JP5959383B2 - Combustion exhaust gas treatment unit and CO2 supply device - Google Patents

Description

The present invention relates to a combustion exhaust gas treatment unit and an apparatus for supplying carbon dioxide (CO ₂ ).

In order to promote plant growth and photosynthesis in enclosed spaces such as plant cultivation houses and containers, it is known that increasing the CO ₂ concentration in the space is effective. For that purpose, a method of intermittently supplying CO ₂ is necessary.

Conventionally, as a method for supplying CO ₂ into a plant cultivation house or container, there are a method of supplying from a CO ₂ gas cylinder and a method of using boiler combustion.

The method of supplying directly from a CO ₂ gas cylinder can supply high-purity CO ₂ gas, but it is expensive to supply intermittently to high-capacity spaces such as plant cultivation houses and containers. The method of using is common.

As a CO ₂ supply device by boiler combustion, exhaust gas generated by boiler combustion is burned at a high temperature and decomposed into CO ₂ (Patent Document 1, Patent Document 2), exhaust gas generated by boiler combustion and CO ₂ in the air A method of accumulating in an adsorbent and heating the adsorbent to release CO ₂ (Patent Document 3) and a method using a catalyst (Patent Document 4 and Patent Document 5) have been reported.
Japanese Patent No. 3793848 JP 2010-124802 A JP 2006-340683 A Utility Model No. 3025591 JP 2008-201649 A

There is concern about the generation of harmful gases such as soot and by-products such as nitrogen oxides (NO _x ), sulfur oxides (SO _x ), hydrocarbons, and carbon monoxide (CO) due to boiler combustion. In the method of decomposing such harmful gas into CO ₂ by direct combustion, the gas combustion temperature becomes 900 ° C. or more, and there is a problem that a large amount of energy is input. In the method using a catalyst, hydrocarbons and CO can be oxidatively decomposed into CO ₂ by heating the catalyst layer at about 300 ° C. However, the combustion temperature of the harmful gas is still high, and impurities and reaction intermediates on the catalyst surface are still present. As a result, the catalyst performance deteriorates due to adsorption of the catalyst, and there is a problem in the sustainability of the catalyst activity.

The present invention has been made to solve the above-described problems, and an object of the present invention is to provide an apparatus for stably supplying CO ₂ for a long period of time by efficiently treating exhaust gas.

  That is, the first invention includes at least a flow path through which a gas to be processed flows, a first electrode, a second electrode, and a dielectric disposed in the flow path, the first electrode and the A plasma generation unit for generating plasma by applying a voltage between the second electrodes to generate discharge; and the processing target provided at a position where the plasma generated by the plasma generation unit is present in the flow path And a catalyst part having a catalyst containing gold particles present on an inorganic oxide.

  According to a second aspect of the invention, the first electrode, the second electrode, the dielectric, and the catalyst portion are arranged side by side in the flow direction of the gas to be treated, and each has air permeability in the flow direction of the gas. The combustion according to claim 1, wherein the catalyst portion is formed downstream of the discharge generation space or the discharge generation space in the flow path in the gas flow direction. This is an exhaust gas treatment unit.

  According to a third aspect of the present invention, the first electrode, the second electrode, the dielectric, and the catalyst portion are arranged side by side in a direction orthogonal to the gas flow direction. A gas processing unit according to the invention.

  In a fourth aspect of the invention, the catalyst portion further includes a base material made of an inorganic material to which the gold particles are fixed, wherein at least a portion in contact with the gold particles is an inorganic oxide. The combustion exhaust gas treatment unit according to any one of the third invention.

  5th invention is characterized by the said catalyst part being further equipped with the inorganic oxide particle to which the said gold particle is fixed on the surface, and the base material which consists of an inorganic material which fixes the said inorganic oxide particle, It is characterized by the above-mentioned. A combustion exhaust gas treatment unit according to any one of the first to third inventions.

  In a sixth aspect of the present invention, the first electrode, the second electrode, and the dielectric are arranged side by side in the flow direction of the gas to be processed, each having gas permeability in the flow direction of the gas, The combustion exhaust gas treatment unit according to any one of the first to third aspects, wherein the catalyst portion is filled with a large number of inorganic oxide particles carrying the gold particles.

7th invention is equipped with the boiler which burns fuel, and discharges | emits gas, and the combustion exhaust gas processing unit in any one of 1st to 6th invention which processes the waste gas discharged | emitted from the said boiler This is a CO ₂ supply device.

The eighth invention further includes a filter that is disposed between the boiler and the combustion exhaust gas treatment unit and removes soot contained in the exhaust gas, and an adsorbent that adsorbs at least one of NOx and SOx. A CO ₂ supply device according to the seventh invention, characterized in that:

The combustion exhaust gas treatment unit of the present invention can maintain the ability to efficiently oxidize and decompose CO and hydrocarbons in boiler combustion exhaust gas into CO ₂ at a lower temperature by the concerted action (combination) of the catalyst and plasma. As a result, it is possible to provide a combustion exhaust gas treatment unit that can supply CO ₂ for a long period of time with reduced harmful substances.

Further, in the CO ₂ supply device according to the present invention, a device capable of supplying high-purity CO ₂ by combining the combustion exhaust gas treatment unit with a filter that collects soot and an adsorbent that adsorbs NO _x and SO _x. Can be provided.

It is a cross-sectional schematic diagram of the combustion exhaust gas processing unit which concerns on embodiment of this invention. It is a schematic diagram of the catalyst body which fixed the catalyst particulates concerning the embodiment of the present invention. It is a schematic diagram of the catalyst body which concerns on other embodiment of this invention. It is a schematic diagram of the catalyst body which concerns on other embodiment of this invention. It is a schematic diagram of the catalyst body which concerns on other embodiment of this invention. It is a schematic diagram of the combustion exhaust gas processing unit which concerns on other embodiment of this invention. It is a schematic diagram of the combustion exhaust gas processing unit which concerns on other embodiment of this invention. It is a cross-sectional schematic diagram of the combustion exhaust gas processing unit which concerns on other embodiment of this invention. It is a cross-sectional schematic diagram of the combustion exhaust gas processing unit which concerns on other embodiment of this invention. It is a cross-sectional schematic diagram of the combustion exhaust gas processing unit which concerns on other embodiment of this invention. It is a schematic diagram of the combustion exhaust gas processing unit which concerns on other embodiment of this invention. It is a schematic diagram of the combustion exhaust gas processing unit which concerns on other embodiment of this invention. It is a schematic diagram of a CO ₂ supply device according to another embodiment of the present invention. It is a figure which shows the structure of the gold fine particle which is a catalyst of embodiment. It is the schematic diagram which showed an example of the combustion exhaust gas processing unit.

  Hereinafter, embodiments of the present invention will be described in detail.

(First embodiment)
FIG. 1 is a diagram schematically showing a cross section of a flue gas treatment unit 200 according to an embodiment of the present invention. The combustion exhaust gas treatment unit 200 is disposed in a flow path to which exhaust gas to be treated is supplied. In FIG. 1, the exhaust gas supplied to the combustion exhaust gas treatment unit 200 in the direction of arrow A is converted into CO ₂ by the plasma generated in the combustion exhaust gas treatment unit 200 and the function of the catalyst body 100. .

  The flue gas treatment unit 200 includes an application electrode 11, a ground electrode 12, a dielectric 13, a catalyst body 100, and a (high voltage) power source 14. In the combustion exhaust gas treatment unit 200, the application electrode 11, the ground electrode 12, the dielectric 13, and the power source 14 are members / devices (plasma generator) for generating plasma, and a voltage is applied by the power source 14. Thus, the application electrode 11, the ground electrode 12, and the dielectric 13 form a low-temperature plasma reaction layer by discharge between the application electrode 11 and the dielectric 13. In the combustion exhaust gas treatment unit 200, the application electrode 11, the catalyst body 100, the ground electrode 12, and the dielectric 13 are configured in close contact with each other. One of the application electrode 11 and the ground electrode 12 is the first electrode, and the other is the second electrode. In another embodiment, when a plurality of application electrodes 11 and a plurality of ground electrodes 12 are combined, each of the plurality of electrodes of any one type is the first electrode and each of the plurality of electrodes of the other type is This is the second electrode.

  The application electrode 11 is an electrode to which a voltage is applied by the power source 14. The ground electrode 12 is grounded by a ground wire 12a. The application electrode 11, the ground electrode 12, and the dielectric 13 have a gas-permeable structure that allows gas to pass through the electrode surface. Specifically, examples of the structure of the application electrode 11, the ground electrode 12, and the dielectric 13 include a lattice shape, a saddle shape, a porous structure by punching, or an expanded mesh structure. A combined structure may also be used. The application electrode 11 and the ground electrode 12 may have a needle-like structure. The application electrode 11, the ground electrode 12, and the dielectric 13 may have the same shape / structure among the shapes / structures described above. In FIG. 1, the application electrode 11 has a small number of openings such as a mesh, and the ground electrode 12 and the dielectric 13 have a large number of openings, such as a porous shape by punching.

  As the application electrode 11 and the ground electrode 12, a material functioning as an electrode can be used. Examples of the material of the application electrode 11 and the ground electrode 12 include metals such as Cu, Ag, Au, Ni, Cr, Fe, Al, Ti, W, Ta, Mo, Co, and alloys thereof, or oxides thereof. Can be used.

The dielectric 13 only needs to have a property of becoming an insulator. Examples of the material of the dielectric 13 include ZrO ₂ , γ-Al ₂ O ₃ , α-Al ₂ O ₃ , θ-Al ₂ O ₃ , η-Al ₂ O ₃ , amorphous Al ₂ O ₃ , and aluminanite. Ride, mullite, stearite, forsterite, cordierite, magnesium titanate, barium titanate, SiC, Si ₃ N ₄ , Si-SiC, mica, glass and other inorganic materials, polyimide, liquid crystal polymer, PTFE, ETFE , Polymer materials such as PVF (polyvinyl fluoride), PVDF (polyvinylidene difluoride), polyetherimide, and polyamideimide. In view of plasma resistance and heat resistance, inorganic materials are more preferable.

