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WO2023032494A1 - Procédé de décomposition de substances organiques halogénées et système de décomposition de substances halogénées - Google Patents

Procédé de décomposition de substances organiques halogénées et système de décomposition de substances halogénées Download PDF

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Publication number
WO2023032494A1
WO2023032494A1 PCT/JP2022/028088 JP2022028088W WO2023032494A1 WO 2023032494 A1 WO2023032494 A1 WO 2023032494A1 JP 2022028088 W JP2022028088 W JP 2022028088W WO 2023032494 A1 WO2023032494 A1 WO 2023032494A1
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Prior art keywords
halogen
compound
containing organic
decomposing
gas
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English (en)
Japanese (ja)
Inventor
利正 大橋
剛 伊藤
祐子 可児
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Hitachi Ltd
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Hitachi Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/745—Iron
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/20—Carbon compounds
    • B01J27/232—Carbonates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
    • B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
    • B09B3/40—Destroying solid waste or transforming solid waste into something useful or harmless involving thermal treatment, e.g. evaporation
    • 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
    • C08J11/16—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 inorganic material
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/62—Plastics recycling; Rubber recycling

Definitions

  • the present invention relates to a method for decomposing halogen-containing substances and a system for decomposing halogen-containing substances.
  • PE Polyethylene
  • PP polypropylene
  • PS polystyrene
  • PVC polyvinyl chloride
  • waste containing these general-purpose plastics has been decomposed by burning and reduced in volume.
  • the combustion becomes incomplete, and a large amount of residue remains, and a sufficient volume reduction effect cannot be obtained in some cases.
  • polymers containing chlorine, such as PVC generate dioxins when burned at a low temperature of about 300.degree.
  • PVC polymers containing chlorine
  • Patent Document 1 a compound to be decomposed (an organic compound such as polycarbonate) is brought into contact with a semiconductor powder such as TiO 2 at a temperature of 100° C. to 600° C. in the presence of oxygen to oxidatively decompose the compound. A method to do so is proposed.
  • Patent Document 2 discloses a process of coating a semiconductor having a thermally active effect on the surface of an object to be treated (containing sulfur, halogen, and silicon as components), and treating the object to be treated, the surface of which is coated with a semiconductor, in an air atmosphere.
  • a method is disclosed having a decomposition treatment step of decomposing the object to be treated into water and carbon dioxide gas by heating the semiconductor to a temperature higher than the temperature at which the semiconductor is thermally activated.
  • halogen-containing organic polymers such as PVC are stable compounds among organic compounds, and require heating at 500-600°C to burn out.
  • Patent Documents 1 and 2 the effect of lowering the combustion temperature is not sufficient even if the semiconductor powder is brought into contact with the halogen-containing organic material such as PVC. I understand.
  • One aspect of the present invention for achieving the above object includes a contact step of contacting a first compound and a second compound with an object to be treated, which is an organic substance containing halogen; and a heating step of heating and decomposing the contacted object to be processed in an atmosphere containing oxygen, wherein the first compound includes an oxide semiconductor, and the second compound is included in the object to be processed.
  • Another aspect of the present invention for achieving the above object is a reaction tank in which an object to be treated which is an organic substance containing halogen, a first compound, and a second compound are brought into contact with each other; and a gas supply unit for supplying a gas containing oxygen into the reaction vessel, wherein the first compound includes an oxide semiconductor, and the second compound is included in the object to be processed
  • the reaction vessel , the reaction in which the halogen contained in the object to be treated and the element contained in the second compound combine to form a halide is the reaction in which the object to be treated is thermally decomposed in the heat treatment by the heating device to produce hydrogen halide.
  • a decomposing system for halogen-containing organic substances characterized in that the reaction takes place preferentially over the reaction to produce.
  • the method for decomposing a halogen-containing organic substance and the system for decomposing a halogen-containing organic substance can significantly lower the heat treatment temperature for decomposing a halogen-containing organic substance. It can provide a decomposition system for things.
