JP2008073571A - Photocatalyst-supported ceramic foam and its manufacturing method - Google Patents
Photocatalyst-supported ceramic foam and its manufacturing method Download PDFInfo
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- 239000000919 ceramic Substances 0.000 title claims abstract description 119
- 239000006260 foam Substances 0.000 title claims abstract description 115
- 238000004519 manufacturing process Methods 0.000 title claims description 25
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 88
- 239000011941 photocatalyst Substances 0.000 claims abstract description 53
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 41
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 39
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- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 13
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- 229910052693 Europium Inorganic materials 0.000 claims description 4
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 4
- 229910052689 Holmium Inorganic materials 0.000 claims description 4
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- 239000003638 chemical reducing agent Substances 0.000 claims description 4
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- 229910052737 gold Inorganic materials 0.000 claims description 4
- 229910052741 iridium Inorganic materials 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
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- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 229910052703 rhodium Inorganic materials 0.000 claims description 4
- 229910052707 ruthenium Inorganic materials 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- 229910052727 yttrium Inorganic materials 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 229910052765 Lutetium Inorganic materials 0.000 claims description 3
- 229910052772 Samarium Inorganic materials 0.000 claims description 3
- 230000001678 irradiating effect Effects 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims 1
- 229910052759 nickel Inorganic materials 0.000 claims 1
- 229910052706 scandium Inorganic materials 0.000 claims 1
- 230000001877 deodorizing effect Effects 0.000 abstract description 7
- 238000012423 maintenance Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 21
- 239000007789 gas Substances 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- 239000002002 slurry Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- 235000019645 odor Nutrition 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- 238000001179 sorption measurement Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 230000001590 oxidative effect Effects 0.000 description 5
- 229910010413 TiO 2 Inorganic materials 0.000 description 4
- 230000001699 photocatalysis Effects 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003463 adsorbent Substances 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000004332 deodorization Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 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
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
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- 150000003464 sulfur compounds Chemical class 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000004887 air purification Methods 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
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- 238000005470 impregnation Methods 0.000 description 1
- 239000002655 kraft paper Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 244000144972 livestock Species 0.000 description 1
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- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
本発明は光触媒担持セラミックフォームおよびその製造方法に係り、特に二酸化チタン光触媒の上に金属粒子等を部分的に点在させて、光触媒の酸化作用を利用し、臭気を効率良く吸着分解するのに適する光触媒担持セラミックフォームおよびその製造方法に関する。 The present invention relates to a photocatalyst-carrying ceramic foam and a method for producing the same, and in particular, by interspersing metal particles and the like partially on a titanium dioxide photocatalyst and utilizing the oxidation action of the photocatalyst to efficiently adsorb and decompose odor. The present invention relates to a suitable photocatalyst-supported ceramic foam and a method for producing the same.
光触媒は太陽や蛍光灯などの光が当たると、その表面で強力な酸化力が生まれ、接触してくる有機化合物や細菌などの有害物質を除去する性質がある。 Photocatalysts have the property of generating strong oxidizing power on their surfaces when exposed to light from the sun or fluorescent lamps, and removing harmful substances such as organic compounds and bacteria that come in contact with them.
しかし、この種光触媒は、硫黄を含む化合物（メチルメルカプタン、硫化水素、硫化メチル、二硫化メチル等）の脱臭には適さない。 However, this type of photocatalyst is not suitable for deodorization of sulfur-containing compounds (methyl mercaptan, hydrogen sulfide, methyl sulfide, methyl disulfide, etc.).
この硫黄化合物は、悪臭防止法では特定悪臭物質として指定され、また、検知閾値がｐｐｂレベルと極めて低く、わずかな量でも悪臭となる。 This sulfur compound is designated as a specific malodorous substance in the Malodor Prevention Law, and the detection threshold is extremely low at the ppb level, and even a slight amount can cause malodor.
この悪臭の発生源は、し尿処理場、下水処理場、畜舎、化製場、クラフトパルプ工場など多岐にわたっている。 There are various sources of bad odor such as human waste treatment plant, sewage treatment plant, livestock barn, chemical production plant and kraft pulp factory.
そこで、硫黄化合物の脱臭のために、活性炭や化学吸着剤、活性汚泥などが用いられている。 Therefore, activated carbon, chemical adsorbents, activated sludge and the like are used for deodorizing sulfur compounds.
活性炭方式は、物理的な吸着による除去方法である。この方式は、温度や湿度など外部環境に左右されやすく、吸着したガスを再放出する可能性がある。また、吸着能力は無限ではなく、飽和に達すると吸着能力は失われるので、定期的な交換が必要であり、コストがかかる。 The activated carbon method is a removal method by physical adsorption. This method is easily influenced by the external environment such as temperature and humidity, and may cause the adsorbed gas to be released again. In addition, the adsorption capacity is not infinite, and when the saturation is reached, the adsorption capacity is lost. Therefore, regular replacement is necessary and costs are increased.
化学吸着剤による方式は、化学薬品を使用する。化学吸着剤は、酸化還元反応によってガスを無害化するので、活性炭のように、ガスを再放出するおそれはなく、また、湿度や温度の影響を受けにくい。しかしながら、薬品は消耗品であり、定期的な交換が必要となり、コストがかかる。さらに、化学薬品は一般廃棄処理ができないため、廃棄によるコストがかかる。 The chemical adsorbent method uses chemicals. Since the chemical adsorbent detoxifies the gas by an oxidation-reduction reaction, unlike the activated carbon, there is no possibility of re-releasing the gas, and it is not easily affected by humidity and temperature. However, chemicals are consumables that require regular replacement and are costly. Furthermore, since chemicals cannot be disposed of in general, disposal costs are incurred.
