JP3202863B2 - Photocatalyst-supported linear articles - Google Patents
Photocatalyst-supported linear articlesInfo
- Publication number
- JP3202863B2 JP3202863B2 JP04820194A JP4820194A JP3202863B2 JP 3202863 B2 JP3202863 B2 JP 3202863B2 JP 04820194 A JP04820194 A JP 04820194A JP 4820194 A JP4820194 A JP 4820194A JP 3202863 B2 JP3202863 B2 JP 3202863B2
- Authority
- JP
- Japan
- Prior art keywords
- light
- photocatalyst
- harmful organic
- article
- organic substances
- 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
- 239000011941 photocatalyst Substances 0.000 claims description 36
- 239000000126 substance Substances 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 7
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 239000000835 fiber Substances 0.000 claims description 3
- 230000001678 irradiating effect Effects 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 16
- 230000001699 photocatalysis Effects 0.000 description 13
- 239000010453 quartz Substances 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000000243 solution Substances 0.000 description 10
- 229910010413 TiO 2 Inorganic materials 0.000 description 9
- 239000004065 semiconductor Substances 0.000 description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical class O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 7
- 239000007789 gas Substances 0.000 description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 6
- 239000013307 optical fiber Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000010419 fine particle Substances 0.000 description 5
- 238000013032 photocatalytic reaction Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 238000007788 roughening Methods 0.000 description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 235000019253 formic acid Nutrition 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 230000031700 light absorption Effects 0.000 description 3
- 239000011146 organic particle Substances 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000003486 chemical etching Methods 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000012417 linear regression Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000005297 pyrex Substances 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- 239000005361 soda-lime glass Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- -1 trihalomethane Chemical class 0.000 description 1
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、光触媒担持線状物
品を用いて水および空気中の有害有機物質を光分解除去
する方法と装置に関する。TECHNICAL FIELD The present invention relates to a photocatalyst-supporting linear object.
An apparatus and photolytic removal <br/> be that way harmful organic substances in water and air with goods.
【０００２】[0002]
【従来の技術】最近、地球規模での環境汚染が問題とな
っている。中でも、飲料水および空気中の有害有機物質
は、人間の体内に直接取り込まれることから、特に深刻
である。水中の有害有機物としては、トリハロメタンな
どの有機ハロゲン化物があり、従来活性炭などを充填し
てフィルターにより除去されてきた。また、空気中で問
題になる有害有機物としては、ＮＯｘ，ＳＯｘ，ＮＨ3
などがあり、その除去方法としては活性炭を始めとする
各種吸着剤が用いられてきた。2. Description of the Related Art Recently, global environmental pollution has become a problem. Above all, harmful organic substances in drinking water and air are particularly serious because they are taken directly into the human body. As harmful organic substances in water, there are organic halides such as trihalomethane, which have been conventionally filled with activated carbon or the like and removed by a filter. NOx, SOx, and NH 3 are harmful organic substances that cause problems in the air.
Various adsorbents such as activated carbon have been used as a removing method.
【０００３】また、エレクトロニクス産業、特に半導体
の製造には、クリーンな環境が求められており、技術の
進歩にともない求められるクリーン度も高くなりつつあ
る。塵埃などはエアフィルターで効率的に除去すること
ができるが、クリーンルーム中に存在する有機分子を除
去することは極低濃度であるために困難である。この分
野で問題となる空気中の有機物としては、ガラスやウエ
ハー基板上に付着する高沸点炭化水素類、例えば、クリ
ーンルーム構成材からの脱離物であるＳｉ化合物などが
ある。Further, a clean environment is required for the electronics industry, particularly for the manufacture of semiconductors, and the degree of cleanliness required is increasing with the progress of technology. Dust and the like can be efficiently removed by an air filter, but it is difficult to remove organic molecules present in a clean room due to the extremely low concentration. Organic substances in the air that pose a problem in this field include high-boiling hydrocarbons adhering to glass and wafer substrates, such as Si compounds that are desorbed from clean room components.
【０００４】一方、ＴｉＯ2 に代表される結晶性半導体
が、光触媒活性を有することは良く知られている（参考
文献，藤島ら，表面，第２０巻，５６３ページ，１９８
２年）。これは、バンドギャップ以上のエネルギーを持
つ波長の光を吸収することにより、価電子帯の電子が伝
導帯に励起され、価電子帯には正孔が生成する。これら
の励起電子および正孔が、結晶性半導体の表面に吸着し
た有機物を分解するものである。On the other hand, it is well known that a crystalline semiconductor typified by TiO 2 has photocatalytic activity (Reference, Fujishima et al., Surface, Vol. 20, p. 563, 198).
2 years). This is because, by absorbing light having a wavelength having energy equal to or greater than the band gap, electrons in the valence band are excited to the conduction band, and holes are generated in the valence band. These excited electrons and holes decompose organic substances adsorbed on the surface of the crystalline semiconductor.
