WO2023157277A1 - Procédé de mise en œuvre d'un traitement de décomposition/carbonisation sur un composé organochloré, et dispositif de mise en œuvre d'un traitement de décomposition/carbonisation sur celui-ci - Google Patents

Procédé de mise en œuvre d'un traitement de décomposition/carbonisation sur un composé organochloré, et dispositif de mise en œuvre d'un traitement de décomposition/carbonisation sur celui-ci Download PDF

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WO2023157277A1
WO2023157277A1 PCT/JP2022/006863 JP2022006863W WO2023157277A1 WO 2023157277 A1 WO2023157277 A1 WO 2023157277A1 JP 2022006863 W JP2022006863 W JP 2022006863W WO 2023157277 A1 WO2023157277 A1 WO 2023157277A1
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catalyst
organic chlorine
compound
decomposing
carbonizing
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PCT/JP2022/006863
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English (en)
Japanese (ja)
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英季 柴田
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有限会社英商事
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Priority to PCT/JP2022/006863 priority Critical patent/WO2023157277A1/fr
Priority to JP2022528955A priority patent/JP7182829B1/ja
Publication of WO2023157277A1 publication Critical patent/WO2023157277A1/fr

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    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
    • A62D3/30—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents
    • A62D3/34—Dehalogenation using reactive chemical agents able to degrade
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
    • A62D3/40—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by heating to effect chemical change, e.g. pyrolysis
    • 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
    • Y02W30/78—Recycling of wood or furniture waste

Definitions

  • the present invention mainly dechlorinates organic chlorine compounds such as polychlorinated biphenyls (hereinafter referred to as "PCBs"), dioxins and dioxin-like compounds, etc. with a catalyst and carbonizes them.
  • PCBs polychlorinated biphenyls
  • the present invention relates to a method for decomposition and carbonization of an organic chlorine compound that causes the decomposition and carbonization, and an apparatus for decomposition and carbonization thereof.
  • PCBs are difficult to thermally decompose, insoluble in water, incombustible, and have chemically stable physical properties.As is well known, PCBs are chemical substances that are toxic and harmful to the human body. Therefore, PCB waste is properly disposed of under strict legal regulations. An example of a waste disposal device used for such disposal is invented in Patent Document 1.
  • Patent document 1 describes a method of dechlorinating and decomposing PCBs to remove chlorine from PCBs, thereby disposing of PCBs by adding chemicals such as alkaline agents to oil containing PCBs. It is a similar processing device.
  • a hydrogen donor, an alkaline agent, and a carbon-based additive are used as agents, and the agent reacts with oil containing PCBs. is carried out under conditions of nitrogen atmosphere, normal pressure and temperature of 300-350°C.
  • dioxins are one type of organic chlorine compounds that are toxic to the human body. Dioxins are mainly produced as a by-product of incomplete combustion of substances containing chlorine when incinerating garbage. Dioxins are colorless and odorless solids that are difficult to dissolve in water, difficult to evaporate, and difficult to decompose. They also have physical properties that do not react with other acidic or alkaline substances, and are chemical substances that maintain a chemically stable state. is. In order to prevent waste materials such as dust containing dioxins from scattering into the atmosphere when incinerating garbage, a processing device that decomposes dioxins has been developed. , is invented in US Pat.
  • Patent Document 1 In the process of dechlorinating and decomposing PCBs as in Patent Document 1 and in the process of dechlorinating and decomposing dioxins as in Patent Document 2, both Patent Documents 1 and 2 require heating. The processing is carried out under a high temperature zone above 300°C. Therefore, as in Patent Documents 1 and 2, a decomposition treatment apparatus that performs dechlorination decomposition with heat treatment for PCB chemical substances and dioxin chemical substances provides heat exceeding 300 ° C. The heating source must be supplied with more energy, which is costly to operate. Moreover, in a decomposition treatment apparatus that performs heat treatment at a high temperature exceeding 300° C. in a treatment furnace, it is necessary to take more serious measures against heat resistance in the heat source and the treatment furnace, and the structure of the apparatus is complicated. However, the equipment cost is also high due to the increase in size and size.
  • the present invention has been made to solve the above-mentioned problems, and in detoxifying and disposing of harmful organic chlorine compounds such as PCBs and dioxins as examples, it is possible to easily remove them at a low cost. It is an object of the present invention to provide a decomposition treatment method for an organic chlorine compound capable of performing chlorination treatment, and a decomposition treatment apparatus therefor.
  • a method for decomposing and carbonizing an organochlorine compound in one aspect of the present invention is an organic compound such as polychlorinated biphenyl (PCB) or dioxin (Dioxins and dioxin-like compounds).
  • PCB polychlorinated biphenyl
  • Dioxins and dioxin-like compounds dioxins and dioxin-like compounds.
  • organic chlorine compounds such as PCBs and dioxins are decomposed and dechlorinated simply by mixing with the catalyst at a temperature of 140 ° C. or less, so the treatments disclosed in Patent Documents 1 and 2 Disposal of organochlorine compounds can be easily carried out without going through complicated steps compared to the apparatus and treatment method.