活性汚泥方式は、対象ガスを分解する微生物を使用する。この方式は、常に微生物が働きやすい環境を保つ必要があり、運転の管理が必要となり、また、装置は比較的大型となってしまう。 The activated sludge method uses microorganisms that decompose the target gas. In this method, it is necessary to always maintain an environment in which microorganisms are easy to work, operation management is required, and the apparatus becomes relatively large.
なお、セラミックハニカムのような耐火性三次元構造物に触媒を担持させ、粒子状の硫化物を燃焼させる触媒組成体が提案されている（特許文献１参照）。
本発明は上述した事情を考慮してなされたもので、効率良く悪臭を脱臭でき、メンテナンスの容易な光触媒担持セラミックフォームを提供することを目的とする。 The present invention has been made in consideration of the above-described circumstances, and an object of the present invention is to provide a photocatalyst-carrying ceramic foam that can efficiently deodorize malodor and is easy to maintain.
また、効率良く悪臭を脱臭でき、メンテナンスの容易な光触媒担持セラミックフォームを製造できる光触媒担持セラミックフォームの製造方法を提供することを目的とする。 Another object of the present invention is to provide a method for producing a photocatalyst-carrying ceramic foam, which can efficiently deodorize bad odors and can be easily produced.
本発明に係る光触媒担持セラミックフォームによれば、効率良く悪臭を脱臭でき、メンテナンスの容易な光触媒担持セラミックフォームを提供することができる。 The photocatalyst-carrying ceramic foam according to the present invention can provide a photocatalyst-carrying ceramic foam that can efficiently deodorize bad odors and is easy to maintain.
また、本発明に係る光触媒担持セラミックフォームの製造方法によれば、効率良く悪臭を脱臭でき、メンテナンスの容易な光触媒担持セラミックフォームを製造できる光触媒担持セラミックフォームの製造方法を提供することができる。 In addition, according to the method for producing a photocatalyst-carrying ceramic foam according to the present invention, it is possible to provide a method for producing a photocatalyst-carrying ceramic foam that can efficiently deodorize bad odors and can produce a photocatalyst-carrying ceramic foam that is easy to maintain.
一般に光触媒は半導体の性質を持つものが多く、そのバンドギャップよりも大きな光エネルギーが照射されると、価電子帯の電子が、伝導帯に励起される。その結果、価電子帯と伝導帯にそれぞれ正孔と電子を生じる。ここで生じた正孔と電子がそれぞれ、酸化、還元反応を引き起こす。酸化還元反応により生じた活性酸素種によって、強力な酸化力を発揮する。 In general, many photocatalysts have semiconductor properties. When light energy larger than the band gap is irradiated, electrons in the valence band are excited to the conduction band. As a result, holes and electrons are generated in the valence band and the conduction band, respectively. The holes and electrons generated here cause oxidation and reduction reactions, respectively. The active oxygen species generated by the redox reaction exerts a strong oxidizing power.
この酸化力を利用し、様々な物質を酸化分解することができる。光触媒には、酸化力の他にさらに超親水性と呼ばれる重要な特性を持つ。超親水性の表面に水滴が落ちると表面に一様に広がり、水滴とならない。これらの光触媒の特性を利用し、大気浄化、浄水、抗菌、脱臭、防汚など、様々な分野に応用されている。 By utilizing this oxidizing power, various substances can be oxidatively decomposed. The photocatalyst has an important characteristic called super hydrophilicity in addition to the oxidizing power. When water drops fall on the superhydrophilic surface, they spread uniformly on the surface and do not form water drops. Utilizing the characteristics of these photocatalysts, they are applied to various fields such as air purification, water purification, antibacterial, deodorization, and antifouling.
一方、臭いを発する物質は、約４０万種あるといわれている。そのほとんどは有機化合物であり、炭化水素化合物は光触媒により、酸化分解されると二酸化炭素と水となる。分解処理量が光触媒の能力を超えない限りは、触媒の劣化は無い。硫黄や窒素を含む化合物は、光触媒により酸化されると、それぞれ、硫酸塩、硝酸塩となり、触媒表面上に付着し、触媒毒となる。しかしながら、これらのような触媒毒は水による洗浄や焼成により、除去可能であり、触媒能力は再生可能である。このような定期的なメンテナンスを施すことにより、長期間使用できる。このため、活性炭のような頻繁な交換の必要が無く、ランニングコストの面で大きなメリットがある。また、大規模な設備は必ずしも必要ではなく、室内のような小規模レベルから工場のような大規模レベルまで、幅広い選択肢がある。さらに、常温で反応可能である。 On the other hand, it is said that there are about 400,000 kinds of substances that emit odors. Most of them are organic compounds, and hydrocarbon compounds become carbon dioxide and water when oxidized and decomposed by a photocatalyst. As long as the decomposition amount does not exceed the capability of the photocatalyst, there is no deterioration of the catalyst. When a compound containing sulfur or nitrogen is oxidized by a photocatalyst, it becomes sulfate and nitrate, respectively, and adheres to the catalyst surface to become catalyst poison. However, catalyst poisons such as these can be removed by washing or calcination with water, and the catalyst capacity can be regenerated. By performing such regular maintenance, it can be used for a long time. For this reason, there is no need for frequent replacement like activated carbon, and there is a great merit in terms of running cost. In addition, large-scale equipment is not necessarily required, and there are a wide range of options from a small-scale level such as a room to a large-scale level such as a factory. Furthermore, it can react at normal temperature.
