JP5786116B2 - Photocatalytic filter and water purification device - Google Patents
Photocatalytic filter and water purification device Download PDFInfo
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- JP5786116B2 JP5786116B2 JP2010237005A JP2010237005A JP5786116B2 JP 5786116 B2 JP5786116 B2 JP 5786116B2 JP 2010237005 A JP2010237005 A JP 2010237005A JP 2010237005 A JP2010237005 A JP 2010237005A JP 5786116 B2 JP5786116 B2 JP 5786116B2
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims description 26
- 238000000746 purification Methods 0.000 title claims description 16
- 230000001699 photocatalysis Effects 0.000 title claims description 15
- 239000011941 photocatalyst Substances 0.000 claims description 62
- 239000000463 material Substances 0.000 claims description 56
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 22
- 239000011230 binding agent Substances 0.000 claims description 14
- 239000000758 substrate Substances 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 4
- 239000010453 quartz Substances 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 32
- 230000000694 effects Effects 0.000 description 17
- 238000010521 absorption reaction Methods 0.000 description 14
- 239000003463 adsorbent Substances 0.000 description 11
- 239000005416 organic matter Substances 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- 238000000354 decomposition reaction Methods 0.000 description 9
- 235000012239 silicon dioxide Nutrition 0.000 description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 239000000377 silicon dioxide Substances 0.000 description 7
- 238000005259 measurement Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 230000001965 increasing effect Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical group [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 4
- 239000004744 fabric Substances 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 230000001954 sterilising effect Effects 0.000 description 3
- 238000004659 sterilization and disinfection Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-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
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004811 liquid chromatography Methods 0.000 description 2
- -1 peroxide anions Chemical class 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- CCYWDIWYFIDBTE-UHFFFAOYSA-N [O-2].[O-2].[F].[Ti+4] Chemical compound [O-2].[O-2].[F].[Ti+4] CCYWDIWYFIDBTE-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000002800 charge carrier Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000001976 improved effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
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Description
本発明は、水質浄化装置に使用される、光触媒を利用したフィルタおよびそのフィルタを用いた水質浄化装置に関するものである。 The present invention relates to a filter using a photocatalyst and a water purification device using the filter used in a water purification device.
光触媒の有機物分解作用は約３０年前に見出された。酸化チタンなどある種の半導体は光照射で電子を励起、正孔を生成し、その電荷担体が半導体表面でスパーオキサイドアニオンやヒドロキシラジカルを生成する。これらが有機分子を攻撃し、有機物を分解する。 The organic matter decomposition action of the photocatalyst was found about 30 years ago. Certain semiconductors such as titanium oxide excite electrons and generate holes when irradiated with light, and the charge carriers generate peroxide anions and hydroxy radicals on the semiconductor surface. These attack organic molecules and decompose organic matter.
この種の作用をもつ半導体材料を光触媒と呼んでいる。特に酸化チタンは、光触媒の代表的な材料の一つである。 A semiconductor material having this kind of action is called a photocatalyst. In particular, titanium oxide is one of typical materials for photocatalysts.
今までにこの光触媒による有機分解作用を利用した製品やデバイスの提案が数多くされており、多様な、フィルタ、デバイスが開発されている。 There have been many proposals for products and devices utilizing the organic decomposition action of this photocatalyst, and various filters and devices have been developed.
こうしたフィルタ、デバイスでは、光触媒による有機物分解活性向上のために、有機物を吸着剤に吸着させて、光触媒近辺の有機物濃度を相対的に高める濃縮効果によって、有機物成分をより効果的に分解する方法があり、その中でもエチレンなど特定の物質に対する吸着剤、例えばハイシリカゼオライトと組み合わせることで、対象とする有機物の分解速度を向上させているものもある（たとえば特許文献１、２参照）。 In such filters and devices, in order to improve the organic substance decomposition activity by the photocatalyst, there is a method of more effectively decomposing the organic component by the concentration effect of adsorbing the organic substance to the adsorbent and relatively increasing the organic substance concentration near the photocatalyst. Among them, there are some which improve the decomposition rate of the target organic matter by combining with an adsorbent for a specific substance such as ethylene, for example, high silica zeolite (for example, see Patent Documents 1 and 2).