  • the temperature at which the organic chlorine compound and the catalyst are mixed and heated is 140° C. or less, which is 200° C. or more lower than the heating temperature performed by the treatment apparatus and treatment method disclosed in Patent Documents 1 and 2. . Therefore, energy to be supplied for heating can be suppressed, and operational costs can be suppressed in dechlorinating organic chlorine compounds.
  • the dechlorinated product obtained by dechlorinating the organochlorine compound becomes a carbide and can be utilized as a raw material or resource.
  • the neutralization reaction product obtained by neutralizing the by-product is, for example, sodium chloride or calcium chloride, water, etc., and can be utilized as a material or resource.
  • the temperature of the mixture to be treated to be held is within the range of 80 to 140°C.
  • the concentrations of PCBs and dioxins can be reduced by, for example, about 99% in terms of concentration ratio before treatment. .
  • the organic chlorine compounds which have been harmful to the human body, are changed into a state in which they can be easily disposed of by dechlorination.
  • an apparatus for decomposing and carbonizing organochlorine compounds is a treatment apparatus for decomposing organochlorine compounds to be disposed of, wherein the organochlorine compounds are: Polychlorinated biphenyl (PCB) or dioxins and dioxins and dioxins (Dioxins and dioxin-like compounds), which promote dissociation of chlorine contained in the organic chlorine compound under mixing with the organic chlorine compound, and the organic a material-to-be-processed container having an internal space capable of containing, in a sealed state, a mixture to be treated, which is a mixture of a catalyst having a physical property that promotes carbonization of a chlorine compound and the organic chlorine compound and the catalyst; heating means for heating the mixture to be treated contained in the internal space, wherein the catalyst is a mixture of at least one substance selected from granular activated carbon, carbon powder, and Bincho charcoal, and concentrated sulfuric acid or fuming sulfur
  • the temperature at which the organochlorine compound and the catalyst are mixed and heated is 140° C. or less. lower than that. Therefore, the energy to be supplied for heating can be suppressed, and the catalyst can be recycled, so that the cost of operation can be suppressed in dechlorinating organic chlorine compounds.
  • the apparatus for decomposing and carbonizing organochlorine compounds does not require heavy heat resistance measures for high temperatures exceeding 300 ° C. as in Patent Documents 1 and 2, and is configured with a simple and miniaturized apparatus structure. In addition, it is possible to reduce the cost of equipment related to the decomposing and carbonizing apparatus for organochlorine compounds. Furthermore, the dechlorinated product obtained by dechlorinating the organochlorine compound becomes a carbide and can be utilized as a raw material or resource.
  • temperature control means for controlling the heating means so that the temperature of the mixture to be treated is 140°C or less.
  • the concentrations of PCBs and dioxins can be reduced by, for example, about 99% in terms of concentration ratio before treatment. .
  • the organic chlorine compounds which have been harmful to the human body, are changed into a state in which they can be easily disposed of by dechlorination.
  • the processed material storage means includes by-product discharging means for discharging by-products produced through the reaction between the organochlorine compound and the catalyst to the outside of the internal space. , is preferred.
  • the catalyst is left in the interior space of the reactor ready for subsequent dechlorination, and the by-product
  • the dechlorinated product, with the impurities removed, is turned into powdered carbon aggregates (carbides), which can be used as a resource for industrial use.
  • harmful organochlorine compounds can be detoxified and disposed of easily, at low cost, using a catalyst. It has an excellent effect of being able to dechlorinate and carbonize.
  • FIG. 2 is a diagram showing a catalyst configured in the cracking carbonization treatment apparatus shown in FIG. 1; BRIEF DESCRIPTION OF THE DRAWINGS FIG.
  • 1 is an explanatory diagram schematically showing a series of steps up to decomposition and carbonization of an organic chlorine compound by the method for decomposition and carbonization of an organic chlorine compound according to the embodiment; Experiments confirming the effects of the method for decomposing and carbonizing organochlorine compounds according to the embodiment, and the conditions and results of Experiments 1 to 4 according to Examples 1 and 2 and Comparative Examples 1 and 2 thereof are shown together. It is a table.
  • the method for decomposing and carbonizing organochlorine compounds according to the present invention mainly removes harmful organochlorine compounds such as polychlorinated biphenyls (PCBs) and dioxins and dioxin-like compounds.
  • organochlorine compounds such as polychlorinated biphenyls (PCBs) and dioxins and dioxin-like compounds.
  • the chlorine contained in the element is decomposed to dissociate from carbon, thereby dechlorinating the organochlorine compound and carbonizing it.
  • the apparatus for decomposing and carbonizing organic chlorine compounds according to the present invention decomposes such organic chlorine compounds by dissociating the chlorine contained in the constituent elements of the organic chlorine compounds with carbon, thereby decomposing the organic chlorine compounds. It is a device that performs chlorination and carbonization.