  • Example 1 Schematic configuration diagram of the halogen-containing organic matter decomposition system of Example 1 Graph showing measurement results of thermogravimetric analysis of sample A (PVC) Graph showing the temperature change of the sample during the measurement of Figure 3 Graph showing the measurement results of thermogravimetric analysis of sample B (a sample in which TiO 2 was brought into contact with PVC) A graph showing the temperature change of the sample during the measurement of FIG. Graph showing measurement results of thermogravimetric analysis of sample C (sample in which TiO 2 and Fe 2 O 3 are brought into contact with PVC) A graph showing the temperature change of the sample during the measurement of FIG.
  • halogen-containing organic matter decomposition method may be simply referred to as “decomposition method”
  • halogen-containing organic matter decomposition system may simply be referred to as “decomposition system”.
  • the first compound containing an oxide semiconductor is reacted with the halogen-containing object to be processed, and the halogen contained in the object to be processed to generate a halide.
  • a second compound containing an element that does not react is brought into contact and heated in an oxygen-containing atmosphere.
  • the technical significance of each of the first compound and the second compound will be explained.
  • the oxide semiconductor contained in the first compound is heated, holes (h + ) and electrons (e ⁇ ) are generated inside the oxide semiconductor due to thermal excitation.
  • the h + generated by thermal excitation has a strong oxidizing power, and decomposes the halogen-containing organic matter in contact with the oxide semiconductor into combustible low molecules. This enables low-temperature combustion of halogen-containing organics.
  • halogen-containing organic substances desorb hydrogen halides by heating and change to stable polymers with double bonds.
  • this desorption reaction of hydrogen halide is an endothermic reaction, it takes heat from the surroundings and inhibits combustion.
  • the endothermic reaction produces HCl. Due to the effect of this stabilization and endothermic reaction, the effect of lowering the combustion temperature of the halogen-containing organic substance is not sufficient just by bringing it into contact with the oxide semiconductor contained in the first compound and heating it.
  • a second compound containing an element that reacts with the halogen contained in the object to be processed to produce a halide is brought into contact with the halogen-containing organic substance together with the first compound.
  • the reaction in which the element in the second compound and the halogen in the halogen-containing organic compound combine to form a halide is an exothermic reaction that occurs preferentially over the desorption of the hydrogen halide. While suppressing the endothermic reaction, the action of the oxide semiconductor decomposes the halogen-containing organic matter into easily combustible low-molecular substances. This allows for low temperature combustion.
  • the combustion of the halogen-containing organic polymer is promoted, and the treatment temperature can be significantly increased compared to conventional methods. can be lowered (250° C.).
  • the degree of reduction in the treatment temperature and the amount of heat generated vary depending on the type and amount of the element that reacts with the halogen contained in the oxide semiconductor and the second compound to produce a halide. can also be processed at significantly lower temperatures.
  • the treatment temperature can be lowered.
  • Calorific value when both the first compound and the second compound are used> The temperature of the object to be treated is raised to a temperature at which halogen-containing organic substances that have not been reduced in molecular weight burn (500° C. in the case of PVC) calorific value necessary for > calorific value in the case of the first compound (oxide semiconductor) alone
  • the heating temperature can be lowered to about 250°C.
  • the heat treatment can be performed at a temperature of 500.degree. C. or lower, preferably in the range of 200.degree.
  • oxide semiconductor In the oxide semiconductor, electrons in the oxide semiconductor are easily excited, that is, the bandgap is not too wide, and the oxidizing power of holes generated by the excitation of electrons is sufficiently large, that is, the bandgap is not too narrow. is desirable. Therefore, an oxide semiconductor having a bandgap of 2.5 eV or more and 3.5 eV or less is desirable as an oxide semiconductor, and one or more selected from these oxide semiconductors is used. Examples include TiO 2 , ZnO, SrTiO 3 , BaTiO 3 , Cr 2 O 3 , Nb 2 O 5 , SnO 2 , In 2 O 3 and WO 3 . By using these oxide semiconductors, decomposition of the halogen-containing organic polymer can be promoted and the treatment temperature can be sufficiently lowered.
