WO2024157483A1 - 樹脂材料の熱分解処理方法、樹脂材料の熱分解処理システムおよびベント装置 - Google Patents

樹脂材料の熱分解処理方法、樹脂材料の熱分解処理システムおよびベント装置 Download PDF

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Publication number
WO2024157483A1
WO2024157483A1 PCT/JP2023/002737 JP2023002737W WO2024157483A1 WO 2024157483 A1 WO2024157483 A1 WO 2024157483A1 JP 2023002737 W JP2023002737 W JP 2023002737W WO 2024157483 A1 WO2024157483 A1 WO 2024157483A1
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Prior art keywords
resin material
heat exchanger
boiling point
cylinder
gas
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PCT/JP2023/002737
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English (en)
French (fr)
Japanese (ja)
Inventor
大吾 佐賀
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Japan Steel Works Ltd
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Japan Steel Works Ltd
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Publication date
Application filed by Japan Steel Works Ltd filed Critical Japan Steel Works Ltd
Priority to EP23918443.5A priority Critical patent/EP4640793A1/en
Priority to JP2024572814A priority patent/JPWO2024157483A1/ja
Priority to PCT/JP2023/002737 priority patent/WO2024157483A1/ja
Priority to TW112145355A priority patent/TW202432333A/zh
Publication of WO2024157483A1 publication Critical patent/WO2024157483A1/ja
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/10—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal from rubber or rubber waste
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J11/00—Recovery or working-up of waste materials
    • C08J11/04—Recovery or working-up of waste materials of polymers
    • C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
    • C08J11/12—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by dry-heat treatment only
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J11/00—Recovery or working-up of waste materials
    • C08J11/04—Recovery or working-up of waste materials of polymers
    • C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
    • C08J11/14—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with steam or water
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J11/00—Recovery or working-up of waste materials
    • C08J11/04—Recovery or working-up of waste materials of polymers
    • C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
    • C08J11/18—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material
    • C08J11/22—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material by treatment with organic oxygen-containing compounds
    • C08J11/24—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material by treatment with organic oxygen-containing compounds containing hydroxyl groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/10—Homopolymers or copolymers of propene
    • C08J2323/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers

Definitions

  • the present invention relates to a method for pyrolysis of resin materials, a system for pyrolysis of resin materials, and a vent device.
  • plastic products are used in a wide range of fields, and the amount of plastic used is enormous.
  • disposing of plastic products is costly, and the impact on the environment is also problematic when plastic products are left in the natural environment, causing their components to flow into rivers and oceans.
  • an object of the present invention is to provide a method and system for thermally decomposing a resin material, which are capable of continuously and efficiently carrying out the thermal decomposition of a resin material.
  • the method for thermally decomposing a resin material disclosed in this application includes the steps of: (a) thermally decomposing the resin material in a cylinder of an extruder having a screw; (b) after step (a), discharging a gas containing multiple components produced by the thermal decomposition of the resin material from a vent; (c) after step (b), cooling and liquefying a portion of the gas in a first heat exchanger; and (d) after step (c), cooling and liquefying the remainder of the gas in a second heat exchanger.
  • the resin material thermal decomposition processing system disclosed in this application has (a) an extruder and (b) a second heat exchanger.
  • the extruder has a cylinder into which the resin material is fed, a heat source section provided in the cylinder for thermally decomposing the resin material, a screw disposed within the cylinder for transporting the resin material, a vent section for discharging a gas containing multiple components generated within the cylinder as the resin material is thermally decomposed, and a first heat exchanger connected to the vent section for liquefying a portion of the gas, and the second heat exchanger cools and liquefies the remainder of the gas that passes through the first heat exchanger in gaseous form.
  • the extruder vent device disclosed in this application has a vent section connected to the extruder; and a heat exchanger provided in the vent section for cooling and liquefying a portion of the exhaust gas discharged from the vent section.
  • the method and system for thermal decomposition of resin materials disclosed in this application make it possible to continuously and efficiently thermally decompose resin materials such as waste plastics.
  • the extruder vent device disclosed in this application provides a vent device that is suitable for an extruder as a component used to efficiently perform pyrolysis in the pyrolysis processing method and pyrolysis processing system described above.
  • FIG. 1 is a diagram showing a schematic configuration of a thermal decomposition treatment system for a resin material in one embodiment
  • FIG. 2 is a diagram showing a schematic configuration of a cylinder used in the thermal decomposition treatment system for resin material in FIG. 1.
  • FIG. 2 is a diagram showing an outline of the internal structure of the vent device of FIG. 1.
  • FIG. 13 is a diagram showing the configuration of a thermal decomposition treatment system for a resin material in another embodiment.
