JPH07102301B2 - Ozone decomposition catalyst filter and ozone decomposer - Google Patents
Ozone decomposition catalyst filter and ozone decomposerInfo
- Publication number
- JPH07102301B2 JPH07102301B2 JP1322374A JP32237489A JPH07102301B2 JP H07102301 B2 JPH07102301 B2 JP H07102301B2 JP 1322374 A JP1322374 A JP 1322374A JP 32237489 A JP32237489 A JP 32237489A JP H07102301 B2 JPH07102301 B2 JP H07102301B2
- Authority
- JP
- Japan
- Prior art keywords
- ozone
- carrier
- catalyst filter
- catalyst
- substance
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 title claims description 101
- 239000003054 catalyst Substances 0.000 title claims description 50
- 238000000354 decomposition reaction Methods 0.000 title claims description 43
- 239000000126 substance Substances 0.000 claims description 35
- 239000013543 active substance Substances 0.000 claims description 27
- 239000007788 liquid Substances 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000000034 method Methods 0.000 description 28
- 239000000835 fiber Substances 0.000 description 14
- 239000007789 gas Substances 0.000 description 12
- 230000000694 effects Effects 0.000 description 10
- 239000011148 porous material Substances 0.000 description 10
- 239000011248 coating agent Substances 0.000 description 9
- 238000000576 coating method Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 239000002002 slurry Substances 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 229910010413 TiO 2 Inorganic materials 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 229920000049 Carbon (fiber) Polymers 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- 239000004917 carbon fiber Substances 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 239000012784 inorganic fiber Substances 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 239000005416 organic matter Substances 0.000 description 3
- 238000005949 ozonolysis reaction Methods 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229920000297 Rayon Polymers 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229920000609 methyl cellulose Polymers 0.000 description 2
- 239000001923 methylcellulose Substances 0.000 description 2
- 235000010981 methylcellulose Nutrition 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 238000006864 oxidative decomposition reaction Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000002964 rayon Substances 0.000 description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- 229910020599 Co 3 O 4 Inorganic materials 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 229920002978 Vinylon Polymers 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000009675 coating thickness measurement Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000004453 electron probe microanalysis Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 210000004072 lung Anatomy 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 210000004400 mucous membrane Anatomy 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- -1 polyethylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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
Landscapes
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Catalysts (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、工場などから排出される廃液や排ガス等の中
に含まれるオゾンを分解するためのオゾン分解用触媒フ
ィルターおよびオゾン分解器に関する。TECHNICAL FIELD The present invention relates to an ozone decomposing catalyst filter and an ozone decomposing device for decomposing ozone contained in waste liquid, exhaust gas and the like discharged from factories and the like.
空気や、水の中に含まれるオゾンは不快臭を発し、喉
や、肺の粘膜を刺激するなど、健康に悪影響を与えるた
め、環境衛生上の見地から、これを除去することが行わ
れている。Ozone contained in air and water gives off an unpleasant odor and has a negative effect on health, such as irritating the throat and mucous membranes of the lungs, so it is removed from the viewpoint of environmental hygiene. There is.
従来のオゾンの除去方法としては、活性炭、ゼオライト
等の多孔性物質を用いる吸着法、MnO2等の触媒を用いる
酸化分解法などがある。Conventional ozone removal methods include an adsorption method using a porous material such as activated carbon and zeolite, and an oxidative decomposition method using a catalyst such as MnO 2 .
しかしながら、上記従来のオゾンの除去方法は、いずれ
も満足し得るものではなかった。However, none of the above-mentioned conventional methods of removing ozone is satisfactory.
すなわち、吸着法では、吸着剤が飽和するたびに再生ま
たは交換を要するので、メンテナンスに多大の労力と費
用を要した。That is, since the adsorption method requires regeneration or replacement each time the adsorbent is saturated, a great deal of labor and cost are required for maintenance.
また、酸化分解法では、吸着法の場合のような問題はな
いものの、既存のオゾン分解用触媒では十分にオゾンを
酸化分解することができなかったり、或いは、高負荷条
件下（高濃度、高SV）において触媒が劣化するという問
題があった。In addition, although the oxidative decomposition method does not have the problem of the adsorption method, the existing ozone decomposition catalyst cannot sufficiently oxidize and decompose ozone, or under high load conditions (high concentration and high concentration). There was a problem that the catalyst deteriorates in SV).
これらの問題を解消するための一策として、オゾン含有
ガスの温度を上げることが考えられるが、昇温のために
多大の費用を要し処理コストが高くなってしまうので、
実用的な解決策とは言い難い。As one measure for solving these problems, it is possible to raise the temperature of the ozone-containing gas, but since it requires a large amount of money to raise the temperature and the processing cost becomes high,
It's hard to say a practical solution.
本発明は以上の事情に鑑みなされたものであって、その
目的とするところは、高負荷条件下（高濃度、高SV）に
おいても大きな反応速度でオゾンを酸化分解することが
でき、しかも経済的なオゾン分解用触媒フィルターおよ
びオゾン分解器を提供するにある。The present invention has been made in view of the above circumstances, and an object thereof is to be able to oxidize and decompose ozone at a large reaction rate even under a high load condition (high concentration, high SV), and to be economical. The present invention provides a catalytic filter for ozone decomposition and an ozone decomposer.
上記目的を達成するための本発明に係るオゾン分解用触
媒フィルターは、オゾン含有ガスまたは液体を通流させ
るための複数の流路が設けられた、導電性の発熱抵抗物
質を含有してなる担体の前記流路を形成する面に、オゾ
ン分解用の触媒活性物質を担持させてなるオゾン分解用
触媒フィルターであって、前記触媒活性物質が10〜200
μｍの厚みに担持されているものであり、また本発明に
係るオゾン分解器は、上記オゾン分解用触媒フィルター
に、前記発熱抵抗物質に通電するための電極が設けられ
てなる。The catalyst filter for ozone decomposition according to the present invention for achieving the above object, a carrier comprising a plurality of flow paths for passing an ozone-containing gas or liquid, containing a conductive heating resistance substance The surface forming the flow path of, is a catalyst filter for ozone decomposition, which comprises a catalytic active substance for ozone decomposition, wherein the catalytic active substance is 10 to 200.
The ozone decomposer according to the present invention is provided with electrodes for energizing the heat generating resistance substance in the ozone decomposition catalyst filter.
