the additive 2B.

[0120] <Plastic Supply Unit 3> The plastic supply unit 3 is a component connected to the reactor 1 and supplied the raw material M containing plastic to the reactor 1. Examples of the plastic supply unit 3 include a raw material distribution unit 3a through which the raw material M containing plastic flows, and a raw material input unit 3b for introducing the raw material M containing plastic into the reactor 1. The plastic supply unit 3 may also supply the raw material M to the reactor 1 using a known pump or the like.

[0121] Furthermore, the plastic supply unit 3 may have a raw material supply stopper, such as a stopper, that can stop the supply of raw materials M containing plastic. If a raw material supply stopper is provided, plastic can be supplied to the reactor 1 intermittently. The raw material supply stopper can be located, for example, at the inlet of the raw material input unit 3b.

[0122] In this disclosure, "connecting" the plastic supply unit 3 to the reactor 1 means that the inside of the raw material distribution section 3a of the plastic supply unit 3 and the inside of the reactor 1 are in communication so that the raw material M can pass through them.

[0123] There are no particular restrictions on the material of the plastic supply unit 3; for example, it can be appropriately selected from the same materials as those used for the reactor 1, depending on the purpose.

[0124] The shape, structure, and size of the plastic supply unit 3 are not particularly limited as long as it can be connected to the reactor 1 and supply the raw material M to the reactor 1. They can be appropriately selected according to the purpose, for example, a cylindrical shape or a rectangular parallelepiped. Also, if a part of the reactor 1 has an opening, this opening can be used as the plastic supply unit 3.

[0125] The location of the plastic supply unit 3 is not particularly limited as long as it can be connected to the reactor 1 and supply raw material M to the granular medium 2. It can be appropriately selected depending on the type of raw material M, but it is preferable that it be in a position where the raw material M can be supplied from above the granular medium 2. Figure 1 shows the plastic supply unit 3 being placed on the upper surface in the longitudinal direction of the reactor 1, but it may also be placed on the side of the reactor 1.

[0126] <Inert Gas Supply Unit 4> The inert gas supply unit 4 is connected to one end of the reactor 1 and is positioned to supply inert gas G to the granular medium 2 from a direction opposite to the direction of gravity. Examples of the inert gas supply unit 4 include an inert gas flow unit 4a through which the inert gas G flows, and a pump 4b that flows the inert gas G in a fixed amount for a fixed period of time.

[0127] In this disclosure, "connecting" the inert gas supply unit 4 to one end of the reactor 1 means that the inside of the inert gas flow section 4a of the inert gas supply unit 4 and the inside of the reactor 1 are in communication at one end of the reactor 1, allowing the inert gas G to pass through.

[0128] There are no particular restrictions on the material of the inert gas supply unit 4; for example, it can be appropriately selected from the same materials as those used for the reactor 1, depending on the purpose.

[0129] The shape, structure, and size of the inert gas supply unit 4 are not particularly limited as long as it can be connected to the reactor 1 and supply inert gas G to the reactor 1. They can be appropriately selected according to the purpose, for example, a cylindrical shape or a rectangular parallelepiped. Also, if a part of the reactor 1 has an opening, this opening can be used as the inert gas supply unit 4.

[0130] When the chemical manufacturing apparatus 100 is not in operation, the granular medium 2 normally accumulates in the internal space of the reactor 1 due to its own weight. That is, the direction of accumulation of the granular medium 2 is in the direction of gravity. In order to position the inert gas supply unit 4 to supply the inert gas G to the granular medium 2 from the opposite direction to gravity in the internal space of the reactor 1, it is preferable to position the inert gas supply unit 4 below the position where the granular medium 2 is placed in the reactor 1, in the direction of gravity. Figure 1 shows the inert gas supply unit 4 being placed on the lower surface in the longitudinal direction of the reactor 1, but the inert gas supply unit 4 may be placed on the side of the reactor 1 as long as the inert gas G can be supplied from below the granular medium 2, preferably from below the stopper 9.

[0131] As for the type of inert gas G, those described in the section (Method of Manufacturing Chemical Products) of this disclosure can be used.