本願発明者等は、上記のような性質を有する光触媒の脱臭効果に着目し、光触媒を三次元網目構造を有するセラミックフォームに担持させ、さらに、金属を光触媒に部分的に点在させて担持することで、光触媒の能力を向上させることで、本発明を完成した。 The inventors of the present application pay attention to the deodorizing effect of the photocatalyst having the above-described properties, and carry the photocatalyst on the ceramic foam having a three-dimensional network structure, and further carry the metal partially scattered on the photocatalyst. Thus, the present invention was completed by improving the ability of the photocatalyst.
すなわち、上述した目的を達成するため、本発明に係る光触媒担持セラミックフォームは、三次元網目構造を有するセラミックフォーム表面上に二酸化チタン光触媒を膜厚１μｍ以下のポーラスな状態で担持してできた５ｍ２／ｃｍ３以上の表面積を有する光触媒担持セラミックフォームの光触媒膜上に、金属粒子または金属酸化物粒子または金属イオンを部分的に点在させて担持したことを特徴とする。 That is, in order to achieve the above-described object, the photocatalyst-carrying ceramic foam according to the present invention is a 5 m product obtained by carrying a titanium dioxide photocatalyst in a porous state with a film thickness of 1 μm or less on a ceramic foam surface having a three-dimensional network structure. It is characterized in that metal particles, metal oxide particles, or metal ions are supported on a photocatalyst film of a photocatalyst-supported ceramic foam having a surface area of 2 / cm 3 or more in a partially dotted manner.
また、本発明に係る光触媒担持セラミックフォームの製造方法は、三次元網目構造をなし５ｍ２／ｃｍ３以上の表面積を有するセラミックフォームを用意し、このセラミックフォームのポーラス状の表層に膜厚１μｍ以下の二酸化チタン膜を担持し、この二酸化チタン膜を担持した光触媒担持セラミックフォームを金属イオン溶液に含浸後に、余剰な金属イオン溶液を除去し、水素雰囲気中５００℃以下で還元し、金属をセラミックフォームの光触媒膜上に部分的に点在させて担持することを特徴とする。 The method for producing a photocatalyst-carrying ceramic foam according to the present invention provides a ceramic foam having a three-dimensional network structure and a surface area of 5 m 2 / cm 3 or more, and a film thickness of 1 μm or less on the porous surface layer of the ceramic foam. After impregnating the photocatalyst-carrying ceramic foam carrying this titanium dioxide film with a metal ion solution, the excess metal ion solution is removed and reduced in a hydrogen atmosphere at 500 ° C. or lower, and the metal is ceramic foam. It is characterized in that it is supported by being partially scattered on the photocatalyst film.
また、本発明に係る光触媒担持セラミックフォームの製造方法は、三次元網目構造をなし５ｍ２／ｃｍ３以上の表面積を有するセラミックフォームを用意し、このセラミックフォームのポーラス状の表層に膜厚１μｍ以下の二酸化チタン膜を担持し、この二酸化チタン膜を担持した光触媒担持セラミックフォームを金属イオン溶液に含浸後に、余剰な金属イオン溶液を除去後、光触媒を活性化させる波長を含む光を照射させることで、金属イオンを酸化し、金属、または、金属酸化物をセラミックフォームの光触媒膜上に部分的に点在させて担持することを特徴とする。 The method for producing a photocatalyst-carrying ceramic foam according to the present invention provides a ceramic foam having a three-dimensional network structure and a surface area of 5 m 2 / cm 3 or more, and a film thickness of 1 μm or less on the porous surface layer of the ceramic foam. After impregnating the photocatalyst-carrying ceramic foam carrying this titanium dioxide film with a metal ion solution, removing excess metal ion solution, and then irradiating with light containing a wavelength that activates the photocatalyst The method is characterized in that metal ions are oxidized and a metal or a metal oxide is partially scattered on the photocatalyst film of ceramic foam.
また、本発明に係る光触媒担持セラミックフォームの製造方法は、三次元網目構造をなし５ｍ２／ｃｍ３以上の表面積を有するセラミックフォームを用意し、このセラミックフォームのポーラス状の表層に膜厚１μｍ以下の二酸化チタン膜を担持し、この二酸化チタン膜を担持した光触媒担持セラミックフォームを金属イオン溶液に含浸後、金属イオンを還元可能な還元剤を含む溶液に含浸させることで、金属または、金属酸化物を析出させ、セラミックフォームの光触媒膜上に部分的に点在させて担持することを特徴とする。 The method for producing a photocatalyst-carrying ceramic foam according to the present invention provides a ceramic foam having a three-dimensional network structure and a surface area of 5 m 2 / cm 3 or more, and a film thickness of 1 μm or less on the porous surface layer of the ceramic foam. A metal or metal oxide is obtained by impregnating a photocatalyst carrying ceramic foam carrying this titanium dioxide film with a metal ion solution and then impregnating the solution with a reducing agent capable of reducing metal ions. It is characterized in that it is deposited and partially scattered on the photocatalyst film of ceramic foam.