  • PCB Polychlorinated biphenyl
  • PCB is a general term for compounds obtained by substituting chlorine atoms for hydrogen atoms of biphenyl (molecular formula: C 12 H 10 ), and has the general formula [C 12 H( 10-n )Cl n (1 ⁇ n ⁇ 10)].
  • PCB has a total of 209 isomers depending on the position of the chlorine atom substituted for the hydrogen atom.
  • PCB is a chemical substance that is difficult to thermally decompose, is sparingly soluble in water, is incombustible, has chemically stable physical properties, and is toxic and harmful to the body.
  • Dioxins are colorless and odorless solids, hardly soluble in water, difficult to evaporate, and difficult to decompose. As shown in , it is a toxic chemical that is harmful to the body. Dioxins is a general term for polychlorinated dibenzo-p-dioxins (PCDD), polychlorinated dibenzofurans (PCDF), and dioxin-like polychlorinated biphenyls (DL-PCB). As shown below, the structural formula of any substance has a structure in which hydrogen atoms are substituted with chlorine atoms for two benzene rings.
  • PCDD polychlorinated dibenzo-p-dioxins
  • PCDF polychlorinated dibenzofurans
  • DL-PCB dioxin-like polychlorinated biphenyls
  • PCDD is represented by a general structural formula (0 ⁇ m ⁇ 4, 0 ⁇ n ⁇ 4, 2 ⁇ m+n ⁇ 8) as shown in [Chemical 1] below.
  • TCDD 2,3,7,8-tetrachlorodibenzo-1,4-dioxin
  • TCDD 2,3,7,8-Tetrachlorodibenzodioxin
  • PCDF is represented by the structural formula shown in [Chemical 3] below.
  • DL-PCB is represented by the general structural formula (1 ⁇ n ⁇ 10) shown in [Chemical 4] below.
  • FIG. 1 is an explanatory view showing an outline of an apparatus for decomposing and carbonizing organochlorine compounds according to an embodiment.
  • Fig. 1 omits illustration of piping equipment such as on-off valves necessary for the first pipe 31 and the second pipe 41, for example.
  • FIG. 2 is a diagram showing a catalyst configured in the cracking carbonization treatment apparatus shown in FIG. 1.
  • FIG. 3 is an explanatory view schematically showing a series of steps up to the decomposition and carbonization treatment of an organic chlorine compound by the method for decomposition and carbonization treatment of an organic chlorine compound according to the embodiment.
  • the compound decomposition and carbonization processing apparatus 1 decomposes organic chlorine compounds 90 (PCBs, dioxins) to be disposed of by dissociating the chlorine contained in the components from carbon.
  • This apparatus dechlorinates the organic chlorine compound 90 and carbonizes it.
  • the compound decomposition carbonization apparatus 1 is roughly divided into a reaction tank 2 (processed material container, processed material container), a catalyst 5, a heating means 11, a temperature control means 12, a temperature measuring means 13, and a by-product. It includes substance discharging means 21, neutralizing means 22, and the like.
  • the reaction tank 2 is a bottomed cylindrical tank having an internal space 3, and has a lid 4 that closes the opening of the internal space 3 in an airtight and liquid-tight state.
  • the internal space 3 has a capacity capable of accommodating a catalyst mixture 91 in which an organic chlorine compound 90 and a catalyst 5 are mixed.
  • the reaction tank 2 is configured to withstand heating up to approximately 200° C. in the internal space 3 .
  • the heating means 11 When heating the catalyst mixture 91 accommodated in the internal space 3, the heating means 11 is arranged so as to be able to conduct heat to the reaction tank 2, such as a mantle heater, an electric heater, an induction heating coil, or the like. Electric heating equipment, etc.
  • a temperature measuring means 13 is provided in the internal space 3 and measures the temperature of the catalyst mixture 91 accommodated in the internal space 3 .
  • the temperature control means 12 is electrically connected to the heating means 11 and the temperature measurement means 13.
  • the temperature control means 12 has a temperature control function of controlling the heating of the heating means 11 based on the measured value of the temperature measurement means 13 so that the temperature of the catalyst mixture 91 accommodated in the internal space 3 is 140° C. or less.
  • the heating means 11 may have the function of the temperature control means 12 .
  • the by-product discharging means 21 has a function of discharging the by-product 92 produced by the reaction between the organic chlorine compound 90 and the catalyst 5 to the outside of the internal space 3 .
  • an absorption section 33 serving as an inflow port for the by-product 92 is provided in the internal space 3, and the by-product discharge means 21 communicates with the absorption section 33 via the first pipe 31. connected.
  • the by-product discharging means 21 has a function of sucking the gas-phase by-product 92 (in PCDD and PCDF, water vapor may also be added) accumulated in the internal space 3 from the absorbing section 33 .
  • the neutralizing means 22 has a function of neutralizing the by-product 92 discharged from the by-product discharging means 21 .