[0132] <Heating section 5> The heating section 5 is a component that heats the reactor 1. There are no particular restrictions on the heating section 5; it may be an external heating method that heats the reactor 1 by heat transfer from the outside, or an internal heating method that heats the reactor 1 from the inside. As a heating section for the external heating method, for example, a known electric furnace can be used. As a heating section for the internal heating method, for example, a resistance heating method can be used in which a resistor such as an electric heating wire is placed inside the reactor 1 and heat is generated by applying a voltage to the resistor.

[0133] The temperature of the reactor 1 can be measured by inserting a thermocouple into the center of the granular medium 2.

[0134] <Other Components> There are no particular restrictions on other components, and they can be appropriately selected according to the purpose. Examples include a storage unit 6, a cooling unit 7, a gaseous product recovery unit 8, a product extraction unit 10, a measuring unit for measuring the yield of useful components, a granular media extraction unit, a granular media transport unit, and a granular media regeneration unit.

[0135] <<Storage Section 6>> The storage section 6 is a component for storing raw materials M, including plastic.

[0136] The structure, shape, material, and size of the storage section 6 are not particularly limited as long as they can store the raw material M, including plastic, and can be appropriately selected according to the purpose.

[0137] There are no particular restrictions on the number of storage units 6; there may be one or multiple units. If the manufacturing apparatus 100 has multiple storage units 6, for example, it can be used to store plastics containing polyolefin and at least one selected from the group consisting of aromatic plastics and chlorine-containing plastics, where the composition and content of each component differ.

[0138] <<Cooling Section 7>> The cooling section 7 is a component that cools the chemical product R obtained by passing through the reactor 1. By cooling the chemical product R, the liquid components in the product can be recovered within the cooling section.

[0139] Examples of the cooling section 7 include a cooling trap 7a for cooling the product and a cooling section 7b for cooling the cooling trap 7a. The structure, shape, material, and size of the cooling trap 7a and the cooling section 7b are not particularly limited as long as they can cool the product, and can be appropriately selected according to the purpose.

[0140] The cooling trap 7a may contain an organic solvent 7c for dissolving the product. The organic solvent 7c can condense useful components in the product, especially liquid useful components. Non-aqueous solvents are preferred as the organic solvent for dissolving the product. Examples of non-aqueous solvents include aromatic organic solvents such as monochlorobenzene, o-dichlorobenzene, and mesitylene. It is preferable that the outlet of the product extraction section 10, preferably the outlet of the chemical distribution section 10a, is placed in the organic solvent 7c so that the chemical R (e.g., the generated gas) bubbles in the organic solvent 7c.

[0141] The useful components dissolved in a non-aqueous solvent can be suitably separated by further distillation at atmospheric pressure.

[0142] The cooling section 7b is not particularly limited as long as it can cool the cooling trap 7a, and may, for example, contain a refrigerant 7d. Examples of refrigerant 7d include ice water.

[0143] <<Gaseous Product Recovery Unit 8>> The gaseous product recovery unit 8 is a component that recovers gaseous products from the chemical product R containing useful components manufactured by the manufacturing apparatus 100. The gaseous product recovery unit 8 may consist of only one unit or two or more units.

[0144] There are no particular restrictions on the structure, shape, material, and size of the gas product recovery unit 8, and they can be appropriately selected according to the purpose and type of product, including known containers.

[0145] Furthermore, the gaseous product recovery unit 8 may contain a solvent capable of separating useful components. There are no particular restrictions on the solvent, and it can be appropriately selected depending on the type of useful component to be recovered. For example, ethanol, hexane, dimethylformamide, cyclopentane, and water can be used as solvents for extracting useful components from liquid products.

[0146] The useful components in the gaseous product can be suitably separated by further pressurized distillation.

[0147] <<Product Extraction Section 10>> The product extraction section 10 is a component that extracts the chemical product R from the reactor 1. Examples of the product extraction section 10 include a chemical distribution section 10a through which the chemical product R flows, and a pump 10b that flows the chemical product R in a fixed amount for a fixed period of time.

[0148] The product extraction unit 10 is connected to the reactor 1. In this disclosure, "connection" of the product extraction unit 10 to the reactor 1 means that the inside of the chemical flow section 10a of the extraction unit 6 and the inside of the reactor 1 are in communication so that the chemical R can pass through them.