さらには、吸着剤による濃縮効果に加えて、フィルタの光入射面での反射による光損失を低減するために、光を吸収する層を表面に設けることで、光触媒への受光効率を高め、脱臭効果を高めたものもある（たとえば特許文献３参照）。 Furthermore, in addition to the concentration effect by the adsorbent, in order to reduce the light loss due to reflection at the light incident surface of the filter, a light absorbing layer is provided on the surface to increase the light receiving efficiency to the photocatalyst and to deodorize it. Some have improved effects (for example, see Patent Document 3).
しかしながら、前記従来例のような吸着剤による有機物濃縮は、吸着剤の細孔の大きさ以上の物質に対する効果は期待できないという課題を有していた。 However, the organic substance concentration by the adsorbent as in the conventional example has a problem that an effect on a substance larger than the pore size of the adsorbent cannot be expected.
一般に用いられる活性炭やゼオライトなどの吸着剤の細孔は、大きくとも数１００ｎｍ程度であり、分子レベルの大きさの物質を吸着することはできるものの、細菌など、数マイクロメートル以上の物体では、吸着剤による濃縮効果は期待できない。 The pores of adsorbents such as activated carbon and zeolite, which are generally used, are about several hundred nm at most, and can adsorb substances of molecular size, but they are adsorbed on objects of several micrometers or more such as bacteria. The concentration effect by the agent cannot be expected.
また、吸着剤による濃縮効果を高めるためには、光触媒に比して、吸着剤の量を多くせねばならず、そのためフィルタ表面での光の反射や吸収による光損失が無視できなくなり、触媒組成の異なる２層にするなどの工夫が必要となる課題を有していた。 In addition, in order to enhance the concentration effect by the adsorbent, the amount of adsorbent must be increased compared to the photocatalyst, so light loss due to reflection and absorption of light on the filter surface cannot be ignored, and the catalyst composition There was a problem that required a device such as making two layers different from each other.
そこで本願発明では、有機物分解だけではなく、殺菌など微生物のような、分子レベルのサイズに比して大きな物体にも、光触媒の効果を高めることを目的として、吸着剤による濃縮効果を利用することなく、フルタ表面で混合物が光を吸収してしまうという光損失を低減し光触媒の効果を最大限に発揮できるフィルタ、および水質浄化装置を提共することを目的とする。 Therefore, in the present invention, not only the decomposition of organic matter but also the concentration effect by the adsorbent is used for the purpose of enhancing the effect of the photocatalyst on the large object compared to the molecular size such as microorganisms such as sterilization. It is another object of the present invention to provide a filter and a water purification device that can reduce the light loss that the mixture absorbs light on the surface of the filter and that can maximize the effect of the photocatalyst.
前記従来の課題を解決するため、本発明の光触媒フィルタは、少少なくとも光触媒と、その光触媒が吸収する波長のうち最も長い波長として４００ｎｍの波長の光を、８９．５％以上反射する反射材料としての石英粒子と、これらを基材に結着するためのバインダーとからなる触媒材料を用い、基材に担持させた光触媒フィルタであって、前記基材に担持した光触媒と、前記反射材料と、バインダーとの重量に占める、前記反射材料の重量％が８％である光触媒フィルタである。
In order to solve the conventional problem, the photocatalyst filter of the present invention includes at least a photocatalyst and a reflective material that reflects 89.5 % or more of light having a wavelength of 400 nm as the longest wavelength among the wavelengths absorbed by the photocatalyst. and quartz particles, these the catalyst material used comprising a binder for binding the substrate, a photocatalyst filter is supported on a substrate, the photocatalyst supported on said substrate, said reflective material If account the weight of the binder, weight percent of the reflective material is a photocatalytic filter is 8%.
本構成により、照射される光の利用効率を促進することができ、吸着剤を利用することなく、混合した反射材料としての石英粒子によって、光触媒による有機物分解や殺菌等の効果を最大限に高めることができる。 With this configuration, it is possible to promote the use efficiency of irradiated light, and to maximize the effects of organic matter decomposition and sterilization by the photocatalyst by using quartz particles as a mixed reflective material without using an adsorbent. be able to.