  • the neutralization means 22 is provided on the first pipe 31 and communicates with the by-product discharge means 21 in series connection.
  • the neutralization processing means 22 has a reaction vessel portion, and stores a neutralizing agent, which is an alkaline substance such as sodium hydroxide (NaOH) or calcium hydroxide (Ca(OH) 2 ), in a storage portion. ing.
  • the neutralizing means 22 brings the acidic by-product 92 supplied from the by-product discharging means 21 through the first pipe 31 into contact with the alkaline neutralizing agent supplied from the reservoir in the reaction vessel section, thereby A neutralization reaction is carried out between the product 92 and a neutralizing agent.
  • the first reservoir 32 is connected in series with the neutralization means 22 on the first pipe 31 .
  • the first reservoir 32 is a part for collecting the by-product 92 and the neutralization reactant 93 neutralized by the neutralizer 22 by the neutralization means 22 .
  • a second pipe 41 is connected to the reaction tank 2 so as to communicate with the internal space 3 , and a second reservoir 42 is connected to the second pipe 41 so as to communicate.
  • the second storage part 42 is a part for collecting the dechlorinated material 95 left in the internal space 3, as will be described later.
  • Catalyst 5 is produced by sulfonating a first mixture or a second mixture described below at a temperature of 160 to 200.degree.
  • the first mixture is obtained by mixing at least one substance selected from granular activated carbon, carbon powder, and Binchotan charcoal with concentrated sulfuric acid or fuming sulfuric acid.
  • the second mixture is obtained by mixing wood chips whose surface layer is intramolecularly dehydrated with concentrated sulfuric acid or fuming sulfuric acid.
  • the catalyst 5 is mixed with the organic chlorine compound 90 such as polychlorinated biphenyl (PCB), dioxins, etc., and reacts with the carbon in the carbon chain skeleton of the structural formula of the organic chlorine compound 90. It has the property of promoting the dissociation of bound chlorine. With the dissociation of chlorine by the catalyst 5, in the organochlorine compound 90, the bond between carbon atoms in the carbon chain skeleton is dissociated, and the bond between carbon and hydrogen is also dissociated. That is, the catalyst 5 has the function of decomposing the organic chlorine compound 90 by dissociating chlorine and hydrogen bound to carbon in the organic chlorine compound 90 from the carbon.
  • the organic chlorine compound 90 such as polychlorinated biphenyl (PCB), dioxins, etc.
  • the catalyst 5 is a black solid substance having a specific gravity of approximately 1.0 g/cm 3 and is formed into pellets as illustrated in FIG.
  • the longest side of the three-dimensional shape formed by one grain of the catalyst 5 is preferably within a length of about 10 mm, more preferably 8 mm or less, and further preferably 5 mm or less. It is preferable that one grain of 5 is formed with such a size.
  • the total surface area of all catalysts can be increased by using a large number of small catalyst particles compared to using large catalyst particles having the longest side length of more than 10 mm. This is because the reaction between the catalyst 5 and the organic chlorine compound 90 is accelerated.
  • the catalyst 5 having a substantially cylindrical shape with a diameter of 4 mm and a total length of 5 mm, as shown in FIG. Therefore, the catalyst 5 exhibits moderate hardness that makes it difficult to crush. Therefore, in carrying out the dechlorination and carbonization of the organic chlorine compound 90, even if the catalyst 5 is stirred together with the organic chlorine compound 90 during the dechlorination process, it is difficult to break into small pieces. It becomes possible to use repeatedly when the dechlorination treatment is performed a plurality of times.
  • units such as reaction tanks used correspond to the respective units such as the reaction tank 2 configured in the compound decomposition and carbonization apparatus 1 described above. , and will be described using the same reference numerals as the units in the compound decomposition carbonization treatment apparatus 1 .
  • the decomposition and carbonization processing apparatus for organic chlorine compounds to be used is not limited to the compound decomposition and carbonization processing apparatus 1 according to the embodiment, and various modifications can be made. It is possible.
  • the organic chlorine compound 90 which is a PCB or a dioxin, is decomposed by the catalyst 5, dechlorinated, and carbonized. 2 process, 3rd process, and 4th process.
  • the first step is a step of supplying the organic chlorine compound 90 and the catalyst 5 to the internal space 3 of the reaction tank 2 and storing them in a sealed state.
  • the second step is a step of heating the catalyst mixture 91 in which the organic chlorine compound 90 and the catalyst 5 are mixed in the internal space 3 and maintaining the temperature at 140° C. or less for a certain period of time.
  • the temperature of the catalyst mixture 91 to be held is preferably within the range of 80-140.degree.
  • the third step is a step of discharging to the outside of the internal space 3 by-products 92 secondarily produced by the reaction between the organochlorine compound 90 and the catalyst 5 in the second step.
  • the fourth step is the step of neutralizing the discharged by-product 92 .
  • Organic chlorine compounds 90 which are PCBs or dioxins, are chemical substances that are toxic and harmful to the body, so the workers took sufficient safety and health protective measures when detoxifying the organic chlorine compounds 90. Above, it corresponds to the work from the first step.