また、本発明に係る光触媒担持セラミックフォームの製造方法は、三次元網目構造をなし５ｍ２／ｃｍ３以上の表面積を有するセラミックフォームを用意し、このセラミックフォームのポーラス状の表層に膜厚１μｍ以下の二酸化チタン膜を担持し、この二酸化チタン膜を担持した光触媒担持セラミックフォームを金属イオン溶液に含浸後、乾燥することで、金属イオンをセラミックフォームの光触媒膜上に部分的に点在させて担持することを特徴とする。 The method for producing a photocatalyst-carrying ceramic foam according to the present invention provides a ceramic foam having a three-dimensional network structure and a surface area of 5 m 2 / cm 3 or more, and a film thickness of 1 μm or less on the porous surface layer of the ceramic foam. The titanium dioxide film is supported, and the photocatalyst-supported ceramic foam supporting the titanium dioxide film is impregnated in a metal ion solution and then dried, so that the metal ions are partially scattered on the ceramic catalyst photocatalyst film. It is characterized by doing.
本発明の一実施形態に係る光触媒担持セラミックフォームについて添付図面を参照して説明する。 A photocatalyst-supported ceramic foam according to an embodiment of the present invention will be described with reference to the accompanying drawings.
図１は本発明の一実施形態に係る光触媒担持セラミックフォームの平面を示す概念図である。 FIG. 1 is a conceptual diagram showing a plane of a photocatalyst-carrying ceramic foam according to an embodiment of the present invention.
図１に示すように、本発明の一実施形態に係る光触媒担持セラミックフォーム１は、三次元網目構造をなし５ｍ２／ｃｍ３以上の表面積を有するセラミックフォーム２に、二酸化チタン（ＴｉＯ２）光触媒３を膜厚１μｍ以下のポーラスな状態で担持し、さらに、二酸化チタン光触媒３の上に金属粒子４または金属酸化物粒子または金属イオンを部分的に点在させて担持する。
As shown in FIG. 1, a photocatalyst-supporting ceramic foam 1 according to an embodiment of the present invention is a titanium dioxide (TiO 2 ) photocatalyst formed on a
光触媒担持セラミックフォームは光触媒の持つ作用を十分に発揮できるような形態のひとつである。三次元網目構造とは、フォームの骨格がアトランダムに形成された状態のことを指し、この表面上に二酸化チタンが担持されている。この二酸化チタンは、光触媒機能を有することでよく知られており、特に、アナターゼ型が好ましい。担持された二酸化チタンは、ポーラスの状態が好ましい。 The photocatalyst-supported ceramic foam is one of the forms that can fully exhibit the action of the photocatalyst. The three-dimensional network structure means a state in which the foam skeleton is formed at random, and titanium dioxide is supported on this surface. This titanium dioxide is well known for having a photocatalytic function, and anatase type is particularly preferable. The supported titanium dioxide is preferably in a porous state.
骨格をセラミックスフォームで構成し、耐熱性、耐火性を付与することで、光触媒担持セラミックフォームを光触媒脱臭セラミックスとして用いても、光源から受ける熱によって骨格が発火したり、光触媒作用で劣化することがない。 By forming the skeleton with ceramic foam and providing heat resistance and fire resistance, even if the photocatalyst-supported ceramic foam is used as a photocatalyst deodorizing ceramic, the skeleton may ignite due to the heat received from the light source or deteriorate due to photocatalytic action Absent.
また、酸化チタン粒子は、セラミックス表面への付着性に優れるため、バインダを用いることなく、膜厚１μｍ以下の薄い酸化チタン膜を形成することができる。 In addition, since the titanium oxide particles are excellent in adhesion to the ceramic surface, a thin titanium oxide film having a thickness of 1 μm or less can be formed without using a binder.
このポーラスな二酸化チタンと三次元網目構造のフォームから大きな表面積が得られ、対象ガスとの接触機会が多くなる。表面積は、５ｍ２／ｃｍ３以上である。上記のように、酸化チタン膜を膜厚１μｍ以下にすることにより、表面積が５ｍ２／ｃｍ３以上の光触媒担持セラミックフォームを容易に得ることができる。表面積が５ｍ２／ｃｍ３以上にすることにより、光触媒作用による光触媒担持セラミックフォームの脱臭効果を向上させることができる。表面積が５ｍ２／ｃｍ３より小さいと、光触媒担持セラミックフォームの光触媒作用を十分に発揮させることができない。 A large surface area is obtained from the porous titanium dioxide and the foam having a three-dimensional network structure, and the chance of contact with the target gas is increased. The surface area is 5 m 2 / cm 3 or more. As described above, a photocatalyst-carrying ceramic foam having a surface area of 5 m 2 / cm 3 or more can be easily obtained by setting the titanium oxide film to a film thickness of 1 μm or less. By setting the surface area to 5 m 2 / cm 3 or more, it is possible to improve the deodorizing effect of the photocatalyst-supported ceramic foam by the photocatalytic action. When the surface area is smaller than 5 m 2 / cm 3 , the photocatalytic action of the photocatalyst-supporting ceramic foam cannot be sufficiently exhibited.