【０００５】従来の研究は、反応面積を大きくするため
に、主に半導体微粒子系で行われてきた。確かに、熱触
媒では、触媒を微粒子化することにより、反応面積を著
しく増大させることが可能である。これに対して、光触
媒では触媒を微粒子化することにより反応面積を増大さ
せることができても、反応を誘起させるに必要な光を効
率的に微粒子に照射することが困難となることから、微
粒子化の効果は小さい。また、水および空気の浄化に用
いる場合には、微粒子の回収が大きな問題になる。[0005] Conventional research has mainly been conducted on semiconductor fine particle systems in order to increase the reaction area. Certainly, in the case of a thermal catalyst, the reaction area can be significantly increased by making the catalyst finer. In contrast, in the case of a photocatalyst, even if the reaction area can be increased by making the catalyst into fine particles, it is difficult to efficiently irradiate the fine particles with light necessary to induce the reaction. The effect of conversion is small. In addition, when used for purification of water and air, collection of fine particles becomes a major problem.
【０００６】現在までに、ＴｉＯ2 などの半導体を固体
支持体に固定化した種々の光反応リアクターが提案され
ている。例えば特開昭６１−９７１０２号公報には、光
ファイバーの側表面に半導体微粒子を担持させて光ファ
イバーを通してその側表面にある反応系に光を照射する
ことが記載されている。また同様に光学ファイバー表面
に膜状半導体を固定化するものが発表されている（参考
文献，Ｄ．Ｃ．Gapen,米国ウイスコンシン−マジソン大
学修士論文，１９９１）。これらによれば、光学ファイ
バー径を小さくし、多数のファイバーをまとめて使用す
ることにより、光反応面積を増大させることが可能にな
る。To date, various photoreactors have been proposed in which a semiconductor such as TiO 2 is immobilized on a solid support. For example, JP 61-97102, JP discloses that by supporting the semiconductor fine particles on the side surface of the optical fiber by passing the optical fiber for irradiating light to the reaction system in its side surface. Similarly, a technique in which a film-like semiconductor is immobilized on the surface of an optical fiber has been published (Reference, DC Gapen, Master's Thesis, University of Wisconsin-Madison, 1991). According to these, the optical reaction area can be increased by reducing the diameter of the optical fiber and using a large number of fibers collectively.
【０００７】しかしながら、この方法でも光反応効率は
十分とは言えず、さらに大きな光反応効率を有する光触
媒担持物品が求められていた。However, the photoreaction efficiency cannot be said to be sufficient even by this method, and a photocatalyst-carrying article having a higher photoreaction efficiency has been demanded.
【０００８】[0008]
【発明が解決しようとする課題】本発明は、光触媒担持
線状物品から構成される高効率で有害有機物質が除去で
きる方法及び装置を提供することを目的としている。SUMMARY OF THE INVENTION An object of the present invention is to provide a method and an apparatus for removing harmful organic substances with high efficiency constituted by a linear article carrying a photocatalyst.
【０００９】[0009]
【課題を解決するための手段】本発明者らは、鋭意研究
の結果、表面を粗面化した性状の光透過性線状物品表面
上に光触媒を担持することにより、光触媒反応速度を著
しく向上させることに成功した。Means for Solving the Problems As a result of intensive studies, the present inventors have remarkably improved the photocatalytic reaction rate by supporting a photocatalyst on the surface of a light-transmitting linear article having a roughened surface. Succeeded.
【００１０】すなわち、本発明は、液体又は気体中の有
害有機物質を除去する方法において、該液体又は気体中
の有害有機物質を、表面が粗面である光透過性線状物品
の表面に光触媒を被覆させた光触媒担持線状物品と、前
記光触媒担持線状物品の端部からその内部に光を導入さ
せることにより得られる光照射下に接触させることを特
徴とする有害有機物質の除去方法である。さらに、本発
明は、液体又は気体中の有害有機物質を除去する装置に
おいて、該有害有機物質を含む液体又は気体の導入口及
び排出口を有し、内部に、表面が粗面である光透過性線
状物品の表面に光触媒を被覆させた１本以上の光触媒担
持線状物品と、該光触媒担持線状物品に光を照射する光
源とを有し、前記光源は、光触媒担持線状物品の端部か
らその内部に光が導入されるように配置されていること
を特徴とする有害有機物質の除去装置である。本発明の
有害有機物質の除去装置において、前記光触媒担持線状
物品は、その複数本が、光導入側の端部で密に束ねられ
ているのがよい。[0010] Namely, the present invention is a method of removing toxic organic substances in the liquid or gas, harmful organic substances liquid or gas, the photocatalyst on the surface of the surface is a rough surface light transmissive linear article and the photocatalyst carrying linear article is coated, before
Light is introduced from the end of the linear article carrying the photocatalyst into the interior.
This is a method for removing harmful organic substances, which is characterized in that it is brought into contact with light obtained by irradiation. Furthermore, the present invention provides an apparatus for removing harmful organic substances in a liquid or a gas, wherein the apparatus has an inlet and an outlet for a liquid or a gas containing the harmful organic substance, and has a light transmitting surface having a rough surface inside. possess one and more photocatalysts carrying wire-like article obtained by coating the photocatalyst on the surface of sexual linear article, and a light source for irradiating light to the photocatalyst carrying wire-like article, said light source, the photocatalyst carrying wire-like article The end
Al is a device for removing toxic organic substances, characterized that you have been arranged so that light is introduced therein. In the harmful organic substance removing apparatus of the present invention , it is preferable that a plurality of the photocatalyst-carrying linear articles are tightly bundled at an end on a light introduction side.