  • FIG. 5 is a diagram showing a modified example of the resin material thermal decomposition treatment system of FIG. 4.
  • FIG. 13 is a diagram showing a schematic configuration of a thermal decomposition treatment system for a resin material in still another embodiment.
  • [Pyrolysis treatment system for resin materials] 1 is an explanatory diagram (side view) showing a schematic configuration of a resin material thermal decomposition treatment system 10 according to embodiment 1.
  • the resin material thermal decomposition treatment system 10 is an apparatus used for thermally decomposing a resin material to be thermally decomposed by heating it therein, separating monomers and low molecular weight compounds produced by the decomposition according to their properties (gas or liquid), and recovering or treating them.
  • This resin material thermal decomposition processing system 10 has a resin material supply section 11, a cylinder 12 with a screw, a rotation drive mechanism 13 that drives the screw of the cylinder 12, a vent device 14 consisting of a vent section 14a and a heat exchanger 14b, a heat exchanger 15, a liquid collection container 16, and a solid collection container 17.
  • the resin material supply unit 11 is a member that supplies the resin material to be decomposed to the cylinder 12.
  • thermoplastic resin or thermosetting resin is supplied as the resin material to be decomposed.
  • the resin material to be supplied may be in various forms such as pellets, powder, or flakes.
  • the resin material is fed from above into the resin material supply unit 11 having a hopper 11a by a feeder or the like, and is then supplied into the cylinder 12.
  • the cylinder 12 has a space formed therein for transporting the resin material, and has a screw 12a for transporting the resin material into that space.
  • Figure 2 shows a cross-sectional view of the cylinder 12 so that the internal structure of the cylinder 12 of the resin material thermal decomposition processing system 10 in Figure 1 can be seen.
  • the cylinder 12 is provided with an opening 12b so that gas generated within the cylinder 12 can be discharged to the outside of the cylinder 12, a tip 12c through which residue can be discharged, and multiple heaters (heat sources) 12d that can heat the cylinder 12 for each cylinder block, and these components form an extruder.
  • a vent device 14, which will be described in detail later, is provided in the opening 12b.
  • the cylinder 12 is, for example, constructed by connecting multiple cylinder blocks, and each cylinder block has a space inside that can transport the resin material.
  • a screw 12a is provided in this space, and the screw 12a is connected to a rotation drive mechanism 13. The screw 12a can be rotated by the rotation drive mechanism 13 to transport the resin material to be decomposed within the cylinder 12.
  • the cylinder 12 is also provided with a heat source such as a heater so that its temperature can be adjusted.
  • the resin material to be decomposed is transported from the resin material supply section 11 towards the tip 12c, during which time it is gradually heated by the heater or the like to become a molten, plasticized resin material.
  • the molten, plasticized resin material thus obtained can be easily transported within the cylinder 12, and is transported downstream while being further heated.
  • the heating temperature is gradually increased until the resin material is heated to a temperature at which it thermally decomposes.
  • the molten resin in the cylinder 12 may also be pressurized by the screw 12a, and heated and pressurized at the same time.
  • the thermal decomposition of the resin material can be further accelerated.
  • the resin material is then decomposed by thermal decomposition into monomers and other low molecular weight compounds that make up the resin. At this time, some of the low molecular weight compounds become gas inside the cylinder 12. This gas generally contains multiple components that are produced during the decomposition process of the resin material.
  • the tip 12c is the part that discharges the residue that remains in a molten state and does not become gas, among the decomposition products of the resin material that is transported inside the cylinder 12 and thermally decomposed, into the solid collection container 17.
  • This residue is a liquid material that has been heated to a high temperature, and if the resin material contains a filler or the like, it may be discharged in a state mixed with solids.
  • the rotary drive mechanism 13 is a device for rotating the screw 12a provided inside the cylinder 12. By using the screw rotated by the rotary drive mechanism 13, the resin material to be decomposed can be transported inside the cylinder 12.
  • twin-screw extruder with two screws in the cylinder 12, or a single-screw extruder with one screw.
  • twin-screw extruder the two screws are arranged parallel to each other and rotate.
  • the two shafts may be arranged so as to mesh with each other, or so as not to mesh with each other.
  • Twin-screw extruders have various advantages, such as high raw material transport efficiency and high kneading performance, and therefore, for the same screw diameter, twin-screw extruders with two screws are preferable to single-screw extruders with one screw because they can increase the extrusion volume. They also have the flexibility to freely change operating conditions such as the screw rotation speed and barrel temperature setting.
  • the extension direction of the cylinder 12 is the same as the extension direction of the screw inside the cylinder 12.