本発明の光触媒フィルタによれば、照射される光の利用効率を促進することで、吸着剤を利用することなく、光触媒による有機物分解や殺菌等の効果を高めることができる。 According to the photocatalyst filter of the present invention, by promoting the utilization efficiency of the irradiated light, it is possible to enhance the effects of organic matter decomposition and sterilization by the photocatalyst without using an adsorbent.
以下、本発明の実施の形態について図面を参照しながら説明する。 Hereinafter, embodiments of the present invention will be described with reference to the drawings.
（光触媒フィルタの作製方法）
測定に用いたフィルタの作製方法は、以下に示すとおりである。
(Method for producing photocatalytic filter)
The method for producing the filter used for the measurement is as follows.
光触媒と反射材料とを反射材料／光触媒＝２．６〜１７．７％にて混合したもの５ｇに、１Ｍ塩酸（和光純薬製を純水にて希釈）２５ｇ、エタノール特級（和光純薬製）１０ｇを加え、氷冷にて１０分ほど撹拌した。 5 g of photocatalyst and reflective material mixed at reflective material / photocatalyst = 2.6 to 17.7%, 25 g of 1M hydrochloric acid (diluted with pure water from Wako Pure Chemical Industries), ethanol special grade (manufactured by Wako Pure Chemical Industries, Ltd.) ) 10 g was added, and the mixture was stirred for about 10 minutes under ice cooling.
その後、テトラエトキシシラン（信越化学製）４．３５ｇを加えて、３０分間撹拌し、１０ｃｍ□のフィルタ基材（ユニチカ製ガラスクロス：Ｖ６３５ＨＴ）を浸漬させ、室温にて１時間、次に８０℃にて１時間、乾燥させた。 Thereafter, 4.35 g of tetraethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) was added, stirred for 30 minutes, and a 10 cm □ filter substrate (Unitika glass cloth: V635HT) was immersed, and then at room temperature for 1 hour and then at 80 ° C For 1 hour.
このようにして作製したフィルタを、純水にて洗浄した後、１５Ｗ型ブラックライトブルー蛍光灯（パナソニック製：ＦＬ１５ＢＬ−Ｂ）を用い、３６１ｎｍの紫外光強度が２．０ｍＷ／ｃｍ2以上の照射下にて２４時間以上静置した。 The filter thus prepared was washed with pure water, and then irradiated with an ultraviolet light intensity at 361 nm of 2.0 mW / cm 2 or more using a 15 W type black light blue fluorescent lamp (manufactured by Panasonic: FL15BL-B). It left still for 24 hours or more below.
紫外線強度は、紫外線積算光量計（ウシオ電機製：ＵＩＴ−２５０）に受光器（ウシオ電機製：ＵＶＤ−Ｓ３６５）を取り付けて測定した。 The ultraviolet intensity was measured by attaching a light receiver (Ushio Electric: UVD-S365) to an ultraviolet integrated light meter (Ushio Electric: UIT-250).
今回用いた光触媒は、堺化学工業製のＳＳＰ−２５の表面をフッ素処理することで、表面の水酸基の一部をフッ素に置き換えた、フッ化酸化チタンである。 The photocatalyst used this time is fluorinated titanium oxide in which the surface of SSP-25 manufactured by Sakai Chemical Industry is treated with fluorine to replace part of the hydroxyl groups on the surface with fluorine.
表１は、今回用いた反射材料の品番並びに種別、粒径、主材料であるに酸化ケイ素の純度を示した表である。 Table 1 is a table showing the product number, type, particle size, and purity of silicon oxide as the main material of the reflective material used this time.
いずれの反射材も組成比で９９．９％以上が二酸化ケイ素からなる材料を用いた。 As each reflector, a material composed of silicon dioxide with a composition ratio of 99.9% or more was used.
（反射率測定）
反射率の測定は、紫外可視分光光度計（日本分光製：Ｖ−５５０）に積分球を装着し、粉末試料セルホルダを用いて測定した。
(Reflectance measurement)
The reflectance was measured using an ultraviolet-visible spectrophotometer (manufactured by JASCO Corporation: V-550) equipped with an integrating sphere and using a powder sample cell holder.
