JP2004050102A - Photocatalytic reaction apparatus - Google Patents
Photocatalytic reaction apparatus Download PDFInfo
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- JP2004050102A JP2004050102A JP2002213019A JP2002213019A JP2004050102A JP 2004050102 A JP2004050102 A JP 2004050102A JP 2002213019 A JP2002213019 A JP 2002213019A JP 2002213019 A JP2002213019 A JP 2002213019A JP 2004050102 A JP2004050102 A JP 2004050102A
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Abstract
Description
【０００１】
【発明の属する技術分野】
本発明は光触媒反応装置に関する。
【０００２】
【従来の技術】
いわゆる半導体光触媒による光反応は、その１つの機構である酸化還元反応により、脱臭、抗菌、防汚作用を生じさせる。この光触媒の作用を利用して種々の製品が検討され、実用化されている。代表的な半導体光触媒である酸化チタンのバンドギャップは約３ｅＶであり、波長に直すと４００ｎｍ程度である。したがって、４００ｎｍ以下の紫外線を照射すると半導体内部に電子（ｅ−）と正孔（ｈ＋）が生じる。この電子は酸素と反応してきわめて大きい酸化力を示すスーパーオキサイドイオン〔Ｏ２ −〕を生成し、一方の正孔は水と反応してヒドロキシラジカル〔・ＯＨ〕を生成する。この２つの活性酸素が酸化還元反応を発現させ、臭気もしくは汚れ物質の分解、さらには有機系塩素化合物等の他の難分解性化合物が酸化分解されることになる。
【０００３】
そして従来、光触媒反応装置としては、種々の目的でその光触媒活性を発揮させるため、種々の構成のものが知られている。
【０００４】
【発明が解決しようとする課題】
本発明は、屋外空気と屋内空気の両方を被処理ガスとして同時に光触媒反応させ、温度の高いほうの空気の熱を有効に利用しうる光触媒反応装置を提供することを目的とする。
【０００５】
【課題を解決するための手段】
本発明の目的は、基材表面に光触媒を被覆した光触媒体および紫外線源を備える光触媒反応装置において、該光触媒体から構成される複数層の流体通路を形成し、該複数層の流体通路は屋外空気と屋内空気が１層ごとに互いに交じり合わないで向流ないし直交流で流れるように構成されてなることを特徴とする光触媒反応装置により達成される。
【０００６】
【発明の実施の形態】
本発明の光触媒体において、上記の基材としては低波長の紫外線による劣化がない点から、金属が好適である。そして、金属としては、好ましくはアルミニウム、チタン、マグネシウム、鋼もしくはステンレス鋼から選択されるが、特に好適にはアルミニウムである。アルミニウム、チタンもしくはマグネシウムは合金であってもよい。たとえばアルミニウム合金としては、Ａｌ−Ｍｇ、Ａｌ−Ｍｇ−Ｓｉ、Ａｌ−Ｃｕ−Ｍｇ−Ｍｎ、Ａｌ−Ｚｎ−Ｍｇ−Ｃｕ等、マグネシウム合金としては、Ｍｇ−Ａｌ、Ｍｇ−Ａｌ−Ｚｎ、Ｍｇ−Ｍｎ等が挙げられる。本発明においてはこれらの金属の基板上に、光触媒のコーティング膜が形成されるが、この形成前に、金属表面は絶縁被覆されるのが好ましい。この絶縁被覆により、光触媒上の電子が金属側に流れることなく、電子の授受を十分に行ないうるので、光分解活性を格段に高めることができる。
【０００７】