  • the vent device 14 is a device that includes a vent section 14a provided in the cylinder 12 and a heat exchanger 14b.
  • the vent section 14a is a member that exhausts the gas generated within the cylinder 12 to the outside of the cylinder 12, and may have a similar configuration to vent sections also provided in known extruders.
  • the vent section 14a is provided so that the gas is subjected to heat exchange processing in sequence by the heat exchanger 14b, which will be described next, and the heat exchanger 15, which will be described later.
  • the heat exchanger 14b is integrally provided above the vent section 14a to form the vent device 14.
  • This heat exchanger 14b is a device that has the function of cooling and liquefying a portion of the gas containing multiple components.
  • the temperature is controlled so that, among the multiple components, the components with high boiling points (high boiling point gas components) are liquefied, and the components with boiling points lower than those of the high boiling point gas components (low boiling point gas components) are allowed to pass through as gases.
  • the temperature of heat exchanger 14b can be controlled by supplying and discharging a refrigerant (cooling medium) maintained at a predetermined temperature to and from piping installed inside.
  • a refrigerant cooling medium
  • the flow of supply and discharge of this refrigerant is indicated by arrows.
  • the temperature of this refrigerant is controlled to be lower than the boiling point of the high boiling point gas components and higher than the melting point of the high boiling point gas components so that a portion of the refrigerant can be cooled and liquefied in heat exchanger 14b. This allows the high boiling point gas components to be cooled and liquefied by heat exchanger 14b.
  • the temperature of the refrigerant so that it is higher than the boiling point of the low-boiling-point gas components.
  • the remainder of the gas that passed through the heat exchanger 14b without being liquefied is supplied to the heat exchanger 15 through the pipe 18.
  • the vent device 14 can be installed at any position in the cylinder 12. In order to efficiently process the generated gas, it is preferable to install the vent device 14 at a location in the cylinder 12 where a large amount of gas is generated or downstream of the location where a large amount of gas is generated (toward the tip 12c of the cylinder 12).
  • Heat exchanger 15 is a device that cools and liquefies the gas (the remainder of the gas) that is not liquefied in heat exchanger 14b among the gas containing multiple components.
  • the temperature is controlled so as to liquefy the low-boiling point gas components among the multiple components.
  • the temperature of heat exchanger 15 can be controlled by supplying and discharging a refrigerant maintained at a predetermined temperature to and from the piping installed inside, similar to that of heat exchanger 14b.
  • a refrigerant maintained at a predetermined temperature to and from the piping installed inside, similar to that of heat exchanger 14b.
  • the flow of supply and discharge of this refrigerant is indicated by arrows.
  • the temperature of this refrigerant is controlled to be lower than the boiling point of the low-boiling gas components and higher than the melting point of the low-boiling gas components as described above, so that the remaining gas can be cooled and liquefied in heat exchanger 15.
  • the low-boiling gas components are cooled and liquefied in heat exchanger 15.
  • the low-boiling gas components become liquid and can be separated, so they can be recovered as liquid.
  • the temperature of the refrigerant is lower than the melting point of the high boiling point gas components.
  • the conditions for the generation of solids in the heat exchanger, which has been an issue in the past, can occur.
  • the high boiling point gas components are not included in the gas (remaining part of the gas) processed in the heat exchanger 15, so such a problem does not occur.
  • this heat exchanger 15 liquefies low boiling point gas components, but if multiple low boiling point gas components are included, some of them may be liquefied and the gas components with lower boiling points may be released into the atmosphere or may be subjected to other treatment such as exhaust gas treatment equipment. Release into the atmosphere should be performed only when it does not adversely affect the environment.
  • the gas components liquefied by the heat exchanger 15 are stored in the liquid recovery container 16 through piping 19.
  • the temperature of the refrigerant in the heat exchangers 14b and 15 can be controlled by providing a control unit that manages the temperatures and maintains the respective set temperatures (for example, the temperatures at which the high boiling point gas components and the low boiling point gas components can be liquefied as described above).
  • the liquid recovery container 16 is a container that stores the components liquefied by the heat exchanger 15.
  • This liquid recovery container 16 may be made of a material that can stably store the liquefied components.
  • the liquid recovery container 16 may be an open system to the atmosphere or a closed system. In cases where the recovered liquid may be altered or other problems may occur due to contact with air, it is preferable to use a closed system.
  • the solid collection container 17 is a container that collects the residual resin material that is not gasified by pyrolysis caused by heating in the cylinder 12 and is discharged from the tip 12c of the cylinder 12.