さらに、この二酸化チタン光触媒膜上に、金属粒子または金属酸化物粒子または金属イオンが部分的に点在させて担持されると、光励起で生じた電子と正孔との再結合が抑制され、その結果、光触媒の能力は向上する。 Furthermore, when metal particles, metal oxide particles, or metal ions are supported on the titanium dioxide photocatalyst film, the recombination of electrons and holes generated by photoexcitation is suppressed. As a result, the ability of the photocatalyst is improved.
上記金属は、Ｐｔ、Ｉｒ、Ｒｈ、Ｒｕ、Ｐｄ、Ａｕ、Ａｇ、Ｃｕ、Ｚｎ、Ｖ、Ｃｒ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ｓｃ、Ｙ、Ｌａ、Ｃｅ、Ｐｒ、Ｎｄ、Ｐｍ、Ｓｍ、Ｅｕ、Ｇｄ、Ｔｂ、Ｄｙ、Ｈｏ、Ｅｒ、Ｔｍ、Ｙｂ、およびＬｕからなる群から選ばれた少なくとも一種であるのが好ましい。なお、上記金属にはその酸化物、イオンを含む。 The metal is Pt, Ir, Rh, Ru, Pd, Au, Ag, Cu, Zn, V, Cr, Mn, Fe, Co, Ni, Sc, Y, La, Ce, Pr, Nd, Pm, Sm, It is preferably at least one selected from the group consisting of Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu. Note that the metal includes oxides and ions thereof.
これら金属は、対象ガスを吸着する性能を向上させることができる。 These metals can improve the performance of adsorbing the target gas.
部分的に点在とは、セラミックフォームに担持される光触媒粒子全体を覆わず、部分的に覆うことを意味する。光触媒粒子の全体を被覆してしまうと、光触媒に光が届かなくなり、その結果、光触媒粒子の性能が低下する。 Partially scattered means that the entire photocatalyst particles supported on the ceramic foam are not covered but partially covered. If the entire photocatalyst particles are coated, light does not reach the photocatalyst, and as a result, the performance of the photocatalyst particles is degraded.
本実施形態に係る光触媒担持セラミックフォームによれば、効率良く悪臭を脱臭でき、メンテナンスの容易な光触媒担持セラミックフォームが実現する。 The photocatalyst-carrying ceramic foam according to the present embodiment realizes a photocatalyst-carrying ceramic foam that can efficiently deodorize bad odors and is easy to maintain.
次に本発明に係る光触媒担持セラミックフォームの製造方法について説明する。 Next, the manufacturing method of the photocatalyst carrying | support ceramic foam concerning this invention is demonstrated.
第１の光触媒担持セラミックフォームの製造方法は、はじめに、セラミックフォームを製造する。 In the first method for producing a photocatalyst-carrying ceramic foam, a ceramic foam is first produced.
例えば、アルミナ原料粉末を溶媒に分散させてスラリーを調製し、このスラリーをウレタンフォームに浸透させて、骨格表面にスラリー層を形成させた後、焼成してウレタンを焼き抜き、セラミックフォームを得るか、スラリーに架橋重合性樹脂を混合撹拌し、泡状として架橋させた後、焼成し、セラミックフォームを得、さらに、このアルミナからなり三次元網目構造をなし５ｍ２／ｃｍ３以上の表面積を有するセラミックフォームを得る。 For example, if alumina raw material powder is dispersed in a solvent to prepare a slurry, this slurry is infiltrated into urethane foam to form a slurry layer on the surface of the skeleton, and then fired to burn out urethane to obtain ceramic foam. The slurry is mixed and stirred with a cross-linkable polymerizable resin, crosslinked in the form of foam, and then fired to obtain a ceramic foam. Further, the slurry is made of alumina and has a three-dimensional network structure and a surface area of 5 m 2 / cm 3 or more. Obtain ceramic foam.
次に、このセラミックフォームをＯＨ基３００ｐｐｍ、窒素３０００ｐｐｍを含有する粒径３０ｎｍの二酸化チタン粒子からなる光触媒粒子１５ｇを水１００Ｌに分散させ、市販のアナターゼ型ＴｉＯ２水溶液と混合してスラリー状としたものを含浸させる。これを乾燥させて、セラミックス骨格の表層に膜厚１μｍ以下のポーラスな状態で二酸化チタン膜を担持する。 Next, 15 g of photocatalyst particles made of titanium dioxide particles having a particle diameter of 30 nm containing OH groups of 300 ppm and nitrogen of 3000 ppm were dispersed in 100 L of water and mixed with a commercially available anatase TiO 2 aqueous solution to form a slurry. Impregnate one. This is dried and a titanium dioxide film is supported on the surface layer of the ceramic skeleton in a porous state with a film thickness of 1 μm or less.
この二酸化チタン膜を担持した光触媒担持セラミックフォームを金属イオン溶液に含浸後に、余剰な金属イオン溶液を除去後、水素雰囲気中５００℃以下で還元し、金属を光触媒担持セラミックフォームに部分的に点在させて担持させる。 After impregnating the photocatalyst-carrying ceramic foam carrying the titanium dioxide film in a metal ion solution, after removing the excess metal ion solution, the metal foam is partially scattered in the photocatalyst-carrying ceramic foam by reducing it in a hydrogen atmosphere at 500 ° C. or lower. And carry it.