【００１１】本発明の光触媒反応機構を、模式的に示し
た図１を用いて説明する。図は光触媒担持線状物品の横
断面を示し、線状物品１はその側表面に多数の凹凸２を
有しており、その表面には光触媒膜３が被覆されてい
る。線状物品１の一端から励起用光（紫外線および／ま
たは可視光線）４を入射させると、光４は線状物品の側
面の凹凸２に衝突散乱して光触媒膜３の中をｈνのエネ
ルギーをもって進行する。そして光触媒膜を構成するＴ
ｉＯ2 粒子に衝突して伝導帯５に励起された電子６と価
電子帯７の正孔８を生じさせる。励起電子６と正孔８は
光触媒膜３の外側表面に吸着している有害有機物粒子９
に向かって移動して有害有機物粒子に到達して光触媒反
応を生じさせて有害有機物粒子を無害の分解生成物１０
に変化させる。The photocatalytic reaction mechanism of the present invention will be described with reference to FIG. The figure shows a cross section of a linear article carrying a photocatalyst. The linear article 1 has a large number of irregularities 2 on its side surface, and its surface is covered with a photocatalyst film 3. When the one end of the linear article 1 is incident four excitation light (ultraviolet rays and / or visible light), the light 4 is the energy of hν through the linear side photocatalyst film irregularities 2 collide scattering of the article 3 Proceed with. And T which constitutes the photocatalyst film
Collision with the iO 2 particles generates electrons 6 excited in the conduction band 5 and holes 8 in the valence band 7. Excited electrons 6 and holes 8 are harmful organic particles 9 adsorbed on the outer surface of photocatalytic film 3.
To the harmful organic particles and cause a photocatalytic reaction to remove the harmful organic particles from the harmless decomposition products 10.
To change.
【００１２】本発明により、光触媒反応速度が著しく向
上するのは、２つの効果に起因するものである。１つ
は、平滑表面線状支持体を用いる場合に比べて、表面の
凹凸によって光反応面積、言いかえれば光触媒の被覆表
面積が一層増大することである。他の１つは、これが最
も重要であるが、光が表面の凹凸で散乱されるために、
効率的に半導体に光が吸収されることである。より詳細
に述べると、光透過性線状物品の内部を通過した光は光
透過性線状物品の屈折率（ガラスの場合約１．５）より
も高い屈折率（約２．５）をもつＴｉＯ2 膜に優先的に
吸収される。光が効率よく作用して光吸収率が増加する
理由はおそらく次の（１）および（２）のいずれかまた
はそれらの組合せによると推定される。The remarkable improvement in the photocatalytic reaction rate according to the present invention is due to two effects. One is that the photoreaction area, in other words, the photocatalyst coating surface area is further increased by the unevenness of the surface as compared with the case of using the smooth surface linear support. The other is, most importantly, because light is scattered by surface irregularities,
Light is efficiently absorbed by the semiconductor. More specifically, light that has passed through the interior of the light-transmitting linear article has a higher refractive index (about 2.5) than the refractive index of the light-transmitting linear article (about 1.5 for glass). It is preferentially absorbed by the TiO 2 film. It is presumed that the reason why light acts efficiently and the light absorption rate increases is probably due to any of the following (1) and (2) or a combination thereof.
【００１３】（１）光触媒膜の外側表面は光透過性線状
物品の表面凹凸の形状がそのまま引き継がれて凹凸形状
をなしているので、光触媒膜外側表面の一つの山形斜面
から外へ出ていった光が向かい合った隣の山形斜面にあ
たって更に光触媒膜内部を進行するので光触媒膜内の光
の通過長さが増大して光吸収効率が増加する。もし平滑
表面線状支持体を用いる場合には、光触媒膜の外側表面
も平坦であるから、このような再帰入射を生じない。(1) Since the outer surface of the photocatalyst film has an irregular shape by inheriting the shape of the surface irregularities of the light-transmitting linear article as it is, the outer surface of the photocatalyst film comes out from one mountain-shaped slope of the outer surface of the photocatalytic film. Since the reflected light further travels inside the photocatalyst film on the adjacent mountain-shaped slope facing each other, the length of light passing through the photocatalyst film increases, and the light absorption efficiency increases. If a linear support having a smooth surface is used, the outer surface of the photocatalyst film is also flat, so that such retro-incidence does not occur.
【００１４】（２）光触媒膜の外側表面は上述のように
凹凸形状をなしているので、光触媒膜の中を通ってその
外側表面の一つの山形の一方斜面に衝突して全反射して
その山の反対側の傾斜に衝突して全反射しこれを複数回
繰り返すため光触媒膜内の光の通過長さが増大して光吸
収効率が増加する。もし平滑表面線状支持体を用いる場
合には、光触媒膜の外側表面も平坦であり、山形形状は
存在しないから、上記の繰り返し全反射は生じない。(2) Since the outer surface of the photocatalyst film has an uneven shape as described above, it passes through the photocatalyst film and collides with one slope of one of the outer surfaces to be totally reflected and reflected. Since the light collides with the slope on the opposite side of the mountain and undergoes total reflection and this is repeated a plurality of times, the light transmission length in the photocatalytic film increases, and the light absorption efficiency increases. If a smooth-surface linear support is used, the outer surface of the photocatalytic film is also flat and has no chevron shape, so that the above-described total repetition does not occur.