[0149] The shape, structure, and size of the product extraction section 10 are not particularly limited as long as it can extract the chemical product R processed in the reactor 1, and can be appropriately selected according to the purpose. Examples include cylindrical and rectangular parallelepiped shapes. Furthermore, if a part of the reactor 1 has an opening, this opening can also be used as the product extraction section 10.

[0150] The location of the product extraction unit 10 is not particularly limited as long as it can be connected to the reactor 1, and can be appropriately selected depending on the type of chemical R. Figure 4 shows the product extraction unit 10 being located on the upper side of the reactor 1 in the Y-axis direction, but the product extraction unit 10 may be located at any position on the side of the reactor 1 as long as the chemical R can be extracted from the reactor 1, or it may be located on the top surface of the reactor 1.

[0151] In reactor 1, chemical product R is produced from raw material M, so raw material M and chemical product R may be mixed inside reactor 1. Therefore, the product extraction unit 10 may extract not only chemical product R, but also a mixture of raw material M and chemical product R. In addition, if by-products are produced inside reactor 1, the product extraction unit 10 may also extract the by-products.

[0152] <<Measurement Unit>> The measurement unit is a component that measures the yield of useful components in the product containing useful components manufactured by the manufacturing apparatus 100.

[0153] The measuring unit may be located inside the manufacturing apparatus 100, or it may be connected to and provided outside the manufacturing apparatus 100.

[0154] The measurement unit is not particularly limited as long as it can measure the yield of useful components in the product, and known measuring devices may be used. Examples of known measuring devices include flame ionization detectors (FIDs) and gas chromatography equipped with thermal conduction detectors (TCDs).

[0155] There are no particular restrictions on the structure, shape, material, and size of the measuring section; they can be appropriately selected according to the purpose and type of product.

[0156] <<Granular Media Extraction Section>> The granular media extraction section is connected to the reactor 1 and is a component that extracts the granular media 2 from the reactor 1.

[0157] In this disclosure, "connection" of the granular medium extraction unit to the reactor 1 means that the inside of the granular medium extraction unit and the inside of the reactor 1 are in communication so that the granular medium 2 can pass through them.

[0158] There are no particular restrictions on the material of the granular media extraction section; for example, it can be appropriately selected from the same materials as those used for reactor 1, depending on the purpose.

[0159] The shape, structure, and size of the granular media extraction section are not particularly limited as long as the granular media 2 can be extracted, and can be appropriately selected according to the purpose. Examples include cylindrical and rectangular parallelepiped shapes. Furthermore, if a part of the reactor 1 has an opening, this opening can also be used as the granular media extraction section.

[0160] There are no particular restrictions on the location of the granular media removal section, as long as it can be connected to the reactor 1, and it can be appropriately selected according to the purpose. However, it is preferable to place it at the bottom of the reactor 1 so that the granular media 2 can be removed by its own weight. In this case, it is preferable that the stopper 9 is openable and closable.

[0161] <<Granular Media Conveying Section>> The granular media conveying section is a component that conveys the granular media 2 to the reaction furnace 1. The shape, structure, and size of the granular media conveying section are not particularly limited as long as it can convey the granular media 2 to the reaction furnace 1, and can be appropriately selected according to the purpose.

[0162] <<Granular Media Regeneration Unit>> The granular media regeneration unit is a component that burns the granular media with air. This allows the caulking on the surface of the granular media to be burned off and removed.

[0163] [Example of operation of the manufacturing apparatus] Next, an example of the operation of the manufacturing apparatus 100 will be described. The manufacturing apparatus 100, for example, introduces an inert gas G into the granular medium 2 in the reactor 1 from the opposite direction to the direction of gravity by an inert gas supply unit 4, thereby causing the granular medium to flow in the method of manufacturing the compound of the present disclosure. Then, the heating unit 5 heats the reactor 1 to a desired temperature, thereby performing the heating in the method of manufacturing the compound of the present disclosure. While the reactor 1 is being heated by the heating unit 5, the raw material M containing plastic stored in the storage unit 6 is supplied to the reactor 1 by the plastic supply unit 3, thereby performing the supply in the method of manufacturing the compound of the present disclosure. The reactor 1 is a fluidized bed reactor in the method of manufacturing the compound of the present disclosure.