この絶縁被覆処理は、好適には陽極酸化、化成処理もしくはガラスコーティング処理から選ばれる。たとえば、アルミニウム、チタンの場合には、それらを電解質水溶液中に浸漬してアノード分極することにより、金属の表面に酸化物皮膜を形成する、いわゆる陽極酸化皮膜が一般的である。また、鋼板の場合には電気めっき、もしくは溶融めっき、さらにはリン酸、およびリン酸塩による化成処理が一般的である。さらにアルミニウムの場合には、陽極酸化に代えて化学薬品による化学的皮膜化成法（化成処理）を採用しうる。この化成処理としてはクロム酸またはクロム酸−リン酸を主体とするもの、すなわちクロメート処理皮膜が好適である。マグネシウムの場合にも、陽極酸化，化成処理が適用されうる。
【０００８】
またアルミニウム等の表面に珪酸ソーダ（水ガラス）を塗布して焼結させるガラスコーティング法を採用することもできる。
【０００９】
ステンレス鋼の場合、表面を酸化させ不働態化を目的とする酸（好適には重クロム酸ソーダ）処理（化成処理）も採用しうる。
【００１０】
絶縁被覆の膜厚は特に制限されないが、通常約０．１〜１μｍ程度から選択される。
【００１１】
本発明における光触媒としては、酸化ジルコニウム、酸化チタン、酸化亜鉛、酸化タングステン、酸化カドミウム、酸化マンガン、酸化銅等の金属酸化物；硫化カドミウム、硫化亜鉛、硫化インジウム、硫化鉛、硫化タングステン等の金属硫化物；ポリパラフェニレン、ポリアニリン、ポリチオフェン等の有機高分子；チタン酸ストロンチウムに各種の金属酸化物を添加した層間化合物、等が挙げられるが、酸化ジルコニウムおよび酸化チタンが好適である。そして最も好適には、酸化ジルコニウムを選択することにより、比較的短波長の紫外光を利用しうるので向上した光触媒活性が得られ易い。酸化チタンとしてはアナタ−ゼ、ルチルもしくはブロッカイト型のいずれでもよいが、触媒活性および入手し易さの点からアナタ−ゼ型が最適である。
【００１２】
これらの光触媒の金属基板へのコーティング膜の形成法自体は、常法によることができるが、液相から析出させる方法、気相から蒸着させる方法が好ましい。たとえば、液相法としてはゾル−ゲル法等、気相法としてはスパッタリング、真空蒸着等の物理蒸着法（ＰＶＤ）または気相化学反応法（ＣＶＤ）等の化学的方法が挙げられるが、得られる被覆の均一性、コスト等の点からゾル−ゲル法が最適である。そしてゾル−ゲル法における出発物質としては、たとえば金属アルコキシド、金属アセチルアセトネート、金属カルボキシレート等の金属有機化合物、たとえばオキシ塩化物、塩化物、硝酸塩等の金属無機化合物が一般的に用いられる。これらの中で、金属アルコキシドが反応性等の点から好適であり、ブトキシド、エトキシド、プロポキシド等の金属（たとえばジルコニウムもしくはチタン）アルコキシドをブタノール、プロパノール等の溶媒を用いて溶液として、これを金属基板に塗布することにより目的とするコーティング膜が形成されうる。塗布は、はけ塗り、ロール塗り、浸漬法、スプレー、スピン等を適宜選択しうる。コーティング膜の厚さは通常３〜５００μｍ、好ましくは５〜２０μｍ程度から選ばれる。たとえば、ゾル−ゲル法を用いて金属アルコキシド溶液に基板を浸漬し、引き上げることによりによりーティング膜を得る。このコーティング膜は常法により、たとえば室温で乾燥され、ついで３００〜５５０℃程度に加熱され基板に固着される。上記のＣＶＤ法としてはプラズマＣＶＤ法が４００〜５００℃程度までの比較的低い温度範囲の気相化学反応で成膜しうるので、基材に制限がなく好適である。
【００１３】
得られたコーティング膜形成基板はついで立体構造体に加工される。この構造体はハニカム、波板および／平板より構成される。ハニカムは六角形のコアに限定されず、いかなる形状であってもよい。波板は、平板と組合わせて（波付け）、平行に配置して使用してもよいが、巻き上げてハニカムを形成することもできる。平板は、平行に配置して、いわゆるパラレルパッセージ形として使用するのが好適である。本発明の構造体は通気抵抗が極めて小さいので効率的な光触媒反応を可能にする。上記の立体構造体を形成するための加工は、接着、切削もしくは切断であり、常法によることができる。接着に際しては、有機接着剤は光触媒により劣化するおそれがあるので、無機接着剤が使用されるのが好ましい。そのような無機接着剤としては、低融点ガラス等のガラス系；Ｓｎ−Ｉｎ，Ｂｉ−Ｐｂ，Ｓｎ−Ｐｂ，Ｐｂ−Ｓｂ等の軟ろう等の金属系；ケイ酸アルカリ（特に水ガラス）、リン酸塩系等、のその他の無機系、等が挙げられるが、接着温度が１００〜５００℃、好ましくは１２０〜２００℃のものが特に好ましい。これらの無機接着剤のうち、最も好適なのは水ガラスである。
