WO2011132741A1 - Production method for ozone gas reduction catalyst support and catalyst support - Google Patents

Production method for ozone gas reduction catalyst support and catalyst support Download PDF

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WO2011132741A1
WO2011132741A1 PCT/JP2011/059841 JP2011059841W WO2011132741A1 WO 2011132741 A1 WO2011132741 A1 WO 2011132741A1 JP 2011059841 W JP2011059841 W JP 2011059841W WO 2011132741 A1 WO2011132741 A1 WO 2011132741A1
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catalyst
ozone gas
catalyst support
catalyst carrier
gas reduction
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PCT/JP2011/059841
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French (fr)
Japanese (ja)
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益夫 平岩
隆時 南
修次 植木
僚一 宮鍋
誠 中八児
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ニチダイフィルタ株式会社
三井造船株式会社
クロリンエンジニアズ株式会社
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Priority to CN2011800035490A priority Critical patent/CN102481567A/en
Publication of WO2011132741A1 publication Critical patent/WO2011132741A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/44—Palladium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0215—Coating
    • B01J37/0225—Coating of metal substrates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0215—Coating
    • B01J37/0225—Coating of metal substrates
    • B01J37/0226—Oxidation of the substrate, e.g. anodisation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/10—Noble metals or compounds thereof
    • B01D2255/102—Platinum group metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/10—Noble metals or compounds thereof
    • B01D2255/102—Platinum group metals
    • B01D2255/1023—Palladium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/209—Other metals
    • B01D2255/2092—Aluminium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/10—Single element gases other than halogens
    • B01D2257/106—Ozone
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8671—Removing components of defined structure not provided for in B01D53/8603 - B01D53/8668
    • B01D53/8675—Ozone
    • 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
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters

Definitions

  • the present invention relates to a catalyst carrier for reducing ozone gas and a method for producing the same.
  • Oxidation or reduction is performed by using alumina as a carrier on a medium substrate, carrying a catalyst substance on the medium, and passing a gas containing a reactant through a linear flow path formed in the structure.
  • Oxidation or reduction is performed by using alumina as a carrier on a medium substrate, carrying a catalyst substance on the medium, and passing a gas containing a reactant through a linear flow path formed in the structure.
  • restoration it reduced by passing the gas containing ozone gas through the catalyst cylinder packed with the granular manganese dioxide.
  • Patent Document 1 discloses that after roughening the surface of a metal, fine particles having catalyst carrying activity are bound to the surface to carry an ultrafine catalyst material, and a sponge-like metal is used. Has been.
  • Patent Documents 2 and 4 a silica-alumina compound to which 2.5 to 10% by mass of silica is added based on the total mass, a gelled product is produced by a gelation reaction from a metal alkoxide of aluminum and silicon. Is freeze-dried to obtain a porous structure.
  • Patent Documents 3 and 4 a mixed conductive oxide of oxygen ion conduction and electron conduction is dispersed in an aqueous solution or organic solvent solution of nitrate, chloride, or chloride of palladium, platinum, and / or rhodium, and the solvent is evaporated and removed. , Heat treatment at 600 ° C. or higher to obtain a catalyst material for removing nitrogen oxides.
  • Patent Documents 1 to 4 relate to improvement of the contact area between the catalyst and a substance that is brought into contact with the catalyst to cause an oxidation or reduction reaction (hereinafter referred to as a reactive substance), or prevent bonding between the catalytic substances, although it has been disclosed for uniform dispersion and the like, no improvement has been considered for the catalyst support substrate.
  • Patent Documents 1 to 4 although it can be understood that the area where the reactant is brought into contact with the catalyst is large to some extent, since the flow path formed in the honeycomb structure is linear, the catalyst substance and the reactant can be contacted. In order to improve the property and increase the reaction efficiency, it is necessary to lengthen the flow path, and it is difficult to make the structure small.
  • Patent Documents 1 to 4 as described above, the reactant is present in the fluid, and the fluid is allowed to pass from one side to the other side. There was a problem that it was scarce, very brittle and vulnerable to impact. Further, in the case of a honeycomb structure made of a stainless steel thin plate, there is a problem that it is difficult to form a flow path smaller than a certain size, and the cost is increased.