  In addition, when the catalyst body 100 to be described later also has a function as a dielectric (for example, when a part of the catalyst body is an insulator), the catalyst body 100 can also be used as a dielectric. It does not have to be provided.

Next, the catalyst body 100 will be described. FIG. 2 is a diagram schematically showing a part of a cross section of the catalyst body 100 of the present embodiment. The catalyst body 100 is a catalyst that promotes a reaction of oxidizing carbon monoxide (CO) contained in exhaust gas into carbon dioxide (CO ₂ ). Furthermore, in this embodiment, since plasma is applied to the catalyst body 100, the oxidation reaction promoted by the catalyst body 100 is further promoted.

  The catalyst body 100 of the present embodiment is a plate-like or sheet-like member having air permeability through which gas can pass, and includes a base 10 and a catalyst 1 fixed to the base 10. The catalyst body 100 is disposed at a position (range) where the plasma generated by the plasma generation unit exists. Specifically, in this embodiment, it is disposed between the application electrode 11 and the dielectric 13 (discharge space). Gas can pass through the catalyst body 100 in the direction indicated by the broken double-pointed arrow B in FIG. Therefore, the catalyst body 100 of the present embodiment is applied to the base body 10 having a plurality of holes in which a punching process such as a punching process is performed on a filter-like or plate-like member, or an air-permeable structure such as a mesh-like. The catalyst 1 is fixed so that the air permeability is maintained. In the combustion exhaust gas treatment unit 200, the catalyst body 100 is preferably arranged with the surface on which the catalyst 1 is fixed facing the application electrode 11 side (upstream side in the gas flow direction). For example, when the substrate 10 is in the form of a filter or mesh, there is a space inside the substrate 10, and the catalyst 1 can be fixed inside the substrate 10 depending on the manufacturing method of the catalyst body 100. Further, the catalyst 1 may be fixed on both surfaces of the substrate 10. When the catalyst 1 is fixed to the inside of the substrate 10 or fixed to both surfaces, the catalyst body 100 may be arranged facing either direction.

  In the catalyst 1, catalyst fine particles 1-a are supported on carrier fine particles 1-b. The catalyst 1 is fixed to the substrate 10 by the silane monomer 2 bonded to the carrier fine particles 1-b being bonded to the substrate 10 by the chemical bond 3. The fixing with the silane monomer 2 will be described later.

The catalyst fine particles 1-a of the catalyst 1 have a catalytic function for promoting the reaction of oxidizing carbon monoxide (CO) contained in the exhaust gas into carbon dioxide (CO ₂ ). The catalyst fine particles 1-a of the present embodiment are gold (Au) fine particles.

The gold fine particles that are the catalyst fine particles 1-a of the present embodiment are preferably fixed to the carrier fine particles 1-b so as to have a polyhedral structure, as shown in FIG. This is because the gold fine particles that are the catalyst fine particles 1-a have a polyhedral structure, so that the catalytic ability to catalyze the reaction of oxidizing CO to CO ₂ is increased, and CO ₂ can be efficiently generated. This is because the gold fine particles have a polyhedral structure, so that the ratio of the peripheral edge portions of the bonding interface such as the corner portion 31 and the edge portion 32 which are coordination unsaturated sites is large, and has a very high oxidation catalytic ability. It is presumed to be. Instead of the carrier fine particles 1-b, inorganic particles 1-c and the substrate 10 may be used.

  The catalyst fine particles 1-a preferably have a particle size of 50 nm or less, more preferably 1 nm or more and 10 nm or less. When the particle diameter is larger than 50 nm, the gold fine particles become stable, so that the catalytic action is difficult to occur. In addition, those having a particle size smaller than 1 nm are very unstable as substances. When the particle size is larger than 10 nm, the length of the peripheral edge of the bonding interface of the gold fine particles becomes short and it becomes difficult to take a polyhedral structure as shown in FIG. 14, but by making the particle size 10 nm or less, catalyst fine particles ( The ratio of the peripheral edge of the bonding interface of (gold fine particles) 1-a becomes sufficiently large.

  The catalyst fine particles 1-a are preferably fixed by 0.1 to 20% by mass, more preferably 0.5 to 10% by mass with respect to the carrier fine particles 1-b. This is because, when 20% by mass or more is supported, the gold fine particles as the catalyst fine particles 1-a are aggregated to reduce the catalytic activity. Less than 0.1% by mass is not preferable because sufficient catalytic activity cannot be obtained.

As described above, the catalyst fine particles 1-a need to contain at least gold fine particles having a catalytic function for promoting the reaction of oxidizing CO to CO ₂ , but may be combined with other substances. Good. Specifically, the catalyst may be a mixture of cocatalyst particles and gold fine particles obtained by combining a cocatalyst and gold fine particles, or a composite catalyst composed of composite fine particles obtained by combining various metal elements with gold fine particles. When the gold fine particles are used alone or when a promoter is mixed with the gold fine particles, the gold fine particles may be in a polyhedral shape and within the above-mentioned size range. Further, in the case of composite fine particles in which gold and other metal elements are combined, the gold portion included in the composite fine particles may have a polyhedral structure, and the size of the gold may be within the above-described size range. Examples of the metal fine particles (nanoparticles) other than the gold fine particles used in the promoter or composite catalyst include noble metals such as Pt, Pd and Ir and their oxides, or base metals and their oxides. Two or more kinds of these noble metals and oxides thereof, base metals and oxides thereof may be mixed and supported on the surface of the carrier fine particles 1-b.

  The carrier fine particles 1-b are particles for supporting the catalyst fine particles 1-a and fixing the catalyst fine particles 1-a to the substrate 10 via the carrier fine particles 1-b. The carrier fine particles 1-b may be anything as long as the catalyst fine particles 1-a can be supported. However, it is preferable to use a metal oxide or an inorganic compound mainly having physical adsorptivity, particularly a metal oxide. Things are preferred.

Examples of the metal oxide include γ-Al ₂ O ₃ , α-Al ₂ O ₃ , θ-Al ₂ O ₃ , η-Al ₂ O ₃ , amorphous Al ₂ O ₃ , TiO ₂ , ZrO ₂ , and SnO. ₂ , SiO ₂ , MgO, ZnO ₂ , Bi ₂ O ₃ , In ₂ O ₃ , MnO ₂ , Mn ₂ O ₃ , Nb ₂ O ₅ , FeO, Fe ₂ O ₃ , Fe ₃ O ₄ , Sb ₂ O ₃ , CuO, Cu ₂ O, NiO, Ni ₃ O ₄ , Ni ₂ O ₃ , CoO, Co ₃ O ₄ , Co ₂ O ₃ , WO ₃ , CeO ₂ , Pr ₆ O ₁₁ , Y ₂ O ₃ , In ₂ O ₃ And single inorganic oxides such as PbO and ThO ₂ . Examples of the metal oxide include SiO ₂ —Al ₂ O ₃ , SiO ₂ —B ₂ O ₃ , SiO ₂ —P ₂ O ₅ , SiO ₂ —TiO ₂ , SiO ₂ —ZrO ₂ , Al ₂ O _{3. -TiO 2, Al 2 O 3 -ZrO} 2, Al 2 O 3 -CaO, Al 2 O 3 -B 2 O 3, Al 2 O 3 -P 2 O 5, Al 2 O 3 -CeO 2, Al 2 O _{3 -Fe 2 O 3, TiO 2} -CeO 2, TiO 2 -ZrO 2, TiO 2 -WO 3, ZrO 2 -WO 3, SnO 2 -WO 3, CeO 2 -ZrO 2, SiO 2 -TiO 2 -ZrO ₂ , Al ₂ O ₃ —TiO ₂ —ZrO ₂ , SiO ₂ —Al ₂ O ₃ —TiO ₂ , SiO ₂ —TiO ₂ —CeO ₂ , complex oxides such as cerium / zirconium / bismuth complex oxides may be used. Note that the cerium-zirconium-bismuth composite oxide is a solid solution represented by the general formula _{Ce 1-X-Y Zr X} Bi Y O 2-δ, X, Y, the value is 0.1 ≦ X ≦ each [delta] 0 .3, 0.1 ≦ Y ≦ 0.3, 0.05 ≦ δ ≦ 0.15.

  Examples of inorganic compounds having physical adsorptivity include, for example, synthetic zeolites such as zeolite A, zeolite P, zeolite X, and zeolite Y, and natural zeolites such as clinoptyllite, sepioolaite, and mordenite. And laminar silicate compounds such as kaolinite, montmorillonite, acid clay, and diatomaceous earth, and cyclic silicate compounds such as orastite and neptite. In addition, phosphate compounds such as tricalcium phosphate, calcium hydrogen phosphate, calcium pyrophosphate, calcium metaphosphate, and hydroxyapatite, activated carbon, and porous glass are also included.

  These carrier fine particles 1-b are selected and used according to the type of gas to be treated. The average particle diameter of the carrier fine particles 1-b may be 0.1 μm or more and 500 μm or less. These carrier fine particles 1-b may be used alone or in combination of two or more. In addition, the average particle diameter here means a volume average particle diameter. In this specification, unless otherwise indicated, the average particle diameter is the volume average particle diameter.

  A method for producing the catalyst 1 will be described. The catalyst 1 may be any method as long as the catalyst fine particles 1-a can be fixed to the carrier fine particles 1-b with a polyhedral structure. Examples of the coprecipitation method, precipitation method, sol-gel method, dropping neutralization precipitation method, reducing agent addition method, pH control neutralization precipitation method, carboxylic acid metal salt addition method, and the like. It can be properly used depending on the type.

  Next, the base body 10 is a base material for fixing the catalyst 1 and configuring the catalyst body 100 as a plate-like member. And the base | substrate 10 becomes a structure which has air permeability as mentioned above, for example, the sheet-like thing in which many through-holes are formed by punching processing, fiber shape, cloth shape, mesh shape, A fiber structure (filter shape) composed of a woven fabric, a net, a non-woven fabric, or the like can be used. In addition, various shapes and sizes suitable for the purpose of use can be used as appropriate.