  • the catalyst 5 can be used repeatedly multiple times with the next organic chlorine compound 90 after being dechlorinated and carbonized with the previous organic chlorine compound 90. In this case, only the organic chlorine compound 90 is supplied and accommodated in the internal space 3 of the reaction vessel 2 containing the catalyst 5 while remaining in the internal space 3 of the reaction vessel 2 .
  • the blending ratio of the catalyst 5 is preferably at least 1 wt% or more, more preferably 5 wt% or more, still more preferably 10 wt% or more, when the organochlorine compound 90 is 100 wt%. If the blending ratio of the catalyst 5 is less than 1 wt %, the catalyst 5 does not evenly spread over the organic chlorine compound 90 to be mixed, and cannot sufficiently come into contact with the chlorine contained in the organic chlorine compound 90, thereby dissociating chlorine effectively. because it cannot.
  • the catalyst 5 is blended in an excessive addition amount exceeding 80 wt %, for example, the catalyst 5 is added to the organic chlorine compound 90 contained in the reaction tank 2 more than necessary. Therefore, the catalyst 5 becomes relatively difficult to flow with the organochlorine compound 90 . Therefore, the catalyst 5 cannot come into contact with the chlorine contained in the organic chlorine compound 90 to be mixed in a sufficient state, the reaction with the catalyst 5 is not effectively promoted, and the chlorine becomes difficult to dissociate from the organic chlorine compound 90. There is fear. Therefore, it is preferable to set the upper limit of the amount of catalyst 5 to be added to 80 wt %.
  • the second step is carried out for the purpose of almost or completely dissociating chlorine atoms, which are constituents of the organic chlorine compound 90 , from the organic chlorine compound 90 by the catalyst 5 .
  • (B) in FIG. convection.
  • the catalyst 5 is relatively fluidized with the organic chlorine compound 90 and evenly stirred, and comes into contact with the chlorine atoms that are the constituents of the organic chlorine compound 90 .
  • the organic chlorine compound 90 has a structure in which hydrogen atoms and chlorine atoms are mainly bonded to the carbon atoms forming the carbon chain skeleton. It is composed of a structure bonded with hydrogen atoms. Skeletons of molecules constituting the organochlorine compound 90, including PCDD and PCDF, are bonded to main carbon atoms with hydrogen atoms and chlorine atoms through covalent bonds. In the covalent bond between a carbon atom and a hydrogen atom, the electronegativity of the hydrogen atom is slightly less than that of the carbon atom, but between the carbon atom and the hydrogen atom, the group of electrons is closer to the nucleus of the carbon atom. is not particularly biased toward
  • the electronegativity of the chlorine atom is larger than that of the carbon atom, and the difference in electronegativity between the carbon atom and the chlorine atom is the same as the charge between the carbon atom and the hydrogen atom.
  • the inductive effect is that the concentration of electrons between the carbon atom and the chlorine atom is greatly biased toward the nucleus of the chlorine atom due to the difference in electronegativity between the two atoms. occurs. Therefore, the organochlorine compound 90 with an inductive effect is polar.
  • the electronegativity of the oxygen atom is greater than that of the hydrogen atom in the covalent bond between the hydrogen atom and the oxygen atom.
  • the difference is significantly larger than the electronegativity difference between carbon and hydrogen atoms. Therefore, in the covalent bond between a hydrogen atom and an oxygen atom, due to the difference in electronegativity between the hydrogen atom and the oxygen atom, the collection of electrons is biased toward the nucleus side of the oxygen atom, and the inductive effect is occur.
  • the catalyst 5 is targeted for the organic chlorine compound 90 having polarity, and mainly for atoms having an electronegativity larger than that of carbon atoms, attracting electrons covalently bonded to the carbon atoms toward the atoms. It is a physical property with
  • the catalyst 5 attracts a collection of electrons covalently bonded between a carbon atom and a chlorine atom to the nucleus side of the chlorine atom, and to the carbon atom side, especially for the organic chlorine compound 90 having polarity. It is a substance that has the effect of separating the main chlorine atom from the carbon atom by reducing the density of a certain shared electron.
  • the catalyst 5 is in direct contact with the organic chlorine compound 90 under heating at a temperature of 80 to 140° C. for a set period of time (for example, about 4 hours). Then, the following chemical reaction occurs between the organochlorine compound 90 and the catalyst 5 .
  • the organochlorine compound 90 is PCDD or PCDF
  • the oxygen atoms become water while being covalently bonded to the hydrogen atoms.
  • the catalyst 5 can dissociate chlorine and hydrogen from the organochlorine compound 90, but the catalyst 5 accelerates the dissociation compared to the case where the heating temperature is 80° C. or higher. It becomes difficult to separate the chlorine atom and the hydrogen atom. As a result, it takes a long time to dechlorinate and carbonize the organic chlorine compound 90, and the dechlorination and carbonization of the organic chlorine compound 90 cannot be performed efficiently.