  • the problem to be solved is to produce a base material for a catalyst carrier that has excellent rigidity and further increases the contact possibility between the catalytic material and the reactant, instead of the honeycomb structure, and the granular material as the catalytic material.
  • Manganese dioxide is easily crushed, easily absorbs moisture, and has the property of becoming liquefied if it absorbs too much moisture, and there is a problem in durability, and therefore, an alternative catalyst material is employed.
  • the present invention is a catalyst having excellent durability and efficiency in place of manganese dioxide, which is currently generally used for reducing ozone gas, and producing a catalyst-supporting substrate having excellent rigidity and economy.
  • a base material of the catalyst carrier is a porous body obtained by sintering a material composed of a single metal mesh or a material in which a plurality of metal meshes are laminated.
  • a reduction catalyst carrier is obtained by forming an alumina thin layer in which a platinum group metal or oxide thereof, or a mixture thereof is dispersed and supported on the surface of the substrate.
  • the present invention can secure a wide surface area of the alumina thin layer as a support by using a porous substrate, can freely select the pore diameter to some extent according to the amount of reactant contained in the gas, There is an advantage that the total thickness can be flexibly adjusted by the number of sheets.
  • a plate-like porous body can be obtained by diffusion bonding, cutting and bending are possible, the degree of freedom of molding is high, and the amount of catalyst supported can be changed for each individual substrate. It is also possible to save expensive catalyst materials.
  • the present invention for the reduction treatment of ozone gas, as a synergistic effect of the above advantages, the treatment efficiency of ozone gas is improved and the economy is excellent.
  • FIGS. 1A and 1B are diagrams showing the results of experiments for confirming the effects of the present invention.
  • the method for producing an ozone gas reduction catalyst carrier of the present invention comprises a catalyst comprising a porous body obtained by sintering a reduction catalyst carrier of ozone gas, a material made of a single metal mesh, or a material in which a plurality of metal meshes are laminated.
  • An ozone gas reduction catalyst carrier is obtained by forming a thin alumina layer on which platinum group metals, oxides thereof, or mixtures thereof are dispersed and supported on the surface of the substrate.
  • the catalyst material a platinum group metal, its oxide, or a mixture thereof can be selected. However, if the catalyst material is palladium metal, a simple substance of its oxide, or a mixture thereof, a suitable ozone gas reduction catalyst.
  • a carrier is obtained.
  • ozone gas reduction catalyst carrier of the present invention for example, a plurality of catalyst carriers are used as necessary, and ozone gas-containing gas is passed through each of them to efficiently reduce the ozone gas.
  • a solution obtained by adding a platinum group metal nitrate powder as a catalyst material to an alumina sol solution is applied to the base material that has been previously roughened, or applied to the solution.
  • the substrate is immersed and adhered, it is formed by firing at a temperature of 600 ° C. to 700 ° C. to produce an ozone gas reduction catalyst carrier.
  • an alumina thin layer is similarly formed on the surface of the base material in advance without adding platinum group metal nitrate powder, and then immersed in a platinum group metal nitrate solution.
  • the ozone gas reduction catalyst carrier is manufactured by baking with.
  • the ozone gas reduction catalyst carrier produced in the present invention is used as follows.
  • a porous material obtained by sintering a material obtained by laminating a plurality of metal meshes is used as a base material for a catalyst support, and a catalyst support in which an alumina thin layer is formed on the surface of the base material by dispersing and supporting platinum group metal as a catalyst material.
  • a plurality of bodies are installed in a container, and a gas containing ozone gas is passed through the container to reduce ozone gas harmful to the human body into harmless oxygen.
  • the reason why the sintered wire mesh is used is that the degree of freedom of opening is high.
  • wire nets that are readily available in the market have abundant apertures ranging from 0.005 mm to 1 cm or more, and the apertures, rigidity, and porosity are different. This is because the material has excellent rigidity.
  • the wires are firmly fused with the wires in contact with the individual wires, and there is an advantage that the wires are not displaced, that is, a stable open state can be secured even when stress is applied.