【００１４】
本発明による光触媒体は、その表面粗さが５０ｎｍＲａ（中心線粗さ）以下であるのが好適であり、このように鏡面を形成し、コーティング膜も透明であると、光の反射率が著しく高くなり、たとえばハニカム光触媒体の内部まで紫外線を乱反射して照射することができ、触媒活性を著しく向上しうる。
【００１５】
本発明装置においては、上記の立体構造体を形成するための加工により、光触媒体から構成される複数層の流体通路が形成される。そして、本発明装置はその複数層の流体通路が屋外空気と屋内空気が１層ごとに互いに交じり合わないで向流ないし直交流で流れるように構成されてなることを特徴とする。屋内空気は、居室、工場、倉庫、病院、商店、事務所等の建物内の空気をいうが、光触媒反応に供されるものであればこれらに限定されない。一方、屋外空気は、外気、排ガス等、上記の屋内空気以外の空気をいう。屋外空気と屋内空気は、好適には温度差を有し、その差は数度以上であるのがさらに好適である。屋内空気温度が屋外空気温度よりも高い場合、もしくは屋外空気温度が屋内空気温度よりも高い場合のいずれであってもよい。
【００１６】
本発明装置において、複数層の流体通路は屋外空気と屋内空気が１層ごとに互いに交じり合わないで向流ないし直交流で流れるように構成されるが、向流は屋外空気と屋内空気の流れの主方向が互いに対向する（すなわち互いに１８０°の角度をなす）ことを意味し、直交流は屋外空気と屋内空気の流れの主方向が互いに９０°の角度をなすことを意味する。このように本発明装置においては、複数層の流体通路は屋外空気と屋内空気が１層ごとに互いに交じり合わないで向流ないし直交流で（すなわち互いに９０°から１８０°の角度をなして）流れるように構成されるが、好適には向流もしくは直交流が採用される。
【００１７】
たとえば、屋内空気が豚舎、養鶏場、その他の畜舎からの廃棄物の堆積物からの臭気を脱臭する際には、たとえば１０〜８０℃程度の室内空気流を本発明装置により脱臭させ、これと向流ないし直交流で導入される外気は０〜３０℃程度に熱交換され、前記室内空気から回収された熱を上記堆積物の加熱に用いて醗酵を促進させる等、有効に利用しうる。さらに、本発明装置は、いわゆる２４時間換気装置として温度調整に好適に利用しうる。
【００１８】
本発明の光触媒反応装置は、このような光触媒体に近接して紫外線源を適宜配置することにより構成され、脱臭装置、殺菌装置、空気清浄化器、水純化装置等に使用しうる。この場合、従来の活性炭等の吸着剤層等を併置することもできる。
【００１９】
脱臭は悪臭物質を拡散現象により光触媒表面に接触させて酸化分解することにより行なわれる。悪臭物質としては硫化水素、メルカプタン、アミン、アンモニア、アルデヒド等が挙げられる。空気中に離散した揮発性有機ハロゲン化合物、例えばトリクロロエタン、トリクロロエチレン等も光触媒反応により分解しうる。
【００２０】
照射に利用される紫外線としてはたとえば波長が１８５ｎｍ、２５４ｎｍ、３００〜４００ｎｍの紫外線が挙げられる。光触媒を光励起する波長は光触媒の種類により異なるが、たとえば二酸化チタンの場合、アナタ−ゼ型で３８０ｎｍ以下、ルチル型で４１５ｎｍ以下であり、さらに酸化ジルコニウムの場合、２５４ｎｍ以下である。このような光線を放射する紫外線源としては、ブラックライト、低圧、中圧もしくは高圧の水銀ランプ等の放電ランプが好適である。紫外線源の配置は光触媒体に近接していれば特に制限されない。
【００２１】
【実施例】
以下、実施例によりさらに本発明を詳細に説明する。
参考例１ Ａｌ板−陽極酸化／ＺｒＯ２／ゾル−ゲル／ハニカム（波板巻き上げ）
アルミニウム（Ａｌ）基板（平板および波板）を次の条件で陽極酸化した。
【００２２】
・ 浴組成 硫酸 １３．７％
・ 処理条件 約２２℃、０．５Ａ／ｄｍ２、ＤＣ，５分間、陰極：カーボン