  • the catalyst 5 when the heating temperature of the catalyst mixture 91 exceeds 140° C., the catalyst 5 reacts with the chlorine atoms (or chlorine molecules) separated from the organic chlorine compound 90, and the chlorine contained in the organic chlorine compound 90 This is because the original property of promoting dissociation is lost. Therefore, when the heating temperature of the catalyst mixture 91 is set within the range of 80 to 140° C., the catalyst 5 can efficiently dechlorinate the organochlorine compound 90 .
  • the neutralizing reactant 93 is sodium chloride and water
  • the neutralizing reactant 93 is calcium chloride and water. is water.
  • the neutralization reaction product 93 is separated into, for example, generated sodium chloride or calcium chloride and water in the first reservoir 32 by a well-known technique. It is collected in the state
  • the oxygen atoms in the organochlorine compound 90 combine with the hydrogen atoms separated in the reaction tank 2 to form water as the by-product 92 .
  • the by-product discharge means 21 is arranged to remove the It is preferable to keep the hydrogen chloride supplied from and water separated, and supply only the hydrogen chloride to the neutralization means 22 to carry out the neutralization treatment.
  • the water supplied to the by-product discharge means 21 may be discharged by the neutralization means 22 to a tank or the like for storing water generated by the neutralization of hydrogen chloride.
  • the dechlorinated product 95 is a powdery carbon aggregate (carbide) such as carbon black containing carbon as the main component. These carbon powders agglomerate over time into particles.
  • the dechlorinated catalyst mixture 94 is separated into the catalyst 5 and the dechlorinated product 95, as shown in (F) in FIGS.
  • the catalyst 5 is left in the internal space 3 of the reaction vessel 2 and the dechlorination product 95 is discharged from the internal space 3 of the reaction vessel 2 and collected in the second reservoir 42 .
  • the collected dechlorinated product 95 can be recycled and utilized as one of industrial materials.
  • the organic chlorine compound 90 is removed from the harmful organic chlorine compound 90 by the decomposition and carbonization method of the organic chlorine compound and the compound decomposition and carbonization apparatus 1 according to the embodiment, and the chlorine and hydrogen, which are the constituent elements thereof, are removed from the organic chlorine compound 90. It can be dechlorinated and carbonized to a harmless material.
  • FIG. 4 shows an experiment for confirming the effect of the method for decomposing and carbonizing an organochlorine compound according to the embodiment. It is a table published collectively.
  • the verification experiments are four types in total: Experiments 1 and 2 according to Examples 1 and 2 and Experiments 3 and 4 according to Comparative Examples 1 and 2 thereof.
  • PCB polychlorinated biphenyl
  • this beaker containing the PCB undiluted solution (organochlorine compound 90) and the catalyst 5 is heated with an electric mantle heater to produce a catalyst mixture (catalyst mixture 91) in which the PCB undiluted solution and the catalyst 5 are mixed.
  • the temperature is raised to the set temperature, and while the by-product (by-product 92) is exhausted from the exhaust pipe, the set temperature is maintained for a predetermined time. Continue to stir evenly.
  • the PCB concentration C2 of the sample after dechlorination treatment was 7700 ppm
  • the PCB concentration difference ⁇ C before and after dechlorination treatment was 18300 ppm
  • the concentration reduction rate Rc was 70.4%
  • the PCB concentration C2 of the sample after dechlorination treatment was 3500 ppm
  • the PCB concentration difference ⁇ C before and after dechlorination treatment was 22500 ppm
  • the concentration reduction rate Rc was 86.5%.
  • hydrogen chloride could be collected in the air collecting bottle in each of Experiments 1 to 4.
  • the present applicant also applied a catalyst mixture obtained by mixing dioxins and catalyst 5 by dechlorination treatment based on the method for decomposing and carbonizing organochlorine compounds according to the embodiment. Another verification experiment was also conducted to confirm whether or not dioxins can also be dechlorinated. In another verification experiment, when the catalyst mixture was heated at 120-140° C. for 4H, the concentration of dioxins was about 30000 ppm before dechlorination and about 100 ppm after dechlorination. Ta.
  • the concentration of dioxins after dechlorination treatment was It was reduced by about 99% or more in comparison with the concentration before the heat treatment.
  • the PCB concentration reduction rate Rc was 99%, and the PCB concentration decreased from 26000 ppm before the experiment to 25800 ppm or more after the experiment. Ta.
  • the reason for this is that the heating temperature of the catalyst mixture 91 in which the PCB undiluted solution and the catalyst 5 are mixed is 140° C., so that the catalyst 5 is heated while the catalyst mixture 91 is being stirred. While atoms and hydrogen atoms are dissociated from this PCB undiluted solution, the catalyst 5 does not react with these chlorine atoms and hydrogen atoms.
  • the concentration decrease rate Rc of PCB was more than 10% to about 30% from the results of Experiments 1 and 2 according to Examples 1 and 2. was getting low.