  • the residue collected in this solid collection container 17 is in a molten state (liquid) heated to a high temperature, and if the resin material contains a filler or the like, it is discharged as a liquid mixed with solids. On the other hand, when this residue is discharged into the solid collection container 17, it gradually cools and solidifies inside the solid collection container 17, and the solid residue gradually accumulates at the bottom of the solid collection container 17.
  • This solid collection container 17 may be made of a material capable of stably storing the liquid flowing out from the tip 12c of the cylinder 12 and the cooled and solidified solid.
  • the solid collection container 17 may be either an open system to the atmosphere or a closed system. If contact with air could cause the residue to deteriorate or pose a risk of combustion, a closed system is preferable.
  • a cooling source may also be provided to promote the solidification of the residue.
  • the resin material is thermally decomposed in the cylinder 12 of the extruder (step (a); thermal decomposition step).
  • step (a) the resin material to be decomposed is supplied to the inside of the cylinder 12 of the thermal decomposition processing system 10 via the resin material supply section 11, and is heated in the cylinder 12 to thermally decompose the resin material.
  • the resin material supplied into the cylinder 12 is gradually heated and thermally decomposed as it is transported inside the cylinder 12 toward the tip 12c by the screw 12a.
  • the resin product to be supplied for decomposition is not particularly limited as long as it is a resin that can be thermally decomposed by heating, and examples of such resin materials include polyethylene (PE) resin, polypropylene (PP) resin, polyamide 6 (PA6) resin, polycarbonate (PC) resin, polyethylene terephthalate (PET) resin, polybutylene terephthalate (PBT) resin, etc.
  • PE polyethylene
  • PP polypropylene
  • PA6 polyamide 6
  • PC polycarbonate
  • PET polyethylene terephthalate
  • PBT polybutylene terephthalate
  • a heat source such as a heater is provided on the outer periphery of the cylinder 12, and the resin material is gradually heated to a high temperature by the heater as it is transported. In addition, by being heated, the resin material becomes molten and plasticized, so that it can be easily transported by the screw 12a.
  • the heating temperature in this thermal decomposition varies depending on the resin material used, but it is preferable to heat the resin to a temperature of, for example, about 250 to 400°C. Pressurization may also be applied in this thermal decomposition process. Pressurization is preferable because it makes it easier for the thermal decomposition to proceed. If pressurization is applied, it is preferable to apply pressure so that the internal pressure is 0.3 to 20.0 MPa.
  • the gas produced by the thermal decomposition of the resin material inside the cylinder 12 is exhausted to the outside of the cylinder 12.
  • the resin material is decomposed as in this embodiment, the resin material is heated and thermally decomposed, that is, the chemical bonds of the resin that constitutes the resin are broken and the resin is converted into smaller molecules, resulting in the production of a large amount of gas.
  • the gas thus generated is the gas to be treated in this embodiment, and the generated gas is exhausted to the outside of the cylinder 12 from the opening 12a.
  • Publicly known extruders are also provided with a vent section for exhausting gas generated within the cylinder, and a vent section 14a may be provided in a similar manner for exhausting the gas.
  • This vent section 14a is provided so as to be disposed at the opening 12a of the cylinder 12, so that the gas inside the cylinder 12 can be exhausted from this opening 12a through the vent section 14a to the outside of the cylinder 12.
  • a heat exchanger 14b is provided in the vent section 14a to constitute the vent device 14.
  • the gas exhausted from the vent 14a is introduced directly into the heat exchanger 14b.
  • this heat exchanger 14b a portion of the gas containing multiple components is cooled and liquefied, and the remainder is allowed to pass through in its gaseous form (step (c); liquefaction step 1).
  • a gas containing multiple components has a unique boiling point for each of the components contained in the gas, and the gas contains a mixture of components with relatively high boiling points (high boiling point gas components) and components with boiling points lower than those of the high boiling point gas components (low boiling point gas components).
  • the heat exchanger 14b is controlled to a temperature at which the high boiling point gas components liquefy. Specifically, the temperature of the heat exchanger 14b is controlled to a temperature lower than the boiling point of the high boiling point gas components and higher than the melting point of the high boiling point gas components. As a result, the high boiling point gas components are cooled in the heat exchanger 14b and become liquid.
  • heat exchanger 14b it is preferable to control the temperature of heat exchanger 14b so that it is higher than the boiling point of the low boiling point gas components.
  • the temperature of heat exchanger 14b it is possible to separate the high boiling point gas components from the low boiling point gas components, and it is particularly preferable to prevent the high boiling point gas components from being included in the gas supplied to heat exchanger 15.
  • the remainder of the gas that passes through heat exchanger 14b without being liquefied is supplied to heat exchanger 15 through pipe 18.