[0164] The chemical product R, which is a product containing useful components obtained by heating, can be recovered and separated in the cooling unit 7 and the gaseous product recovery unit 8 in the method for producing the compound of this disclosure.

[0165] The chemicals produced by the manufacturing apparatus 100 of this disclosure are as described in the method for producing compounds of this disclosure.

[0166] The timing and speed of supplying the raw material M containing plastic by the plastic supply unit 3, the timing and speed of supplying the inert gas G by the inert gas supply unit 4, the timing of heating by the heating unit 5, the heating temperature, and the heating time are all determined by the signal processing unit processing signals to each unit. The signal processing unit is an electronic circuit such as a CPU, FPGA, or ASIC, and performs the various processes described in this specification by executing instruction codes stored in memory or by designing the circuit for special applications.

[0167] (Granular medium and method of use thereof) The granular medium of this disclosure is a granular medium used in a fluidized bed for the thermal decomposition of raw materials including plastics, comprising a fluidizing agent A and a pore volume of 0.01 cm³. ３ / g or more 10cm ３ Contains additive B at a concentration of less than / g.

[0168] The fluidizing agent A, additive B, and raw materials including plastics are as described in the section (Method of Manufacturing Chemicals) of this disclosure.

[0169] Furthermore, the method of using the granular medium is also included in this disclosure. Specifically, this disclosure relates to a fluid material A and a pore volume of 0.01 cm³. ３ / g or more 10cm ３ This invention relates to a method for using a granular medium containing additive B at a concentration of 0.01 cm³ or less in a fluidized bed for the thermal decomposition of raw materials including plastics. Furthermore, this disclosure relates to a method for using a granular medium used to produce chemicals by thermal decomposing raw materials including plastics, wherein the granular medium contains a fluidizing agent A and a pore volume of 0.01 cm³. ３ / g or more 10cm ３ This relates to a method for using granular media containing additive B at a concentration of 1 / g or less.

[0170] The present disclosure will be specifically described below with reference to test examples, embodiments, and comparative examples, but the present disclosure is not limited in any way to these test examples, embodiments, and comparative examples.

[0171] (Test Example 1) <Preparation of the apparatus> The manufacturing apparatus 100 shown in Figure 1 was prepared. Specifically, a sieve was placed in the center of a quartz tube with an inner diameter of 15 mm and a height of 550 mm, which served as the reaction furnace 1. Quartz wool was laid on top, a stopper 9 was placed, and then filler was added to form a granular medium 2. For the granular medium 2, the type and amount of fluid material A and additive B described in Examples 1 to 3 or Comparative Example 1 in Table 1 were used. The quartz tube was placed inside a cylindrical electric furnace (product name: ARF-30MC, manufactured by Asahi Rika Seisakusho Co., Ltd.) which was installed vertically, and the quartz tube was positioned so that the granular medium 2 was in the center of the cylindrical electric furnace. The electric furnace is an external heating type heating section 5. A manual powder input device (airless feed cock, manufactured by Asahi Seisakusho Co., Ltd.) as the raw material input section 3b of the raw material supply section 3 and one end of the gas extraction piping as the chemical distribution section 10a of the product extraction section 10 for extracting the gas as the chemical product R were connected to the top of the electric furnace. Furthermore, a gas inlet, serving as an inert gas supply unit 4, was connected to the bottom of the electric furnace. The other end of the gas extraction pipe was connected to the inlet side of a cooling trap 7a containing 15 mL of o-dichlorobenzene (reagent grade, manufactured by Kanto Chemical Co., Ltd.). The cooling trap 7a was installed in a cooling unit 7b containing ice water as the refrigerant 7d. One end of another gas extraction pipe was connected to the outlet side of the cooling trap 7a, and the other end of the other gas extraction pipe was connected to a gas bag (volume 10 L) serving as a gas product recovery unit 8. A thermocouple was inserted into the center of a filler packed in a quartz tube. Nitrogen gas, serving as the inert gas G, was blown in from the gas inlet at a flow rate of 1,600 mL / min, and the electric furnace temperature was set to 800°C to begin heating.