  • the heating temperature of the catalyst mixture 91 which is a mixture of the PCB undiluted solution and the catalyst 5, was 160°C, which is 20°C above the allowable upper limit of 140°C.
  • the PCB concentration reduction rate Rc is about 16% higher than the result of Experiment 3 according to Comparative Example 1. The reason for this is that, of the total amount of the blended catalyst 5, a portion of the catalyst 5 in a normal state that has not been deteriorated remains, and the reduced amount of the catalyst 5 in a normal state makes the catalyst 5 lower than the conditions of Experiment 3. It takes twice as long to dechlorinate the PCB stock solution. Therefore, in Experiment 4, the PCB concentration reduction rate Rc is considered to be larger than the PCB concentration reduction rate Rc in Experiment 3.
  • the organic chlorine compounds 90 which are polychlorinated biphenyls or dioxins, are decomposed by the catalyst 5, and the organic chlorine compounds 90 and the catalyst 5 are placed in a reaction tank.
  • the catalyst 5 is a first mixture obtained by mixing at least one substance selected from granular activated carbon, carbon powder, or Bincho charcoal with concentrated sulfuric acid or fuming sulfuric acid, or the surface layer is A second mixture obtained by mixing intramolecularly dehydrated wood chips with concentrated sulfuric acid or fuming sulfuric acid is generated by sulfonation at a temperature of 160 to 200° C. to promote dissociation of chlorine contained in the organic chlorine compound 90. and having physical properties that promote carbonization of the organic chlorine compound 90 .
  • the compound decomposition carbonization treatment apparatus 1 is a treatment apparatus for organic chlorine compounds that performs decomposition treatment on the organic chlorine compounds 90 to be disposed of, in which the organic chlorine compounds 90 are polychlorinated biphenyls or dioxins.
  • the organic chlorine compounds 90 are polychlorinated biphenyls or dioxins.
  • a reaction tank 2 having an internal space 3 capable of accommodating a catalyst mixture 91 obtained in a sealed state, and a heating means 11 for heating the catalyst mixture 91 contained in the internal space 3 of the reaction tank 2.
  • the second mixture obtained by mixing with sulfuric acid is produced by sulfonation treatment at a temperature of 160 to 200°C.
  • the organic chlorine compounds 90 which are PCBs and dioxins, are decomposed and dechlorinated simply by mixing with the catalyst 5 at a temperature of 140° C. or less.
  • the organic chlorine compound 90 can be disposed of easily without going through a complicated process as compared with the treatment apparatus and treatment method described above.
  • the dechlorinated product 95 obtained by dechlorinating the organic chlorine compound 90 becomes a carbide and can be utilized as a raw material or resource.
  • the catalyst mixture 91 obtained by mixing the organic chlorine compound 90 and the catalyst 5 is heated to 140° C. or less, it is 200° C. or more compared to the heating temperature performed by the treatment apparatus and treatment method disclosed in Patent Documents 1 and 2. is also low.
  • the catalyst 5 can be used repeatedly over multiple times. Therefore, the energy to be supplied for heating can be suppressed, and the running cost as well as the initial cost for the dechlorination of the organochlorine compound 90 is low.
  • the compound decomposition carbonization treatment apparatus 1 does not require heavy heat resistance measures against high temperatures exceeding 300° C. as in Patent Documents 1 and 2, and can be configured with a simplified and downsized apparatus structure. In addition, the equipment cost for the compound decomposition carbonization treatment apparatus 1 can be kept low.
  • the catalyst 5 can be used to detoxify and dispose of the harmful organic chlorine compounds 90, such as PCBs and dioxins. It has an excellent effect of being able to dechlorinate and carbonize easily at a low cost. Further, the compound decomposition carbonization processing apparatus 1 for organic chlorine compounds according to the present embodiment also has the same effect as the decomposition carbonization method for organic chlorine compounds according to the present embodiment.
  • the method for decomposing and carbonizing organic chlorine compounds according to the present embodiment is characterized in that the temperature of the catalyst mixture 91 held in the second step is within the range of 80 to 140°C.
  • the compound decomposition carbonization apparatus 1 according to the present embodiment is characterized by comprising temperature control means 12 for controlling the heating means 11 so that the temperature of the catalyst mixture 91 is 140° C. or lower.
  • the concentration of PCBs and dioxins can be reduced by approximately 99% compared to the concentration before treatment.
  • the organic chlorine compound 90 which has been harmful to the human body, is changed into a state that can be easily disposed of by dechlorination.
  • the disposal of organic chlorine compounds 90 by the method for decomposing and carbonizing organic chlorine compounds according to the present embodiment is subject to strict legal regulations. If the criteria are not met, the method for decomposing and carbonizing organochlorine compounds according to the present embodiment may be used as the primary step of waste treatment. As a result, in carrying out the secondary process after the primary process, the residual concentration of PCBs and dioxins was reduced to about 1% of the pretreatment concentration by the decomposition carbonization treatment method for organochlorine compounds according to the present embodiment. in a state. Therefore, in the secondary process, it is possible to simplify the process and treatment for lowering the residual concentration of PCBs and the like to the standard values of strict legal regulations.