  • the wire mesh used for the base material of the catalyst carrier is preferably made of, for example, a stainless material. This is because it has excellent corrosion resistance, is marketable, and is easily available. Of course, a wire mesh made of copper other than stainless steel, a copper alloy, nickel, or the like may be used, but the other metal to be mixed is preferably a material considering corrosion resistance.
  • the SV value (l / h) obtained by dividing the reaction capacity (m 3 / hour) by the amount of filtration material (for example, 1 liter). ) Is preferably carried out at 1000 to 100,000 l / h. The reason is that if it is less than 1000 l / h, the catalyst becomes excessive, and its capacity cannot be fully used. If it is greater than 100000 l / h, the catalyst capacity is exceeded, and there is a high possibility that the reduction cannot be performed sufficiently. Because.
  • the LV value (cm / sec) obtained by dividing the reaction capacity (m 3 / hour) by the area (m 2 ) is 10 to 200 cm / sec. It is desirable to do. The reason for this is that if it is less than 10 cm / sec, the catalyst does not function sufficiently and the efficiency with respect to the catalyst capacity is lowered, and if it is greater than 200 cm / sec, the catalyst capacity is exceeded and it becomes difficult to treat the entire amount.
  • Palladium nitrate was added into an alumina sol solution, and the above-mentioned catalyst supporting substrate was immersed in this solution. Then, this was dried and fired at a temperature of about 650 ° C. in an air atmosphere. As a result, an alumina thin layer was obtained on the surface of the substrate, and at the same time, a catalyst carrier in which palladium, palladium oxide, or a mixture thereof as a catalyst material was dispersed and supported in the alumina thin layer was produced.
  • the estimated thickness of the alumina thin layer was 0.005 mm, the palladium catalyst material particle diameter was about 10 to 20 nm, and the catalyst loading was about 1.7 g / liter of catalyst.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Organic Chemistry (AREA)
  • Environmental & Geological Engineering (AREA)
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Abstract

Conventional ceramic substrates break easily with impact and are even more susceptible to breakage if the openings are made larger. Substrates made of thin stainless steel plate cannot be manufactured at low cost, small flow paths are difficult to form thereon, and flow paths are linear because of the honeycomb structure, which means that the flow paths need to be lengthened to increase the chance of contact between a catalyst substance and a reactant, which makes reducing the size of the structure difficult. To solve these issues, disclosed is an ozone gas reduction catalyst support which uses a porous body wherein a raw material of one sheet of metal mesh or a raw material of a plurality of laminated metal meshes have been sintered, as a substrate for the catalyst support and which forms an alumina thin layer, which supports a platinum group metal or a platinum group metal oxide catalytic substance dispersed thereon, on the surface of this substrate.

Description

オゾンガス還元触媒担持体の製造方法及び触媒担持体Production method of ozone gas reduction catalyst carrier and catalyst carrier
　本発明は、オゾンガスを還元する触媒担持体およびその製造方法に関するものである。 The present invention relates to a catalyst carrier for reducing ozone gas and a method for producing the same.
　従来、特に自動車の排気ガスの浄化処理に関する酸化触媒あるいは還元触媒の製造の多くは、例えば以下の特許文献１～４に示すように、ステンレス薄板から成形した、あるいは焼成したセラミックのハニカム構造の触媒体用基材にアルミナを担持体として、これに触媒物質を担持させて、この構造体中に成形した直線的な流路に、反応物質を含む気体を通過させて、酸化あるいは還元を行うことが通例であった。また、オゾンガス還元については、粒状の二酸化マンガンを詰めた触媒筒にオゾンガスを含む気体を通過させることで、還元を行うことが多かった。 Conventionally, most of the production of an oxidation catalyst or a reduction catalyst particularly for an automobile exhaust gas purification treatment is performed by using a ceramic honeycomb structure formed or fired from a thin stainless steel plate as shown in, for example, Patent Documents 1 to 4 below. Oxidation or reduction is performed by using alumina as a carrier on a medium substrate, carrying a catalyst substance on the medium, and passing a gas containing a reactant through a linear flow path formed in the structure. Was customary. Moreover, about ozone gas reduction | restoration, it reduced by passing the gas containing ozone gas through the catalyst cylinder packed with the granular manganese dioxide.