得られた陽極酸化アルミニウム基板（酸化皮膜厚さ：約０．５μｍ）をジルコニウムブトキシドのエタノール溶液（ジルコニウムブトキシド２０ｇ、エタノール４５ｇ、水２０ｇ、塩酸０．３ｇ）に浸漬し、引き上げ、乾燥（室温）を繰り返して、ついで焼成（約５００℃）して厚さ約１０μｍのＺｒＯ２コーティング膜（５０ｎｍＲａ以下）を作製した。ついで得られた陽極酸化膜／ＺｒＯ２コーティング膜／アルミニウム基板から水ガラス接着剤を用いて、平板および波板を組合わせて波付けし、これをハニカム状に巻き上げることによりハニカム光触媒体を得た。
参考例２ Ａｌ板−陽極酸化／ＴｉＯ２／ゾル−ゲル／ハニカム（波板巻き上げ）
参考例１において、ＺｒＯ２コーティング膜に代えてＴｉＯ２コーティング膜（厚さ約１０μｍ）を作製する以外は同様にしてハニカム光触媒体を得た。チタンイソプロポキシドのエタノール溶液（チタンイソプロポキシド２５ｇ、エタノール４０ｇ、水２５ｇ、塩酸０．３ｇ）を用いた。
参考例３ Ａｌ板−化成処理／ＺｒＯ２／ゾル−ゲル／ＰＰＲ
参考例１において、Ａｌ基板の陽極酸化に代えて化成処理を採用した以外は同様にしてＺｒＯ２コーティング膜を作製した。化成処理はクロム酸−リン酸法により、処理方法：浸漬、濃度：４．５％、温度：４０〜５０℃、時間：３０秒で行った（膜厚：０．２μｍ）。ついで得られた化成皮膜／ＺｒＯ２コーティング膜／アルミニウム基板から、平板もしくは波板を間隔約０．５ｃｍで常法により平行に配置することによりＰＰＲ光触媒体を得た。
参考例４ 鋼板−めっき／ＴｉＯ２／ＣＶＤ／ハニカム（波板巻き上げ）
鋼基板を次の条件でめっきして亜鉛めっき皮膜（厚さ０．３μｍ）を形成させた。
【００２３】
【００２４】
反応装置：対向電極型プラズマＣＶＤ装置
反応ガス：ＴｉＣｌ４
雰囲気：Ａｒ＋Ｏ２
温度：３００〜４００℃
圧力：１．０Ｔｏｒｒ
参考例５ Ｍｇ板−陽極酸化／ＴｉＯ２／ゾル−ゲル／ハニカム（波板巻き上げ）
マグネシウム合金（Ｍｇ−Ａｌ−Ｚｎ）基板を次の条件で陽極酸化した。
【００２５】
実施例１
参考例１で得られたハニカム光触媒体を用いて図１および２に示すような向流型の脱臭装置を作製した。図１および２はその平面および側面概略図である。脱臭装置（１）は光触媒体（２）および紫外線ランプ（３）を備えており、光触媒体（２）の複数層の流体通路は屋外空気と屋内空気が１層ごとに互いに交じり合わないで向流で流れるように構成されている。たとえば、屋内空気が豚舎、養鶏場、その他の畜舎からの廃棄物の堆積物からの臭気を脱臭する際には、たとえば１０〜８０℃程度の室内空気流を本発明装置により脱臭させ、これと向流で導入される外気は０〜３０℃程度に熱交換され、前記室内空気から回収された熱を上記堆積物の加熱に用いて醗酵を促進させるために有効に利用しうる。
実施例２
参考例２で得られたハニカム光触媒体を用いて図３に示すような直交流型の脱臭装置を作製した。図３はその概略図であり、脱臭装置（１）は光触媒体（２）および紫外線ランプ（３）を備えており、光触媒体（２）の複数層の流体通路は屋外空気と屋内空気が１層ごとに互いに交じり合わないで直交流で流れるように構成されている。たとえば、屋内空気が豚舎、養鶏場、その他の畜舎からの廃棄物の堆積物からの臭気を脱臭する際には、たとえば１０〜８０℃程度の室内空気流を本発明装置により脱臭させ、これと直交流で導入される外気は０〜３０℃程度に熱交換され、前記室内空気から回収された熱を上記堆積物の加熱に用いて醗酵を促進させるために有効に利用しうる。
実施例３
本発明のハニカム光触媒体を用いて図１および２に示すような向流型の脱臭装置を作製した。図１および２はその平面および側面概略図である。
【図面の簡単な説明】
【図１】本発明の向流型光触媒反応装置の１態様を示す平面概略図。
【図２】図１の向流型光触媒反応装置の側面概略図。
【図３】本発明の直交型光触媒反応装置の１態様を示す概略図。
【図４】本発明の向流型光触媒反応装置の１態様を示す平面概略図。
【図５】図４の向流型光触媒反応装置の側面概略図。
【符号の説明】
１…脱臭装置
２…光触媒体
３…紫外線ランプ[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a photocatalytic reactor.