  The substrate 10 is preferably made of an inorganic material having excellent heat resistance because the temperature of the exhaust gas generated by combustion, which is the treatment target gas of the combustion exhaust gas treatment unit 200, is high. An inorganic material is preferable because it has higher plasma resistance. However, the inorganic material used for the substrate 10 is preferably a metal material, ceramics, glass or the like. When the catalyst fine particles 1-a are directly fixed, the material of the catalyst fine particle fixing portion is preferably a metal oxide. Further, in this embodiment, the carrier fine particles 1-b on which the catalyst fine particles 1-a are supported are fixed to the substrate 10 by the silane monomer 2, but the silane monomer 2 is covalently bonded to the substrate 10 by a dehydration condensation reaction. In this case, the base 10 preferably has an oxide thin film formed on the surface thereof.

  Examples of the metal material used for the substrate 10 of the present invention include refractory metals such as tungsten, molybdenum, tantalum, niobium, TZM (Titanium Zirconium Molybdenum), W-Re (tungsten-rhenium), noble metals such as silver and ruthenium, and the like. Alloys or oxides thereof, special metals such as titanium, nickel, zirconium, chromium, inconel and hastelloy, general metals such as aluminum, copper, stainless steel, zinc, magnesium and iron and alloys containing these general metals or these general metals These oxides can be used. In addition, a member on which the above-described metal, alloy, or oxide film is formed by various plating and vacuum deposition, a CVD method, a sputtering method, or the like may be used as a metal material.

  Note that a natural oxide thin film is usually formed on the metal surface and the alloy surface described above, and this natural oxide thin film can be used for bonding the silane monomer 2. In this case, it is preferable to remove the oil and dirt adhering to the surface of the oxide thin film in advance by an ordinary known method in order to fix the carrier fine particles 1-b stably and uniformly. . Instead of using a natural oxide film for bonding of the silane monomer 2, a thin oxide film is chemically formed on a metal surface or alloy surface by a known method, or by an electrochemical known method such as anodization. An oxide thin film may be formed.

  Furthermore, as ceramics used for the substrate 10 of the present invention, ceramics such as earthenware, earthenware, plaster and magnetism, ceramics such as glass, cement, gypsum, enamel and fine ceramics can be used. As the composition of the ceramics to be constructed, elemental, oxide, hydroxide, carbide, carbonate, nitride, halide, and phosphate ceramics can be used. These composites may be used.

  Further, as the ceramic used for the substrate 10 of the present invention, barium titanate, lead zirconate titanate, ferrite, alumina, forsterite, zirconia, zircon, mullite, steatite, cordierite, aluminum nitride, nitride Ceramics such as silicon, silicon carbide, new carbon, and new glass, high strength ceramics, functional ceramics, superconducting ceramics, nonlinear optical ceramics, antibacterial ceramics, biodegradable ceramics, and bioceramics can be used. is there.

  As the glass used for the substrate 10 of the present invention, soda lime glass, potash glass, crystal glass, quartz glass, chalcogen glass, organic glass, uranium glass, acrylic glass, water glass, polarizing glass, tempered glass, laminated glass, Glasses such as heat-resistant glass, borosilicate glass, bulletproof glass, glass fiber, dichroic, gold stone (brown stone, sand gold stone, purple gold stone), glass ceramics, low melting glass, metallic glass, and saphiret can be used. .

  In addition, the substrate 10 of the present invention includes, in addition to ordinary Portland cement, early-strength Portland cement, ultra-high-strength Portland cement, medium heat Portland cement, low heat Portland cement, sulfate-resistant Portland cement, Portland cement, blast furnace slag, fly Cement such as ash, blast furnace cement, silica cement, and fly ash cement, which is a mixed cement to which a siliceous mixed material is added, can be used.

  In addition, titania, zirconia, alumina, ceria (cerium oxide), zeolite, apatite, silica, activated carbon, diatomaceous earth, or the like can be used for the substrate 10 of the present invention. Furthermore, a metal oxide made of chromium, manganese, iron, cobalt, nickel, copper, tin, or the like can be used as the inorganic oxide of the present embodiment.

  Next, a method for fixing the catalyst 1 to the substrate 10 will be described. In the present embodiment, the catalyst 1 has a substrate 10 formed by a chemical bond 3 (covalent bond) formed by a dehydration condensation reaction between the silane monomer 2 bonded to the surface of the carrier fine particle 1-b on which the catalyst fine particle 1-a is supported. Is held by the substrate 10.

  A mechanism for binding the carrier fine particles 1-b on which the catalyst fine particles 1-a are supported by the silane monomer 2 to the substrate 10 will be described. The silane monomer 2 bonded to the carrier fine particle 1-b is oriented and bonded to the carrier fine particle 1-b with the unsaturated bond portion or the reactive functional group facing outward. This is because the silanol group at one end of the silane monomer 2 is hydrophilic, so that it is easily attracted to the surface of the carrier fine particle 1-b, which is also hydrophilic, while the unsaturated bond or reactive functional group at the reverse end. This is because the group is hydrophobic and tends to leave the surface of the carrier fine particle 1-b. For this reason, the silanol group of the silane monomer 2 is covalently bonded to the surface of the carrier fine particle 1-b by a dehydration condensation reaction, and the silane monomer 2 is easily oriented with the unsaturated bond portion or the reactive functional group facing outward. Therefore, many silane monomers 2 are covalently bonded to the carrier fine particles 1-b with the unsaturated bond portion or the reactive functional group facing outward. And the unsaturated bond part or the reactive functional group that faces the outside of the silane monomer 2 bonded to the surface of the carrier fine particle 1-b is bonded to the unsaturated bond part or the reactive functional group. The carrier fine particles 1-b are fixed to the substrate 10 by bonding 1-b together with the surface of the substrate 10.

  In other words, in the catalyst body 100 used in the present embodiment, by using the silane monomer 2 having an unsaturated bond portion or a reactive functional group and excellent in reactivity, the chemical bond 3 between the silane monomers is used on the substrate 10. A plurality of carrier fine particles 1-b are bonded to each other by an unsaturated bond portion or a reactive functional group, and between the silane monomer 2 on the surface of the carrier fine particle 1-b facing the substrate 10 and the surface of the substrate 10 The carrier fine particles 1-b are fixed on the substrate 10 by forming a chemical bond 3 by a saturated bond portion or a reactive functional group.

  Examples of the unsaturated bond portion or reactive functional group of the silane monomer 2 covalently bonded to the carrier fine particle 1-b by dehydration condensation include a vinyl group, an epoxy group, a styryl group, a methacrylo group, an acryloxy group, and an isocyanate group. .

  Examples of the silane monomer 2 having an unsaturated bond part or a reactive functional group include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ. -Aminopropyltrimethoxysilane, hydrochloride of N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyl Trimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxy Examples include propylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, and 3-isocyanatopropyltriethoxysilane.

  Next, a manufacturing method for manufacturing the catalyst body 100 by fixing the catalyst 1 to the substrate 10 will be described.

  First, the silane monomer 2 having an unsaturated bond portion or a reactive functional group is covalently bonded to the carrier fine particle 1-b on which the catalyst fine particle 1-a is supported. Bonding of the silane monomer 2 to the carrier fine particles 1-b can be formed by a usual method. For example, the carrier fine particle 1-b on which the catalyst fine particle 1-a is supported is dispersed in a dispersion liquid in which a carrier fine particle 1-b is dispersed in a dispersion medium such as water, methanol, ethanol, MEK (methyl ethyl ketone), acetone, xylene, and toluene. In addition, there is a method in which the silane monomer 2 is covalently bonded to the surface of the carrier fine particles 1-b by a dehydration condensation reaction while being heated under reflux.

  As another method, the carrier fine particles 1-b carrying the catalyst fine particles 1-a are pulverized into fine particles, and the pulverized fine particles are dispersed in one of the above dispersion media. 2 is added, or the silane monomer 2 is added to the carrier fine particles 1-b and then pulverized into fine particles and dispersed in a dispersion medium. Then, the dispersion may be solid-liquid separated and heated at 100 ° C. to 180 ° C. to covalently bond the silane monomer 2 to the surface of the carrier fine particles 1-b by a dehydration condensation reaction.

  Here, the amount of the silane monomer 2 in the catalyst 1 depends on the average particle diameter of the carrier fine particles 1-b, but is 0.01% by mass to 40.0% by mass with respect to the mass of the carrier fine particles 1-b. If so, the bond strength between the carrier fine particles 1-b and the bond between the carrier fine particles 1-b and the substrate 10 are not problematic in practice. In addition, there may be an excess silane monomer 2 that does not participate in bonding.

  Next, the carrier fine particles 1-b in which the silane monomer 2 is chemically bonded to the surface are mixed and dispersed in a dispersion medium such as methanol, ethanol, MEK (methyl ethyl ketone), acetone, xylene, or toluene. Here, in order to promote the dispersion, a surfactant, a mineral acid such as hydrochloric acid or sulfuric acid, a carboxylic acid such as acetic acid or citric acid, or the like may be added as necessary. Subsequently, the carrier fine particles 1-b are pulverized and dispersed in a dispersion medium using an apparatus such as a bead mill, a ball mill, a sand mill, a roll mill, a vibration mill, or a homogenizer to produce a slurry containing the carrier fine particles 1-b.

  Subsequently, the slurry in which the carrier fine particles 1-b obtained as described above are dispersed is applied to the surface of the substrate 10. As a method for applying the slurry to the substrate 10, generally used spin coating method, dip coating method, spray coating method, cast coating method, bar coating method, micro gravure coating method, gravure coating method may be used. There is no particular limitation as long as it can be applied to suit.

  Then, if necessary, the substrate 10 and the carrier fine particles 1-b are chemically bonded by removing the dispersion medium by heat drying or the like. Specifically, by removing the dispersion medium, chemical bonds 3 are formed between the silane monomers 2 on the surfaces of the carrier fine particles 1-b to bond the carrier fine particles 1-b to each other, and the silane monomer 2 and the substrate. By forming the chemical bond 3 with the carrier 10, the carrier fine particles 1-b are fixed on the substrate 10.