[0172] To confirm the behavior of granular media 2, a blank test was conducted by introducing only nitrogen gas as the inert gas G, without adding any raw materials. As a result, it was confirmed that the granular media 2 of Examples 1-3 and Comparative Example 1 all rose to a height of 7 cm from the sieve in the center of the quartz tube.

[0173] (Example 1) <Preparation of Mixed Plastic> Polyethylene (HDPE, High-Zex (registered trademark) 1300J, manufactured by Prime Polymer Co., Ltd.), polypropylene (Prime Polypro (registered trademark) J108M, manufactured by Prime Polymer Co., Ltd.), polystyrene (PSJ - Polystyrene (registered trademark) SGP10, manufactured by PS Japan Corporation), and polyethylene terephthalate (PET, NEH - 2070, manufactured by Unitika Ltd.) were mixed at a ratio of PE:PP:PS:PET = 32:32:20:16 (w / w) to prepare a mixed plastic.

[0174] <Decomposition of Mixed Plastic> The mixed plastic was decomposed using the apparatus described in Test Example 1. The granular medium 2 was prepared by adding 0.2 g of silica having pores (trade name: CARiACT (registered trademark) Q - 10, particle size 1.18 mm to 2.36 mm, specific surface area: 283 m ２ / g, pore volume: 1.0 cm －３ / g, average pore diameter: 10 nm, manufactured by Fuji Silysia Chemical Ltd.) to 5 g of silica sand (trade name: Ube Silica Sand No. 6, particle size: 0.6 mm to 0.07 mm, specific surface area: 1.3 m ３ / g, pore volume: 3.5×10 ２ cm ３ / g, average pore diameter: 4.2 nm, manufactured by Ube Sand Co., Ltd.). After the inside of the reactor 1 reached the set temperature of 800°C and the temperature became stable, 0.8 g of the mixed plastic was supplied into the quartz tube over 5 minutes from a manual powder feeder while introducing nitrogen gas at a flow rate of 1,600 mL / min from the gas inlet. Thereafter, the liquid component was recovered in the cooling trap 7b, and the gas component was collected in the gas bag. Five minutes after the supply of the mixed plastic was completed, the gas bag was detached from the apparatus. Also, after the cooling trap 7b was returned to room temperature (25°C ± 5°C) and about 3 minutes had elapsed, it was detached from the apparatus.

[0175] (Example 2) In Example 1, the decomposition of the mixed plastic was carried out in the same manner as in Example 1, except that the composition of the granular medium 2 was changed to 5 g of silica sand (trade name: Ube Silica Sand No. 6) and 0.4 g of silica having pores (trade name: CARiACT (registered trademark) Q - 10).

[0176] (Example 3) The mixed plastic was decomposed in the same manner as in Example 1, except that the composition of the granular medium 2 was changed to 5 g of silica sand (product name: Ube Silica Sand No. 6) and 0.8 g of porous silica (product name: CARiACT® Q-10).

[0177] (Comparative Example 1) The mixed plastic was decomposed in the same manner as in Example 1, except that the granular medium 2 was 5 g of silica sand (product name: Ube Silica Sand No. 6) and no porous silica (product name: CARiACT® Q-10) was added.

[0178] <<Analysis of granular media>> The specific surface area of ​​silica sand (Ube Silica Sand No. 6) and silica (CARiACT® Q-10) was measured in accordance with ISO 9277:2010 using a specific surface area analyzer (e.g., BELSORP® MAX II, manufactured by Microtrac-Bell Co., Ltd.) at liquid nitrogen temperature, with nitrogen molecules as the probe.

[0179] Furthermore, the pore volume and pore diameter of silica sand (Ube Silica Sand No. 6) and silica (CARiACT® Q-10) were measured in accordance with ISO 15901-2:2006 and analyzed by the BET method.

[0180] The particle size of the silica sand (Ube Silica Sand No. 6) is the value disclosed by the manufacturer.

[0181] <<Analysis of Gas Bag Contents>> In Examples 1 to 3 and Comparative Example 1, the yield (mass%) of useful components and by-products in the pyrolysis gas recovered in the gas bag was determined by the following method.