  • an element contained in the second compound that combines with the halogen in the halogen-containing organic material to form a halide an element whose Gibbs energy of the halide is lower than that of the oxide is preferable.
  • examples include alkali metals, alkaline earth metals, Fe, Cu, Ag and Cr.
  • an element that can be easily used as the second compound by becoming an oxide by decomposition treatment is particularly preferable, and an oxide, hydroxide or carbonate containing one or more selected from Fe, Cu, Ag and Cr. is desirable.
  • the element contained in the second compound preferentially reacts with the halogen-containing organic matter to form a halide, thereby suppressing detachment of hydrogen halide from the halogen-containing organic matter and promoting decomposition of the halogen-containing organic matter. can sufficiently reduce the processing temperature.
  • wastes containing halogen-containing organic substances to be treated include polymers containing chlorine such as PVC and polyvinylidene chloride, and polymers containing fluorine such as polyvinyl fluoride. and wastes containing organic polymers containing halogens. Also, a mixture of a plurality of types of organic polymers, such as a mixture of PVC and other organic polymers, may be used.
  • the amount of non-organic substances be as small as possible in the target waste.
  • the contact area between the halogen-containing organic substance and the first compound and the second compound is reduced, and the thermal decomposition reaction of the halogen-containing organic substance is less likely to occur.
  • the heat generated by the thermal decomposition reaction of the halogen-containing organic substances is also consumed to warm the substances other than the organic substances, resulting in an increase in the temperature of the halogen-containing organic substances to be decomposed. does not occur sufficiently, and heating at a higher temperature is required to maintain the pyrolysis reaction.
  • the heating step is performed in a state in which separation cannot be performed, and the residue is disposed of.
  • PVC which is a halogen-containing organic substance
  • the composite material is brought into contact with the first compound and the second compound and heated in an oxygen-containing atmosphere. This allows the PVC in the composite to be pyrolyzed, and after treatment the PVC is removed leaving only the fibers. This fiber is treated as non-combustible waste.
  • the present invention can thermally decompose halogen-containing organic substances even when the object to be treated contains substances other than halogen-containing organic substances.
  • oxygen gas for example, oxygen gas, air and water vapor can be used.
  • oxygen-containing components are necessary for activating the oxide semiconductor contained in the first compound to cause a thermal decomposition reaction, and the higher the concentration, the better.
  • oxygen gas it is desirable to supply it at a concentration higher than the oxygen concentration in air (approximately 20%).
  • the atmosphere when the atmosphere is controlled to contain oxygen by continuously supplying gas, if the gas flow rate is high, the heat generated during the thermal decomposition reaction is taken away, so the temperature of the object to be processed does not rise sufficiently, resulting in thermal decomposition. Heating at higher temperatures is required to sustain the reaction. Therefore, when the atmosphere is controlled to contain oxygen by continuously supplying the gas, the flow rate of the gas is desirably as low as possible to maintain the atmosphere.
  • a method of bringing the first compound and the second compound into contact with the halogen-containing organic substance for example, particles (powder) of the first compound and the second compound are mixed with the halogen-containing organic substance (solid phase method).
  • a method of adding a halogen-containing organic substance to a solution serving as a raw material for the first compound and the second compound and depositing it by heating (liquid phase method).
  • the liquid phase method is preferable because the contact area between the halogen-containing organic substance and the first compound and the second compound can be increased.
  • the first compound and the second compound are placed on the wall surface of the reaction vessel. It is also possible to attach the first compound and the second compound to the halogen-containing organic substance after attaching them to a stirring blade.
  • the first compound and the second compound are brought into contact by being mixed with the halogen-containing organic substance in the form of particles (powder) rather than adhering to the wall surface of the reaction tank or the stirring blade.
  • the heating temperature can be significantly lowered (250° C.) compared with the conventional decomposition method in which combustion is performed at a high temperature, and the decomposition rate is about the same as the conventional method.
  • a volume reduction rate can be achieved. Since the heating temperature can be lowered, the operating energy can be reduced, so the operating cost can be reduced.