【００１５】本発明において、光透過性線状物品の材料
としては、その物品の上に被覆する光触媒膜を励起する
ことができる光すなわち、紫外光および／または可視
光、を透過するもの、好ましくは関係する光の波長に対
して透過率が材料の長さ１ｃｍあたり、９６．０％以
上、より好ましくは９８．０％以上のものであれば何で
も用いることができるが、特に耐光性に優れた石英ガラ
ス，パイレックスガラス，ソーダライムガラスなどのガ
ラスファイバーを好適に用いることができる。光透過性
線状物品はその断面が円形、楕円形、多角形等の断面を
有する細長い物品であり、その太さは、細ければ細い程
良いが、あまり細くなると機械的強度が低下するので、
直径が０．１ｍｍ以上であることが望ましい。また、太
さの上限は無いが、太くなるほどファイバーの体積当り
の光反応効率は低下するので１０ｍｍ以下が好ましい。
特に好ましい直径は０．２〜１ｍｍである。また、光透
過性線状物品の長さは、特に限定はないが、太さの１０
倍〜１０万倍（好ましくは３０倍〜３万倍、より好まし
くは１００倍〜５０００倍）で、通常は５ｃｍ〜１０ｍ
である。In the present invention, the light-transmitting linear article is preferably made of a material which transmits light capable of exciting a photocatalytic film coated on the article, ie, ultraviolet light and / or visible light, and is preferable. Any material can be used as long as it has a transmittance of 96.0% or more, more preferably 98.0% or more, per 1 cm of the length of the material with respect to the wavelength of the light involved, but is particularly excellent in light resistance. Glass fibers such as quartz glass, Pyrex glass, and soda lime glass can be suitably used. A light-transmitting linear article is an elongated article having a cross section such as a circle, an ellipse, or a polygon, and the thinner the better, the thinner the better, but if too thin, the mechanical strength decreases. ,
It is desirable that the diameter is 0.1 mm or more. Although there is no upper limit for the thickness, the photoreaction efficiency per volume of the fiber decreases as the thickness increases, so that the thickness is preferably 10 mm or less.
A particularly preferred diameter is between 0.2 and 1 mm. The length of the light-transmitting linear article is not particularly limited, but may be 10
Times 100,000 times (preferably 30 times to 30,000 times, more preferably 100 times to 5000 times), usually 5 cm to 10 m
It is.
【００１６】なお、光透過性線状物品表面の側面粗面化
法としては、特に限定されず、ＨＦ水溶液による化学的
エッチングおよび研磨材による物理的なスリ加工などを
用いれば良い。粗面化は光透過性線状物品表面だけでな
く、その末端表面に施してもよく、また光を入射させる
側の端面に施してもよい。凹凸のディメンジョンとして
は、紫外および／または可視光を散乱するために、深さ
約２００ｎｍ以上が必要になる。しかし、凹凸サイズが
大きすぎると、担体の機械的強度が小さくなることか
ら、効率は低下することになる。その結果、上限は０．
１ｍｍであることが望ましく、特に０．５〜１０μｍの
範囲が特に好適である。凹凸のピッチは特に限定されな
いが、当然凹凸深さによって異なる。通常は凹凸の深さ
の１０倍程度のものが使用される。The method for roughening the side surface of the light-transmitting linear article is not particularly limited, and chemical etching with an HF aqueous solution, physical polishing with an abrasive, or the like may be used. The surface roughening may be performed not only on the surface of the light-transmitting linear article, but also on the end surface thereof, or may be performed on the end surface on the light incident side. The unevenness needs to have a depth of about 200 nm or more in order to scatter ultraviolet and / or visible light. However, if the size of the concavities and convexities is too large, the mechanical strength of the carrier is reduced, so that the efficiency is reduced. As a result, the upper limit is 0.
It is preferably 1 mm, and particularly preferably in the range of 0.5 to 10 μm. The pitch of the unevenness is not particularly limited, but naturally depends on the depth of the unevenness. Usually, a material having a depth of about 10 times the depth of the unevenness is used.
【００１７】光透過性線状物品上に担持する光触媒の種
類は、対象となる有害有機物質および光源の種類などを
考慮の上、ＴｉＯ2 ，ＺｎＯ，ＺｎＳ，ＷＯ3 ，Ｆｅ2
Ｏ3，ＧａＡｓＰ，ＣｄＳｅ，ＧａＡｓ，ＣｄＳ，Ｓｒ
ＴｉＯ3 ，ＧａＰ，Ｉｎ2 Ｏ3 ，ＭｏＯ2 ，ＴｉＯ2 −
Ｐｔ−ＲｕＯ2 合金などの中から選定される。光触媒活
性の高さと化学的な安定性から、現在最も広範に用いら
れている光触媒はＴｉＯ2 であり、本発明にも特に好適
に使用することが可能である。しかしながら、本発明に
使用される光触媒はこれに限定されることはなく、従来
光触媒として知られているものは如何なるものでも使用
することができる。The type of the photocatalyst supported on the light-transmitting linear article is determined by taking into account the type of the harmful organic substance to be treated and the type of the light source, and the like, and is determined by using TiO 2 , ZnO, ZnS, WO 3 , and Fe 2.