特開昭６２－２３７９４７号公報JP-A-62-237947 特開２００７－２２３８５６号公報JP 2007-223856 A 特開２００５－２５４２１７号公報JP 2005-254217 A 特表２００６－４１１７０号公報Special table 2006-41170 gazette
　特許文献１では、金属の表面を粗面化した後、該表面に触媒担持活性を有する微粒子を結着し、超微粒子の触媒物質を担持すること、また、海綿状の金属を用いることが開示されている。 Patent Document 1 discloses that after roughening the surface of a metal, fine particles having catalyst carrying activity are bound to the surface to carry an ultrafine catalyst material, and a sponge-like metal is used. Has been.
　特許文献２，４では、シリカが全質量ベースで２．５～１０質量％添加されたシリカ－アルミナ系化合物で、アルミニウムとシリコンの金属アルコキシドからゲル化反応によりゲル化物を作製し、このゲル化物を凍結乾燥して、多孔質構造体を得ることが開示されている。 In Patent Documents 2 and 4, a silica-alumina compound to which 2.5 to 10% by mass of silica is added based on the total mass, a gelled product is produced by a gelation reaction from a metal alkoxide of aluminum and silicon. Is freeze-dried to obtain a porous structure.
　特許文献３、４では、パラジウム、白金、及び／又はロジウムの硝酸塩あるいは塩化物の水溶液あるいは有機溶媒溶液に、酸素イオン伝導と電子伝導の混合伝導酸化物を分散し、該溶媒を蒸発除去した後、６００℃以上で加熱処理して窒素酸化物除去用触媒材料を得ることが開示されている。 In Patent Documents 3 and 4, a mixed conductive oxide of oxygen ion conduction and electron conduction is dispersed in an aqueous solution or organic solvent solution of nitrate, chloride, or chloride of palladium, platinum, and / or rhodium, and the solvent is evaporated and removed. , Heat treatment at 600 ° C. or higher to obtain a catalyst material for removing nitrogen oxides.
　しかしながら、特許文献１～４では、触媒と触媒に接触させて酸化又は還元反応をさせる物質（以下、反応物質）との接触面積の向上に関して、あるいは触媒物質同士の結合を防止したり、微粒子化、均一分散化等に関しては開示されているものの、触媒担持体用基材の改善については何ら考慮されていなかった。 However, Patent Documents 1 to 4 relate to improvement of the contact area between the catalyst and a substance that is brought into contact with the catalyst to cause an oxidation or reduction reaction (hereinafter referred to as a reactive substance), or prevent bonding between the catalytic substances, Although it has been disclosed for uniform dispersion and the like, no improvement has been considered for the catalyst support substrate.
　すなわち、特許文献１～４では、反応物質を触媒と接触させる面積はある程度は広いことは把握できるものの、ハニカム構造体に形成する流路が直線的であるため、触媒物質と反応物質の接触可能性を高めて反応効率を上げるために、流路を長くすることが必要で、当該構造体を小さくすることが難しかった。 That is, in Patent Documents 1 to 4, although it can be understood that the area where the reactant is brought into contact with the catalyst is large to some extent, since the flow path formed in the honeycomb structure is linear, the catalyst substance and the reactant can be contacted. In order to improve the property and increase the reaction efficiency, it is necessary to lengthen the flow path, and it is difficult to make the structure small.
　また、特許文献１～４では、上記のように反応物質が流体中に存在し、かつその流体を一方側から他方側へ通過させるが、セラミック製のハニカム構造体の場合、基本的に剛性に乏しく、非常に脆くて衝撃に弱いといった問題があった。また、ステンレス薄板製のハニカム構造体の場合、流路を一定以上に小さく成形することが難しく、コストも高くなるといった問題点があった。 In Patent Documents 1 to 4, as described above, the reactant is present in the fluid, and the fluid is allowed to pass from one side to the other side. There was a problem that it was scarce, very brittle and vulnerable to impact. Further, in the case of a honeycomb structure made of a stainless steel thin plate, there is a problem that it is difficult to form a flow path smaller than a certain size, and the cost is increased.