  In the present embodiment, it is preferable to use a bonding method by graft polymerization as a method for chemically bonding 3 the substrate 10 and the silane monomer 2. Examples of the graft polymerization that can be used include graft polymerization using a peroxide catalyst, graft polymerization using heat and light energy, and graft polymerization by radiation (radiation graft polymerization). It is appropriately selected depending on the form.

  In order to perform graft polymerization of the silane monomer 2 efficiently and uniformly, the surface of the substrate 10 is previously subjected to corona discharge treatment, plasma discharge treatment, flame treatment, chromic acid or perchloric acid. Hydrophilic treatment such as chemical treatment with an aqueous solution of an oxidizing acid such as an alkaline aqueous solution containing sodium hydroxide or the like may be performed.

  The above is the structure and manufacturing method of the catalyst body. According to the catalyst body 100 described above, the carrier fine particles 1-b bonded to the substrate 10 are firmly held on the substrate 10 by the silane monomer 2, so that the catalyst 1 is reliably prevented from peeling off from the substrate 10. be able to.

  Next, the power supply 14 used for the combustion exhaust gas treatment unit 200 is a power supply capable of applying a high voltage. As the power source 14, a high voltage power source such as an AC high voltage, a pulse high voltage, a DC high voltage, a DC bias superimposed with AC or a pulse, or a microwave can be used. A predetermined potential may be applied to the application electrode 11 and the ground electrode 12 by the power supply 14 so that plasma is generated in a discharge space formed by the application electrode 11, the ground electrode 12, and the dielectric 13. The voltage applied by the power source 14 varies depending on the concentration of the processing substance or the like in the exhaust gas to be treated, but is usually 1 to 20 kV, preferably 2 to 10 kV. The frequency is several tens of Hz to several kHz, and in the case of microwaves, several GHz.

  The above is the configuration of the flue gas treatment unit 200 of the present embodiment.

  Next, the flue gas treatment by the flue gas treatment unit 200 in the present embodiment described above will be described. Substances to be processed by the combustion exhaust gas processing unit 200 of the present embodiment are CO and hydrocarbons contained in the combustion exhaust gas. The hydrocarbon is not particularly limited, and examples thereof include methane, ethane, propane, butane, propylene, ethylene, and benzene.

First, when treating combustion exhaust gas, first, in the combustion exhaust gas treatment unit 200 disposed in the flow path for supplying exhaust gas, the voltage applied to the application electrode 11 by the power source 14 is applied in FIG. Exhaust gas is supplied from the electrode 11 side to the ground electrode 12 side (arrow A direction). The supplied exhaust gas is decomposed into CO ₂ by oxidizing CO and unburned fuel with plasma and a gold catalyst.

In the course of treating the exhaust gas, the gold fine particles as the catalyst fine particles 1-a may be poisoned on the surface due to contact with the gas and lose the catalytic activity. However, in this embodiment, the plasma for promoting the oxidation reaction from CO to CO ₂ cleans the gold catalyst surface, so that the catalytic activity is maintained. Therefore, the catalyst fine particles 1-a can maintain the catalytic activity for a long time and can stably supply CO ₂ .

Incidentally, the combustion exhaust gas treatment unit 200 of the present embodiment processes the exhaust gas is decomposed into CO _2, it is possible to supply the CO _2, as can be processed exhaust in the exhaust gas treatment unit 200 of this embodiment For example, in addition to heavy oil and kerosene, liquefied petroleum gas (LPG), city gas, and the like are used as fuel, and CO and unburned fuel gas generated by combustion of a burner. By flowing such exhaust gas to the catalyst body 100 and causing plasma to act, CO in the combustion exhaust gas can be efficiently oxidized to CO ₂ and unburned fuel can be oxidized and decomposed to CO ₂ .

  In the present embodiment, the flue gas treatment unit 200 has been described as including the catalyst 1 as an independent catalyst body 100, but is not limited thereto. The catalyst 1 may have a configuration in which the catalyst fine particles 1-a are fixed on the surface of the application electrode 11, the ground electrode 12, or the dielectric 13. Moreover, you may combine these structures. In this case, when the catalyst fine particles 1-a are directly fixed to the electrode (11, 12) or the dielectric 13, an inorganic oxide is preferable as the material of the electrode or the dielectric.

  In the present embodiment, the dielectric 13 is in close contact with the ground electrode 12, but the present invention is not limited to this. It is only necessary that plasma can be generated, and it is sufficient that the dielectric 13 is in close contact with at least one of the application electrode 11 and the ground electrode 12. Further, the dielectric 13 may be in close contact with the application electrode 11 and the ground electrode 12, and the catalyst body 100 may be provided between the dielectrics 13.

  In FIG. 1, the application electrode 11, the catalyst body 100, and the dielectric body 13 are disposed in close contact with each other, but the present invention is not limited thereto. As long as the dielectric 13 is disposed in close contact with either the application electrode 11 or the ground electrode 12, the other portions may be disposed with a gap. In the example of FIG. 1, a gap may be opened between the application electrode 11 and the catalyst body 100 or between the catalyst body 100 and the dielectric body 13.

In the present embodiment, the catalyst body 100 has been described as being disposed between the application electrode 11 and the dielectric 13, but is not limited thereto. If the catalyst body 100 is present at a position where plasma is present in the gas flow path, the oxidation reaction from CO to CO ₂ can be further promoted. For example, the application electrode 11, the dielectric 13, and the ground electrode 12 are configured. You may arrange | position in the downstream of the plasma generation part in the gas flow direction.

  Further, in the present embodiment, the application electrode 11 is described as being arranged on the upstream side in the gas flow direction. However, the present invention is not limited to this, and the gas may flow from the ground electrode 12 side.

  According to the present embodiment described above, according to the catalyst body 100 carrying the gold catalyst fine particles, the carrier fine particles 1-b bonded to the base 10 are firmly held on the base 10 by the silane monomer 2. Peeling can be suppressed.

(Second Embodiment)
Next, a second embodiment will be described. FIG. 3 is a view schematically showing a part of a cross section of the catalyst body 100 in the present embodiment. In the following description, components that are the same as those in the first embodiment are denoted by the same reference numerals and description thereof is omitted.

In the catalyst body 100 of this embodiment, gold fine particles that are catalyst fine particles 1-a are fixed to the surface of the substrate 10 by van der Waals force or physical adsorption. The gold fine particles of the present embodiment are not fixed to the inorganic fine particles but are fixed to the surface of the base 10, and preferably have a polyhedral shape as in the first embodiment. The particle size of the catalyst fine particles 1-a is also the same, and is preferably 50 nm or less, more preferably 1 nm or more and 10 nm or less. The reason why the polyhedral shape and the particle size are preferably in the predetermined range is as described in the first embodiment because the catalytic action of the oxidation reaction from CO to CO ₂ is further enhanced.

  The amount of catalyst fine particles 1-a supported on the substrate 10 is preferably 0.5 to 20% by mass, more preferably 0.5 to 10% by mass with respect to the substrate 10. The reason for this is that when 20% by mass or more is supported, the catalyst fine particles 1-a aggregate and the catalytic activity decreases.

  The method for supporting the catalyst fine particles 1-a on the substrate 10 is not particularly limited, but specific examples include coprecipitation method, precipitation precipitation method, sol-gel method, dropping neutralization precipitation method, reducing agent. Examples of the method include an addition method, a pH-controlled neutralization precipitation method, and a carboxylic acid metal salt addition method, and these methods can be appropriately used depending on the type of the carrier.

  Hereinafter, the method for preparing the catalyst body of the present invention will be described in detail by taking the precipitation method as an example. As a specific method of the precipitation method, first, the aqueous solution in which the gold compound is dissolved is heated to 20 to 90 ° C., preferably 50 to 70 ° C., and stirred to pH 3 to 10, preferably pH 5 to 8. It adjusts with an alkaline solution so that it may become, Then, after adding to the base | substrate 10, it heat-drys at 100-200 degreeC.

Examples of the gold compound aqueous solution used include HAuCl ₄ · 4H ₂ O, NH ₄ AuCl ₄ , KauCl ₄ · nH ₂ O, Kau (CN) ₄ , Na ₂ AuCl ₄ , KauBr ₄ · 2H ₂ O, NaAuBr _{4 and the} like can be mentioned, and the concentration of the gold compound is preferably 1 × 10 ⁻² to 1 × 10 ⁻⁵ mol / L.

  According to the present embodiment described above, since the gold catalyst fine particles 1-a are directly fixed to the substrate 10, the substrate itself becomes a carrier, so that the supported fine particles are not required, and the aggregation of the gold catalyst fine particles can be suppressed. Is obtained.

  In the present embodiment, the catalyst fine particles 1-a may be mixed particles with a promoter or composite particles.

  Further, the catalyst body 100 may be obtained by further supporting oxide fine particles such as manganese and cobalt on the surface of the base 10 in addition to the catalyst fine particles 1-a. This is because these oxide fine particles suppress the adhesion of harmful substances to the catalyst fine particles 1-a, so that the activity of the catalyst can be stably maintained over a long period of time.

(Third embodiment)
Next, a third embodiment will be described. FIG. 4 is a diagram schematically showing a part of a cross section of the catalyst body 100 of the present embodiment. In the catalyst body 100 of the third embodiment, a large number of inorganic particles 1-c, to which catalyst fine particles 1-a are fixed, are filled in a container having air permeability in the ventilation direction. Therefore, the flow exhaust gas to be treated in the ventilation direction shown in FIG. 4, flows the gaps between the inorganic particles 1-c in contact with the catalyst fine particles 1-a on the inorganic particles 1-c, CO to CO ₂ The oxidation reaction of is promoted. In addition, the container which accommodates the inorganic particle 1-c carrying the catalyst fine particle 1-a of the present embodiment has a surface where the gas enters and a surface where the gas exits from the particle size of the inorganic particle 1-c. In other words, the inorganic particles 1-c may have a structure that prevents the inorganic particles 1-c from leaking outside while ensuring air permeability. Further, the material of the container is not particularly limited, but the material of the base material 10 in the above-described embodiment may be used.