O 3 , GaAsP, CdSe, GaAs, CdS, Sr
TiO 3 , GaP, In 2 O 3 , MoO 2 , TiO 2 −
It is selected from Pt-RuO 2 alloy and the like. From height and chemical stability of the photocatalytic activity, photocatalyst currently most widely used is TiO 2, it can be particularly preferably used in the present invention. However, the photocatalyst used in the present invention is not limited to this, and any of those conventionally known as photocatalysts can be used.
【００１８】光触媒膜の厚みは、薄すぎると、光を十分
に吸収できない。一方、厚すぎると、膜中で生じた光キ
ャリアーが表面まで拡散できないために、触媒活性が低
下する。従って、最適値が存在することになる。その値
は、用いる光触媒の種類によって異なるが、５ｎｍ〜５
μｍの範囲、より好ましくは５０〜５００ｎｍの範囲の
中にある。If the thickness of the photocatalyst film is too small, light cannot be sufficiently absorbed. On the other hand, if it is too thick, the photocarriers generated in the film cannot diffuse to the surface, so that the catalytic activity decreases. Therefore, there is an optimal value. The value varies depending on the type of photocatalyst to be used.
It is in the range of μm, more preferably in the range of 50-500 nm.
【００１９】この光触媒担持線状物品の複数本の一端は
光源からの光を最大限に導入するために密に束ね、反応
部分は反応効率を上げるために粗に束ねて、汚染空気ま
たは汚染水が入る入り口と出ていく出口を有するジャケ
ットの中に収納することにより、有害有機物質の除去装
置にすることができる。One end of a plurality of the photocatalyst-carrying linear articles is tightly bundled in order to introduce light from a light source to the maximum, and the reaction part is loosely bundled in order to increase the reaction efficiency. Of harmful organic substances by being housed in a jacket that has an entrance into and an exit from
Can be placed .
【００２０】[0020]
【実施例】以下、実施例に基づいて本発明を詳細に説明
するが、本発明はかかる実施例にのみに限定されるもの
ではない。光触媒担持体として、表面が平滑な石英製ロ
ッド（直径１０ｍｍ，長さ＝１００ｍｍ、可視光透過率
（４００〜８００ｎｍ）は約１００％、紫外線透過率
（３６０ｎｍ）は約１００％）を３本用意し、その内の
２本の側面の表面を研磨砂（番手＃１０００）を用い、
回転する鉄製テーブル上に研磨砂と水の混合層を作り、
ロッド表面を手で押し付けて研磨し、粗面化した。Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples. Three quartz catalyst rods (diameter 10 mm, length = 100 mm, visible light transmittance (400-800 nm) about 100%, ultraviolet transmittance (360 nm) about 100%) are prepared as photocatalyst carriers. Then, the surface of two of the side surfaces is polished using sand (count # 1000),
Create a mixed layer of sand and water on a rotating iron table,
The rod surface was pressed and polished by hand and roughened.
【００２１】チタン（ＩＶ）プロポキシド２８．３９ｇ
を１８．４３ｇの無水エタノールに添加し、室温で約３
分間撹拌した後に、氷冷した（溶液Ａ）。エタノール１
８．４３ｇ、水１．８ｇ、および塩酸０．２９ｇの混合
水溶液を調製した（溶液Ｂ）。溶液Ａを撹拌しながら、
溶液Ｂをビュレットを用いてゆっくり滴下することによ
り、均一混合溶液とした（溶液Ｃ）。28.39 g of titanium (IV) propoxide
Was added to 18.43 g of absolute ethanol, and at room temperature, about 3
After stirring for minutes, the mixture was ice-cooled (solution A). Ethanol 1
A mixed aqueous solution of 8.43 g, 1.8 g of water, and 0.29 g of hydrochloric acid was prepared (solution B). While stirring solution A,
The solution B was slowly dropped using a burette to obtain a homogeneous mixed solution (solution C).
【００２２】粗面化した前記石英製ロッドの内の１本を
溶液Ｃ中に浸漬した後に、１．８ｃｍ／分の一定速度で
垂直に引き上げた。空気中で十分に乾燥させた後に、５
００℃で１０分間焼成した。これにより石英製ロッドの
表面には厚みが約５０ｎｍのＴｉＯ2 が被覆された。こ
の被覆石英製ロッド（サンプルロッドＢ）の断面の模式
図を図１に示した。One of the roughened quartz rods was immersed in the solution C, and then vertically pulled up at a constant speed of 1.8 cm / min. After thoroughly drying in air, 5
Baking was performed at 00 ° C. for 10 minutes. As a result, the surface of the quartz rod was coated with TiO 2 having a thickness of about 50 nm. FIG. 1 shows a schematic view of a cross section of the coated quartz rod (sample rod B).