  • exhaust heat from a power plant or the like can be used in the heating step of the method for decomposing a halogen-containing organic substance of the present invention.
  • FIG. 1 is a flow chart of the method for decomposing halogen-containing organic matter in Example 1.
  • FIG. 1 in the method for decomposing a halogen-containing organic substance of the present invention, a first compound (oxide semiconductor) 102 and a second compound (halide Gibbs energy
  • the oxide semiconductor 102 the above oxide semiconductor (eg, TiO 2 or the like) is used.
  • the compound 103 containing an element whose halide has a low Gibbs energy a compound (eg, oxide, hydroxide, carbonate) containing the above-described transition metal element (eg, Fe) is used.
  • the atmosphere gas 104 the gas containing oxygen (for example, oxygen gas) described above is used.
  • the object 101 to be treated is decomposed into a solid residue 105 and a gaseous exhaust gas 106 .
  • the first compound 102 and the second compound 103 are brought into contact with the object 101 to be treated, and then the object 101 is heated in the atmospheric gas 104 .
  • the decomposition temperature of the object to be treated containing the halogen-containing organic matter it is possible to lower the decomposition temperature of the object to be treated containing the halogen-containing organic matter and reduce the volume.
  • FIG. 2 will be used to explain a decomposition system that implements the decomposition method for halogen-containing organic matter shown in FIG. 1 described above.
  • FIG. 2 is a schematic configuration diagram of the halogen-containing organic matter decomposition system of Example 1.
  • the halogen-containing organic matter decomposition system 100a of Example 1 includes a reaction tank 6, a heating device 4, and a recovery device 8. As shown in FIG.
  • the reaction tank 6 has an air supply port 5 and an exhaust port 7 .
  • the reaction tank 6 accommodates the object 2 to be treated (including halogen-containing organic matter).
  • the air supply port 5 is provided on the lower surface of the reaction vessel 6
  • the exhaust port 7 is provided on the upper surface of the reaction vessel 6 .
  • the air supply port 5 is connected to a gas supply unit 3 that supplies gas containing oxygen.
  • gas supply unit 3 includes, for example, a vaporizer for generating water vapor, a gas cylinder (such as an oxygen cylinder), a compressor for supplying air, a gas refiner, and the like. Then, the gas supply port 5 supplies the oxygen-containing gas supplied from the gas supply unit 3 into the reaction vessel 6 .
  • the heating device 4 heats the gas containing oxygen supplied from the gas supply unit 3 to heat the inside of the reaction tank 6, and causes the object to be processed contained in the reaction tank 6 to react with the atmospheric gas. disassemble.
  • the volume of the object to be treated can be reduced as described below.
  • a mixture 1 of a first compound and a second compound is placed in advance in a reaction vessel 6 together with an object 2 to be treated.
  • Heating is performed by supplying a gas containing oxygen into the reaction vessel 6 from the air supply port 5 and heating the gas with the heating device 4 , thereby heating the inside of the reaction vessel 6 .
  • the object 2 to be treated reacts with the gas and is decomposed to generate residue and exhaust gas.
  • Exhaust gas generated by the reaction of the object 2 to be treated during heating is discharged from the exhaust port 7 .
  • Exhaust gas discharged from the exhaust port 7 is recovered by a recovery device 8 .
  • the residue remaining in the reaction vessel 6 (and the mixture 1 of the first compound and the second compound) is removed. In this way, the object to be processed can be decomposed.
  • the mixture 1 of the first compound and the second compound and the object to be treated 2 containing the halogen-containing organic substance are placed in the reaction tank 6 again and heated.
  • halogen-containing organic substance decomposition system 100a shown in FIG. can be contacted.
  • the heating device 4 and the air supply port 5 are provided, a gas containing oxygen is supplied from the air supply port 5, and the mixture 1 of the first compound and the second compound accommodated in the reaction tank 6 is treated.
  • the object 2 can be heated in an oxygen-containing atmosphere and decomposed.