[0002]
[Prior art]
A photoreaction by a so-called semiconductor photocatalyst causes deodorization, antibacterial and antifouling actions by an oxidation-reduction reaction, which is one of the mechanisms. Various products have been studied by utilizing the action of the photocatalyst and have been put to practical use. The band gap of titanium oxide, which is a typical semiconductor photocatalyst, is about 3 eV, which is about 400 nm in terms of wavelength. Therefore, when ultraviolet light of 400 nm or less is irradiated, electrons (e − ) and holes (h + ) are generated inside the semiconductor. These electrons react with oxygen to generate superoxide ions [O 2 − ] exhibiting extremely large oxidizing power, and one hole reacts with water to generate hydroxyl radicals [.OH]. These two active oxygens cause an oxidation-reduction reaction to decompose odors or dirt substances, and further oxidatively decompose other hardly decomposable compounds such as organic chlorine compounds.
[0003]
Conventionally, various types of photocatalytic reactors have been known in order to exhibit their photocatalytic activity for various purposes.
[0004]
[Problems to be solved by the invention]
SUMMARY OF THE INVENTION An object of the present invention is to provide a photocatalytic reaction device capable of simultaneously performing a photocatalytic reaction using both outdoor air and indoor air as gas to be treated, and effectively utilizing the heat of the higher temperature air.
[0005]
[Means for Solving the Problems]
An object of the present invention is to provide a photocatalyst having a photocatalyst having a photocatalyst coated on a substrate surface and an ultraviolet light source, and forming a plurality of layers of fluid passages composed of the photocatalyst, wherein the plurality of layers of fluid passages are outdoors. This is achieved by a photocatalytic reactor characterized in that the air and the indoor air are configured to flow countercurrently or crossflow without intermingling with each other layer by layer.
[0006]
BEST MODE FOR CARRYING OUT THE INVENTION
In the photocatalyst of the present invention, a metal is preferable as the above-mentioned base material since it is not deteriorated by ultraviolet light having a low wavelength. The metal is preferably selected from aluminum, titanium, magnesium, steel or stainless steel, and is particularly preferably aluminum. Aluminum, titanium or magnesium may be an alloy. For example, as an aluminum alloy, Al-Mg, Al-Mg-Si, Al-Cu-Mg-Mn, Al-Zn-Mg-Cu, etc., and as a magnesium alloy, Mg-Al, Mg-Al-Zn, Mg- Mn and the like. In the present invention, a coating film of a photocatalyst is formed on a substrate of such a metal, and it is preferable that the metal surface is coated with an insulating film before this formation. By this insulating coating, the electrons on the photocatalyst can be sufficiently exchanged without flowing to the metal side, so that the photolytic activity can be remarkably enhanced.
[0007]
This insulating coating treatment is preferably selected from anodic oxidation, chemical conversion treatment or glass coating treatment. For example, in the case of aluminum and titanium, a so-called anodic oxide film that forms an oxide film on a metal surface by immersing them in an aqueous electrolyte solution and subjecting them to anodic polarization is generally used. In the case of a steel sheet, electroplating or hot-dip plating, and furthermore, chemical conversion treatment with phosphoric acid and phosphate are common. Further, in the case of aluminum, a chemical film formation method (chemical conversion treatment) using a chemical agent may be adopted instead of anodic oxidation. As the chemical conversion treatment, a treatment mainly composed of chromic acid or chromic acid-phosphoric acid, that is, a chromate treatment film is preferable. Also in the case of magnesium, anodic oxidation and chemical conversion treatment can be applied.
[0008]
Further, a glass coating method in which sodium silicate (water glass) is applied to the surface of aluminum or the like and then sintered may be employed.
[0009]
In the case of stainless steel, an acid (preferably sodium dichromate) treatment (chemical conversion treatment) for oxidizing the surface to passivate the surface may be employed.
[0010]
The thickness of the insulating coating is not particularly limited, but is usually selected from about 0.1 to 1 μm.