  As the material used for the inorganic particles 1-c of the present embodiment, the same material as the carrier fine particles 1-b may be used, which is selected and used according to the type of harmful organic compound to be decomposed. is there. The average particle diameter of the inorganic particles 1-c is 100 μm or more and 5000 μm or less, preferably 100 to 1000 μm. These inorganic particles may be used alone or in combination of two or more.

  The catalyst fine particles 1-a are fixed to the surfaces of the inorganic particles 1-c. Composite particles of the inorganic particles 1-c and the catalyst fine particles 1-a (when other functional fine particles are used in combination, the inorganic particles 1-c, the catalyst fine particles 1-a, and other functional fine particles which are mother particles) The method for producing the composite particles) is not particularly limited as long as the inorganic particles 1-c and the catalyst fine particles 1-a can be composited. For example, the inorganic particles 1-c and the child particles (catalyst fine particles 1-a) can be used in a mortar or the like. Can be combined to form composite particles in which the catalyst fine particles 1-a are embedded in the inorganic particles 1-c. In addition, for example, a high-speed airflow impact method in which the inorganic particles 1-c and the catalyst fine particles 1-a are collided to mechanically bond the inorganic particles 1-c and the child particles, or the inorganic particles 1-c and the catalyst. It can also be formed by a mechanochemical method such as a surface fusion method in which the inorganic particles 1-c and the child particles are bonded by energy generated by applying a strong pressure to the fine particles 1-a.

  Specifically, as an apparatus capable of producing composite fine particles by embedding and fixing the catalyst fine particles 1-a in the inorganic particles 1-c, in addition to a general-purpose ball mill, a rotary blade type is a super mixer of Kawata Corporation, The shaker type can be exemplified by a paint shaker from Asada Tekko Co., Ltd., as well as a hybridization system (registered trademark) manufactured by Nara Machinery Co., Ltd. However, the present invention is not limited to these devices.

  Furthermore, as another mixing method, for example, a rolling ball mill, a high-speed rotary pulverizer, a high-speed airflow impact pulverizer, a medium stirring mill, or a mechanical fusion device can be used. As these operating factors, for example, in a high-speed rotary pulverizer, the degree of embedding of catalyst fine particles 1-a into the inorganic particles 1-c (depth of embedding) by adjusting the stirring speed, media mass, stirring time, etc. In the high-speed airflow impact pulverizer, the degree of embedding of the catalyst fine particles 1-a into the inorganic particles 1-c can be adjusted by adjusting the pressure of the carrier gas, the residence time, or the like.

  In the complexing treatment, the catalyst fine particles 1-a with respect to the mother particles are put into a composite device capable of producing the composite fine particles as described above so that the ratio is 0.5% by mass or more and less than 40% by mass. Further, in the complexing treatment by the above-described apparatus, complex particles of the antiviral agent having a smooth surface can be formed by adjusting the stirring time and the like. That is, in the compounding process, after the catalyst fine particles 1-a are embedded in the mother particles, the catalyst fine particles 1-a are buried deeper in the mother particles by further colliding the composite fine particles with each other. A smooth surface is formed in which a does not protrude from the surface of the mother particle.

  According to the present embodiment, the structure in which the gold catalyst fine particles are supported on the inorganic particles having a relatively large particle size prevents the catalyst fine particles from aggregating, and further, because the particle size is large, the gold catalyst fine particles are not easily scattered and do not need to be fixed to the substrate. .

(Fourth embodiment)
Next, a fourth embodiment will be described. FIG. 5 is a diagram schematically showing a part of a cross section of the catalyst body 100 according to the present embodiment. The present embodiment is characterized in that the catalyst body 100 has a structure in which catalyst fine particles 1-a are fixed in pores of a porous oxide film.

  In the catalyst body 100 of this embodiment, the oxide film 4 is formed on the surface of the substrate 10. A large number of pores 5 are formed in the oxide film 4. Then, the catalyst fine particles 1-a are filled in the numerous pores 5 of the oxide film 4. Since the catalyst body 100 needs air permeability, a plurality of holes penetrating the catalyst body 100 are formed by punching, for example. The catalyst body 100 of the present embodiment is preferably disposed in the combustion exhaust gas treatment unit 200 such that the oxide film 4 side faces the electrode and faces the upstream direction in the gas flow direction.

  The catalyst body 100 may be formed by fixing a metal, which is an oxide film formed by anodizing a metal plate, to the surface of the substrate 10 formed of any of the materials exemplified in the first embodiment by bonding or the like. Alternatively, a metal plate as the substrate 10 may be oxidized to form the oxide film 4 on the surface of the substrate 10. Examples of the metal plate include aluminum, tantalum, niobium, titanium, hafnium, zirconium, zinc, tungsten, bismuth, and antimony. Preferably, aluminum or titanium that can easily form pores by anodic oxidation is preferable. The shape of the metal plate is not particularly limited, but the total thickness is preferably 0.05 to 1.0 mm, more preferably 0.08 to 0.35 mm, and still more preferably 0.1 to 0.3 mm. is there.

  As a method for the oxidation treatment, a known method can be used. For example, in a solution having an acid concentration of 1 to 10% by mass, a method of energizing a metal plate forming an oxide film as an anode can be used. In order to control, you may heat-process. In addition, when forming an oxide film having crystallinity such as γ-alumina or α-alumina, a method of forming a spark discharge on aluminum in an aqueous solution containing sodium carbonate or sodium phosphate, sodium hydrogen sulfate and sulfuric acid A method of anodizing in a molten salt containing ammonium hydrogen is used. As the solution used for the anodizing treatment, for example, phosphoric acid, chromic acid, succinic acid, sulfuric acid, citric acid, malonic acid, tartaric acid aqueous solution and the like can be used. Depending on the metal material of the metal plate, the pores 5 are formed by anodic oxidation, and the diameter of the pores 5, the interval between the pores, the film thickness, etc. are adjusted according to conditions such as applied voltage, treatment temperature, and treatment time in the oxidation treatment. can do.

  The catalyst fine particles 1-a are adsorbed on the surface of the oxide film 4, and are fixed to the oxide film 4 to such an extent that they do not desorb even when they come into contact with the combustion exhaust gas. The method for fixing the catalyst fine particles 1-a to the oxide film 4 is not particularly limited. For example, the precipitation method, the precipitation reduction method, the impregnation method, the ion exchange method, the coprecipitation method, the deposition method, the kneading method, the hydrothermal method. Known methods such as a synthesis method and a gas phase synthesis method can be used.

  According to the present embodiment, when the catalyst fine particles 1-a are fixed to a metal material or the like, since the catalyst fine particles 1-a are fixed to the surface of the oxide film 4, an effect of being firmly fixed is obtained. In particular, when the catalyst fine particles 1-a are fixed in the pores 5 formed by the anodic oxidation treatment, the catalyst fine particles 1-a are fixed more firmly, and the catalyst fine particles 1-a are prevented from falling off, and the catalyst is stable for a long time. The effect is obtained.

  In the present embodiment, the catalyst fine particles 1-a are described as being directly supported on the oxide film 4, but the present invention is not limited to this. The carrier fine particles 1-b may be deposited on the surface of the oxide film 4, and the catalyst fine particles 1-a may be supported on the surface of the carrier fine particles 1-b. However, the method of directly supporting the catalyst fine particles 1-a on the oxide film 4 is easier to manufacture.

(Fifth embodiment)
Next, a fifth embodiment will be described. FIG. 6 is a schematic diagram of the flue gas treatment unit 300 of the present embodiment. This embodiment is another embodiment of the flue gas treatment unit. Specifically, the flue gas treatment unit 300 of the present embodiment has a configuration in which a plurality of flue gas treatment units 200 described in the first embodiment are stacked in the flow direction of the gas to be treated. To do.

  In the present embodiment, the flue gas treatment unit 300 includes a plurality of application electrodes 11, a plurality of ground electrodes 12, a plurality of dielectrics 13, a plurality of catalyst bodies 100, and a power source 14. In the flue gas treatment unit 300 of this embodiment, the application electrode 11, the ground electrode 12, and the dielectric 13 are alternately arranged to form the low temperature plasma reaction layer 8, and the application electrode 11 in the low temperature plasma reaction layer 8 is configured. And the ground electrode 12, a catalyst body 100 carrying catalyst fine particles is disposed. Note that one set of the application electrode 11, the catalyst body 100, the dielectric body 13, and the ground electrode 12 corresponds to the combustion exhaust gas treatment unit 200 of the first embodiment. One of the plurality of application electrodes 11 and the plurality of ground electrodes 12 is the first electrode, and the other is the second electrode. The plurality of application electrodes 11, the plurality of ground electrodes 12, the plurality of dielectrics 13, and the power source 14 constitute a plasma generation unit.

  Exhaust gas flows into the combustion exhaust gas treatment unit 300 in the direction of arrow a, and the decomposed exhaust gas is discharged from the apparatus in the direction of arrow b. In the flue gas treatment unit 300, as described above, the plasma reaction layer 8 has a multilayer structure in which a plurality of the application electrode 11, the ground electrode 12, and the catalyst body 100 are laminated. By providing a catalyst body 100 carrying a gold catalyst in each layer and making it a multilayer structure, harmful gases and the like can be highly removed between the respective electrodes.

  According to this embodiment, the harmful gas in a large amount of gas can be efficiently decomposed by the multilayer structure.