いずれの反射材料も、用いた光触媒の吸収端である４００ｎｍ以下の光を反射している。 Any of the reflective materials reflects light of 400 nm or less, which is the absorption edge of the used photocatalyst.
表２は、各波長における反射率を示した表である。 Table 2 is a table showing the reflectance at each wavelength.
（光触媒活性の測定）
光触媒の活性評価は、ＪＩＳ Ｒ １７０４、ファインセラミックス−活性酸素生成能力測定による光触媒材料の水質浄化性能試験方法に従った。
(Measurement of photocatalytic activity)
The evaluation of the activity of the photocatalyst was in accordance with JIS R 1704, a test method for water purification performance of the photocatalyst material by measuring fine ceramics-active oxygen generation ability.
その方法の概略を以下に記載する。 The outline of the method is described below.
ＪＩＳ Ｒ １７０４記載の試験装置に、上記方法にて作製した光触媒フィルタをセットして、２０Ｗ型ブラックライトブルー蛍光灯（パナソニック製：ＦＬ２０Ｓ・ＢＬ−Ｂ）２本を用い、フィルタ面での、３６１ｎｍの紫外光強度が２．０ｍＷ／ｃｍ2となるように調整した。 The photocatalytic filter produced by the above method is set in the test apparatus described in JIS R 1704, and two 20W type black light blue fluorescent lamps (manufactured by Panasonic: FL20S / BL-B) are used, and the filter surface is 361 nm. The ultraviolet light intensity was adjusted to 2.0 mW / cm 2 .
次に、ジメチルスルホキシド１０ｍｇ／Ｌの水溶液を５００ｍＬ、試験装置に入れ、初期濃度測定のために１０ｍＬ採取する。 Next, 500 mL of an aqueous solution of 10 mg / L of dimethyl sulfoxide is put into a test apparatus, and 10 mL is collected for initial concentration measurement.
その後、液流量が５００ｍＬ／ｍｉｎ となるようにポンプを作動させ、１時間光照射せずに循環し、暗所での吸着が飽和に達していることを確認してから、２時間光照射を行った。 Then, operate the pump so that the liquid flow rate becomes 500 mL / min, circulate without irradiating light for 1 hour, confirm that the adsorption in the dark has reached saturation, and then irradiate with light for 2 hours. went.
この間、３０分ごとにサンプルを採取し、採取した溶液は液体クロマトグラフィーによってジメチルスルホキシドの濃度を測定し、その減少量から半減時間を計算した。 During this time, a sample was taken every 30 minutes, and the concentration of dimethyl sulfoxide was measured by liquid chromatography for the collected solution, and the half time was calculated from the decreased amount.
半減時間が早いほど、光触媒フィルタの活性が高いことを示すため、数値が小さいほど、光触媒フィルタの性能が高いこととなる。 The faster the half time, the higher the activity of the photocatalytic filter. Therefore, the smaller the numerical value, the higher the performance of the photocatalytic filter.
（実施の形態１）
上記、光触媒フィルタの作製方法に従って作製した、光触媒フィルタの構成を、図１を用いて説明する。
(Embodiment 1)
The structure of the photocatalyst filter produced according to the photocatalyst filter production method will be described with reference to FIG.
光触媒１０１としてフッ化酸化チタンを、反射材料１０２として表１に示した二酸化ケイ素を用いた。このとき、フィルタ基材１０３に担持される材料には、少なくとも、光触媒１０１、反射材料１０２、そしてバインダー１０４に用いたテトラエトキシシラン由来の二酸化ケイ素が含まれる。そのため、反射材料の混合比率は、式１に従って求めた。
Fluorine titanium oxide was used as the
反射材料の重量（％）
＝反射材料の重量／（光触媒の重量＋反射材料の重量＋バインダーの重量）・・・式１
Reflective material weight (%)
= Weight of reflective material / (weight of photocatalyst + weight of reflective material + weight of binder) Formula 1
上記、光触媒フィルタの作製方法に従うと、分母の値は、バインダー１０４に用いたテトラエトキシシラン由来の二酸化ケイ素の質量が、１．２５５ｇと、光触媒１０１と反射材料１０２との混合物の重量が５ｇとを足した、６．２５５ｇとなる。
According to the above photocatalyst filter manufacturing method, the denominator value is 1.255 g of tetraethoxysilane-derived silicon dioxide used for the
表３は、上記式１で求めた反射材料１０２の比率を変えたときの、上記光触媒活性の測定から求めたジメチルスルホキシド（ＤＭＳＯ）の半減時間を示したものである。上段にジメチルスルホキシド（ＤＭＳＯ）の半減時間、下段に、判定結果を○または×で示した。
Table 3 shows the half time of dimethyl sulfoxide (DMSO) obtained from the measurement of the photocatalytic activity when the ratio of the
判定基準は、比較例として用いた、反射材料を混合しない場合、すなわち光触媒のみのときのジメチルスルホキシド（ＤＭＳＯ）の半減時間、１．７２時間より、小さいときを○、同じかそれより大きいときを×とした。 Judgment criteria are ○ when the reflective material used as a comparative example is not mixed, that is, when the dimethyl sulfoxide (DMSO) has a half time of 1.72 hours or less when it is only photocatalyst, and when it is the same or larger. X.