[0182] In the gas bag, cyclopentane (>98.0%, density 0.75 g / cm³) was used as an internal standard substance. ３40 μL of (manufactured by Tokyo Chemical Industry Co., Ltd.) was added. The gas bag was heated to approximately 40°C to completely vaporize the contents, and then the contents were mixed by gently kneading the gas bag. The obtained contents were used as an analytical sample and analyzed by gas chromatography (GC) under the following GC analysis conditions. The ratio of the peak area of ​​cyclopentane to the peak area of ​​each component was used to determine the proportion of each component (Cmol%) relative to carbon atoms in the pyrolysis gas in the gas bag. The mass of each component in the pyrolysis gas in the gas bag was calculated from this value and the amount of cyclopentane (40 μL) added to the gas bag, and the yield (mass%) relative to the mixed plastic added was determined. The results are shown in Table 1. [GC Analysis Conditions] ・Instrument: Nexus GC-2030 (Shimadzu Corporation) ・Column: Rt-Alumina BOND (Diameter: 0.32 mm, Length: 30 m, Restek) ・Carrier gas type: Ar ・Carrier gas flow rate: 360 mL / min ・Injection temperature: 200°C ・Sample injection volume: 1 mL ・Split ratio: 1 / 200 ・Column temperature: Held at 120°C for 9 minutes, then increased to 200°C at 10°C / min, and held at 200°C for 30 minutes.

[0183] • Detector: Flame ionization detector (FID) • Detector temperature: 200°C

[0184] <<Analysis of Cooling Trap Contents>> In Examples 1 to 3 and Comparative Example 1, the yield (mass%) of useful components and by-products in the pyrolysis components recovered in the cooling trap 7a was determined by the following method.

[0185] The contents of the cooling trap were transferred to a sample vial. Two mL of o-dichlorobenzene (reagent grade, manufactured by Kanto Chemical Co., Ltd.) was added to the nearly empty cooling trap 7a to dissolve the remaining contents, which were then transferred to the sample vial. This process was repeated three times to thoroughly wash the cooling trap 7a. Approximately 0.3 g of cyclopentane (>98.0%, manufactured by Tokyo Chemical Industry Co., Ltd.) was weighed and added to the sample vial as an internal standard to prepare the analytical sample, which was then analyzed by gas chromatography (GC) under the following GC analysis conditions. The ratio of the peak area of ​​cyclopentane to the peak area of ​​each component was used to determine the carbon-based percentage (Cmol%) of each component in the pyrolysis components in the cooling trap 7a. The mass of each component in the pyrolysis components in the cooling trap 7a was calculated from this value and the amount of cyclopentane added to the sample vial (0.3 g), and the yield (mass%) relative to the raw material M was determined. The results are shown in Table 1. [GC Analysis Conditions] • Instrument: Nexus GC-2030 (Shimadzu Corporation) • Column: DB-1 (Diameter: 0.25 mm, Length: 30 m, Agilent Technology) • Carrier Gas Type: He • Carrier Gas Flow Rate: 97 mL / min • Injection Temperature: 350°C • Sample Injection Volume: 1 μL • Split Ratio: 1 / 50 • Column Temperature: Temperature increase program set in the following order: 35°C (10 mins) → Increase (5°C / min) → 350°C (10 mins) • Detector: Flame Ionization Detector (FID) • Detector Temperature: 350°C

[0186] In Table 1, "Yield of useful components" and "Yield of by-products" refer to the ratio of the mass of each product listed in Table 1 to the mass of the mixed plastic added.

[0187] In Table 1, the "total yield of useful components" is the ratio of the total mass of olefins having 2 to 4 carbon atoms and useful aromatic hydrocarbons in the product to the mass of the mixed plastics input. "Useful components" represent ethylene, propylene, olefins having 4 carbon atoms (trans-2-butene, 1-butene, 2-methylpropene, cis-2-butene, 1,3-butadiene, and isobutene), and useful aromatic hydrocarbons (benzene, toluene, ethylbenzene, three positional isomers of xylene (p-xylene, m-xylene, and o-xylene), and styrene).