本発明における担体は、押出成形法、抄紙法等の従来公
知の手段により導電性の発熱抵抗物質を含有させて作製
される。The carrier in the present invention is produced by incorporating a conductive heat-generating resistance substance by a conventionally known means such as an extrusion molding method or a papermaking method.
かかる導電性の発熱抵抗物質としては、通電により発熱
する抵抗物質であれば特に制限されず、例えばグラファ
イト、カーボンファイバー、炭化ケイ素、銀、ニッケル
クロム合金、クロムアルミニウム合金、ステンレス粉な
どを用いることができる。その形状は、特に制限される
ものではなく、粉体、ウイスカー状、短繊維等の種々の
形状のものを用いることができる。The conductive heat generating resistance substance is not particularly limited as long as it is a resistance substance that generates heat by energization, and for example, graphite, carbon fiber, silicon carbide, silver, nickel chrome alloy, chrome aluminum alloy, stainless powder and the like can be used. it can. The shape is not particularly limited, and various shapes such as powder, whiskers, and short fibers can be used.
発熱抵抗物質の発熱温度は、30℃以上が好ましく、40℃
以上がより好ましく、50℃以上がさらに好ましい。発熱
温度が30℃を下回ると、オゾンが触媒と反応し、生成す
る高原子価酸化物が分解されず、触媒中に酸素が蓄積す
るので、分解サイクル速度が徐々に低下し、その結果分
解反応速度（分解活性）が低下するため、好ましくな
い。The exothermic temperature of the exothermic resistance substance is preferably 30 ° C or higher, 40 ° C
The above is more preferable, and 50 ° C. or more is further preferable. When the exothermic temperature falls below 30 ° C, ozone reacts with the catalyst, the generated high-valent oxide is not decomposed, and oxygen accumulates in the catalyst, so the decomposition cycle speed gradually decreases, and as a result, the decomposition reaction It is not preferable because the speed (decomposition activity) decreases.
発熱抵抗物質の含有量は、該発熱抵抗物質の種類および
製造方法により異なるが、押出成形法による場合は、約
70〜30％の範囲が好ましい。70％を越えると、押出材料
の可塑性が損なわれ押出が不可能となり、また30％未満
であると、抵抗値が極めて大きくなり絶縁体に近くなっ
て電流が流れ難くなり、その結果触媒活性物質を加熱す
るのに必要とされる充分な発熱が得られない。The content of the exothermic resistance substance varies depending on the kind of the exothermic resistance substance and the manufacturing method, but in the case of the extrusion molding method, it is about
The range of 70-30% is preferred. If it exceeds 70%, the plasticity of the extruded material will be impaired and extrusion will be impossible, and if it is less than 30%, the resistance value will be extremely large and it will be close to the insulator, making it difficult for current to flow, and as a result, the catalytically active substance The sufficient exotherm needed to heat the can is not obtained.
なお、必要に応じて、その他にアビセル、ポリオレフィ
ン樹脂、ナイロン樹脂粉などを細孔付与剤として配合し
てもよい。In addition, Avicel, polyolefin resin, nylon resin powder, and the like may be added as a pore-providing agent, if necessary.
担体の形状は、オゾン含有ガスまたは液体を通流させる
ための複数の流路が設けられたものであれば特に制限さ
れず、例えば第３図に示すようなハニカム状、第４図に
示すようなコルゲート状、第５図に示すような複数の平
板を所定寸法離隔して平行に配した形状など、種々の形
状とすることができる。なお、第６図は第３図に示した
ハニカム状担体の流路近傍を拡大して示したものであ
る。The shape of the carrier is not particularly limited as long as it is provided with a plurality of flow paths for allowing the ozone-containing gas or liquid to flow therethrough. For example, a honeycomb shape as shown in FIG. 3 or a honeycomb shape as shown in FIG. Various shapes such as a corrugated shape and a shape in which a plurality of flat plates as shown in FIG. Note that FIG. 6 is an enlarged view of the vicinity of the flow path of the honeycomb-shaped carrier shown in FIG.
押出成形法によりハニカム状担体などを製造する場合
は、例えば成形材料として、Al2O3、SiO2、Al2O3−Si
O2、TiO2、クレー、ZrO2等の無機粉を、また成形助剤と
して、メチルセルロース、ポリビニルアルコール、ポリ
塩化ビニル、ポリエチレンオキサイド等の有機材料を、
さらに発熱抵抗物質として、上記例示のものを用いるこ
とができる。When manufacturing a honeycomb-shaped carrier or the like by an extrusion molding method, for example, as a molding material, Al 2 O 3 , SiO 2 , Al 2 O 3 -Si
O 2 , TiO 2 , clay, inorganic powders such as ZrO 2 as a molding aid, organic materials such as methyl cellulose, polyvinyl alcohol, polyvinyl chloride, polyethylene oxide,
Further, as the heat generating resistance substance, the substances exemplified above can be used.
ハニカム状担体における流路の断面形状は、特に限定さ
れるものではなく、第３図および第６図に示した四角形
のほか、必要に応じて六角形、三角形等の任意の形状に
することが可能である。The cross-sectional shape of the channels in the honeycomb-shaped carrier is not particularly limited and may be any shape such as a hexagon or a triangle, if necessary, in addition to the quadrangle shown in FIGS. 3 and 6. It is possible.
また、ハニカム状担体の壁厚（第６図におけるｔ）は約
0.1〜1.0mm程度、ピッチ（第６図におけるｐ）は約1.0
〜7.0mm程度が適当である。The wall thickness of the honeycomb-shaped carrier (t in FIG. 6) is about
0.1 to 1.0 mm, pitch (p in Fig. 6) is about 1.0
About 7.0mm is suitable.
次に、抄紙法により担体を製造する場合について説明す
る。Next, the case where the carrier is manufactured by the papermaking method will be described.
抄紙法における抄紙材料としては、セラミックファイバ
ー、ガラスファイバー、カーボンファイバー、アルミナ
ファイバー等の無機繊維、または親水性で水中分散性の
良い、例えばレーヨン、セルロース繊維（パルプ）など
が用いて最適である。その他、ビニロン、アクリル、ポ
リエステル繊維などの有機繊維を用いることもできる。As a papermaking material in the papermaking method, inorganic fibers such as ceramic fibers, glass fibers, carbon fibers and alumina fibers, or hydrophilic and good dispersibility in water, such as rayon and cellulose fibers (pulp), are optimally used. In addition, organic fibers such as vinylon, acrylic and polyester fibers can be used.