　解決しようとする課題は、ハニカム構造に代えて、剛性に優れて、かつ触媒物質と反応物質の接触可能性をより高める触媒担持体用の基材を製造すること、及び触媒物質としての粒状の二酸化マンガンは、砕けやすく、水分を吸収しやすく、水分を吸いすぎると液状化する性質があり、耐久性に問題があるので、これに代わる触媒物質を採用すること、である。 The problem to be solved is to produce a base material for a catalyst carrier that has excellent rigidity and further increases the contact possibility between the catalytic material and the reactant, instead of the honeycomb structure, and the granular material as the catalytic material. Manganese dioxide is easily crushed, easily absorbs moisture, and has the property of becoming liquefied if it absorbs too much moisture, and there is a problem in durability, and therefore, an alternative catalyst material is employed.
　本発明は、剛性に優れ、かつ経済性に優れた触媒担持体の基材を製造すること、及びオゾンガスの還元に現在一般的に使用される二酸化マンガンに代わる耐久性と効率性に優れた触媒物質の採用と当該触媒物質を担持する触媒担持体の構造を提供すべく、１枚の金網からなる素材、又は複数枚の金網を積層した素材を焼結した多孔体を触媒担持体の基材とし、当該基材の表面に、白金族金属あるいはその酸化物、あるいはそれらの混合物を分散担持させたアルミナ薄層を形成して還元触媒担持体を得ることとした。 The present invention is a catalyst having excellent durability and efficiency in place of manganese dioxide, which is currently generally used for reducing ozone gas, and producing a catalyst-supporting substrate having excellent rigidity and economy. In order to provide a structure of a catalyst carrier that supports the use of the substance and the catalyst substance, a base material of the catalyst carrier is a porous body obtained by sintering a material composed of a single metal mesh or a material in which a plurality of metal meshes are laminated. Then, a reduction catalyst carrier is obtained by forming an alumina thin layer in which a platinum group metal or oxide thereof, or a mixture thereof is dispersed and supported on the surface of the substrate.
　本発明は、多孔体の基材を用いることで担持体となるアルミナ薄層の表面積を広く確保できること、気体中に含有される反応物質の量に応じて開孔径をある程度自由に選択できること、金網の枚数によって全体の厚さを柔軟に調整できるといった利点がある。 The present invention can secure a wide surface area of the alumina thin layer as a support by using a porous substrate, can freely select the pore diameter to some extent according to the amount of reactant contained in the gas, There is an advantage that the total thickness can be flexibly adjusted by the number of sheets.
　また、焼結した金網を用いることで、拡散結合により板状の多孔体が得られ、切断と曲げ加工が可能で成形の自由度が高く、個々の基材毎に触媒担持量を変化させて、高価な触媒物質の節約を図るといったことも可能となる。 In addition, by using a sintered wire mesh, a plate-like porous body can be obtained by diffusion bonding, cutting and bending are possible, the degree of freedom of molding is high, and the amount of catalyst supported can be changed for each individual substrate. It is also possible to save expensive catalyst materials.
　したがって、本発明をオゾンガスの還元処理に用いることで、以上の利点の相乗効果として、オゾンガスの処理効率が向上し、さらに経済性に優れることとなる。 Therefore, by using the present invention for the reduction treatment of ozone gas, as a synergistic effect of the above advantages, the treatment efficiency of ozone gas is improved and the economy is excellent.
図１（ａ）（ｂ）は、本発明の効果を確認するための実験の結果を示す図である。FIGS. 1A and 1B are diagrams showing the results of experiments for confirming the effects of the present invention.
　本発明のオゾンガス還元触媒担持体の製造方法は、オゾンガスの還元触媒担持体を、１枚の金網からなる素材、又は複数枚の金網を積層した素材を焼結した多孔体を触媒担持体の基材とし、この基材の表面に、白金族金属、その酸化物、あるいはそれらの混合物を分散担持させたアルミナ薄層を形成してオゾンガス還元触媒担持体を得る。触媒物質としては、白金族金属、その酸化物、あるいはそれらの混合物を選択することができるが、触媒物質がパラジウム金属あるいは、その酸化物の単体、あるいはそれらの混合物であれば好適なオゾンガス還元触媒担持体が得られる。 The method for producing an ozone gas reduction catalyst carrier of the present invention comprises a catalyst comprising a porous body obtained by sintering a reduction catalyst carrier of ozone gas, a material made of a single metal mesh, or a material in which a plurality of metal meshes are laminated. An ozone gas reduction catalyst carrier is obtained by forming a thin alumina layer on which platinum group metals, oxides thereof, or mixtures thereof are dispersed and supported on the surface of the substrate. As the catalyst material, a platinum group metal, its oxide, or a mixture thereof can be selected. However, if the catalyst material is palladium metal, a simple substance of its oxide, or a mixture thereof, a suitable ozone gas reduction catalyst. A carrier is obtained.