[0011]
Examples of the photocatalyst in the present invention include metal oxides such as zirconium oxide, titanium oxide, zinc oxide, tungsten oxide, cadmium oxide, manganese oxide, and copper oxide; metals such as cadmium sulfide, zinc sulfide, indium sulfide, lead sulfide, and tungsten sulfide. Sulfides; organic polymers such as polyparaphenylene, polyaniline, and polythiophene; intercalation compounds obtained by adding various metal oxides to strontium titanate; and zirconium oxide and titanium oxide are preferable. Most preferably, by selecting zirconium oxide, an ultraviolet light having a relatively short wavelength can be used, so that an improved photocatalytic activity can be easily obtained. Titanium oxide may be any of an anatase, rutile or blockite type, but an anatase type is optimal from the viewpoint of catalytic activity and availability.
[0012]
The method of forming the coating film of the photocatalyst on the metal substrate itself can be a conventional method, but a method of depositing from a liquid phase and a method of depositing from a gas phase are preferable. For example, the liquid phase method includes a sol-gel method and the like, and the gas phase method includes a chemical method such as a physical vapor deposition method (PVD) such as sputtering and vacuum vapor deposition or a gas phase chemical reaction method (CVD). The sol-gel method is optimal from the viewpoint of uniformity of coating to be obtained, cost and the like. As a starting material in the sol-gel method, a metal organic compound such as a metal alkoxide, a metal acetylacetonate, or a metal carboxylate, for example, a metal inorganic compound such as an oxychloride, a chloride, or a nitrate is generally used. Among these, metal alkoxides are preferable from the viewpoint of reactivity and the like. Metal alkoxides such as butoxide, ethoxide and propoxide (for example, zirconium or titanium) are used as a solution using a solvent such as butanol or propanol, and this is converted to a metal. A desired coating film can be formed by applying the composition to a substrate. For application, brushing, roll coating, dipping, spraying, spinning, or the like can be appropriately selected. The thickness of the coating film is generally selected from the range of 3 to 500 μm, preferably about 5 to 20 μm. For example, a substrate is immersed in a metal alkoxide solution using a sol-gel method, and is lifted to obtain a coating film. The coating film is dried by a conventional method, for example, at room temperature, and then heated to about 300 to 550 ° C. and fixed to the substrate. As the above-mentioned CVD method, a plasma CVD method can be used for forming a film by a gas phase chemical reaction in a relatively low temperature range of about 400 to 500 ° C., and thus there is no limitation on the base material, which is suitable.
[0013]
The obtained coating film forming substrate is then processed into a three-dimensional structure. This structure comprises a honeycomb, a corrugated sheet and / or a flat sheet. The honeycomb is not limited to a hexagonal core and may have any shape. The corrugated plate may be used in combination with a flat plate (corrugation) and arranged in parallel, or may be rolled up to form a honeycomb. The flat plates are preferably arranged in parallel and used as a so-called parallel passage type. The structure of the present invention enables efficient photocatalytic reaction because of extremely low airflow resistance. The processing for forming the three-dimensional structure is bonding, cutting, or cutting, and can be performed by an ordinary method. At the time of bonding, an organic adhesive is likely to be degraded by a photocatalyst, so that an inorganic adhesive is preferably used. Examples of such inorganic adhesives include glass based materials such as low melting point glass; metal based materials such as soft solder such as Sn-In, Bi-Pb, Sn-Pb and Pb-Sb; alkali silicate (particularly water glass); Other inorganic materials such as phosphates and the like can be mentioned, and those having an adhesion temperature of 100 to 500 ° C, preferably 120 to 200 ° C, are particularly preferable. Of these inorganic adhesives, the most preferred is water glass.
[0014]
The photocatalyst according to the present invention preferably has a surface roughness of 50 nmRa (center line roughness) or less. When the mirror surface is formed and the coating film is transparent, the light reflectance is remarkable. Thus, for example, the inside of the honeycomb photocatalyst body can be irradiated with ultraviolet rays with irregular reflection, and the catalytic activity can be significantly improved.
[0015]
In the apparatus of the present invention, a plurality of layers of fluid passages composed of photocatalysts are formed by the processing for forming the three-dimensional structure. The apparatus of the present invention is characterized in that the fluid passages of the plurality of layers are configured such that the outdoor air and the indoor air flow in a countercurrent or crossflow without intermingling with each other for each layer. Indoor air refers to air in buildings such as living rooms, factories, warehouses, hospitals, shops, offices, and the like, but is not limited thereto as long as it is subjected to a photocatalytic reaction. On the other hand, the outdoor air refers to air other than the indoor air described above, such as outside air and exhaust gas. Outdoor air and indoor air preferably have a temperature difference, more preferably the difference is a few degrees or more. Either when the indoor air temperature is higher than the outdoor air temperature or when the outdoor air temperature is higher than the indoor air temperature.