これらの抄紙材料は、１種単独で用いてもよく、必要に
応じて２種以上併用してもよい。These papermaking materials may be used alone or in combination of two or more as required.
すなわち、例えばオゾン負荷が大きいため触媒加熱温度
を高くする必要がある場合にあっては、耐熱性の高い抄
紙材料を用いる必要があり、かかる場合には無機繊維を
多く使用して抄造した紙を用いることが好ましい。この
場合の好適な抄紙材料の配合比は、通常無機繊維80〜96
重量％（以下、「％」と略記する）、有機繊維２〜10
％、有機結合剤２〜10％である。なお、有機物が多いほ
ど、抄紙および焼成前の成形加工は容易になるが、仕上
品たる担体に強度不足が生じ易いので、有機物総量を15
％以内に押さえることが望ましい。That is, for example, when it is necessary to raise the catalyst heating temperature because the ozone load is large, it is necessary to use a papermaking material with high heat resistance, and in such a case, paper made using a large amount of inorganic fibers is used. It is preferable to use. In this case, the preferred papermaking material compounding ratio is usually 80 to 96 inorganic fibers.
% By weight (hereinafter abbreviated as “%”), organic fiber 2 to 10
%, Organic binder 2-10%. It should be noted that as the amount of organic matter increases, the papermaking and the forming process before firing become easier, but the strength of the carrier as a finished product tends to be insufficient, so the total amount of organic matter should be 15
It is desirable to keep it within%.
なお、上記有機結合剤は、繊維の分散性を高めるととも
に、繊維相互を接着して焼成前の紙力を大きくするため
に用いられるものである。かかる有機結合剤としては、
繊維状のポリビニルアルコール樹脂が抄造時の歩留まり
が良く最適である。その他、有機結合剤として、アクリ
ル樹脂、酢酸ビニル樹脂、ポリエチレン、酢酸ビニル樹
脂、尿素樹脂、メラミン樹脂、CMC（カルボキシメチル
セルロース）、デンプンなども、水溶液、エマルジョ
ン、粉末、繊維などの形態で用いることができる。The organic binder is used to enhance the dispersibility of the fibers and to bond the fibers to each other to increase the paper strength before firing. As such an organic binder,
A fibrous polyvinyl alcohol resin is suitable because it has a good yield during papermaking. In addition, as an organic binder, acrylic resin, vinyl acetate resin, polyethylene, vinyl acetate resin, urea resin, melamine resin, CMC (carboxymethyl cellulose), starch, etc. may be used in the form of aqueous solution, emulsion, powder, fiber, etc. it can.
抄紙法による場合においても、以上の他に先に例示した
ところの発熱抵抗物質が配合される。この発熱抵抗物質
の紙中への配合量は30〜50％とすることが好ましい。30
％未満の場合、抵抗が大きくなり、また50％を越えた場
合、抄造が極めて難しくなる。なお、発熱抵抗物質の配
合は、抄紙段階で行ってもよく、また抄紙法により担体
を製造した後で、該担体に発熱抵抗物質を含浸担持させ
てこれに導電性を付与するようにしてもよい。Even in the case of the papermaking method, the exothermic resistance substances as exemplified above are blended in addition to the above. It is preferable that the heat-resistant substance is incorporated in the paper in an amount of 30 to 50%. 30
If it is less than 50%, the resistance becomes large, and if it exceeds 50%, papermaking becomes extremely difficult. The exothermic resistance substance may be compounded at the papermaking stage, or after the carrier is manufactured by the papermaking method, the exothermic resistance substance may be impregnated and carried on the carrier to impart conductivity thereto. Good.
抄紙法においては、先ず上記抄紙材料を、常法により0.
1〜0.3％程度の濃度のスラリーとする。次いで、このス
ラリーを長網式または丸網式等の抄紙機にて、厚さ0.15
〜0.50mm、密度0.2〜0.4g/cm3（いずれも乾燥後の値）
の紙に抄造した後で、必要に応じて触媒担体としてより
好ましい適宜の形状、例えばコルゲート状などに成形加
工する。この成形工程では、例えば段ボール製造用のコ
ルゲート加工機を用いて、任意の波高および波間隔の波
形を付与したりすることが行い得る。もっとも、平板状
のままで担体として用いる場合においては、かかる加工
は必要とされない。なお、紙の成形加工は、接着や穿孔
など曲げを伴わないものであれば最終製品について行う
こともできるが、波状に型付けするような曲げ加工はこ
の段階で行っておく必要がある。In the papermaking method, first, the above papermaking material is subjected to a conventional method of 0.
Use a slurry with a concentration of about 1 to 0.3%. Then, this slurry is used in a fourdrinier or round-net paper machine to obtain a thickness of 0.15.
~ 0.50 mm, density 0.2 ~ 0.4 g / cm 3 (value after drying)
After the paper is made into paper, it is formed into an appropriate shape more preferable as a catalyst carrier, such as a corrugated shape, if necessary. In this molding step, for example, a corrugating machine for corrugated board production can be used to impart a waveform with an arbitrary wave height and wave interval. However, such processing is not required when the plate-shaped product is used as a carrier as it is. It should be noted that the paper can be formed on the final product as long as it does not cause bending such as adhesion or perforation, but it is necessary to perform the bending such as corrugation at this stage.
加工形状は波状以外にも任意に選ぶことができる。ま
た、波状とする場合でも、その波形は正弦波状に限定さ
れるものではなく、矩形状、鋸歯状など、適宜の形状と
することができる。The processing shape can be arbitrarily selected other than the wavy shape. Further, even in the case of the wavy shape, the waveform is not limited to the sine wave shape, but may have an appropriate shape such as a rectangular shape or a sawtooth shape.
本発明に係るオゾン分解用触媒フィルターは、以上の如
くして得られた導電性の担体に、触媒活性物質を担持さ
せて作製される。The catalyst filter for ozone decomposition according to the present invention is produced by supporting the catalytically active substance on the conductive carrier obtained as described above.