  • the balance of energy is heat generation when the thermal decomposition proceeds completely. Therefore, once the pyrolysis reaction starts, the heat generated by the pyrolysis reaction contributes to the heating, so that the energy to be applied for heating can be reduced. In some cases, once the thermal decomposition reaction starts, the heat generated by the reaction may be sufficient for heating.
  • the exhaust port 7 and the recovery device 8 are provided, the exhaust gas generated by heating can be discharged to the outside of the reaction tank 6 through the exhaust port 7 and recovered by the recovery device 8 . Then, in the reaction tank 6, the mixture 1 of the first compound and the second compound is heated by the heating device 4 while being in contact with the processing object 2 containing the halogen-containing organic substance in an oxygen-containing atmosphere. As a result, the decomposition temperature of the processing object containing the halogen-containing organic matter can be lowered, and the volume can be reduced.
  • sample A A sample of PVC only (Sample A) using PVC as the halogen-containing organic substance, a sample of PVC contacted with only TiO 2 as the first compound (Sample B), TiO 2 as the first compound in PVC, and TiO 2 as the first compound in contact with PVC (Sample B)
  • sample C A sample (sample C) in which Fe 2 O 3 was contacted as the compound of 2
  • sample D a sample in which PVC was contacted with TiO 2 as the first compound and Na 2 CO 3 as the second compound.
  • the contacting of TiO2 , Fe2O3 and Na2CO3 to PVC was done by mixing PVC with TiO2 particles, Fe2O3 particles and Na2CO3 particles .
  • Sample B was made by mixing PVC and TiO 2 at a weight ratio of 1:1.
  • Sample C was produced by mixing PVC with TiO 2 and Fe 2 O 3 at a weight ratio of 2:1:1.
  • Sample D was prepared by mixing PVC with TiO 2 and Na 2 CO 3 at a weight ratio of 2:1:1. Particles with a particle size of 1 ⁇ m or less (specific surface area of 300 m 2 /g) were used as TiO 2 .
  • Fe 2 O 3 and Na 2 CO 3 used particles with a particle size of 10 to 100 ⁇ m.
  • Thermogravimetry (TG) measurements were performed from room temperature to 800°C using the samples A to D described above. The rate of temperature increase was 10° C./min. Each sample was heated in air.
  • FIG. 3 is a graph showing the measurement results of thermogravimetric analysis of sample A (PVC), and FIG. 4 is a graph showing temperature changes of the sample during the measurement of FIG.
  • sample A made of PVC only generated heat at a heating temperature of 420 to 450.degree. C., and the sample temperature was 500.degree.
  • the weight (volume reduction rate) of the sample becomes 5% or less when the heating temperature is 500° C. or higher.
  • FIG. 5 is a graph showing the measurement results of thermogravimetric analysis of sample B (a sample in which PVC is brought into contact with TiO 2 ), and FIG. 6 is a graph showing temperature changes of the sample during the measurement of FIG.
  • sample B in which TiO 2 is brought into contact with PVC generates heat when the heating temperature is 250 to 300°C, and the sample temperature is 300°C.
  • the heating temperature at which heat generation occurs and the sample temperature rises is lower due to the effect of adding the oxide semiconductor.
  • the amount of weight reduction (volume reduction) at around 400° C. is greater than that of Sample A with only PVC, but the sample weight (volume reduction rate) is reduced to 5% or less at It turns out that it is 500 degreeC or more.
  • FIG. 7 is a graph showing the measurement results of thermogravimetric analysis of sample C (a sample in which TiO 2 and Fe 2 O 3 are brought into contact with PVC), and FIG. 8 is a graph showing the temperature change of the sample during the measurement of FIG. is.
  • sample C a sample in which TiO 2 and Fe 2 O 3 are brought into contact with PVC
  • FIG. 8 is a graph showing the temperature change of the sample during the measurement of FIG. is.
  • heat is generated when the heating temperature is around 250° C., and the sample temperature rises to 500° C. or higher at once.
  • the weight (volume reduction rate) of the sample is reduced to 5% or less when the heating temperature is around 250.degree.