[0016]
In the apparatus of the present invention, the fluid passages of the plurality of layers are configured so that the outdoor air and the indoor air flow countercurrently or cross-flow without intermingling with each other for each layer. Mean that the main directions of the air flow are opposite to each other (ie, form an angle of 180 ° with each other), and the cross flow means that the main directions of the flow of the outdoor air and the flow of the indoor air form an angle of 90 ° with each other. Thus, in the apparatus of the present invention, the fluid passages of the plurality of layers are in a countercurrent or cross-flow (ie, at an angle of 90 ° to 180 ° with each other) without the outdoor air and the indoor air intermingling with each other for each layer. It is configured to flow, but preferably countercurrent or crossflow.
[0017]
For example, when indoor air deodorizes odors from waste deposits from pig houses, poultry farms, and other livestock houses, for example, an indoor air stream at about 10 to 80 ° C. is deodorized by the present invention device, and The outside air introduced by countercurrent or cross flow is heat-exchanged to about 0 to 30 ° C., and the heat recovered from the room air can be used for heating the sediment to promote the fermentation. Furthermore, the device of the present invention can be suitably used for temperature control as a so-called 24-hour ventilation device.
[0018]
The photocatalyst reaction device of the present invention is constituted by appropriately arranging an ultraviolet light source near such a photocatalyst, and can be used for a deodorizing device, a sterilizing device, an air purifier, a water purifying device and the like. In this case, a conventional adsorbent layer of activated carbon or the like may be provided.
[0019]
Deodorization is performed by bringing a malodorous substance into contact with the photocatalyst surface by a diffusion phenomenon and oxidatively decomposing it. Examples of the offensive odor include hydrogen sulfide, mercaptan, amine, ammonia, aldehyde and the like. Volatile organic halogen compounds dispersed in the air, such as trichloroethane and trichloroethylene, can also be decomposed by a photocatalytic reaction.
[0020]
Examples of the ultraviolet light used for the irradiation include ultraviolet light having a wavelength of 185 nm, 254 nm, or 300 to 400 nm. The wavelength of photoexcitation of the photocatalyst varies depending on the type of photocatalyst. For example, in the case of titanium dioxide, it is 380 nm or less for anatase type and 415 nm or less for rutile type, and further, it is 254 nm or less for zirconium oxide. As an ultraviolet light source that emits such a light beam, a discharge lamp such as a black light, a low pressure, a medium pressure or a high pressure mercury lamp is suitable. The arrangement of the ultraviolet light source is not particularly limited as long as it is close to the photocatalyst.
[0021]
【Example】
Hereinafter, the present invention will be described in more detail with reference to examples.
Reference Example 1 Al plate - anodic oxidation / ZrO 2 / sol - gel / honeycomb (hoisting corrugated)
An aluminum (Al) substrate (flat plate and corrugated plate) was anodized under the following conditions.
[0022]
・ Bath composition sulfuric acid 13.7%
Treatment conditions: about 22 ° C., 0.5 A / dm 2 , DC, 5 minutes, cathode: carbon Anodized aluminum oxide substrate (oxide film thickness: about 0.5 μm) was prepared by using an ethanol solution of zirconium butoxide (zirconium butoxide 20 g). Immersed in ethanol, 45 g, water 20 g, hydrochloric acid 0.3 g), pulled up, dried (room temperature) repeatedly, and then fired (about 500 ° C.) to form a ZrO 2 coating film (about 50 nm Ra or less) having a thickness of about 10 μm. did. Then, a flat plate and a corrugated plate were combined and corrugated from the obtained anodic oxide film / ZrO 2 coating film / aluminum substrate using a water glass adhesive, and this was rolled up in a honeycomb shape to obtain a honeycomb photocatalyst. .
Reference Example 2 Al plate - anodic oxidation / TiO 2 / sol - gel / honeycomb (hoisting corrugated)
A honeycomb photocatalyst was obtained in the same manner as in Reference Example 1, except that a TiO 2 coating film (about 10 μm in thickness) was formed instead of the ZrO 2 coating film. An ethanol solution of titanium isopropoxide (25 g of titanium isopropoxide, 40 g of ethanol, 25 g of water, 0.3 g of hydrochloric acid) was used.