本発明にお触媒活性物質としては、従来公知の種々のオ
ゾン分解用触媒、例えばMnO2、MoO3、CuO、Fe2O3、Ag
2O、NiO、Co3O4、WO3、V2O5、MoO3、SnO2、Pt、Pdなど
を用いることができる。これらのオゾン分解用触媒は、
１種単独で用いてもよく、必要に応じて２種以上併用し
てもよい。As the catalytically active substance in the present invention, various conventionally known ozone decomposition catalysts, for example, MnO 2 , MoO 3 , CuO, Fe 2 O 3 and Ag are used.
2 O, NiO, Co 3 O 4 , WO 3 , V 2 O 5 , MoO 3 , SnO 2 , Pt, Pd and the like can be used. These ozone decomposition catalysts are
They may be used alone or in combination of two or more as required.
その他、本出願人が先に出願した、MnO2−TiO2、MnO2−
アルカリ金属及び／またはアルカリ土類金属酸化物、酸
化物生成エンタルピーが100Kcal/g酸素原子以下の金属
を担持したゼオライト触媒などを用いることも可能であ
る（特願昭63−277090、特願平１−55796号、特願平１
−57259、特願平１−35304、特願平１−41330号）。In addition, the present applicant has previously filed, MnO 2 -TiO 2, MnO 2 -
It is also possible to use an alkali metal and / or alkaline earth metal oxide, a zeolite catalyst supporting a metal having an enthalpy of oxide formation of 100 Kcal / g or less oxygen atoms (Japanese Patent Application No. 63-277090, Japanese Patent Application No. 1-277090). -55796, Japanese Patent Application No. 1
-57259, Japanese Patent Application No. 1-35304, Japanese Patent Application No. 1-41330).
この場合、担体の触媒担持性を良好にするために導電性
の担体の細孔容積量は0.2cc/g以上であることが好まし
い。In this case, the pore volume of the conductive carrier is preferably 0.2 cc / g or more in order to improve the catalyst carrying property of the carrier.
担体への触媒活性物質の担持は、例えば次に示す如き含
浸法や、ウオッシュコート法を用いて行うことができ
る。The support of the catalytically active substance on the carrier can be carried out, for example, by the following impregnation method or washcoat method.
（含浸法） 触媒活性物質前駆体を含有する溶液中に、オゾン含有ガ
スまたは液体の通流方向に沿って複数の流路が設けられ
た、導電性の発熱抵抗物質を含有する担体を浸漬して該
溶液を該成形体に含浸し、過剰の溶液を除去した後に乾
燥し、焼成などの手段によって前駆体を活性物質となす
ことによってオゾン分解用触媒フィルターを得る方法で
ある。(Impregnation Method) A carrier containing a conductive heat generating resistance substance, in which a plurality of flow paths are provided along the flowing direction of an ozone-containing gas or liquid, is immersed in a solution containing a catalyst active substance precursor. Is a method for obtaining a catalyst filter for ozone decomposition by impregnating the shaped body with the solution, removing the excess solution, and then drying and making the precursor an active substance by means such as firing.
この方法においては、触媒活性物質の量はオゾン分解用
触媒フィルターの前重量基準で、５％以上が好ましい。
５％未満では充分な分解活性が得られないからである。
もっとも、通常の方法では、30％を越える量の触媒活性
物質を担持させることは困難である。In this method, the amount of the catalytically active substance is preferably 5% or more on the basis of the weight of the catalyst filter for ozone decomposition.
This is because if it is less than 5%, sufficient decomposition activity cannot be obtained.
However, it is difficult to carry a catalytically active substance in an amount exceeding 30% by a usual method.
（ウオッシュコート法） 触媒活性物質を含有するスラリー中に前記同様の担体を
浸漬し、次いで過剰スラリーを除去した後乾燥すること
によってオゾン分解用触媒フィルターを得る方法であ
る。(Washcoat Method) This is a method of obtaining a catalyst filter for ozone decomposition by immersing the same carrier as described above in a slurry containing a catalytically active substance, then removing excess slurry and then drying.
この方法における担体の触媒担持量は、担持される触媒
が例えば平均細孔径300〜400Å、単位重量あたりの細孔
容積量0.26〜0.29ml/gのとき、0.05〜0.5g/ccであるこ
とが好ましい。0.05g/cc未満の場合、触媒効果が不十分
で所望のオゾン分解率が得られず、0.5g/ccを越えた場
合、触媒の担持が極めて不均一で、担持量に相応した触
媒効果が得られない。しかし、これらの値は、担持され
た触媒の細孔構造によっても多少異なる。The catalyst loading amount of the carrier in this method is, for example, 0.05 to 0.5 g / cc when the loaded catalyst has an average pore diameter of 300 to 400 Å and a pore volume amount per unit weight of 0.26 to 0.29 ml / g. preferable. If it is less than 0.05 g / cc, the catalytic effect is insufficient and the desired ozone decomposition rate cannot be obtained, and if it exceeds 0.5 g / cc, the loading of the catalyst is extremely uneven, and the catalytic effect corresponding to the loading amount is obtained. I can't get it. However, these values also vary somewhat depending on the pore structure of the supported catalyst.
本発明に係るオゾン分解用触媒フィルター及びオゾン分
解器の触媒活性物質の厚み（以下、「被覆厚」という）
は、10〜200μｍである。被覆厚を10μｍより薄くした
場合、単位容積当たりのオゾン分解効率が低くなってし
まい、また被覆厚を200μｍより厚くしても、オゾン分
解速度は大きくならない。Thickness of the catalytically active substance of the ozone decomposing catalyst filter and ozone decomposing device according to the present invention (hereinafter referred to as "coating thickness")
Is 10 to 200 μm. When the coating thickness is less than 10 μm, the ozone decomposition efficiency per unit volume becomes low, and even when the coating thickness is more than 200 μm, the ozone decomposition rate does not increase.
その他、被覆厚を200μｍを越えて厚くすると、下記
（１）〜（３）に示す如き問題が生じる傾向がある。In addition, if the coating thickness is made thicker than 200 μm, the following problems (1) to (3) tend to occur.
（１）圧損が大きくなり、送風に多大の動力および費用
を要し経済的でない。(1) The pressure loss becomes large, and a large amount of power and cost are required for blowing air, which is not economical.