(Sixth embodiment)
Next, a sixth embodiment will be described. FIG. 7 is a schematic diagram of the flue gas treatment unit 400 of the present embodiment. FIG. 8 is a schematic diagram showing a cross section of the flue gas treatment unit 400 of the present embodiment. FIG. 7 is an exploded perspective view showing a state in which the flue gas treatment unit 400 having the structure shown in FIG. 8 is disassembled. The flue gas treatment unit 400 is characterized in that an application electrode 11 is installed on one side of a plate- or sheet-like dielectric 13 and a ground electrode 12 is installed on the opposite side, and discharge occurs on both sides of the dielectric 13 to generate plasma. Further, the flue gas treatment unit 400 of the present embodiment is different from the flue gas treatment units 200 and 300 in that the gas to be treated is flowed along the surface of the catalyst body 100 for treatment. Hereinafter, although the structure of the flue gas processing unit 400 of this embodiment is demonstrated, about the structure which is common in the structure in embodiment mentioned above, the same code | symbol is attached | subjected and description is abbreviate | omitted.

  The application electrode 11 and the ground electrode 12 of this embodiment are comb-like electrodes each composed of a large number of electrodes. The application electrode 11, the ground electrode 12, and the dielectric 13 are arranged in a state where the dielectric 13 is in contact with at least one of the application electrode 11 and the ground electrode 12. Therefore, the application electrode 11, the ground electrode 12, and the dielectric 13 may all be in close contact and stacked. Further, in order for the catalyst body 100 and the plasma existence region 9 to overlap, it is preferable that the thicknesses of the application electrode 11 and the ground electrode 12 are thin.

  When a high voltage is applied between the application electrode 11 and the ground electrode 12 as an alternating current, creeping discharge occurs on the dielectric 13 between the application electrode 11 and the dielectric 13 to generate plasma. Similarly, creeping discharge occurs on the surface of the dielectric 13 between the ground electrode 12 and the dielectric 13, and plasma is generated.

Next, the catalyst body 100 has the same configuration as the catalyst body of the embodiments described so far. And the catalyst body 100 of this embodiment is arrange | positioned on the outer side of the application electrode 11, and the outer side of the ground electrode 12, as shown in FIG. Further, as described above, in the flue gas treatment unit 400, the gas to be treated does not flow so as to penetrate the catalyst body 100, but flows along the surface of the catalyst body 100 to react to CO ₂ . Facilitate. Therefore, the catalyst body 100 of the present embodiment may have a breathable structure used in the above-described combustion exhaust gas treatment units 200 and 300, or may have a non-breathable sheet shape or a structure on a plate.

Further, when the catalyst body 100 has a structure having no air permeability, the surface may be formed with unevenness by embossing or the like. When irregularities are formed on the surface of the catalyst body 100, the contact area with the flowing gas increases, and the oxidation reaction from CO to CO ₂ can be further promoted.

  When the gas is processed in the flue gas treatment unit 400 of the present embodiment having the above configuration, as shown in FIG. 7 (indicated by arrows cd), a comb is formed between the comb teeth of the application electrode 11 and the comb teeth. Flow gas along the teeth. The gas passing between the comb teeth escapes beyond the combustion exhaust gas treatment unit 400 or passes through the catalyst body 100 when the catalyst body 100 has air permeability. Further, when the gas is allowed to flow to the ground electrode 12 side, the comb-like electrode may be made to be air permeable, as indicated by an arrow cd on the ground electrode 12 side. Similarly, the gas can flow along the comb-tooth direction of the application electrode 11 through the ventable portion. In this case, if the catalyst body 100 has air permeability, the gas may pass from the electrode side to the adjacent catalyst body 100 or pass through from the catalyst body 100 to the electrode. it can.

Further, when the electrode is thin, the plasma existence region 9 is also outside the catalyst body 100 as shown in FIG. 8, so that the outside of the catalyst body 100 is shown as indicated by arrows ab in FIG. A gas may be flowed through. As a result, the flowing gas flows while in contact with the catalyst body 100 disposed on the outer sides of the application electrode 11 and the ground electrode 12, thereby promoting the oxidation reaction from CO to CO ₂ . Further, the plasma generated by the discharge between the application electrode 11 and the dielectric 13 and the plasma generated by the discharge between the ground electrode 12 and the dielectric 13 further promote the oxidation reaction from CO to CO ₂ . To do.

According to the present embodiment, even when the gas is treated by flowing the gas along the surface of the catalyst body 100, the combustion exhaust gas that promotes the oxidation reaction from CO to CO ₂ and efficiently supplies CO ₂ from the exhaust gas. A processing unit 400 can be provided. In particular, for the flow of gas along the surface of the catalyst body 100, increasing the contact time between the gas and the catalyst body 100, in the oxidation reaction of CO to CO _2, the reaction promoting effect more by the catalyst body 100 is obtained.

  Further, in the present embodiment, plasma due to discharge can be generated on both sides of the dielectric 13, and gas can be processed efficiently with one set of the application electrode 11, the ground electrode 12, and the dielectric 13.

  In the present embodiment, as the flue gas treatment unit 400, the application electrode 11 is disposed on one surface side of the dielectric 13 and the ground electrode 12 is disposed on the other surface side of the dielectric 13, Although the structure which has arrange | positioned the catalyst body 100 on the outer side was demonstrated, it is not restricted to this. The catalyst body 100 comes into contact with the flowing gas to be processed, and the processing target gas flows into the plasma generation space generated by the application electrode 11, the ground electrode 12, and the dielectric 13, and the plasma is in response to the processing target gas. Any structure may be used. Specifically, in the case of the catalyst body 100 having a function as a dielectric, a method in which the catalyst body 100 is fixed to the dielectric body 13 and an electrode is disposed outside the catalyst body 100, or the catalyst body 100 is disposed on the electrode surface. A fixing method or a combination of two or more of these may be used. Further, when the catalyst body 100 or the dielectric body 13 has air permeability, the gas to be treated may be circulated not in the direction along the comb teeth but in the direction orthogonal to the surface of the catalyst body 100 or the dielectric body 13. Needless to say, it is good.

(Seventh embodiment)
Next, a seventh embodiment will be described. FIG. 9 is a diagram schematically showing the flue gas treatment unit 500 of the present embodiment. The flue gas treatment unit 500 of this embodiment is a modification of the flue gas treatment unit 400 of the sixth embodiment.

The flue gas treatment unit 500 is configured by laminating a plurality of flue gas treatment units 400 of the sixth embodiment in the lamination direction of the electrodes (11, 12) and the dielectric 13. In this flue gas treatment unit 500, the gas to be treated passes through the catalyst body 100 from between the comb teeth of the electrodes or stacks the flue gas treatment unit 400, similarly to the gas flow path in the flue gas treatment unit 400. At this time, a gap is provided between the units so that the plasma existing region is not interrupted, and the gas flows through the gap. The flowing gas promotes the oxidation reaction from CO to CO ₂ by using the catalyst body 100 and plasma.

According to the present embodiment, the flue gas treatment unit 500 has a configuration in which a plurality of the flue gas treatment units 400 are stacked, and thus can remove harmful gases at a high level and supply CO ₂ more efficiently. The effect is obtained.

(Eighth embodiment)
Next, an eighth embodiment will be described. FIG. 10 is a diagram schematically showing a part of a cross section of a flue gas treatment unit 600 which is an example of the present embodiment. The flue gas treatment unit 600 of this embodiment generates plasma by silent discharge.

  The combustion exhaust gas treatment unit 600 includes a catalyst body 100 between two electrodes in a low-temperature plasma reaction layer in which an application electrode 11, a ground electrode 12, and a dielectric 13 that generate a plasma by applying a voltage using a high-voltage power supply 14 are installed. Is installed. These electrodes, dielectric 13 and catalyst body 100 are stacked in close contact with each other. In FIG. 10, the dielectrics 13 are stacked in close contact with both the application electrode 11 and the ground electrode 12, but only one of the dielectrics 13 may be provided.

  Further, the catalyst body 100 may or may not be in close contact with the dielectric 13. The catalyst body 100 needs to be air permeable when it is in close contact with both dielectrics, but the catalyst body 100 may not be air permeable when it is not in close contact with at least one of the dielectric bodies 13. In the case of the combustion exhaust gas treatment unit 600 of the present embodiment, gas is decomposed by allowing gas to flow in from the direction of arrow a in FIG. 10 and discharging gas from the other end side in the direction of arrow b. The flue gas treatment unit 600 has a multi-layer structure, so that a large amount of gas to be treated can be efficiently decomposed, and the gas to be treated is efficiently treated according to the amount of gas to be treated (concentration) and the use conditions such as the flow rate. Installed for oxidative degradation. The catalyst body 100 may be either a single layer or divided into a plurality of layers, and can be arbitrarily set.

(Ninth embodiment)
Next, a ninth embodiment will be described. FIG. 11 is a diagram schematically showing a part of a cross section of the flue gas treatment unit 700 of the present embodiment.

  The flue gas treatment unit 700 has a cylindrical structure in which a cylindrical application electrode 11, a ground electrode 12, and a catalyst body 100 are laminated radially outward in a ring shape. In the low temperature plasma reaction layer 8 in which the application electrode 11 that generates a plasma by applying a voltage using a high voltage power supply 14, the ground electrode 12, and the dielectric 13 is installed, the catalyst body 100 is installed between the two electrodes. In the figure, both the application electrode 11 and the ground electrode 12 are laminated in close contact with the dielectric 13, but only one dielectric 13 may be provided. In the case of the processing unit 700, the gas is decomposed by flowing the gas from one of the circular end faces and discharging it from the other end face side. The plasma reaction layer 8 of the processing unit 700 may have an annual ring-like multilayer structure. By adopting a multilayer structure, the flue gas treatment unit 300 (FIG. 6) of the fifth embodiment or the flue gas of the seventh embodiment is used. As in the case of the multilayer structure of the unit 500 (FIG. 9), a large amount of exhaust gas can be decomposed efficiently. Depending on the usage conditions such as the amount of exhaust gas and the flow rate, the number of cylindrical annual rings of the catalyst body 100 installed in the plasma reaction layer 8 can be set arbitrarily so that the exhaust gas can be efficiently decomposed. it can.

(10th Embodiment)
Next, a tenth embodiment will be described. FIG. 12 is a schematic diagram showing the configuration of the flue gas treatment unit 800 of the present embodiment. The flue gas treatment unit 800 of the present embodiment is configured by combining four cylindrical flue gas treatment units 700 described in the ninth embodiment. Thus, by combining a plurality of cylindrical combustion exhaust gas treatment units 700, a larger amount of exhaust gas can be efficiently decomposed.