  • step (c) the gas that was not liquefied in step (c) (the remainder of the gas) is introduced into heat exchanger 15, where the gas is cooled and liquefied (step (d); liquefaction step 2). That is, here, the temperature is controlled so as to liquefy the low boiling point gas components among the multiple components. As a result, the low boiling point gas components are cooled in heat exchanger 15 and become liquid.
  • the temperature of the heat exchanger 15 is lower than the melting point of the high boiling point gas components.
  • the conditions for solidification in the heat exchanger which has been an issue in the past, can occur.
  • the high boiling point gas components are not included in the gas (remaining part of the gas) processed by the heat exchanger 15, so such a problem does not occur.
  • the liquid thus obtained in step (d) is stored in the liquid recovery container 16 and recovered.
  • the liquid recovered here can be used as a raw material (monomer) for the production of new resin (polymerization reaction) or as a material for other reactions, or it can be disposed of by subjecting it to the appropriate disposal treatment.
  • the high boiling point gas components and low boiling point gas components can be determined arbitrarily depending on the purpose. If three or more types of components are mixed in the gas, in step (d), some may be liquefied and the gas components with lower boiling points may be allowed to pass through as is and released into the atmosphere, or may be subjected to other treatment such as an exhaust gas treatment device. Release into the atmosphere should be performed only when it does not adversely affect the environment.
  • the gas components liquefied in the heat exchanger 15 are stored in the liquid recovery container 16 through piping 19.
  • step (d) if gas components with lower boiling points are passed through heat exchanger 15, a similar liquefaction process can be carried out one or more times to separate each component in turn.
  • the residue that is not gasified from the resin material that has been treated by pyrolysis in the cylinder 12 moves as a heated liquid through the cylinder 12 to the tip 12c, and is discharged from the tip 12c into the solid collection container 17.
  • the discharged residue is gradually cooled in the solid collection container 17 and solidifies.
  • Heat exchanger function The configurations and operations of the heat exchanger 14b and the heat exchanger 15 have already been described above, but will be described in more detail below with reference to FIG.
  • FIG. 3 is a cross-sectional view showing the internal structure of the vent device 14.
  • the vent section 14a is provided in the cylinder 12, and is a member that receives the gas generated in the cylinder 12 and introduces it to the heat exchanger 14b.
  • Heat exchanger 14b has a lower opening 141 that connects to vent portion 14a, and an upper opening 142 that connects to heat exchanger 15 via piping. Heat exchanger 14b also has a refrigerant inlet 143 that introduces refrigerant into the interior, a refrigerant circulation pipe 144 that circulates the introduced refrigerant, and a refrigerant outlet 145 that discharges the refrigerant after it has circulated through refrigerant circulation pipe 144.
  • gas containing multiple components generated in the cylinder 12 is introduced into the heat exchanger 14b from the lower opening 141 via the vent portion 14a. Part of the introduced gas is liquefied, and the remainder passes through in gas form. The components that are liquefied at this time are determined by the temperature of the heat exchanger 14b, and this temperature is controlled by the temperature of the refrigerant used.
  • heat exchanger 14b acts as follows:
  • the gas comes into contact with the refrigerant flow pipe 144 (indirectly comes into contact with the refrigerant), and the high-boiling-point gas components contained in the gas are cooled and liquefied, and the liquefied high-boiling-point gas components drip downward due to the action of gravity.
  • the dripped liquid moves in the opposite direction to the gas flow direction, returns to the cylinder 12 via the lower opening 141 and vent section 14a, and is remixed into the heated molten material.
  • the low-boiling-point gas components in the gas are not liquefied even when they come into contact with the refrigerant flow pipe 144 (indirectly come into contact with the refrigerant), but are discharged as a gas from the upper opening 142 and sent to the heat exchanger 15 via the pipe 18.
  • the temperature control of this heat exchanger 14b is appropriately determined depending on the type of resin material to be thermally decomposed, but is controlled to a relatively high temperature of 100°C or higher. For this reason, a fluid that can be circulated as a liquid even at high temperatures of 100°C or higher, such as oil, is used as the refrigerant.
  • a fluid that can be circulated as a liquid even at high temperatures of 100°C or higher such as oil
  • the refrigerant inlet 143 and refrigerant outlet 145 are generally connected to a thermal oil unit, and the heat exchanger 14b is configured to be controlled to a predetermined temperature while circulating the oil for the refrigerant by this thermal oil unit.
  • the heat exchanger 14b By providing the heat exchanger 14b directly above the vent section 14a and allowing the liquefied components to fall directly back into the cylinder 12 as described above, the high boiling point gas components are remixed with the molten material in the cylinder 12, further advancing the decomposition into smaller molecules through thermal decomposition.