（２）触媒活性物質による担体の被覆が不均一になるた
め、ガス流路が不均一になり、その結果、担体に担持さ
れた触媒への反応物質の気相拡散の有効係数が次第に低
下して、被覆量を多くしたにもかかわらず、容積あたり
の活性度が低下してしまう。(2) Since the coating of the carrier with the catalytically active substance becomes non-uniform, the gas flow path becomes non-uniform, and as a result, the effective coefficient of vapor phase diffusion of the reaction substance to the catalyst carried on the carrier gradually decreases. As a result, the activity per unit volume is reduced even though the coating amount is increased.
（３）一度担持された触媒活性物質の剥離量が増加し、
周囲の環境がひどく汚染される。(3) The amount of peeling of the catalytically active substance once supported increases,
The surrounding environment is heavily polluted.
本発明においては、触媒活性物質とともに、さらに必要
に応じて繊維状物質を担体に担持させてもよい。In the present invention, if necessary, a fibrous substance may be supported on the carrier together with the catalytically active substance.
この場合の繊維状物質としては、耐オゾン性を有し、担
体に担持させることが容易であるものであればよく、例
えばムライト質のセラミックファイバー、ＣもしくはＥ
ガラスなどのガラスファイバー、ステンレスファイバー
などのL/Dの大きな繊維状物質あるいはチタン酸カリ、
炭化珪素ウィスカーなどのようなL/Dの小さな繊維状物
質などが挙げられる。なお、担体への担持、機械的オゾ
ン分解、および触媒活性物質と繊維状物質とのオゾン分
解相乗作用の点から、繊維直径は0.1〜20μｍ、L/Dは担
体に担持された状態で10〜1000が好ましい。この範囲を
逸脱すると担体への担持が困難となり、機械的オゾン分
解効果が低下し触媒活性物質と繊維状物質とのオゾン分
解相乗作用が低下する。In this case, the fibrous substance may be any substance that has ozone resistance and can be easily supported on a carrier, such as mullite ceramic fiber, C or E.
Glass fiber such as glass, fibrous substance with large L / D such as stainless fiber or potassium titanate,
Examples include fibrous substances having a small L / D such as silicon carbide whiskers. From the viewpoint of supporting on a carrier, mechanical ozonolysis, and synergistic action of ozone decomposition between a catalytically active substance and a fibrous substance, the fiber diameter is 0.1 to 20 μm, and L / D is 10 to 10 in a state of being supported on the carrier. 1000 is preferred. If it deviates from this range, it becomes difficult to carry it on the carrier, the mechanical ozone decomposing effect is lowered, and the ozone decomposing synergistic effect between the catalytically active substance and the fibrous substance is lowered.
上記繊維状物質は、担持物質全重量を基準として２〜20
％の割合で配合するのが好ましい。２％未満であると繊
維状物質の添加効果が充分に発揮されず、20％を越える
と担体に担持させることが極めて難しくなったり、担持
が不均一になったり、担持された触媒が有効に触媒機能
を発揮しなくなったりする。The fibrous material is 2 to 20 based on the total weight of the supported material.
It is preferable to blend in a ratio of%. If it is less than 2%, the effect of adding the fibrous substance is not sufficiently exerted, and if it exceeds 20%, it becomes extremely difficult to support it on the carrier, the carrier becomes uneven, and the supported catalyst becomes effective. It may not function as a catalyst.
本発明に係るオゾン分解器は、上記オゾン分解用触媒フ
ィルターに、さらに電極が装着されてなる。The ozonolysis device according to the present invention is configured by further mounting electrodes on the above-mentioned catalytic filter for ozonolysis.
この場合の電極は、発熱抵抗物質に通電し得るものであ
ればよく、銅、ステンレス、アルミニウム、活性炭等の
従来公知の材料からなる電極を用いることができ、その
形状も板状、円柱状、筒状、線状など、用いる担体の形
状に合わせて種々の形状とすることができる。The electrode in this case may be one that can conduct electricity to the heating resistance substance, and an electrode made of a conventionally known material such as copper, stainless steel, aluminum, or activated carbon can be used, and the shape thereof is also plate-like, cylindrical, Various shapes such as a tubular shape and a linear shape can be adopted depending on the shape of the carrier used.
以下、本発明に係るオゾン分解器を用いてオゾン分解処
理を行う方法を、ハニカム状のオゾン分解用触媒フィル
ターを組み込んだオゾン分解器を用いる場合を一例にし
て、図を参照しつつ説明する。Hereinafter, a method of performing an ozone decomposing process using the ozone decomposing device according to the present invention will be described with reference to the drawings, taking a case of using an ozone decomposing device incorporating a honeycomb-shaped catalyst filter for ozone decomposition as an example.
第１図は本発明に係るオゾン分解器１の一例を示し、同
図において、オゾン分解器１は、オゾン含有ガスまたは
液体の少なくとも通流方向に沿って貫通した複数の流路
14を有する導電性のオゾン分解用触媒フィルターおよび
電極板12、12から構成されている。FIG. 1 shows an example of an ozone decomposer 1 according to the present invention. In the figure, the ozone decomposer 1 has a plurality of flow passages that pass through at least the flow direction of an ozone-containing gas or liquid.
It is composed of a conductive ozone decomposition catalyst filter having 14 and electrode plates 12, 12.
オゾン分解用触媒フィルターは、発熱抵抗物質を含有す
る直方体状のハニカム状担体11に、触媒活性物質が流路
14の表面に担持されてなる。The catalyst filter for ozone decomposition has a rectangular parallelepiped honeycomb carrier 11 containing a heat-generating resistance substance, and a catalytically active substance in the channel.
It is supported on 14 surfaces.
オゾン分解用触媒フィルターの両側面には、厚み0.1〜
0.2mm程度の銅や、ステンレスなどからなる電極板12、1
2がハニカム状担体11に密着して設けられている。On both sides of the catalyst filter for ozone decomposition, the thickness of 0.1 ~
Electrode plates 12 and 1 made of about 0.2 mm copper or stainless steel
2 is provided in close contact with the honeycomb-shaped carrier 11.
以上の如き構成のオゾン分解器１を用いてオゾン分解を
行うには、両電極板12、12に導電線（リード線）13,13
を接続して発熱抵抗物質を含有するハニカム状担体11内
に通電する一方、ハニカム状担体11内にオゾン含有ガス
または液体を両電極板12、12の板面と平行方向（図中、
矢符で示す方向）通流させる。In order to perform ozone decomposition using the ozone decomposer 1 having the above-described structure, conductive wires (lead wires) 13 and 13 are attached to both electrode plates 12 and 12.