  In FIG. 12, the flue gas treatment unit 800 has the flue gas treatment units 700 arranged in two vertical rows and two horizontal rows, but is not limited thereto. They can be arranged appropriately according to the shape of the place where the combustion exhaust gas treatment unit 800 is installed. For example, a plurality of flue gas treatment units 700 may be arranged so that the flue gas treatment unit 800 may be arranged in a line vertically or horizontally, and the cross section of the flue gas treatment unit 800 may be various polygons such as a rectangle, a trapezoid, a triangle, or a circle. May be.

(Eleventh embodiment)
Next, an eleventh embodiment will be described. FIG. 13 is a configuration diagram showing the configuration of the CO ₂ supply device 900 of the present embodiment. This embodiment has been described in the above embodiments, through the use of combustion exhaust gas treatment unit (200-800), which is an example of a CO ₂ supply device for supplying CO ₂ processes the exhaust gas discharged from the boiler .

The CO ₂ supply device 900 of this embodiment includes a boiler 20, a fan 21, a filter 22, an adsorbent 23, a flue gas treatment unit 24, and a power source 14. The boiler 20, the filter 22, the adsorbent 23, the combustion exhaust gas treatment unit 24, and the fan 21 are connected by a pipe 30, and all the gas discharged from the boiler 20 is disposed on the downstream side of the boiler 20. After passing through these members and being subjected to exhaust gas treatment, the fan 21 supplies the CO ₂ supply target space. Hereinafter, each configuration of the CO ₂ supply device 900 will be described.

The boiler 20 is a device that burns fuel to obtain water vapor, but the CO ₂ supply device 900 of this embodiment functions as a supply device for exhaust gas that is the original gas of CO ₂ . The boiler 20 may be a dedicated boiler for discharging exhaust gas in the CO ₂ supply device 900, or a boiler used for the purpose of supplying water vapor or hot water.

The fan 21 supplies the gas discharged from the boiler 20 and passing through the combustion exhaust gas treatment unit 24 from the CO ₂ supply device 900 to the CO ₂ supply target space.

  The filter 22 is disposed upstream of the combustion exhaust gas treatment unit 24 in the gas flow direction. The filter 22 is a bag filter that removes soot generated by combustion of fuel in the boiler 20. The shape and structure of the filter 22 may be any shape that allows gas to pass through. For example, a filter shape, a plate shape in which a hole exists in punching, a mesh shape, or a combination of two or more of these may be used.

  The adsorbent 23 adsorbs at least one of NOx and SOx and removes it from the gas. However, depending on the type of fuel used in the boiler 20, when there is a gas component that is not discharged from NOx or SOx, it is not necessary to be able to adsorb the gas component that is not discharged.

  The adsorbent 23 only needs to have a structure through which gas can pass. For example, a filter shape, a plate shape in which a hole exists in punching processing, a mesh shape, or a combination of two or more of these may be used.

The adsorbent 23 is disposed between the filter 22 and the flue gas treatment unit 24 as shown in FIG. By arranging the adsorbent 23 between the filter 22 and the plasma discharge space (combustion exhaust gas treatment unit 24), NOx and SOx are removed in the adsorbent 23 with respect to the gas from which the smoke has been removed by the filter 22. The gas is supplied to the combustion exhaust gas treatment unit 24. Therefore, the effect that the yield of CO ₂ by the combustion exhaust gas treatment unit 24 can be further improved is obtained. However, it may be arranged downstream of the combustion exhaust gas treatment unit 24 in the gas flow direction.

Examples of the adsorbent used in the adsorbent 23 used in the present embodiment include inorganic oxides, silicates, and phosphate compounds. As the inorganic oxide, for example, a single inorganic oxide such as SiO ₂ , Al ₂ O ₃ , TiO ₂ , ZrO ₂ , SnO ₂ , Fe ₂ O ₃ , Sb ₂ O ₃ , WO ₃ , CeO ₂ , SiO ₂・ Al ₂ O ₃ , SiO ₂・ B ₂ O ₃ , SiO ₂・ P ₂ O ₅ , SiO ₂・ TiO ₂ , SiO ₂・ ZrO ₂ , Al ₂ O ₃・ TiO ₂ , Al ₂ O ₃・ ZrO ₂ , Al ₂ O ₃・ CaO, Al ₂ O ₃・ B ₂ O ₃ , Al ₂ O ₃・ P ₂ O ₅ , Al ₂ O ₃・ CeO ₂ , Al ₂ O ₃・ Fe ₂ O ₃ , TiO ₂・ _{CeO 2, TiO 2 · ZrO 2} , SiO 2 · TiO 2 · ZrO 2, Al 2 O 3 · TiO 2 · ZrO 2, SiO 2 · Al 2 O 3 · TiO 2, SiO 2 · TiO 2 · CeO 2 etc. A composite oxide is mentioned. In addition, adsorbent silicates include synthetic zeolites such as zeolite A, zeolite P, zeolite X and zeolite Y, natural zeolites such as clinoptyllite, sepioolaite and mordenite, kaolinite, montmorillonite and acid clay. And lamellar silicate compounds such as diatomaceous earth, and cyclic silicate compounds such as orastite and neptunite. In addition, phosphate compounds such as tricalcium phosphate, calcium hydrogen phosphate, calcium pyrophosphate, calcium metaphosphate, and hydroxyapatite, and activated carbon and porous glass are also included. These adsorbents are used depending on the purpose of use, and may be in the form of a powder or may be pressed into a tablet.

  And the combustion exhaust gas treatment unit 24 of this embodiment can use any of the combustion exhaust gas treatment units of the first embodiment and the fifth to tenth embodiments described so far. An optimum combustion exhaust gas treatment unit may be selected according to conditions such as the gas flow rate and the type of gas to be treated.

  The power source 14 is the same as the power source in the embodiments described so far, and a high voltage is applied between the application electrode and the ground electrode in the flue gas treatment unit 24 to generate plasma.

The above is the configuration of the CO ₂ supply device 900 of the present embodiment.

  In the embodiment described above, any of the catalyst bodies 100 described in the first embodiment to the fourth embodiment may be used as the catalyst body 100 in the fifth embodiment to the tenth embodiment.

Next, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to only these examples.

(Production of catalyst body (alumina fabric) carrying gold fine particles)
As inorganic fine particles, commercially available zirconia (zirconium oxide) fine particles (manufactured by Nippon Electric Works Co., Ltd., PCS) are 10.0% by mass with respect to methanol as a solvent, and 3-methacryloxypropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd.) as silane monomer Manufactured by KBM-503) was added in an amount of 5.0% by mass to the inorganic fine particles, and the pH was adjusted to 3.0 using hydrochloric acid. After adjustment, the particles were pulverized and dispersed to an average particle size of 20 nm by a bead mill.

  Thereafter, solid-liquid separation was performed with a freeze dryer, and heating was performed at 120 ° C., and a silane monomer was chemically bonded to the surface of the zirconia fine particles by a dehydration condensation reaction to form a coating. The obtained surface-treated zirconia fine particles were prepared so as to be 10.0% by mass with respect to methanol, and pulverized and dispersed again to an average particle size of 17 nm by a bead mill to prepare a zirconia fine particle dispersion.

  Next, after the surface is washed with an alkaline detergent, washed with ion-exchanged water, immersed in methanol, and dried with a dryer, an alumina (aluminum oxide) fabric (manufactured by Nichibi Co., Ltd.) is added to the zirconia fine particle dispersion. After dipping and removing the surplus with an air blower, it was dried at 110 ° C. for 2 minutes. Next, the alumina fabric coated with the zirconia fine particle dispersion was irradiated with an electron beam at an acceleration voltage of 200 kV for 5 Mrad to prepare a precursor in which the zirconia fine particles were bonded to the alumina fabric by graft polymerization of a silane monomer.

Subsequently, as a treatment for supporting gold on the inorganic fine particles, 0.5 mmol of chloroauric acid (HAuCl ₄ · 4H ₂ O) is dissolved in 100 ml of water, heated to 70 ° C. and adjusted to pH 7 with an aqueous NaOH solution, The precursor was immersed for 1 hour. Next, the alumina fabric was taken out from the aqueous solution and washed with water three times. Thereafter, the mixture was heated at 100 ° C. for 4 hours under a nitrogen atmosphere to obtain an alumina fabric carrying gold fine particles. The amount of gold supported was measured by ICP and found to be 1.3 wt%.

(Production of catalyst body (silicon carbide fabric) carrying gold fine particles)
In the catalyst body supporting the gold fine particles, the gold fine particles were prepared in the same procedure as described above except that a Tyranno (registered trademark) fabric (made by Ube Industries) made of silicon carbide fibers was used instead of the alumina fabric. A supported silicon carbide fabric was obtained. The gold loading was measured by ICP and found to be 1.3 wt%.

(Production of catalyst body (zirconia fabric) carrying gold fine particles)
In the catalyst body supporting the gold fine particles, the gold fine particles were supported in the same procedure as described above except that a zirconia (zirconium oxide) woven fabric (manufactured by Sakai Kogyo Co., Ltd., ZYW-15) was used instead of the alumina woven fabric. A zirconia fabric was obtained. The gold loading was measured by ICP and found to be 1.3 wt%.

(Preparation of catalyst body (PET nonwoven fabric) carrying gold fine particles)
In the catalyst body carrying the gold fine particles, a PET non-woven fabric carrying gold fine particles was carried out in the same procedure as above except that a PET non-woven fabric (40 g / m 2, manufactured by Asahi Kasei Fibers Co., Ltd.) was used instead of the alumina woven fabric. Obtained. The amount of gold supported was measured by ICP and found to be 1.3 wt%.