　そして、本発明のオゾンガス還元触媒担持体の実施に関しては、例えば触媒担持体を必要に応じて複数個使用して、これらそれぞれにオゾンガス含有の気体を通過させて、オゾンガスを効率的に還元する。 Then, regarding the implementation of the ozone gas reduction catalyst carrier of the present invention, for example, a plurality of catalyst carriers are used as necessary, and ozone gas-containing gas is passed through each of them to efficiently reduce the ozone gas.
　当該基材の表面に形成するアルミナ薄層については、アルミナゾル溶液に触媒物質となる白金族金属の硝酸塩の粉末を加えた溶液を、予め粗面化した当該基材に塗布するか、当該溶液に当該基材を浸漬して付着させてから、これを６００℃から７００℃の温度で焼成することにより形成して、オゾンガス還元触媒担持体を製造する。又は、該基材の表面に予め白金族金属の硝酸塩の粉末を加えずにアルミナ薄層を同様に形成してから、白金族金属の硝酸塩溶液に浸漬し、その後にこれを同じく６００～７００℃で焼成することにより、オゾンガス還元触媒担持体を製造する。 For the alumina thin layer to be formed on the surface of the base material, a solution obtained by adding a platinum group metal nitrate powder as a catalyst material to an alumina sol solution is applied to the base material that has been previously roughened, or applied to the solution. After the substrate is immersed and adhered, it is formed by firing at a temperature of 600 ° C. to 700 ° C. to produce an ozone gas reduction catalyst carrier. Alternatively, an alumina thin layer is similarly formed on the surface of the base material in advance without adding platinum group metal nitrate powder, and then immersed in a platinum group metal nitrate solution. The ozone gas reduction catalyst carrier is manufactured by baking with.
　本発明で製造されたオゾンガス還元触媒担持体は、以下のようにして使用される。例えば、複数枚の金網を積層した素材を焼結した多孔体を触媒担持体の基材とし、この基材の表面に白金族金属を触媒物質として分散担持させたアルミナ薄層を形成した触媒担持体を、必要に応じて複数個容器に設置し、この容器にオゾンガスを含有した気体を通過させて、人体に有害なオゾンガスを無害な酸素に還元する。 The ozone gas reduction catalyst carrier produced in the present invention is used as follows. For example, a porous material obtained by sintering a material obtained by laminating a plurality of metal meshes is used as a base material for a catalyst support, and a catalyst support in which an alumina thin layer is formed on the surface of the base material by dispersing and supporting platinum group metal as a catalyst material. If necessary, a plurality of bodies are installed in a container, and a gas containing ozone gas is passed through the container to reduce ozone gas harmful to the human body into harmless oxygen.
　本発明において、焼結した金網を採用した理由は、開孔の自由度が高いためである。例えば、市場で容易に入手できる金網はその開孔が０．００５ｍｍから１ｃｍ以上まで豊富に存在しており、開孔、剛性、空隙率がそれぞれ相違しており、これらを組み合わせて焼結することで、剛性にも優れた素材となるからである。 In the present invention, the reason why the sintered wire mesh is used is that the degree of freedom of opening is high. For example, wire nets that are readily available in the market have abundant apertures ranging from 0.005 mm to 1 cm or more, and the apertures, rigidity, and porosity are different. This is because the material has excellent rigidity.
　また、金網を焼結することにより、個々の線材が接する線材と強固に融合し、線材が位置ずれを起こさず、すなわち、応力が加わっても安定した開孔状態を確保できる利点がある。 Also, by sintering the wire mesh, the wires are firmly fused with the wires in contact with the individual wires, and there is an advantage that the wires are not displaced, that is, a stable open state can be secured even when stress is applied.