While supplying electricity to the honeycomb-shaped carrier 11 containing the heating resistance material by connecting the ozone-containing gas or liquid in the honeycomb-shaped carrier 11 in a direction parallel to the plate surfaces of both electrode plates 12 and 12 (in the figure,
Flow in the direction indicated by the arrow.
そうすると、通電により発熱した発熱抵抗物質が触媒活
性物質を加熱してその触媒活性を高め、その結果オゾン
含有ガスまたは液体中に含まれるオゾンが効率よく分解
される。Then, the exothermic resistance substance that has generated heat due to energization heats the catalytically active substance to enhance its catalytic activity, and as a result, ozone contained in the ozone-containing gas or liquid is efficiently decomposed.
なお、第２図に示す如く、上記オゾン分解器１を周囲と
絶縁すべく、電気絶縁性の高いケーシング21内に収容し
てもよい。As shown in FIG. 2, the ozone decomposer 1 may be housed in a casing 21 having high electric insulation so as to insulate it from the surroundings.
かかるオゾン分解器のオゾン分解率は、同一温度、同一
オゾン濃度の条件下ではAVによって規定されるが、使用
した担体の空孔の大きさや触媒活性物質の担持状態等に
よっても若干変化する。The ozone decomposition rate of such an ozone decomposer is defined by AV under the same temperature and same ozone concentration conditions, but it slightly changes depending on the size of the pores of the carrier used and the state of carrying the catalytically active substance.
本発明において、オゾン分解用触媒フィルターに設けら
れた電極に導電線を接続して、発熱抵抗物質に通電する
と、該発熱抵抗物質が発熱し、これによって触媒活性物
質が加熱されてその活性度が高められる。この状態でオ
ゾン含有ガスまたは液体を担体の流路に通流させると、
オゾンの分解が効率よく行われる。In the present invention, when a conductive wire is connected to an electrode provided in a catalyst filter for ozone decomposition and a heating resistance substance is energized, the heating resistance substance generates heat, whereby the catalytically active substance is heated and its activity is reduced. To be enhanced. When the ozone-containing gas or liquid is caused to flow through the flow path of the carrier in this state,
Ozone is efficiently decomposed.
以下、本発明を実施例に基づいてさらに詳細に説明する
が、本発明は下記実施例に何ら限定されるものではな
く、その要旨を変更しない範囲において適宜変更して実
施することが可能なものである。Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to the following examples and can be carried out by appropriately changing the scope without changing the gist thereof. Is.
I.オゾン分解用触媒フィルターの作製 （実施例１） 比表面積58m2/g、平均粒子径17μｍのアナタース型酸化
チタン2kgとグラファイト粉末600g（中越黒鉛工業所製
合成黒鉛Ｇ−6S）とメチルセルロース（信越化学製、商
品名「Hi−メトローズ」）60gと水とを充分に混練し
た。I. Preparation of catalyst filter for ozone decomposition (Example 1) 2 kg of anatase-type titanium oxide having a specific surface area of 58 m 2 / g and an average particle diameter of 17 μm, and 600 g of graphite powder (synthetic graphite G-6S manufactured by Chuetsu Graphite Industry Co., Ltd.) and methylcellulose ( Shin-Etsu Chemical, trade name "Hi-Metroses") 60 g and water were sufficiently kneaded.
次いで、得られた混練物を、ピッチが1.3mm、壁厚が0.2
mmのハニカム成形用ダイスを装着した押出機にて押出
し、このようにして得られた成形体を通風乾燥後、さら
に100℃で18時間乾燥し、その後450℃で３時間焼成して
導電性のハニカム状担体を得た。Then, the obtained kneaded product, pitch 1.3mm, wall thickness 0.2
Extruded by an extruder equipped with a honeycomb forming die of mm, air-dried the thus obtained molded body, further dried at 100 ° C. for 18 hours, and then baked at 450 ° C. for 3 hours to make it conductive. A honeycomb carrier was obtained.
得られたハニカム状担体の細孔容積量および平均細孔径
は、それぞれ0.33cc/g、185Åであった。The pore volume and average pore diameter of the obtained honeycomb-shaped carrier were 0.33 cc / g and 185 Å, respectively.
次に、比表面積32m2/g、平均粒子径30μｍのMnO2−Ag2O
−TiO2（MnO2:70％、Ag2O:10％、TiO2:20％）100gとシ
リカゲル（日産化学社製、商品名「スノーテックス
Ｏ」）80mlとを混合し、さらにこれにアルミナビーズ15
0mlを加えて30分間湿式粉砕してスラリーを得た。Next, MnO 2 -Ag 2 O with a specific surface area of 32 m 2 / g and an average particle size of 30 μm
-TiO 2 (MnO 2: 70% , Ag 2 O: 10%, TiO 2: 20%) 100g and silica gel (manufactured by Nissan Chemical Industries, Ltd., trade name "Snowtex O") were mixed with 80 ml, further alumina thereto Beads 15
0 ml was added and wet-milled for 30 minutes to obtain a slurry.
このスラリー中に、前記したハニカム成形体を浸漬し、
エアブローにて過剰スラリーを除去した後、50℃で18時
間乾燥して、オゾン分解用触媒フィルターを作製した。In this slurry, dip the honeycomb formed body described above,
After removing excess slurry by air blow, it was dried at 50 ° C. for 18 hours to prepare a catalyst filter for ozone decomposition.
乾燥後、得られたオゾン分解用触媒フィルターの単位容
積あたりの触媒活性物質担持量を重量測定法により、ま
た触媒の担体被覆厚をコート層を剥離しその厚みを走査
型電子顕微鏡により目視にてそれぞれ測定したところ、
それぞれ0.21g/ccおよび63μｍであった。なお、上記触
媒の担体被覆厚は50箇所における被覆厚測定値の平均値
として求めたものである。After drying, the amount of the catalytically active substance supported per unit volume of the obtained ozone decomposition catalyst filter was measured by a gravimetric method, and the carrier coating thickness of the catalyst was peeled off the coating layer and the thickness was visually observed by a scanning electron microscope. When I measured each,
It was 0.21 g / cc and 63 μm, respectively. The carrier coating thickness of the above catalyst was obtained as an average value of coating thickness measurement values at 50 locations.