【００２３】このＴｉＯ2 膜のＸ線回折パターンを測定
したところ、ＴｉＯ2 は結晶化しており、結晶形はアナ
ターゼであることがわかる。比較のために、粗面化しな
い表面平滑の石英製ロッドを上記と同じ条件で処理し
て、その表面に厚みが約５０ｎｍのＴｉＯ2 を被覆させ
た。この光触媒担持石英製ロッドをサンプルロッドＡと
する。 When the X-ray diffraction pattern of this TiO2 film was measured, it was found that TiO2 was crystallized and the crystal form was anatase. For comparison, a quartz rod having a smooth surface without roughening was treated under the same conditions as above, and its surface was coated with TiO2 having a thickness of about 50 nm. This photocatalyst-supporting quartz rod is referred to as a sample rod A.
I do.
【００２４】次に、これらの光触媒担持石英製ロッド
（サンプルロッドＢおよびサンプルロッドＡ）の光触媒
活性の評価を行った。この評価方法として、蟻酸の分解
反応を採用した。光触媒活性評価実験の模式図、図２に
示すように、蓋２０を有する反応容器２１（内容積＝３
６２ｃｃ）の中にモル濃度１Ｍの蟻酸溶液１３を２５６
ｃｃを入れ、容器の蓋２０に設けた孔に光触媒担持石英
ロッド１を通してロッドの先端が液面から３．２ｃｍの
深さまで浸漬するようにした後、ゴム製ストッパー１７
を用いて容器２１を密閉してから、導入管１５、排気口
１６によりＮ2 ガスを溶液１３の中に５００ｃｃ／分で
１５分間バブリングして溶液中の溶存Ｏ2をパージし、
容器２１中の上部空間を窒素ガス１４で充填した。系を
閉じて光照射を開始し、発生したＣＯ2 をガスクロマト
グラフィーを用いて定量した。この光照射の光源２３に
は２５０Ｗ高圧水銀灯（松尾産業，ＭＳスポットキュア
ー）を用い、光ファイバー製ライトガイド１１によりカ
ップラー１２で接続した光導入用石英製ロッド２２から
ロッド１の内部に光を導入した。サンプルとしてはＴｉ
Ｏ2 を担持した粗面表面石英ロッド（サンプルロッド
Ｂ）の他に、比較のために、ＴｉＯ2 を担持した平滑表
面石英ロッド（サンプルロッドＡ）およびＴｉＯ2 を担
持していない粗面表面石英ロッド（サンプルロッドＣ）
をテストした。各サンプルロッド毎に光照射をそれぞれ
約７０時間継続して、溶液中に発生するＣＯ2 ガスの発
生量をガスクロマトグラフィーを用いて測定した。図３
は上記各種サンプルロッドを用いた場合の累積ＣＯ2 発
生量（単位：１０のマイナス５乗モル）の経時変化であ
る。図中、ａ、ｂ、およびｃはそれぞれサンプルロッド
Ａ、Ｂ、およびＣについてのデータである。これより、
いずれのサンプルにおいてもＣＯ2 が光照射時間にほぼ
比例して増加していることがわかる。この傾きから、直
線回帰法により反応速度を求めると、０．１３×１０-5
ｍｏｌ／ｈ（サンプルロッドＢ）、０．０４９×１０-5
ｍｏｌ／ｈ（サンプルロッドＡ）、および０．０１６×
１０-5ｍｏｌ／ｈ（サンプルロッドＣ）である。これよ
り、石英製ロッド表面を予め粗面化することにより、光
触媒反応効率が約３．５倍に増大していることがわか
る。Next, the photocatalytic activity of these photocatalyst-supporting quartz rods (sample rod B and sample rod A) was evaluated. As the evaluation method, a decomposition reaction of formic acid was employed. As shown in the schematic diagram of the photocatalytic activity evaluation experiment and FIG. 2, a reaction vessel 21 having a lid 20 (internal volume = 3)
The formic acid solution 13 having a molar concentration of 1 M was added to
After the photocatalyst carrying quartz rod 1 is passed through the hole provided in the lid 20 of the container and the tip of the rod is immersed to a depth of 3.2 cm from the liquid surface, the rubber stopper 17 is placed.
, The N 2 gas is bubbled into the solution 13 through the introduction pipe 15 and the exhaust port 16 at 500 cc / min for 15 minutes to purge dissolved O 2 from the solution.
The upper space in the container 21 was filled with nitrogen gas 14. The system was closed, light irradiation was started, and the generated CO 2 was quantified using gas chromatography. A 250 W high-pressure mercury lamp (Matsuo Sangyo, MS Spot Cure) was used as a light source 23 for this light irradiation, and light was introduced into the rod 1 from the light-introducing quartz rod 22 connected by the coupler 12 by the optical fiber light guide 11. . The sample is Ti
The O 2 in addition to carrying the roughened surface of quartz rods (sample rod B), for comparison, smooth surface quartz rod carrying a TiO 2 (sample rod A) and the TiO 2 not carrying rough surface surface quartz Rod (sample rod C)
Tested. Light irradiation was continued for about 70 hours for each sample rod, and the amount of CO 2 gas generated in the solution was measured using gas chromatography. FIG.