　触媒担持体の基材に用いる金網は、例えばステンレス材を主材料とすることが望ましい。この理由は耐食性に優れており、市場性があり入手が容易であるためである。もちろん、ステンレス以外の銅あるいは銅合金製、あるいはニッケル製等の金網でもよいが、混合する他金属は耐食性を考慮した材料とすることが好ましい。 The wire mesh used for the base material of the catalyst carrier is preferably made of, for example, a stainless material. This is because it has excellent corrosion resistance, is marketable, and is easily available. Of course, a wire mesh made of copper other than stainless steel, a copper alloy, nickel, or the like may be used, but the other metal to be mixed is preferably a material considering corrosion resistance.
　さらに、本発明において、触媒担持体を設置し、気体を通過させる処理に関しては、例えば、反応能力（ｍ3 ／ｈｏｕｒ）をろ過材料量（例えば１リットルなど）で除算したＳＶ値（ｌ／ｈ）を１０００～１０００００ｌ／ｈで行うことが望ましい。この理由は、１０００ｌ／ｈより小さいと触媒が過剰となり、その能力を十分に使用することができず、１０００００ｌ／ｈより大きいと触媒能力を超えてしまい、還元が十分に行えない可能性が高いためである。 Furthermore, in the present invention, with respect to the treatment in which the catalyst carrier is installed and the gas is allowed to pass through, for example, the SV value (l / h) obtained by dividing the reaction capacity (m 3 / hour) by the amount of filtration material (for example, 1 liter). ) Is preferably carried out at 1000 to 100,000 l / h. The reason is that if it is less than 1000 l / h, the catalyst becomes excessive, and its capacity cannot be fully used. If it is greater than 100000 l / h, the catalyst capacity is exceeded, and there is a high possibility that the reduction cannot be performed sufficiently. Because.
　また、触媒担持体を設置し、気体を通過させる処理に関しては、例えば、反応能力（ｍ3 ／ｈｏｕｒ）を面積（ｍ2 ）で除算したＬＶ値（ｃｍ／ｓｅｃ）を１０～２００ｃｍ／ｓｅｃで行うことが望ましい。この理由は１０ｃｍ／ｓｅｃより小さいと触媒を十分に機能させてなく触媒能力に対する効率が低くなり、２００ｃｍ／ｓｅｃより大きいと触媒能力を超えてしまい全量処理が困難となるためである。 In addition, with regard to the process of installing a catalyst carrier and allowing gas to pass, for example, the LV value (cm / sec) obtained by dividing the reaction capacity (m 3 / hour) by the area (m 2 ) is 10 to 200 cm / sec. It is desirable to do. The reason for this is that if it is less than 10 cm / sec, the catalyst does not function sufficiently and the efficiency with respect to the catalyst capacity is lowered, and if it is greater than 200 cm / sec, the catalyst capacity is exceeded and it becomes difficult to treat the entire amount.
　以下に、本発明のオゾンガスの還元処理方法による効果を確認するために行った実験を説明する。 Hereinafter, an experiment conducted for confirming the effect of the ozone gas reduction treatment method of the present invention will be described.
（製造）
　ＳＵＳ３１６製の１６、２０、６０、及び３０メッシュの各１枚、計４枚の金網を積層し、真空熱処理炉で真空及び加圧下で約１２００～１３００℃で金網同士を焼結して、厚さ１．８ｍｍ、最小開孔径０．２５ｍｍ（２５０μｍ）、空隙率約６０％の多孔体の触媒担持体の基材を得て、直径５０ｍｍの円板状に成形した。 (Manufacturing)
A total of 4 wire meshes, each of 16, 20, 60, and 30 mesh made of SUS316, are laminated, and the wire meshes are sintered at about 1200-1300 ° C under vacuum and pressure in a vacuum heat treatment furnace. A base material of a porous catalyst support having a thickness of 1.8 mm, a minimum opening diameter of 0.25 mm (250 μm), and a porosity of about 60% was obtained and molded into a disk shape having a diameter of 50 mm.