[0188] In Table 1, "D / C (NmL / cm ２ ·s)" represents the flow rate of the inert gas per unit cross-sectional area of 1 cm ２ at the lower end of the portion accommodating the granular medium 2 inside the reactor 1. "D" indicates the flow velocity of the inert gas (mL / min), and "C" indicates the cross-sectional area of the reactor 1 (cm ２ ). When calculating "D / C (NmL / cm ２ ·s)", in order to convert the unit of the flow velocity D of the inert gas to "NmL", the actual calculation formula is D / 60 / C.

[0189]

[0190] From the comparison between Examples 1 to 3 and Comparative Example 1, it was found that by adding silica having pores as an additive to the granular medium, the yields of ethylene and propylene were improved. In particular, in Examples 2 and 3 where the mass ratio [B / A] of the fluidizing material A and the additive B was 0.08 or more and 0.16 or less, the yields of ethylene and propylene were greatly improved.

[0191] As described above, this disclosure has been explained based on specific embodiments and examples, but these embodiments and examples are merely presented as examples, and this disclosure is not limited to the above embodiments and examples. The above embodiments can be implemented in various other forms, and various combinations, omissions, substitutions, additions, modifications, etc., are possible without departing from the spirit of the invention. These embodiments and their variations are included in the scope and spirit of the invention, as well as in the claims of the invention and its equivalents.

[0192] This international application claims priority under Japanese Patent Application No. 2024-226825, filed on 23 December 2024, which is incorporated herein by reference to the entire contents of Japanese Patent Application No. 2024-226825.

[0193] 100: Manufacturing equipment 1: Reactor 2: Granular medium 2A: Fluidized material 2B: Additives 3: Plastic supply section 3a: Raw material distribution section 3b: Raw material input section 4: Inert gas supply section 4a: Inert gas distribution section 4b: Pump 5: Heating section 6: Storage section 7: Cooling section 7a: Cooling trap 7b: Cold retention section 7c: Organic solvent 7d: Refrigerant 8: Gaseous product recovery section 9: Stopper 10: Product removal section 10a: Chemical distribution section 10a 10b: Pump M: Raw materials including plastic G: Inert gas R: Chemicals

Claims

1. A method for producing a chemical product, wherein the fluid material A and the pore volume are 0.01 cm³. ３ / g or more 10cm ３ A method for producing a chemical product, comprising: introducing an inert gas into a reactor containing a granular medium containing additive B at a concentration of 1 / g or less, and causing the granular medium to flow; heating the reactor; and supplying a raw material containing plastic to the heated reactor.

2. The specific surface area of ​​additive B is 20 m². ２ / g or more 3,000m ２ A method for producing a chemical product according to claim 1, wherein the amount is less than or equal to / g.

3. A method for producing a chemical product according to claim 1 or claim 2, wherein the additive B contains silica.

4. A method for producing a chemical product according to any one of claims 1 to 3, wherein the mass ratio [B / A] of the fluid material A to the additive B is 0.04 or more and 0.20 or less.

5. The method for producing a chemical product according to any one of claims 1 to 4, wherein the temperature of the reactor is 500°C or more and 1,000°C or less during the heating process.

6. A method for producing a chemical product according to any one of claims 1 to 5, wherein the raw material containing the plastic includes a mixed plastic containing polyethylene and polypropylene.

7. A method for producing a chemical product according to any one of claims 1 to 6, wherein the chemical product comprises ethylene and propylene.

8. Chemical manufacturing apparatus, wherein the fluid material A and the pore volume are 0.01 cm ３ / g or more 10cm ３ A chemical manufacturing apparatus comprising: a reaction furnace containing a granular medium containing additive B at a concentration of 1 / g or less; a plastic supply unit connected to the reaction furnace for supplying raw materials including plastic to the reaction furnace; an inert gas supply unit connected to one end of the reaction furnace and positioned to supply inert gas to the granular medium from a direction opposite to the direction of gravity; and a heating unit for heating the reaction furnace.

9. A granular medium used in a fluidized bed for the thermal decomposition of raw materials including plastics, comprising fluid material A and having a pore volume of 0.01 cm³. ３ / g or more 10cm ３ A granular medium characterized by containing additive B at a concentration of 1 / g or less.

10. The granular medium according to claim 9, wherein the raw material containing the plastic includes a mixed plastic containing polyethylene and polypropylene.

Images