  • FIG. 9 is a graph showing the measurement results of thermogravimetric analysis of sample D (a sample in which TiO 2 and Na 2 CO 3 are brought into contact with PVC), and FIG. 10 is a graph showing the temperature change of the sample during the measurement of FIG. is.
  • sample D a sample in which TiO 2 and Na 2 CO 3 are brought into contact with PVC
  • FIG. 10 is a graph showing the temperature change of the sample during the measurement of FIG. is.
  • the sample temperature rises to 500.degree. C. or higher at a heating temperature of 250.degree.
  • the weight (volume reduction rate) of the sample is reduced to 5% or less when the heating temperature is around 250.degree.
  • sample C in which PVC is contacted with TiO 2 and Fe 2 O 3 and sample D in which PVC is contacted with TiO 2 and Na 2 CO 3 reduce the volume to less than 5% at a temperature of 250 ° C. , which can be significantly lower for samples A and B.
  • FIG. 11 is a flow chart of the method for decomposing halogen-containing organic matter in Example 2.
  • the flow of this embodiment shown in FIG. 11 differs from the flow of Embodiment 1 shown in FIG. (a compound containing an element having a low Gibbs energy of halide) 103 is recovered.
  • the obtained first compound (oxide semiconductor) 102 and second compound (compound containing an element whose halide has a low Gibbs energy) 103 are recovered and supplied again to the object 101 to be processed in the contact step S1.
  • the incombustible waste 107 separated in the solid separation step S30 is disposed of.
  • the solid separation step S30 can be performed using a sieve or the like having openings smaller than the particles of the first compound (oxide semiconductor) 102 and the second compound (compound containing an element whose halide has a low Gibbs energy). can. Since other configurations are the same as those of the first embodiment, redundant description will be omitted.
  • the method for decomposing a halogen-containing organic matter of the present embodiment in addition to the effect of the first embodiment, by performing the solid separation step S30 for solid separation of the residue 105, the non-combustible waste 107, the first compound and the first 2 compounds, and the obtained first compound and second compound are recovered and supplied to the object 101 to be treated. Since the first compound and the second compound are recovered and reused in this manner, the amount of the first compound and the second compound used can be reduced, and the cost can be reduced.
  • FIG. 12 is a schematic diagram of the system for decomposing halogen-containing organic matter of Example 2.
  • FIG. FIG. 12 is an example of a system that implements the decomposition method of FIG.
  • a halogen-containing organic substance system 100b shown in FIG. 12 differs from the system of Example 1 shown in FIG.
  • the stirring blade 10 is provided inside the reaction tank 6 .
  • the stirring blade 10 stirs the mixture 1 of the first compound and the second compound and the object 2 to be treated by rotating the shaft powered by the stirrer 9 .
  • the discharge port 12 is provided in the lower part of the reaction vessel 6, and the discharge port 12 is equipped with a sieve with openings smaller than the particles of the mixture 1 of the first compound and the second compound. This sieve can separate the mixture 1 of the first compound and the second compound from the non-combustible waste produced after the material to be treated is decomposed. Non-combustible waste passes through the openings of the sieve and is discharged from the discharge port 12 .
  • the inlet 11 is provided on the upper surface of the reaction tank 6. Since the incombustible waste is discharged from the discharge port 12, a new processing target 2 can be added from the input port 11, and the processing target can be heated and decomposed. Since other configurations are the same as those of the volume reduction processing system shown in FIG. 2, redundant description will be omitted.
  • a discharge port 12 having a sieve having openings smaller than the particles of the mixture 1 of the first compound and the second compound is provided in the lower part of the reaction vessel 6.
  • the inlet 11 is provided on the upper surface of the reaction tank 6, by additionally injecting a new processing object 2 from the inlet 11, the processing object 2, the first compound, and the second compound can be obtained. can be maintained in contact with the mixture 1 of and the object 2 to be treated can be treated continuously. can do.
  • stirring blades 10 are provided in the reaction tank 6, by stirring with the stirring blades 10, the processing object 2 additionally input from the input port 11 and the first compound and the second compound are mixed. Contact with Mixture 1 can be maintained.