  • This configuration is preferable as it allows for more efficient thermal decomposition.
  • Heat exchanger 15 may have a similar configuration to heat exchanger 14b, although the controlled temperature is different. However, unlike heat exchanger 14b, an outlet is provided for the liquefied gas components, separate from the inlet for the gas (remaining part of the gas), so that the liquid is discharged. In this regard, it is preferable to use a heat exchanger 15 having a general configuration as a known heat exchanger. Furthermore, if gas that was not liquefied in heat exchanger 15 is included, a further outlet is provided to separate the liquid and gas components.
  • the gas comes into contact with the refrigerant flow pipe (indirectly comes into contact with the refrigerant), and the low-boiling-point gas components contained in the gas are cooled and liquefied.
  • the liquefied low-boiling-point gas components are sent to the liquid recovery container 16.
  • all of the components in the gas containing the low boiling point gas components may be liquefied, or a portion of them may be liquefied and recovered, and the components with boiling points even lower than the low boiling point compounds may be exhausted as gas.
  • the exhaust may be released into the atmosphere as long as it does not have a negative impact on the environment, or it may be recovered and reused or disposed of.
  • this heat exchanger 15 is controlled appropriately depending on the type of resin material to be thermally decomposed, but is controlled to a relatively low temperature of less than 100°C. Therefore, the refrigerant used here can be water, which is a commonly used refrigerant, and generally the refrigerant inlet and outlet are configured to circulate while being controlled to a predetermined temperature by a chiller unit or the like.
  • PC Polycarbonate
  • the temperature of heat exchanger 14b is set to 182°C or higher and lower than 220°C to liquefy bisphenol A, and the temperature of heat exchanger 15 is set to less than 182°C to liquefy phenol.
  • the temperature of heat exchanger 15 is set to 100°C or higher and lower than 182°C, it is possible to recover phenol as a liquid and release water (steam) into the atmosphere.
  • the temperature of the heat exchanger 14b is set to 100° C. or higher and lower than 267° C. to liquefy caprolactam
  • the temperature of the heat exchanger 15 is set to lower than 100° C. to liquefy water vapor.
  • the resin material to be thermally decomposed is polyethylene terephthalate (PET)
  • PET polyethylene terephthalate
  • water or ethylene glycol is added as a reaction aid or additive, and the thermal decomposition process is carried out in the cylinder 12.
  • the temperature of the cylinder 12 is heated to, for example, 255 to 320°C to allow the thermal decomposition process to proceed.
  • the temperature of heat exchanger 14b is set to 244°C or higher and lower than 317°C to liquefy bis(2-hydroxyethyl) terephthalate, and the temperature of heat exchanger 15 is set to less than 244°C to liquefy ethylene glycol.
  • polyethylene (PE) and polypropylene (PP) are decomposed into many types of hydrocarbon compounds with different carbon numbers.
  • Examples of the hydrocarbons that are gasified at this time include the compounds shown in Table 1, which also shows the melting points and boiling points of these hydrocarbon compounds.
  • the gas generated in the cylinder 12 contains many types of hydrocarbon compounds with carbon numbers between 1 and 21 as described above. Depending on the temperature conditions, hydrocarbon compounds with a large number of carbon numbers are not gasified in the cylinder 12 but remain in a molten state, and are discharged from the tip 12c of the cylinder 12 into the solid collection container 17 and collected.
  • the generated gas is first introduced into the heat exchanger 14b as described above.
  • the high boiling point gas component to be liquefied can be any compound, but it may be determined taking into consideration the control temperature in the next heat exchanger 15. For example, if the control temperature in the heat exchanger 15 is 15°C, and the gas component cooled in the heat exchanger 15 has a melting point of 15°C or higher, solid matter will precipitate in the heat exchanger 15.
  • the high boiling point gas component liquefied in heat exchanger 14b it is preferable to set to a hydrocarbon having a carbon number of 16 (hexadecane, chemical formula: C16H34 ).
  • hexadecane since hexadecane is liquefied in heat exchanger 14b, hexadecane is not included in the gas components introduced into heat exchanger 15. Therefore, even if the control temperature of heat exchanger 15 is set to 15°C, no components with melting points of 15°C or higher are included, and therefore no components solidify in heat exchanger 15, thereby preventing the above-mentioned problems from occurring.
  • the controlled temperature of the heat exchanger 14b may be, for example, a temperature above the melting point and below the boiling point (18°C or higher and less than 287°C).
  • a temperature above the melting point and below the boiling point (18°C or higher and less than 287°C).