Reference Example 3 Al plate - chemical treatment / ZrO 2 / sol - gel / PPR
A ZrO 2 coating film was produced in the same manner as in Reference Example 1, except that a chemical conversion treatment was employed instead of the anodic oxidation of the Al substrate. The chemical conversion treatment was performed by a chromic acid-phosphoric acid method at a treatment method: immersion, concentration: 4.5%, temperature: 40 to 50 ° C., and time: 30 seconds (film thickness: 0.2 μm). Then, a PPR photocatalyst was obtained by arranging flat plates or corrugated plates in parallel by a conventional method at intervals of about 0.5 cm from the obtained chemical conversion film / ZrO 2 coating film / aluminum substrate.
Reference Example 4 steel - Plating / TiO 2 / CVD / honeycomb (hoisting corrugated)
A steel substrate was plated under the following conditions to form a galvanized film (thickness 0.3 μm).
[0023]
[0024]
Reactor: Counter electrode type plasma CVD device Reactant gas: TiCl 4
Atmosphere: Ar + O 2
Temperature: 300-400 ° C
Pressure: 1.0 Torr
Reference Example 5 Mg plate - anodic oxidation / TiO 2 / sol - gel / honeycomb (hoisting corrugated)
A magnesium alloy (Mg-Al-Zn) substrate was anodized under the following conditions.
[0025]
Example 1
Using the honeycomb photocatalyst obtained in Reference Example 1, a countercurrent deodorizing apparatus as shown in FIGS. 1 and 2 was produced. 1 and 2 are schematic plan and side views thereof. The deodorizing device (1) is provided with a photocatalyst (2) and an ultraviolet lamp (3). The fluid passages of the photocatalyst (2) in a plurality of layers are arranged so that the outdoor air and the indoor air do not mix with each other one by one. It is configured to flow in the flow. For example, when indoor air deodorizes odors from waste deposits from pig houses, poultry farms, and other livestock houses, for example, an indoor air stream at about 10 to 80 ° C. is deodorized by the present invention device, and The outside air introduced in the countercurrent is heat-exchanged to about 0 to 30 ° C., and the heat recovered from the room air can be used for heating the sediment and effectively used to promote fermentation.
Example 2
Using the honeycomb photocatalyst obtained in Reference Example 2, a cross-flow type deodorizer as shown in FIG. 3 was produced. FIG. 3 is a schematic view thereof. The deodorizing device (1) is provided with a photocatalyst (2) and an ultraviolet lamp (3). The layers are configured to flow in a cross flow without intermingling with each other. For example, when indoor air deodorizes odors from waste deposits from pig houses, poultry farms, and other livestock houses, for example, an indoor air stream of about 10 to 80 ° C. is deodorized by the present invention device, and The outside air introduced by the cross flow is heat-exchanged to about 0 to 30 ° C., and the heat recovered from the room air can be used for heating the sediment to be effectively used for promoting fermentation.
Example 3
Using the honeycomb photocatalyst of the present invention, a countercurrent deodorizing apparatus as shown in FIGS. 1 and 2 was produced. 1 and 2 are schematic plan and side views thereof.
[Brief description of the drawings]
FIG. 1 is a schematic plan view showing one embodiment of a countercurrent photocatalytic reactor of the present invention.
FIG. 2 is a schematic side view of the countercurrent photocatalytic reactor of FIG.
FIG. 3 is a schematic view showing one embodiment of the orthogonal photocatalytic reactor of the present invention.
FIG. 4 is a schematic plan view showing one embodiment of a countercurrent photocatalytic reactor of the present invention.
FIG. 5 is a schematic side view of the countercurrent photocatalytic reactor of FIG.
[Explanation of symbols]
DESCRIPTION OF
Claims (13)
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| Application Number | Priority Date | Filing Date | Title |
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| JP2002213019A JP2004050102A (en) | 2002-07-22 | 2002-07-22 | Photocatalytic reaction apparatus |
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| Application Number | Priority Date | Filing Date | Title |
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| JP2002213019A JP2004050102A (en) | 2002-07-22 | 2002-07-22 | Photocatalytic reaction apparatus |
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| JP2004050102A true JP2004050102A (en) | 2004-02-19 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010036172A (en) * | 2008-08-08 | 2010-02-18 | Sumitomo Electric Ind Ltd | Metal material and manufacturing method thereof, and case for electronic equipment using the same |
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| JPH1190237A (en) * | 1997-07-23 | 1999-04-06 | Toshiba Lighting & Technology Corp | Photocatalytic body, its production, deodorization device and lighting fixture |
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