  • the reaction tank 2 discharges the by-product 92 produced through the reaction between the organic chlorine compound 90 and the catalyst 5 to the outside of the internal space 3. It is characterized by comprising a by-product discharge means 21 that causes the
  • the catalyst 5 is left in the internal space 3 of the reaction vessel 2 in a state that can be used as it is for the next dechlorination treatment, and the dechlorination product 95 is a powdered carbon aggregate. It is turned into a resource and can be utilized as one of the industrial materials.
  • the method for decomposing and carbonizing organic chlorine compounds according to the present embodiment is characterized by having a fourth step of neutralizing the discharged by-product 92 .
  • the generated neutralization reaction product 93 is, for example, sodium chloride or calcium chloride, water, etc., and can be utilized as a material or resource.
  • the catalyst mixture 91 is heated in the reaction vessel 2 and the catalyst 5 and the organic chlorine compound 90 are stirred based on the convection generated in the organic chlorine compound 90 .
  • the catalyst physically The organic chlorine compound may be stirred with the organic chlorine compound by means of stirring means for imparting a physically generated external force to the organic chlorine compound.
  • the method for decomposition and carbonization of organic chlorine compounds and the apparatus for decomposition and carbonization of the organic chlorine compounds according to the present invention can be used in facilities for detoxifying and disposing of harmful organic chlorine compounds.
  • Materials that detoxify compounds can be used at facilities that recycle them as resources.

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  • General Health & Medical Sciences (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
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Abstract

La présente invention concerne un procédé de mise en œuvre d'un traitement de décomposition/carbonisation sur un composé organochloré, le procédé comprenant : une première étape dans laquelle, lorsqu'un traitement de décomposition est mis en œuvre sur un composé organochloré qui est un biphényle polychloré (PCB) ou une dioxine, le composé organochloré et un catalyseur ayant des propriétés physiques qui favorisent la dissociation du chlore inclus dans le composé organochloré et qui favorisent la carbonisation du composé organochloré sont fournis dans un espace intérieur à l'intérieur d'un corps de réception de substance de traitement pour recevoir ces composants dans un état hermétiquement scellé ; une deuxième étape dans laquelle un mélange étant traité qui est obtenu par mélange du composé organochloré et du catalyseur est chauffé puis maintenu pendant une période de temps donnée à une température de 140 °C ou moins ; et une troisième étape dans laquelle des sous-produits qui sont produits secondairement en raison de la réaction du composé organochloré et du catalyseur sont évacués à l'extérieur de l'espace intérieur.
PCT/JP2022/006863 2022-02-21 2022-02-21 Procédé de mise en œuvre d'un traitement de décomposition/carbonisation sur un composé organochloré, et dispositif de mise en œuvre d'un traitement de décomposition/carbonisation sur celui-ci WO2023157277A1 (fr)

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PCT/JP2022/006863 WO2023157277A1 (fr) 2022-02-21 2022-02-21 Procédé de mise en œuvre d'un traitement de décomposition/carbonisation sur un composé organochloré, et dispositif de mise en œuvre d'un traitement de décomposition/carbonisation sur celui-ci
JP2022528955A JP7182829B1 (ja) 2022-02-21 2022-02-21 有機塩素化合物の分解炭化処理方法、及びその分解炭化処理装置

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08206250A (ja) * 1995-02-02 1996-08-13 Eiwa:Kk Ｐｃｂの分解方法
JPH10146574A (ja) * 1996-11-20 1998-06-02 Mitsubishi Materials Corp 飛灰の処理方法
US20110237857A1 (en) * 2008-12-19 2011-09-29 Universidad Del Valle Process for the destruction of toxic residues via oxidation in presence of water and oxygen and continuous mobile unit to treat hazardous compounds
JP2015174076A (ja) * 2014-03-18 2015-10-05 コスモ石油株式会社 固体酸触媒及びその製造方法
JP2018130683A (ja) * 2017-02-16 2018-08-23 フタムラ化学株式会社 木質由来固体酸の製造方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08206250A (ja) * 1995-02-02 1996-08-13 Eiwa:Kk Ｐｃｂの分解方法
JPH10146574A (ja) * 1996-11-20 1998-06-02 Mitsubishi Materials Corp 飛灰の処理方法
US20110237857A1 (en) * 2008-12-19 2011-09-29 Universidad Del Valle Process for the destruction of toxic residues via oxidation in presence of water and oxygen and continuous mobile unit to treat hazardous compounds
JP2015174076A (ja) * 2014-03-18 2015-10-05 コスモ石油株式会社 固体酸触媒及びその製造方法
JP2018130683A (ja) * 2017-02-16 2018-08-23 フタムラ化学株式会社 木質由来固体酸の製造方法

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