  • compounds with similar molecular weights, melting points, and boiling points are included. Therefore, it is preferable to efficiently liquefy the target compound and avoid mixing in compounds with lower boiling points than the target compound as much as possible, so as not to mix in unnecessary compounds. Therefore, it is preferable to control the temperature of the heat exchanger 14b when performing thermal decomposition under the above conditions to about 230 to 260°C.
  • the hydrocarbon compounds with 16 or more carbon atoms are returned to the cylinder 12 and remixed with the molten material in the extruder. When remixed, they receive thermal energy again in the heated cylinder 12, and are further thermally decomposed into hydrocarbon compounds with 15 or less carbon atoms.
  • FIG. 4 is an explanatory diagram (side view) showing a schematic configuration of a resin material thermal decomposition processing system 20 according to the second embodiment.
  • the resin material thermal decomposition processing system 20 has the same configuration as the resin material thermal decomposition processing system 10 shown in FIG. 1 described above, except that it has two sets of a vent device 14, a heat exchanger 15, and a liquid collection container 16.
  • the resin material thermal decomposition processing system 20 shown in Figure 4 has a resin material supply section 11, a cylinder 12 having a screw, a rotation drive mechanism 13 that drives the screw of the cylinder 12, a vent device 14 consisting of a vent section 14a and a heat exchanger 14b, a heat exchanger 15, a liquid recovery container 16, and a solid recovery container 17.
  • the elements that make up the device are the same as those in the above embodiment. Below, explanations of the same configuration as those already explained will be omitted, and differences will be mainly described in detail.
  • this resin material thermal decomposition processing system 20 differs from the resin material thermal decomposition processing system 10 in that it is provided with two sets of vent devices 14, heat exchangers 15, and liquid collection containers 16.
  • the resin material thermal decomposition processing system 20 has an upstream vent device 14 and a downstream vent device 14.
  • the gas generated in the cylinder 12 is first heat exchanged in the upstream vent device 14, a portion of it is liquefied and remixed in the cylinder 12, and the remainder is sent to the heat exchanger 15.
  • the liquefied and remixed components are compounds that have not been sufficiently broken down into smaller molecules, and are further thermally decomposed in cylinder 12 to become even smaller molecules.
  • the monomers and low molecular weight compounds that are remixed in this way and then thermally decomposed again are then heat exchanged in downstream vent device 14, and some of them are liquefied and remixed in cylinder 12, while the remainder is sent to heat exchanger 15.
  • the upstream vent device 14 removes the components that have been sufficiently broken down into smaller molecules from the cylinder 12, and the components that have not been sufficiently broken down into smaller molecules are returned into the cylinder 12 to be subjected to pyrolysis again. Then, the downstream vent device 14 removes the components that have been sufficiently broken down into smaller molecules from the cylinder 12, and the components that have not been sufficiently broken down into smaller molecules are returned into the cylinder 12.
  • the relative positions of the upstream vent device 14 and the downstream vent device 14 can be determined arbitrarily depending on the thermal decomposition state of the resin material inside the cylinder 12. If the two vent devices 14 are placed too close to each other, the above-mentioned effect cannot be fully exerted, so it is preferable to ensure that there is enough time for the resin to be broken down into smaller molecules again.
  • the upstream vent device 14 and the downstream vent device 14, and the upstream heat exchanger 15 and the downstream heat exchanger 15 may be controlled to the same temperature for processing, or may be controlled to different temperatures for processing.
  • the resin material thermal decomposition treatment system 30 can be configured to treat the gas discharged from two vent devices 14 in a single heat exchanger 15, as compared to the resin material thermal decomposition treatment system 20 in Figure 4 described above.
  • This resin material thermal decomposition processing system 30 has a resin material supply section 11, a cylinder 12 with a screw, a rotation drive mechanism 13 that drives the screw of the cylinder 12, a vent device 14 consisting of a vent section 14a and a heat exchanger 14b, a heat exchanger 15, a liquid collection container 16, and a solid collection container 17.
  • the elements that make up the device are the same as those in the above embodiment.
  • FIG. 6 is an explanatory diagram (side view) showing a schematic configuration of a resin material thermal decomposition processing system 40 according to the third embodiment.
  • the resin material thermal decomposition processing system 40 has the same configuration as the resin material thermal decomposition processing system 10 shown in FIG. 1 described above, except that the heat exchanger 14b of the vent device 14 is separated from the vent section 14a and connected via piping.
  • the resin material thermal decomposition processing system 40 shown in Figure 6 has a resin material supply section 11, a cylinder 12 having a screw, a rotation drive mechanism 13 that drives the screw of the cylinder 12, a vent section 14a, a heat exchanger 15, a liquid recovery container 16, a solid recovery container 17, a heat exchanger 41, and a liquid recovery container 42.