　硝酸パラジウムをアルミナゾル溶液中に加えて、この溶液中に上記の触媒担持用の基材を浸漬し、その後、これを乾燥し、大気雰囲気下、約６５０℃の温度で焼成した。この結果、該基材の表面にアルミナ薄層を得ると同時にこのアルミナ薄層中に触媒物質であるパラジウム、パラジウム酸化物、あるいはそれらの混合物が分散担持された触媒担持体を製造した。該アルミナ薄層の推定厚さは０．００５ｍｍ、パラジウム触媒物質粒子径が約１０～２０ｎｍ、触媒担持量が約１．７ｇ／触媒リットルとなった。 Palladium nitrate was added into an alumina sol solution, and the above-mentioned catalyst supporting substrate was immersed in this solution. Then, this was dried and fired at a temperature of about 650 ° C. in an air atmosphere. As a result, an alumina thin layer was obtained on the surface of the substrate, and at the same time, a catalyst carrier in which palladium, palladium oxide, or a mixture thereof as a catalyst material was dispersed and supported in the alumina thin layer was produced. The estimated thickness of the alumina thin layer was 0.005 mm, the palladium catalyst material particle diameter was about 10 to 20 nm, and the catalyst loading was about 1.7 g / liter of catalyst.
（実施）
　上記のようにして製造した本発明の触媒担持体について、オゾナイザーで発生させたオゾンガスをそのままの状態で上記の触媒担持体中を通過させて、オゾンガス濃度が５～６００００ｐｐｍ（ｗ）の範囲で、還元率を測定した。その測定結果を、図１（ａ）（ｂ）に示す。 (Implementation)
About the catalyst carrier of the present invention produced as described above, the ozone gas generated by the ozonizer is passed through the catalyst carrier as it is, and the ozone gas concentration is in the range of 5 to 60000 ppm (w). The reduction rate was measured. The measurement results are shown in FIGS.
　なお、還元率の測定は、図１（ａ）では、ＳＶ値（ｌ／ｈ）を変化させて、図１（ｂ）では、ＬＶ値（ｃｍ／ｓｅｃ）を変化させて、各々行った。 Note that the reduction rate was measured by changing the SV value (l / h) in FIG. 1A and changing the LV value (cm / sec) in FIG. 1B.
　図１（ａ）の結果からは、触媒との接触時間の逆数であるＳＶ値を、１０００００ｌ／ｈ以下とすることで、オゾンガスの９０％以上を還元分解可能であることが判明した。また、図１（ｂ）の結果からは、ＬＶ値が１０～２００ｃｍ／ｓｅｃとすることで、オゾンガスの９０％以上の還元分解が可能であることが判明した。 From the results of FIG. 1 (a), it was found that 90% or more of ozone gas can be reduced and decomposed by setting the SV value, which is the reciprocal of the contact time with the catalyst, to 100000 l / h or less. Further, from the results of FIG. 1B, it was found that reductive decomposition of ozone gas by 90% or more is possible by setting the LV value to 10 to 200 cm / sec.

Claims (3)

  1. 　１枚の金網からなる素材、又は複数枚の金網を積層した素材を焼結した多孔体を触媒担持体の基材とし、当該基材の表面に、白金族金属あるいはその酸化物、あるいはそれらの混合物を分散担持させたアルミナ薄層を形成することを特徴とするオゾンガス還元触媒担持体の製造方法。 A porous body obtained by sintering a material composed of a single metal mesh or a material obtained by laminating a plurality of metal meshes is used as a base material of a catalyst carrier, and a platinum group metal or an oxide thereof, A method for producing an ozone gas reduction catalyst carrier, comprising forming an alumina thin layer on which a mixture is dispersed and supported.
  2. 　触媒物質がパラジウム金属あるいは、その酸化物の単体、あるいはそれらの混合物であることを特徴とする請求項１記載のオゾンガス還元触媒担持体の製造方法。 2. The method for producing an ozone gas reduction catalyst carrier according to claim 1, wherein the catalyst substance is palladium metal, an oxide simple substance, or a mixture thereof.
  3. 　請求項１または２のいずれかに記載された製造方法により製造される触媒担持体。 A catalyst carrier produced by the production method according to claim 1 or 2.
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