(Production of catalyst body (aluminum plate) carrying gold fine particles)
An aluminum plate having a thickness of 99.7 wt% and a thickness of 0.2 mm is immersed in molten salt formed by mixing NaHSO ₄ and NH ₄ HSO ₄ at a weight ratio of 1: 1 and heating to 170 ° C. An α-alumina oxide film was formed on the surface of the aluminum plate by applying the electric potential of 170 V using immersed aluminum as an anode and SUS304 as a counter electrode. Subsequently, an aqueous solution of chloroauric acid in which 0.5 mmol of chloroauric acid (HAuCl ₄ · 4H ₂ O) was dissolved in 100 ml of water was heated to 70 ° C., adjusted to pH 7 with NaOH aqueous solution, and the α- The aluminum plate on which the alumina oxide film was formed was immersed for 1 hour. Next, the aluminum plate on which the α-alumina film was formed was taken out of the aqueous solution and washed with water three times. Thereafter, the mixture was heated at 100 ° C. for 4 hours in a nitrogen atmosphere to obtain an α-alumina film-formed aluminum plate (catalyst body) carrying gold fine particles. The amount of gold supported was measured by ICP and found to be 1.3 wt%.

(Production of catalyst body (alumina beads) carrying gold fine particles)
Α-alumina beads (catalyst) carrying gold fine particles on α-alumina (aluminum oxide) beads (manufactured by Daimei Chemical Co., Ltd.) having a diameter of 500 μm and a purity of 99.99 wt% were obtained. The amount of gold supported was measured by ICP and found to be 0.5 wt%.

(Production of catalyst body (zirconia beads) carrying gold fine particles)
Zirconia beads (catalyst bodies) carrying gold fine particles were obtained in the same procedure as described above except that zirconia (zirconium oxide) beads having a diameter of 500 μm and a purity of 99.5 wt% were used. The amount of gold supported was measured by ICP and found to be 0.5 wt%.

(Low temperature plasma reactor)
In this example, the plasma reactor 1000 provided with the low temperature plasma applying means shown in FIG. 15 was used. Reference numeral 12 denotes a ground electrode in which a high-voltage electrode is provided on a cylindrical glass tube, and reference numeral 11 denotes an applied electrode in which an electrode is formed by applying a silver paste on the outer wall and using a copper tape. Reference numeral 100 denotes a catalyst body supporting gold fine particles used for the reaction. Reference numeral 14 denotes an AC high voltage power source. In addition, a voltage is applied to the application electrode 11 by the power source 14 to generate discharge, and plasma is generated in the plasma existence region 9.

  An AC high-voltage power source composed of a function generator and a high-voltage amplifier was used for plasma generation. The applied voltage was set in the range of 0-30 kVpk-pk, and the frequency was fixed at 50 Hz. The discharge power was determined by the V-Q Lissajous method.

A CO oxidation reaction test was conducted as a test for removing harmful gases contained in combustion exhaust gas. In the CO oxidation reaction test, the initial concentration of CO gas was adjusted to 1000 ppm, and the flow rate was adjusted to 500 mL / min. In the gas analysis, the gas passing through the plasma reactor 1000 was quantitatively analyzed for CO and CO ₂ by FTIR equipped with a gas cell having an optical path length of 2.4 m. The CO oxidation reaction rate was calculated from the following formula.
CO oxidation reaction rate (%) = {(initial CO concentration-CO concentration after reaction) / initial CO concentration} x 100

Example 1
An alumina fabric carrying gold fine particles was placed in the reactor, a plasma was applied, and a CO oxidation reaction test was performed. The applied voltage was 26.28 kVpk-pk discharge power was 0.38W.

(Comparative Example 1)
The alumina fabric carrying the gold fine particles of Example 1 was put in the reactor, and a CO oxidation reaction test was conducted without applying plasma.

(Comparative Example 2)
A CO oxidation reaction test was conducted by applying plasma without putting an alumina fabric carrying gold fine particles in the reactor. The applied voltage was 26.28 kVpk-pk discharge power was 0.38W.

  Table 1 shows the conditions of Example 1 and Comparative Examples 1 and 2.

CO gas was allowed to flow under the conditions of Example 1 and Comparative Examples 1 and 2, and a CO oxidation reaction test was performed. The results are shown in Table 2. The CO oxidation reaction rate is the CO reaction rate obtained by the above formula, and indicates that CO is oxidized to CO ₂ by the amount of the obtained oxidation reaction rate, and CO ₂ is generated.

  From the above results, CO could not be oxidized only with plasma (Comparative Example 2). It was confirmed that with only the gold catalyst without applying plasma (Comparative Example 1), the CO oxidation reaction rate decreased with time, and the CO oxidation reaction rate was maintained by using the gold catalyst and plasma in combination. .

  Subsequently, CO gas was circulated and a CO oxidation reaction test over time was performed at room temperature. It was made to distribute | circulate to the gas processing apparatus 600 shown in FIG. The ground electrode 12 is formed of an alumina plate, and the application electrode 11 is an electrode formed of copper tape outside the dielectric 13. The dielectric 13 is α-alumina. The catalyst body 100 was arranged in a gap (gap is 1 mm) between the dielectric 13 in contact with the application electrode 11 and the dielectric 13 in contact with the ground electrode 12. An AC high-voltage power source composed of a function generator and a high-voltage amplifier was used for plasma generation. The applied voltage was set in the range of 0-30 kVpk-pk, and the frequency was fixed at 50 Hz. The discharge power was determined by the V-Q Lissajous method.

The initial concentration of the CO gas was adjusted to 1000 ppm and the flow rate was adjusted to 500 mL / min, and the CO gas was circulated through the gas processing apparatus 600. In the gas analysis, CO and CO ₂ were quantitatively analyzed by FTIR equipped with a gas cell having an optical path length of 2.4 m.

(Example 2)
A silicon carbide woven fabric carrying gold fine particles was placed in the reactor, plasma was applied, and a CO oxidation reaction test was performed. The applied voltage was 7.2 Vpk-pk discharge power was 0.5 W.

Example 3
A zirconia fabric carrying gold fine particles was placed in the reactor, a plasma was applied, and a CO oxidation reaction test was performed. The applied voltage was 7.2 kVpk-pk discharge power was 0.5 W.

Example 4
An α-alumina film-formed aluminum plate carrying gold fine particles was placed in the reactor, plasma was applied, and a CO oxidation reaction test was performed. The applied voltage was 7.2 kVpk-pk discharge power was 0.5 W.

(Example 5)
Α-alumina beads carrying gold fine particles were placed in the reactor, plasma was applied, and a CO oxidation reaction test was performed. The applied voltage was 7.2 kVpk-pk discharge power was 0.5 W.

(Example 6)
Zirconia beads carrying gold fine particles were placed in the reactor, plasma was applied, and a CO oxidation reaction test was performed. The applied voltage was 7.2 kVpk-pk discharge power was 0.5 W.

(Example 7)
A PET nonwoven fabric carrying gold fine particles was placed in the reactor, plasma was applied, and a CO oxidation reaction test was performed. The applied voltage was 7.2 kVpk-pk discharge power was 0.5 W.

  Table 3 shows the conditions of Examples 2 to 7.

  CO gas was allowed to flow under the conditions of Examples 2 to 7, and a CO oxidation reaction test was performed. The results are shown in Table 4.

  From the above results, in Example 7, the CO oxidation reaction rate after 0.5 hours of gas flow was high, but when the state of the substrate after 20 hours was confirmed, the PET nonwoven fabric itself, which is an organic material, was deteriorated. It was confirmed. In Examples 2 to 6 using an inorganic material for the substrate, it was confirmed that the CO oxidation reaction rate was maintained. By using an inorganic material for the substrate, the substrate is not deteriorated and a decrease in catalytic activity can be suppressed.

DESCRIPTION OF SYMBOLS 100 Catalyst body 200 Flue gas processing unit 300 Flue gas processing unit of other embodiment 400 Flue gas processing unit of other embodiment 500 Flue gas processing unit of other embodiment 600 Flue gas processing unit of other embodiment 700 Other Flue gas treatment unit 800 CO ₂ supply device 900 plasma reactor 1-a catalyst fine particle 1-b carrier fine particle 1-c inorganic particle 2 silane monomer 3 chemical bond 4 oxide film 5 pore 8 discharge space 9 plasma presence Region 10 Substrate 11 Applied electrode 12 Ground electrode 13 Dielectric 14 Power supply 20 Boiler 21 Blower fan 22 Filter 23 Adsorbent 24 Combustion exhaust gas treatment unit 31 Bonding interface peripheral portion (corner portion)
32 Bonding interface edge (edge)

Claims (4)

A flow path through which the gas to be treated flows,
A first electrode, a second electrode, and a dielectric disposed between the first electrode and the second electrode and disposed in close contact with at least one of the electrodes disposed in the flow path A plasma generating unit that generates plasma by applying a voltage between the first electrode and the second electrode to generate a discharge, and
A catalyst part that promotes the reaction of the gas to be treated provided at a position where the plasma generated by the plasma generation part is present in the flow path, wherein the gold particles and the gold particles are fixed on the surface. A catalyst part having oxide particles and a woven fabric made of fibers containing silicon carbide to which the inorganic oxide particles are fixed ;
A filter that removes soot and smoke contained in the gas, and an adsorbent that adsorbs at least one of NOx and SOx, disposed upstream of the plasma generation unit and the catalyst unit in the gas flow direction;
A flue gas treatment unit comprising: The first electrode, the second electrode, the dielectric, and the catalyst unit are arranged side by side in the flow direction of the gas to be treated, and each has air permeability in the flow direction of the gas,
2. The combustion exhaust gas treatment unit according to claim 1, wherein the catalyst unit is formed downstream of the discharge generation space or the discharge generation space in the flow path in the gas flow direction. Wherein the first electrode and the second electrode dielectric and front Symbol catalyst section, the combustion exhaust gas according to claim 1, characterized in that it is arranged in a direction perpendicular to the flow direction of the gas Processing unit. A boiler that burns fuel and discharges gas;
Processing the exhaust gas discharged from the boiler, CO ₂ supply device, wherein the combustion exhaust gas treatment unit, in that it comprises a according to any of claims 1 to 3.

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