  • the object 2 to be treated is additionally introduced, and the additionally introduced treatment By maintaining contact between the object 2 and the mixture 1 of the first and second compounds, less energy can be applied for heating.
  • the heat generated by the reaction may be sufficient for heating, and in this case, the heating by the heating device 4 is sufficient only at the start of the reaction.
  • such an arrangement of the first compound and the second compound can be applied to the system of FIG. 2 for batch processing, or applied to the system of FIG. 12 for continuous processing. is.
  • FIG. 13 is a flow chart of the method for decomposing halogen-containing organic matter in Example 3.
  • the flow of this embodiment shown in FIG. 13 differs from the flow of Embodiment 1 shown in FIG. It is a point to have.
  • a step of gas-separating the exhaust gas 106 generated by the heating step S2 is performed to separate the exhaust gas 106 into an exhaust gas 108 and a halogen-containing gas (such as HCl and Cl 2 ) 109.
  • a halogen-containing gas such as HCl and Cl 2
  • removal of HCl and Cl2 through an aqueous alkaline trap can reduce the concentration of halogen-containing gases in the exhaust gas. Since other configurations are the same as those of the first embodiment, redundant description will be omitted.
  • the generated exhaust gas is separated into the exhaust gas 108 and the halogen-containing gas 109 by the step of gas separation of the exhaust gas 106. Since the halogen-containing gas concentration in the exhaust gas can be reduced, it is possible to prevent the halogen-containing gas from being released into the atmosphere, thereby preventing environmental pollution.
  • FIG. 14 is a schematic configuration diagram of the system for decomposing halogen-containing organic matter of Example 3.
  • FIG. FIG. 14 is an example of a system that implements the decomposition method of FIG. 14 differs from the system of Example 1 shown in FIG. 2 in that a trap 13 connected to the exhaust port 7 on the upper surface of the reaction vessel 6 is provided.
  • the trap 13 puts an alkaline aqueous solution inside, and reacts the halogen-containing gas (HCl, Cl2, etc.) in the exhaust gas from the exhaust port 7 with the alkali. This prevents the halogen-containing gas from dissolving in the aqueous solution and being discharged as gas to the outside. If necessary, the trap 13 is replenished with an alkaline aqueous solution for the reaction.
  • halogen-containing gas HCl, Cl2, etc.
  • the trap 13 connected to the exhaust port 7 on the upper surface of the reaction vessel 6 is provided, thereby trapping the halogen-containing gas in the exhaust gas from the exhaust port 7. , the emission of halogen-containing gases into the atmosphere can be prevented.
  • FIG. 15 is a schematic configuration diagram of the halogen-containing organic matter decomposition system of Example 4.
  • FIG. A cracking system 100d shown in FIG. 15 outlines one form of a cracking system that utilizes waste heat from a plant.
  • the heat exchanger 14 is connected to the exhaust port 7 on the top surface of the reaction tank 6 and to the air supply port 5 on the bottom surface of the reaction tank 6 .
  • a gas containing oxygen is supplied to the heat exchanger 14 from the lower side in the figure.
  • a gas containing oxygen is supplied to the air supply port 5 on the bottom surface of the reaction vessel 6 through the heat exchanger 14 .
  • exhaust gas is supplied to the heat exchanger 14 from the exhaust port 7 .
  • the exhaust gas passes through the heat exchanger 14 and is discharged from the heat exchanger 14 to the right side in the drawing.
  • the oxygen-containing gas flow path and the exhaust gas flow path are composed of separate tubes so that the gases do not mix with each other.
  • the contact area between the two tubes is designed to be large so that heat exchange can take place.
  • the heat exchanger 15 is connected to the high temperature exhaust system 18 of the plant 16 and also to the air inlet 5 on the bottom surface of the reaction vessel 6 .
  • a gas containing oxygen is supplied to the heat exchanger 15 from the lower side in the figure.