（実施例２） 実施例１と同様にしてハニカム状担体を得、これを酢酸
マンガン水溶液（MnO2として300g/）中に浸漬し、過
剰溶液をエアブローにて除去した後、さらに80℃で通風
乾燥した。次いで、100℃で18時間乾燥し、その後450℃
で３時間焼成してオゾン分解用触媒フィルターを作製し
た。(Example 2) A honeycomb-shaped carrier was obtained in the same manner as in Example 1, immersed in a manganese acetate aqueous solution (300 g / MnO 2 ) to remove excess solution by air blow, and then ventilated at 80 ° C. Dried. Then, dry at 100 ℃ for 18 hours, then 450 ℃
It was calcined for 3 hours to prepare a catalyst filter for ozone decomposition.
このオゾン分解用触媒フィルター中のMnO2含有率は9.1
％であった。また、その流路壁面における触媒活性物質
の分布をEPMAを用いて測定したところ触媒活性物質は壁
面より60μｍ以内に大部分が存在していた。The MnO 2 content in this ozone decomposition catalyst filter was 9.1.
%Met. When the distribution of the catalytically active substance on the wall surface of the flow channel was measured by using EPMA, most of the catalytically active substance was present within 60 μm from the wall surface.
（実施例３） アルミナシリカ系セラミック繊維（太さ2.6〜3.0μｍ、
長さ５〜30mm、ニチアス社製、商品名「ファインフレッ
クス」）70重量部（以下、「部」と略記する）、レーヨ
ン繊維（太さ1.5デニール、長さ5mm）５部、カーボンフ
ァイバー（関西タール社製、商品コード「Ｓ−231」）3
5部および有機結合剤としての繊維状ポリビニルアルコ
ール樹脂５部を配合し、これを340倍量の水に分散させ
た後、丸網式抄紙機にて常法により抄造し、得られた紙
を段ボール加工機により180℃でコルゲート加工した
（波高2.2mm）。(Example 3) Alumina-silica ceramic fiber (thickness 2.6 to 3.0 μm,
5 to 30 mm in length, manufactured by Nichias, trade name "Fineflex") 70 parts by weight (hereinafter abbreviated as "part"), 5 parts rayon fiber (thickness 1.5 denier, length 5 mm), carbon fiber (Kansai Made by Tar Co., product code "S-231") 3
5 parts and 5 parts of a fibrous polyvinyl alcohol resin as an organic binder were blended and dispersed in 340 times the amount of water, and then papermaking was carried out by a conventional method on a round net paper machine to obtain the obtained paper. Corrugated at 180 ° C with a corrugated board machine (wave height 2.2 mm).
次いで、これにエチルシリケート（シリカ固形分40％）
8.0部、エチルアルコール13部、水６部および５％の塩
酸１部からなる混合液を、SiO2として100g/紙100gの割
合で吹付け、３時間湿空中に放置した後乾燥し、その後
450℃の酸化性雰囲気下で焼成して、有機物を焼去し、
コルゲート状担体を得た。Then, to this, ethyl silicate (silica solid content 40%)
8.0 parts of ethyl alcohol 13 parts, a mixed solution comprising 6 parts of water and 5% of 1 part hydrochloric acid, dried after standing as SiO 2 only spray at a rate of 100 g / paper 100 g, the air humidity 3 hours, then
Burning in an oxidizing atmosphere at 450 ° C to burn off organic matter,
A corrugated carrier was obtained.
このコルゲート状担体の細孔容積量および平均細孔径
は、それぞれ0.71cc/g、2362Åであった。The pore volume and average pore diameter of this corrugated carrier were 0.71 cc / g and 2362Å, respectively.
上記コルゲート状担体を、実施例１と同様にして作製し
たスラリー中に浸漬し、次いで過剰スラリーを除去した
後通風乾燥した。この操作を２回繰り返した後、100℃
で18時間乾燥してオゾン分解用触媒フィルターを作製し
た。The corrugated carrier was immersed in a slurry prepared in the same manner as in Example 1, and then excess slurry was removed, followed by ventilation drying. After repeating this operation twice, 100 ℃
And dried for 18 hours to prepare a catalyst filter for ozone decomposition.
このオゾン分解用触媒フィルターの触媒活性物質担持量
および触媒の担体被覆厚を実施例１と同様にして測定し
たところ、それぞれ0.34g/cc及び156μｍであった。The amount of the catalytically active substance supported on this catalyst filter for ozone decomposition and the carrier coating thickness of the catalyst were measured in the same manner as in Example 1, and they were 0.34 g / cc and 156 μm, respectively.
II.オゾン分解器の作製 実施例１〜３で得た各オゾン分解用触媒フィルターを、
縦30mm×横30mm×厚み20mmの直方体にカットし、この相
対向する両側面にステンレス（SUS304）電極を取り付
け、通電してその抵抗値を測定したところ、それぞれ93
Ω、91Ω、258Ωであった。II. Manufacture of Ozone Decomposing Device Each of the ozone decomposing catalyst filters obtained in Examples 1 to 3 is
It was cut into a rectangular parallelepiped measuring 30 mm in length × 30 mm in width × 20 mm in thickness, and stainless steel (SUS304) electrodes were attached to both sides facing each other.
It was Ω, 91Ω, and 258Ω.
次いで、これらをそれぞれ電気絶縁性のケーシング21内
に収容してオゾン分解器を作製した。Next, each of these was housed in an electrically insulating casing 21 to produce an ozone decomposer.
III.オゾン分解試験 上記IIで得た各オゾン分解器についてオゾン分解試験を
行った。すなわち、エアーをオゾン発生器に通じてこれ
に所定濃度のオゾンを含有させた後、オゾン分解器に導
入し、オゾン分解器を通過したエアー中のオゾン濃度を
オゾン分析計にて測定し、次式によりオゾン分解率を求
めた。III. Ozone decomposition test An ozone decomposition test was conducted on each of the ozone decomposers obtained in II above. That is, air is passed through an ozone generator to contain a predetermined concentration of ozone therein, and then introduced into the ozone decomposer, and the ozone concentration in the air passing through the ozone decomposer is measured by an ozone analyzer. The ozone decomposition rate was calculated by the formula.