上記金属としては、Ｐｔ、Ｉｒ、Ｒｈ、Ｒｕ、Ｐｄ、Ａｕ、Ａｇ、Ｃｕ、Ｚｎ、Ｖ、Ｃｒ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ｓｃ、Ｙ、Ｌａ、Ｃｅ、Ｐｒ、Ｎｄ、Ｐｍ、Ｓｍ、Ｅｕ、Ｇｄ、Ｔｂ、Ｄｙ、Ｈｏ、Ｅｒ、Ｔｍ、Ｙｂ、およびＬｕからなる群から選ばれた少なくとも一種を用いるのが好ましい。 Examples of the metal include Pt, Ir, Rh, Ru, Pd, Au, Ag, Cu, Zn, V, Cr, Mn, Fe, Co, Ni, Sc, Y, La, Ce, Pr, Nd, Pm, and Sm. It is preferable to use at least one selected from the group consisting of Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu.
金属イオン溶液に含浸させるが、三次元網目構造をなし５ｍ２／ｃｍ３以上の大きな表面積を持つ光触媒担持セラミックフォームは、多くの金属イオンを含むことができる。水素還元によって、金属イオンを金属化する。温度は、二酸化チタンのアナターゼ型を保つために、５００℃以下が好ましい。 Although impregnated with a metal ion solution, the photocatalyst-supported ceramic foam having a large surface area of 5 m 2 / cm 3 or more that has a three-dimensional network structure can contain many metal ions. Metal ions are metallized by hydrogen reduction. The temperature is preferably 500 ° C. or lower in order to keep the anatase type of titanium dioxide.
また、第２の光触媒担持セラミックフォームの製造方法は、第１の製造方法と同様にして得られた三次元網目構造をなし５ｍ２／ｃｍ３以上の表面積を有するセラミックフォームに、ＯＨ基３００ｐｐｍ、窒素３０００ｐｐｍを含有する粒径３０ｎｍの二酸化チタン粒子からなる光触媒粒子１５ｇを水１００リットルに分散させ、市販のアナターゼ型ＴｉＯ２水溶液と混合してスラリー状としたものを含浸させる。これを乾燥させて、セラミックス骨格の表層に膜厚１μｍ以下のポーラスな状態で二酸化チタン膜を担持する。 Further, the second photocatalyst-supported ceramic foam is produced by a method of producing a ceramic foam having a three-dimensional network structure obtained in the same manner as the first production method and having a surface area of 5 m 2 / cm 3 or more. 15 g of photocatalyst particles made of titanium dioxide particles having a particle diameter of 30 nm containing 3000 ppm of nitrogen are dispersed in 100 liters of water and mixed with a commercially available anatase TiO 2 aqueous solution to impregnate a slurry. This is dried and a titanium dioxide film is supported on the surface layer of the ceramic skeleton in a porous state with a film thickness of 1 μm or less.
この二酸化チタン膜を担持した光触媒担持セラミックフォームを金属イオン溶液に含浸後に、余剰な金属イオン溶液を除去後、光触媒を活性化させる波長を含む光を照射させることで、金属イオンを酸化し、金属、または、金属酸化物を光触媒担持セラミックフォームに部分的に点在させて担持させる。 After impregnating the photocatalyst-carrying ceramic foam carrying this titanium dioxide film in a metal ion solution, removing the excess metal ion solution, and irradiating with light containing a wavelength that activates the photocatalyst, the metal ions are oxidized and the metal Alternatively, the metal oxide is supported by being partially scattered on the photocatalyst-supported ceramic foam.
光照射にて、光触媒を活性化し、光触媒の酸化作用によって、金属イオンを金属、あるいは、金属酸化物にすることできる。二酸化チタン光触媒を活性化させるため３８０ｎｍｍ以下の波長の光照射であるのが好ましい。 By photoirradiation, the photocatalyst is activated, and the metal ion can be converted into a metal or a metal oxide by the oxidizing action of the photocatalyst. In order to activate the titanium dioxide photocatalyst, light irradiation with a wavelength of 380 nm or less is preferable.
さらに、第３の光触媒担持セラミックフォームの製造方法は、第１の製造方法と同様にして得られた三次元網目構造をなし５ｍ２／ｃｍ３以上の表面積を有するセラミックフォームに、ＯＨ基３００ｐｐｍ、窒素３０００ｐｐｍを含有する粒径３０ｎｍの二酸化チタン粒子からなる光触媒粒子１５ｇを水１００リットルに分散させ、市販のアナターゼ型ＴｉＯ２水溶液と混合してスラリー状としたものを含浸させる。これを乾燥させて、セラミックス骨格の表層に膜厚１μｍ以下のポーラスな状態で二酸化チタン膜を担持する。 Furthermore, a third method for producing a photocatalyst-supported ceramic foam has a three-dimensional network structure obtained in the same manner as in the first production method, a ceramic foam having a surface area of 5 m 2 / cm 3 or more, 300 ppm of OH groups, 15 g of photocatalyst particles made of titanium dioxide particles having a particle diameter of 30 nm containing 3000 ppm of nitrogen are dispersed in 100 liters of water and mixed with a commercially available anatase TiO 2 aqueous solution to impregnate a slurry. This is dried and a titanium dioxide film is supported on the surface layer of the ceramic skeleton in a porous state with a film thickness of 1 μm or less.