  • the elements that make up the device are the same as those in the above embodiment. Below, explanations of the same configuration as those already explained will be omitted, and differences will be mainly described in detail.
  • this resin material thermal decomposition processing system 40 differs from the resin material thermal decomposition processing system 10 in that the vent section 14a and the heat exchanger 14b are separated and provided as separate elements. That is, a heat exchanger 41 is provided in place of the heat exchanger 14b, the vent section 14a and the heat exchanger 41 are connected by a pipe 43, and the liquid recovery container 42 is connected to the heat exchanger 41 by a pipe 44. Furthermore, the heat exchanger 41 is connected to the heat exchanger 15 via a pipe 18.
  • the gas exhausted from the vent section 14a is introduced into the heat exchanger 41 via piping 43, where the high boiling point gas components are cooled and liquefied.
  • the liquefied high boiling point gas components are recovered in the liquid recovery container 42 via piping 44.
  • the remainder of the gas that was not liquefied in the heat exchanger 41 is sent to the heat exchanger 15 via piping 18. Subsequent processing is the same as in the above embodiment.
  • gas is introduced into the heat exchanger 15 with the solidifying components removed, so problems such as blockage of the heat exchanger 15 can be avoided. Furthermore, by making the vent portion 14a and the heat exchanger 41 separate in this way, cleaning of each component is easier, improving maintainability, and reducing maintenance costs.
  • liquid high-boiling-point gas components are collected in the liquid collection container 42, but it is also possible to return this to the cylinder 12 and perform the thermal decomposition process again.
  • Resin material pyrolysis treatment system 11 Resin material supply section 12 Cylinder 12a Screw 12b Opening 12c Tip section 13 Rotation drive mechanism 14 Vent device 14a Vent section 14b, 15, 41 Heat exchanger 16, 42 Liquid recovery container 17 Solid recovery container 18, 19, 43, 44 Piping

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Development (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Physics & Mathematics (AREA)
  • Wood Science & Technology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Thermal Sciences (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
  • Processing Of Solid Wastes (AREA)
PCT/JP2023/002737 2023-01-27 2023-01-27 樹脂材料の熱分解処理方法、樹脂材料の熱分解処理システムおよびベント装置 Ceased WO2024157483A1 (ja)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP23918443.5A EP4640793A1 (en) 2023-01-27 2023-01-27 Resin material thermal decomposition treatment method, resin material thermal decomposition treatment system, and vent device
JP2024572814A JPWO2024157483A1 (https=) 2023-01-27 2023-01-27
PCT/JP2023/002737 WO2024157483A1 (ja) 2023-01-27 2023-01-27 樹脂材料の熱分解処理方法、樹脂材料の熱分解処理システムおよびベント装置
TW112145355A TW202432333A (zh) 2023-01-27 2023-11-23 樹脂材料的熱分解處理方法、樹脂材料的熱分解處理系統及排氣裝置

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PCT/JP2023/002737 WO2024157483A1 (ja) 2023-01-27 2023-01-27 樹脂材料の熱分解処理方法、樹脂材料の熱分解処理システムおよびベント装置

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5118996B1 (https=) * 1971-05-10 1976-06-14
JPH06316695A (ja) * 1991-10-09 1994-11-15 Norio Mitsui 廃プラスチックの油化方法
JPH07207278A (ja) * 1994-01-25 1995-08-08 Chiba Fine Chem Kk 廃プラスチックの熱分解油化方法
JPH07331251A (ja) * 1994-06-08 1995-12-19 Kubota Corp プラスチックの熱分解油化装置および熱分解油化方法
JP2005349838A (ja) 2005-08-12 2005-12-22 Japan Steel Works Ltd:The 廃プラスチックの処理装置
JP2008302555A (ja) 2007-06-06 2008-12-18 Japan Steel Works Ltd:The 廃プラスチックの処理方法及びその装置

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5118996B1 (https=) * 1971-05-10 1976-06-14
JPH06316695A (ja) * 1991-10-09 1994-11-15 Norio Mitsui 廃プラスチックの油化方法
JPH07207278A (ja) * 1994-01-25 1995-08-08 Chiba Fine Chem Kk 廃プラスチックの熱分解油化方法
JPH07331251A (ja) * 1994-06-08 1995-12-19 Kubota Corp プラスチックの熱分解油化装置および熱分解油化方法
JP2005349838A (ja) 2005-08-12 2005-12-22 Japan Steel Works Ltd:The 廃プラスチックの処理装置
JP2008302555A (ja) 2007-06-06 2008-12-18 Japan Steel Works Ltd:The 廃プラスチックの処理方法及びその装置

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP4640793A1

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