（C1−C2）/C1×100 ただし、 C1……オゾン分解器の入口でのオゾン濃度 C2……オゾン分解器の出口でのオゾン濃度 その結果を次表に示す。このとき、オゾン分解器内のハ
ニカム成形体には電流を通じて次表に示す温度に加熱し
た。その他の反応条件は次表に示す通りである。なお、
触媒層の温度およびガス出口温度はそれぞれ測温低抗体
により測定した。(C 1 -C 2 ) / C 1 × 100 However, C 1 ...... ozone concentration at the ozone decomposer inlet C 2 ...... ozone concentration at the ozone decomposer outlet The results are shown in the following table. At this time, the honeycomb formed body in the ozone decomposer was heated to the temperature shown in the following table by passing an electric current. Other reaction conditions are as shown in the following table. In addition,
The temperature of the catalyst layer and the gas outlet temperature were measured by the low temperature antibody.
表より、発熱抵抗物質への通電により担体が高温になる
ほど、オゾン分解率が高く、その効果が長時間にわたっ
て持続していることが分かる。 From the table, it can be seen that the higher the temperature of the carrier due to energization of the exothermic resistance substance, the higher the ozone decomposition rate and the longer lasting the effect.
以上、詳細に説明したように、本発明に係るオゾン分解
用触媒フィルターおよびオゾン分解器は、高負荷条件下
（高濃度、高SV）においても大きな反応速度でオゾンを
酸化分解することができ、しかもオゾン含有ガスまたは
液体自体を昇温させるものではないため経済的である
等、本発明は優れた特有の効果を奏する。As described above in detail, the catalyst filter for ozone decomposition and the ozone decomposer according to the present invention can oxidize and decompose ozone at a high reaction rate even under high load conditions (high concentration, high SV), In addition, the present invention has excellent peculiar effects in that it is economical because it does not raise the temperature of the ozone-containing gas or liquid itself.
第１図および第２図は本発明に係るオゾン分解器の斜視
図であり、第３図〜第５図は本発明における担体の斜視
図であり、第６図は第３図に示したハニカム状担体の流
路近傍の部分拡大図である。 １……オゾン分解器、11……担体、12……電極板（電
極）、13……導電線、14……流路、21……ケーシング1 and 2 are perspective views of an ozone decomposer according to the present invention, FIGS. 3 to 5 are perspective views of a carrier according to the present invention, and FIG. 6 is a honeycomb shown in FIG. It is a partial enlarged view of the vicinity of the flow path of the carrier. 1 ... Ozone decomposer, 11 ... Carrier, 12 ... Electrode plate (electrode), 13 ... Conductive wire, 14 ... Flow path, 21 ... Casing
───────────────────────────────────────────────────── フロントページの続き (72)発明者 永野 一彦 大阪府堺市戎島町５丁１番地 堺化学工業 株式会社内 (56)参考文献 特開 平３−8414（ＪＰ，Ａ) 特開 平２−284628（ＪＰ，Ａ) 特開 平２−298317（ＪＰ，Ａ) ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Kazuhiko Nagano 5-1, Ebishima-cho, Sakai City, Osaka Prefecture Sakai Chemical Industry Co., Ltd. (56) Reference JP 3-8414 (JP, A) JP JP 2 -284628 (JP, A) JP-A-2-298317 (JP, A)
Claims (3)
めの複数の流路が設けられた、導電性の発熱抵抗物質を
含有してなる担体の前記流路を形成する面に、オゾン分
解用の触媒活性物質を担持させてなるオゾン分解用触媒
フィルターであって、前記触媒活性物質が10〜200μｍ
の厚みに担持されていることを特徴とするオゾン分解用
触媒フィルター。1. A surface for forming a flow path of a carrier containing a conductive heat generating resistance substance, which is provided with a plurality of flow paths for passing an ozone-containing gas or liquid, for ozone decomposition. A catalyst filter for ozone decomposition, which carries the above-mentioned catalytically active substance, wherein said catalytically active substance is 10 to 200 μm.
The catalyst filter for ozone decomposition, characterized in that it is carried in the thickness of.
ーに、前記発熱抵抗物質に通電するための電極が設けら
れてなるオゾン分解器。2. An ozone decomposing device comprising an ozone decomposing catalyst filter according to claim 1 and electrodes provided thereon for energizing the heating resistance substance.
絶縁性のケーシング内に収容されてなるオゾン分解器。3. An ozone decomposer in which the ozone decomposer according to claim 2 is further housed in an electrically insulating casing.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1322374A JPH07102301B2 (en) | 1989-12-12 | 1989-12-12 | Ozone decomposition catalyst filter and ozone decomposer |
| DE69019228T DE69019228T2 (en) | 1989-05-19 | 1990-05-21 | Ozone splitting. |
| EP90305507A EP0398765B1 (en) | 1989-05-19 | 1990-05-21 | Ozone decomposition |
| US07/525,597 US5160586A (en) | 1989-05-19 | 1990-05-21 | Ozone decomposing reactor |
| US07/827,388 US5232882A (en) | 1989-05-19 | 1992-01-29 | Ozone decomposing reactor regeneration |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1322374A JPH07102301B2 (en) | 1989-12-12 | 1989-12-12 | Ozone decomposition catalyst filter and ozone decomposer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03181320A JPH03181320A (en) | 1991-08-07 |
| JPH07102301B2 true JPH07102301B2 (en) | 1995-11-08 |
Family
ID=18142934
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1322374A Expired - Fee Related JPH07102301B2 (en) | 1989-05-19 | 1989-12-12 | Ozone decomposition catalyst filter and ozone decomposer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07102301B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6598730B2 (en) * | 2016-05-12 | 2019-10-30 | 東芝三菱電機産業システム株式会社 | Discharge ozonolysis equipment |
| KR102473318B1 (en) * | 2020-09-15 | 2022-12-02 | 주식회사 캐스트 | Decomposition device of ozone |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0732863B2 (en) * | 1989-04-26 | 1995-04-12 | 株式会社日本触媒 | Waste ozone treatment method for corona discharger |
| JPH0738936B2 (en) * | 1989-05-11 | 1995-05-01 | 株式会社日本触媒 | Ozone decomposition method |
| JPH038414A (en) * | 1989-06-06 | 1991-01-16 | Sakai Chem Ind Co Ltd | Method for regenerating catalyst |
-
1989
- 1989-12-12 JP JP1322374A patent/JPH07102301B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH03181320A (en) | 1991-08-07 |
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