Is the change with time of the cumulative amount of CO 2 generated (unit: 10 minus the fifth power mol) when the above various sample rods are used. In the figure, a, b, and c are data for sample rods A, B, and C, respectively. Than this,
It can be seen that in all the samples, CO 2 increased almost in proportion to the light irradiation time. From this slope, the reaction rate was found to be 0.13 × 10 −5 by the linear regression method.
mol / h (sample rod B), 0.049 × 10 −5
mol / h (sample rod A), and 0.016 ×
10 −5 mol / h (sample rod C). This shows that the photocatalytic reaction efficiency is increased about 3.5 times by roughening the surface of the quartz rod in advance.
【００２５】[0025]
【発明の効果】以上説明したように、本発明の光触媒担
持線状物品およびそれにより構成された有害有機物質の
除去方法と装置は、著しく高い光触媒反応効率を有する
ものである。従って、水および空気中の有害有機物を効
率よく分解除去することが可能になる。As explained above, the photocatalyst-carrying linear article of the present invention and the harmful organic substance
The removal method and apparatus have significantly higher photocatalytic efficiency. Therefore, harmful organic substances in water and air can be efficiently decomposed and removed.
【図１】本発明の光触媒担持線状物品およびその作用を
模式的に示した説明図である。FIG. 1 is an explanatory view schematically showing a photocatalyst-carrying linear article of the present invention and its operation.
【図２】光触媒活性評価実験の方法を模式的に示した説
明図である。FIG. 2 is an explanatory view schematically showing a method of a photocatalytic activity evaluation experiment.
【図３】各種サンプルの光触媒活性評価結果を表わす説
明図である。FIG. 3 is an explanatory diagram showing evaluation results of photocatalytic activities of various samples.
１：表面線状物品、２：表面線状物品表面の凹凸、３：
光触媒膜、４：紫外および／または可視光線、５：伝導
帯、６：励起電子、７：価電子帯、８：正孔、９：有害
有機物、１０：無害分解生成物、１１：光ファイバー製
ライトガイド、１２：カップラー、１３：蟻酸水溶液
（１Ｍ）、１４：窒素ガス、１５：Ｎ2 導入管、１６：
Ｎ2 排気口、１７：ゴム製ストッパー、２０：蓋、２
１：容器、２３：光源（高圧水銀灯）1: surface linear article, 2: surface linear article surface irregularities, 3:
Photocatalytic film, 4: ultraviolet and / or visible light, 5: conduction band, 6: excitation electron, 7: valence band, 8: hole, 9: harmful organic substance, 10: harmless decomposition product, 11: optical fiber light guide, 12: coupler 13: aqueous formic acid (1M), 14: nitrogen gas, 15: N 2 inlet, 16:
N 2 exhaust port, 17: rubber stopper, 20: lid, 2
1: container, 23: light source (high pressure mercury lamp)
───────────────────────────────────────────────────── フロントページの続き (72)発明者 藤井敏昭 大和市つきみ野８−８−３ (56)参考文献 特開 平６−134476（ＪＰ，Ａ) 特開 平５−337337（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) B01J 19/00 - 19/32 B01J 21/00 - 38/74 ──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Toshiaki Fujii 8-8-3 Tsukimino, Yamato (56) References JP-A-6-134476 (JP, A) JP-A-5-337337 (JP, A) ( 58) Field surveyed (Int.Cl. 7 , DB name) B01J 19/00-19/32 B01J 21/00-38/74
Claims (7)
る方法において、該液体又は気体中の有害有機物質を、
表面が粗面である光透過性線状物品の表面に光触媒を被
覆させた光触媒担持線状物品と、前記光触媒担持線状物
品の端部からその内部に光を導入させることにより得ら
れる光照射下に接触させることを特徴とする有害有機物
質の除去方法。1. A method for removing harmful organic substances in a liquid or gas, comprising the steps of:
A photocatalyst-carrying wire-like article obtained by coating the photocatalyst on the surface of the light transmissive linear article surface is rough, the photocatalyst carrying linear material
By introducing light from the edge of the product into the interior.
A method for removing harmful organic substances, which is carried out under light irradiation.
イバー状である請求項１記載の有害有機物質の除去方
法。 2. The method for removing harmful organic substances according to claim 1, wherein the light-transmitting linear article has a columnar or fiber shape.
Law.
〜０．１ｍｍの深さの凹凸を有する粗面である請求項１
または２記載の有害有機物質の除去方法。3. The light-transmissive linear article has a surface of 200 nm.
Claim 1 is a rough surface having a depth of unevenness of ~0.1mm
Or the method for removing harmful organic substances according to 2 .