この二酸化チタン膜を担持した光触媒担持セラミックフォームを金属イオン溶液に含浸後、金属イオンを還元可能な還元剤を含む溶液に含浸させることで、金属、または、金属酸化物を光触媒担持セラミックフォームに部分的に点在させて担持させる。 After impregnating the photocatalyst-carrying ceramic foam carrying the titanium dioxide film into a metal ion solution, the metal or metal oxide is partially impregnated into the photocatalyst-carrying ceramic foam by impregnating the solution containing a reducing agent capable of reducing metal ions. It is made to be scattered and carried.
金属イオンを還元可能な還元剤を含む溶液に含浸させることで、金属イオンを還元し、金属または、金属酸化物を析出させ、担持させる。 By impregnating a solution containing a reducing agent capable of reducing metal ions, the metal ions are reduced, and a metal or a metal oxide is deposited and supported.
また、第４の光触媒担持セラミックフォームの製造方法は、第１の製造方法と同様にして得られた三次元網目構造をなし５ｍ２／ｃｍ３以上の表面積を有するセラミックフォームに、ＯＨ基３００ｐｐｍ、窒素３０００ｐｐｍを含有する粒径３０ｎｍの二酸化チタン粒子からなる光触媒粒子１５ｇを水１００リットルに分散させ、市販のアナターゼ型ＴｉＯ２水溶液と混合してスラリー状としたものを含浸させる。これを乾燥させて、セラミックス骨格の表層に膜厚１μｍ以下のポーラスな状態で二酸化チタン膜を担持する。 Further, a fourth photocatalyst-supported ceramic foam production method comprises a three-dimensional network structure obtained in the same manner as in the first production method, a ceramic foam having a surface area of 5 m 2 / cm 3 or more, OH group 300 ppm, 15 g of photocatalyst particles made of titanium dioxide particles having a particle diameter of 30 nm containing 3000 ppm of nitrogen are dispersed in 100 liters of water and mixed with a commercially available anatase TiO 2 aqueous solution to impregnate a slurry. This is dried and a titanium dioxide film is supported on the surface layer of the ceramic skeleton in a porous state with a film thickness of 1 μm or less.
この二酸化チタン膜を担持した光触媒担持セラミックフォームを金属イオン溶液に含浸後、乾燥することで、金属イオンを光触媒担持セラミックフォームに部分的に点在させて担持させる。 The photocatalyst-carrying ceramic foam carrying the titanium dioxide film is impregnated in a metal ion solution and then dried, whereby metal ions are partially scattered on the photocatalyst-carrying ceramic foam.
金属イオン溶液に含浸後乾燥するのみである。これにより、金属イオンがフォーム上に担持される。 It is only dried after impregnating the metal ion solution. Thereby, metal ions are supported on the foam.
上述各実施形態に係る光触媒担持セラミックフォームの製造方法によれば、効率良く悪臭を脱臭でき、メンテナンスの容易な光触媒担持セラミックフォームの製造方法が実現する。 According to the method for producing a photocatalyst-carrying ceramic foam according to each of the above-described embodiments, a method for producing a photocatalyst-carrying ceramic foam that can efficiently deodorize bad odor and is easy to maintain is realized.
（実施例１）
０．０３ｗｔ％の硝酸銀水溶液に１５０×１５０×１０ｍｍの直方体で１．５×１０３ｍ２の表面積を有する光触媒担持セラミックフォームを含浸後に、余剰な金属イオン溶液を除去し、水素雰囲気中４００℃で還元した。
(Example 1)
After impregnating a 0.03 wt% silver nitrate aqueous solution with a photocatalyst-supported ceramic foam having a surface area of 1.5 × 10 3 m 2 in a rectangular parallelepiped of 150 × 150 × 10 mm, the excess metal ion solution is removed and 400 ° C. in a hydrogen atmosphere. Reduced.
（実施例２）
実施例１と同様の光触媒担持セラミックフォームを含浸後に、余剰な金属イオン溶液を除去し、３ｍＷ／ｃｍ２の光強度を有する紫外線ランプを１時間照射し、１１０℃で２時間乾燥した。
(Example 2)
After impregnating the same photocatalyst-carrying ceramic foam as in Example 1, the excess metal ion solution was removed, irradiated with an ultraviolet lamp having a light intensity of 3 mW / cm 2 for 1 hour, and dried at 110 ° C. for 2 hours.
（実施例３）
０．０３ｗｔ％のジアンミン銀水溶液に１５０×１５０×１０ｍｍの直方体で１．５×１０３ｍ２の表面積を有する光触媒担持セラミックフォームを含浸後に、２ｍｏｌ／Ｌ水酸化ナトリウム水溶液２ｍＬを加えたホルマリン溶液にさらに含浸させた後、１１０℃で２時間乾燥した。
(Example 3)
Formalin solution in which 0.03 wt% diammine silver aqueous solution is impregnated with 150 × 150 × 10 mm rectangular parallelepiped ceramic foam having a surface area of 1.5 × 10 3 m 2 and 2 mL of 2 mol / L sodium hydroxide aqueous solution is added. After further impregnation, the mixture was dried at 110 ° C. for 2 hours.