  • the gas containing oxygen is supplied to the air supply port 5 on the bottom surface of the reaction vessel 6 through the heat exchanger 15 .
  • the heat exchanger 15 is supplied with high-temperature exhaust gas from the high-temperature exhaust system 18 of the plant 16 .
  • the high-temperature exhaust passes through the heat exchanger 15 and is discharged from the heat exchanger 15 to the right side in the drawing.
  • the flow path for the gas containing oxygen and the flow path for the high-temperature exhaust gas are composed of separate tubes so that the gases do not mix with each other.
  • the two tubes are configured to have a large contact area so that heat can be exchanged between the two tubes.
  • a steam discharge device 17 of the plant 16 joins the gas supply section 3 and is connected to the gas supply port 5 .
  • the steam exhaust device 17 supplies steam generated from the residual heat generated in the plant 16 as part of the oxygen-containing gas.
  • the decomposition system 100d shown in FIG. Since it can be warmed by heat exchange with, the energy applied from the heating device 4 can be reduced.
  • the steam discharged from the steam discharge device 17 can be used as part of the atmospheric gas supplied to the reaction tank 6. You can use less energy.
  • the present invention provides a method for decomposing a halogen-containing organic substance and a system for decomposing a halogen-containing substance, in which the heat treatment temperature for decomposing a halogen-containing organic substance can be made lower than before. shown that it can be done.

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Abstract

La présente invention concerne un procédé pour décomposer des substances organiques halogénées et un système pour décomposer des substances halogénées, dans lequel une température de traitement thermique pour décomposer des substances organiques halogénées peut être inférieure à auparavant. Ce procédé de décomposition de substances organiques halogénées comprend : une étape de contact (S1) pour amener des substances organiques halogénées à être traitées en contact avec un premier composé et un second composé; et une étape de chauffage (S2) pour décomposer les substances à traiter qui ont été mises en contact avec le premier composé et le second composé par chauffage des substances dans une atmosphère oxygénée. Le premier composé contient un oxyde semi-conducteur. Le second composé contient un élément qui génère un halogénure lors de la réaction avec un halogène contenu dans les substances à traiter.
PCT/JP2022/028088 2021-09-01 2022-07-19 Procédé de décomposition de substances organiques halogénées et système de décomposition de substances halogénées Ceased WO2023032494A1 (fr)

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JP2021142364A JP2023035480A (ja) 2021-09-01 2021-09-01 ハロゲン含有有機物の分解方法およびハロゲン含有物の分解システム

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JP2024170954A (ja) * 2023-05-29 2024-12-11 株式会社日立製作所 無機材の製造方法、無機材の製造装置、及び構造物

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009270123A (ja) * 2006-04-19 2009-11-19 Kusatsu Electric Co Ltd 廃プラスチック・有機物の分解方法、分解装置及び分解システム
WO2013089222A1 (fr) * 2011-12-15 2013-06-20 堺化学工業株式会社 Corps granulaire en oxyde de titane supportant un métal de transition et/ou un oxyde de métal de transition sur sa surface, et procédé de décomposition de déchets plastiques/organiques l'utilisant
JP2015048427A (ja) * 2013-09-03 2015-03-16 国立大学法人信州大学 物品の分解処理方法
JP2020028850A (ja) * 2018-08-22 2020-02-27 三菱重工業株式会社 プラスチック複合材の分解方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009270123A (ja) * 2006-04-19 2009-11-19 Kusatsu Electric Co Ltd 廃プラスチック・有機物の分解方法、分解装置及び分解システム
WO2013089222A1 (fr) * 2011-12-15 2013-06-20 堺化学工業株式会社 Corps granulaire en oxyde de titane supportant un métal de transition et/ou un oxyde de métal de transition sur sa surface, et procédé de décomposition de déchets plastiques/organiques l'utilisant
JP2015048427A (ja) * 2013-09-03 2015-03-16 国立大学法人信州大学 物品の分解処理方法
JP2020028850A (ja) * 2018-08-22 2020-02-27 三菱重工業株式会社 プラスチック複合材の分解方法

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