る装置において、該有害有機物質を含む液体又は気体の
導入口及び排出口を有し、内部に、表面が粗面である光
透過性線状物品の表面に光触媒を被覆させた１本以上の
光触媒担持線状物品と、該光触媒担持線状物品に光を照
射する光源とを有し、前記光源は、光触媒担持線状物品
の端部からその内部に光が導入されるように配置されて
いることを特徴とする有害有機物質の除去装置。4. An apparatus for removing a harmful organic substance in a liquid or gas, comprising an inlet and an outlet for a liquid or gas containing the harmful organic substance, and a light-transmitting material having a rough surface inside. possess one and more photocatalysts carrying wire-like article on the surface of the linear article was coated photocatalyst, a light source for irradiating light to the photocatalyst carrying linear article, said light source, the photocatalyst carrying linear article
A device for removing harmful organic substances, which is arranged so that light is introduced into the inside from the end .
イバー状である請求項４記載の有害有機物質の除去装5. The apparatus for removing harmful organic substances according to claim 4, wherein the apparatus is in the form of var.
置。Place.
〜０．１ｍｍの深さの凹凸を有する粗面である請求項４A rough surface having irregularities with a depth of 0.1 mm.
または５記載の有害有機物質の除去装置。Or a device for removing harmful organic substances according to 5.
が光導入側の端部で密に束ねられていることを特徴とす
る請求項４〜６のいずれか１項に記載の有害有機物質の
除去装置。7. The harmful organic substance according to claim 4, wherein a plurality of the photocatalyst-carrying linear articles are tightly bundled at an end on a light introduction side. Material removal device.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP04820194A JP3202863B2 (en) | 1994-03-18 | 1994-03-18 | Photocatalyst-supported linear articles |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP04820194A JP3202863B2 (en) | 1994-03-18 | 1994-03-18 | Photocatalyst-supported linear articles |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07256089A JPH07256089A (en) | 1995-10-09 |
| JP3202863B2 true JP3202863B2 (en) | 2001-08-27 |
Family
ID=12796776
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP04820194A Expired - Fee Related JP3202863B2 (en) | 1994-03-18 | 1994-03-18 | Photocatalyst-supported linear articles |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3202863B2 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08309202A (en) * | 1995-05-22 | 1996-11-26 | Bridgestone Corp | Photocatalytic body |
| JP2005349373A (en) * | 2004-06-08 | 2005-12-22 | Shinshu Univ | Light-leaking photocatalyst fiber |
| JP2007021278A (en) * | 2005-07-12 | 2007-02-01 | Furukawa Electric Co Ltd:The | Photocatalyst cleaning apparatus and photocatalyst cleaning method |
| JP6916622B2 (en) * | 2017-01-27 | 2021-08-11 | 信越石英株式会社 | Manufacturing method of porous quartz glass base material |
-
1994
- 1994-03-18 JP JP04820194A patent/JP3202863B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH07256089A (en) | 1995-10-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Blount et al. | Transparent thin-film TiO2 photocatalysts with high activity | |
| Lin et al. | Development of an optical fiber monolith reactor for photocatalytic wastewater treatment | |
| Bestetti et al. | Photocatalytic degradation activity of titanium dioxide sol–gel coatings on stainless steel wire meshes | |
| Chen et al. | Effect of mass transfer and catalyst layer thickness on photocatalytic reaction | |
| Monge et al. | Ozone formation from illuminated titanium dioxide surfaces | |
| US20050224335A1 (en) | Apparatus and method for photocatalytic purification and disinfection of fluids | |
| WO1997031703A1 (en) | Glass material for carrying a photocatalyst, filter device using the same and light irradiating method | |
| US20080308405A1 (en) | Optical Fiber Photocatalytic Reactor And Process For The Decomposition Of Nitrogen Oxide Using Said Reactor | |
| US7858552B2 (en) | Composite catalytic material and process for manufacture of such material | |
| Benmami et al. | Supported nanometric titanium oxide sols as a new efficient photocatalyst | |
| US20020081246A1 (en) | Photocatalytic filter | |
| JP3731217B2 (en) | Photoreactor | |
| JPS6397234A (en) | Fixation photocatalyst | |
| JP3202863B2 (en) | Photocatalyst-supported linear articles | |
| Wan Ismail et al. | New TiO 2/DSAT immobilization system for photodegradation of anionic and cationic dyes | |
| CN1150980C (en) | Process for preparing photocatalytic TiO2 film used to clean water and air | |
| JPH09225262A (en) | Photocatalytic filter, device therefor and treatment of liquid using the same | |
| Foran et al. | Photoinduced superhydrophilicity: a kinetic study of time dependent photoinduced contact angle changes on TiO2 surfaces | |
| JP2007229667A (en) | Method for coating polyester fiber with photocatalyst | |
| WO1999064357A1 (en) | Apparatus for photocatalytic reaction with and method for fixing photocatalyst | |
| Nasr-Esfahani et al. | Alumina/TiO 2/hydroxyapatite interface nanostructure composite filters as efficient photocatalysts for the purification of air | |
| SG188983A1 (en) | Glass with photocatalytic function | |
| JPH11183728A (en) | Gas treatment apparatus and gas treatment filter | |
| JP2008142636A (en) | Method of applying photocatalyst on polyolefin based resin molding | |
| JP4757593B2 (en) | photocatalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| LAPS | Cancellation because of no payment of annual fees |