（実施例４）
０．０３ｗｔ％の硝酸銀水溶液に１５０×１５０×１０ｍｍの直方体で１．５×１０３ｍ２の表面積を有する光触媒担持セラミックフォームを含浸後、１１０℃で２時間乾燥した。
Example 4
A 0.03 wt% aqueous silver nitrate solution was impregnated with a 150 × 150 × 10 mm rectangular parallelepiped photocatalyst-carrying ceramic foam having a surface area of 1.5 × 10 3 m 2 and then dried at 110 ° C. for 2 hours.
（比較例１）
実施例１と同様の光触媒担持セラミックフォーム。
(Comparative Example 1)
The same photocatalyst-supported ceramic foam as in Example 1.
（比較例２）
１５０×１５０×１０ｍｍの金属網内に、ペレット型の活性炭を敷き詰めたもの。
(Comparative Example 2)
Plating-type activated carbon spread in a 150 x 150 x 10 mm metal mesh.
［脱臭試験方法］
実施例１〜４および比較例１、２のフィルター２枚を、図２のように、配置して脱臭装置とした。入口から出口に向けて、約２ｐｐｍの硫化水素ガスを５Ｌ／ｍｉｎで流した。温度は２５℃、湿度は５０％に保った。ガス程度は入口と出口で測定し、測定器はガスクロマトグラフを用いた。
Two filters of Examples 1 to 4 and Comparative Examples 1 and 2 were arranged as shown in FIG. About 2 ppm of hydrogen sulfide gas was allowed to flow at 5 L / min from the inlet toward the outlet. The temperature was kept at 25 ° C. and the humidity at 50%. The gas level was measured at the inlet and outlet, and a gas chromatograph was used as the measuring instrument.
［結果と考察］
表１に示すように、実施例１〜４では、初期状態で若干の吸着が見られた。その後、光照射により、ガスクロマトグラフの検出限界レベルまで吸着分解した。
[Results and discussion]
As shown in Table 1, in Examples 1 to 4, slight adsorption was observed in the initial state. Then, it was adsorbed and decomposed to the detection limit level of the gas chromatograph by light irradiation.
これに対して、比較例１では、若干の吸着後、光照射により、大幅に吸着分解するが、完全には分解しきれていなかった。また、比較例２では、初期状態から、ほとんどのガスを吸着した。しかしながら、時間経過につれて、分解能力が悪化していった。 On the other hand, in Comparative Example 1, although it was adsorbed and decomposed by light irradiation after some adsorption, it was not completely decomposed. In Comparative Example 2, most of the gas was adsorbed from the initial state. However, the decomposition ability deteriorated with time.
このことから、実施例１〜４のように金属類を担持した光触媒担持セラミックフォームは、吸着、分解効果があることがわかった。 From this, it turned out that the photocatalyst carrying | support ceramic foam which carry | supported metals like Examples 1-4 has an adsorption | suction and a decomposition effect.
１ 光触媒担持セラミックフォーム
２ セラミックフォーム
３ 二酸化チタン光触媒
４ 金属粒子
1 Photocatalyst-supporting
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011104518A (en) * | 2009-11-17 | 2011-06-02 | Toshiba Corp | Discharge type photocatalyst and method of manufacturing the same |
| CN103599791A (en) * | 2013-10-22 | 2014-02-26 | 范崇政 | Alloy net supported multicomponent composite nanometer photocatalyst and manufacturing method thereof |
| JP2015521104A (en) * | 2012-05-25 | 2015-07-27 | エルジー・ハウシス・リミテッドＬｇ Ｈａｕｓｙｓ，Ｌｔｄ． | Photocatalyst material, method for producing the same, and photocatalyst apparatus |
| CN113842927A (en) * | 2021-08-31 | 2021-12-28 | 哈尔滨理工大学 | Preparation method of bismuth oxyiodide/aluminum oxide microporous honeycomb ceramic composite photocatalyst |
| CN114345338A (en) * | 2021-12-24 | 2022-04-15 | 广东工业大学 | High-selectivity catalyst for converting mercaptan compounds, and preparation method and application thereof |
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2006
- 2006-09-19 JP JP2006252615A patent/JP2008073571A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011104518A (en) * | 2009-11-17 | 2011-06-02 | Toshiba Corp | Discharge type photocatalyst and method of manufacturing the same |
| JP2015521104A (en) * | 2012-05-25 | 2015-07-27 | エルジー・ハウシス・リミテッドＬｇ Ｈａｕｓｙｓ，Ｌｔｄ． | Photocatalyst material, method for producing the same, and photocatalyst apparatus |
| CN103599791A (en) * | 2013-10-22 | 2014-02-26 | 范崇政 | Alloy net supported multicomponent composite nanometer photocatalyst and manufacturing method thereof |
| CN103599791B (en) * | 2013-10-22 | 2017-05-03 | 范崇政 | Alloy net supported multicomponent composite nanometer photocatalyst and manufacturing method thereof |
| CN113842927A (en) * | 2021-08-31 | 2021-12-28 | 哈尔滨理工大学 | Preparation method of bismuth oxyiodide/aluminum oxide microporous honeycomb ceramic composite photocatalyst |
| CN114345338A (en) * | 2021-12-24 | 2022-04-15 | 广东工业大学 | High-selectivity catalyst for converting mercaptan compounds, and preparation method and application thereof |
| CN114345338B (en) * | 2021-12-24 | 2023-11-14 | 广东工业大学 | High-selectivity catalyst for converting mercaptan compound and preparation method and application thereof |
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