この結果が示すように、ＳＩＯ１７ＰＢ以外の材料ではすべて、反射材料１０２の混合比率が２％より大きく、１２％より小さい範囲において、比較例である、光触媒１０１のみの半減時間より、反射材料１０２を混合したときの半減時間のほうが小さいことがわかった。
As shown in this result, in all materials other than SIO17PB, the
また、反射材料１０２の混合比率が４％以上１０％以下において、確実に半減時間が小さくなり、８％のとき、半減時間が最も小さくなった。
In addition, when the mixing ratio of the
このことは、反射材料１０２によって反射された、照射光１０５の反射光１０６が光触媒１０１の照射光側からみて裏側に照射されることで、本来自らの影になって活用されなかった部分を有効に活用できるようになったからである。
This is because the reflected
表２からわかるように、ＳＩＯ１７ＰＢは、光触媒１０１の吸収端である４００ｎｍにおいて、光を４６．４％しか反射していないことから、反射材料１０２としての機能を十分に発揮していなかったと考えられる。
As can be seen from Table 2, SIO17PB reflects only 46.4% of light at 400 nm, which is the absorption edge of the
したがって、少なくとも、光触媒１０１の吸収端の波長において、４６．４％より反射率が大きくないと、反射材料１０２としての効果は示せない。
Therefore, at least at the wavelength of the absorption edge of the
また、反射材料１０２として効果の見られた４つのうち、４００ｎｍでの反射率が最も小さいＳＩＯ１８ＰＢは、反射率が７４．４％であることから、光触媒１０１の吸収端の波長において、反射率７４．４％以上の反射材料１０２を用いることが望ましい。
In addition, among the four
図２に、光触媒の吸収端の求め方を示した。光触媒の吸収端の波長とは、光触媒が吸収できる波長のうち、最も長い波長のことであり、図２の反射率曲線の接線２０１と、吸収のない長波長域のベースライン２０２との交点２０３から求めることができる。図２の場合、交点２０３の垂線２０４から約３９５ｎｍのところであると求められるが、この方法は誤差を含むため、長波長側で１０ｎｍ刻みに繰上げすることと定義し、図２に示したフッ化酸化チタンの吸収端の波長は４００ｎｍであると読み取る。
FIG. 2 shows how to obtain the absorption edge of the photocatalyst. The wavelength of the absorption edge of the photocatalyst is the longest wavelength among the wavelengths that can be absorbed by the photocatalyst, and the
本発明の実施の形態１には、反射材料として、二酸化ケイ素を９９．９％以上含む反射材料を用いたが、それ以外にも、ダイヤモンド、ジルコニア、アルミナ、アルミニウムなど、光触媒の吸収端の波長を反射する材料であればよい。特に二酸化ケイ素は、安価で、純度が高く、光の吸収が少ないことから望ましいが、不純物の混合によって吸収が増大することが多いため、９９．９％以上の組成比を持つ材料が好ましい。中でも石英は、可視光から紫外光まで、幅広い領域での光吸収がほぼないことから、最も好ましい。 In Embodiment 1 of the present invention, a reflective material containing 99.9% or more of silicon dioxide is used as the reflective material. In addition, the wavelength of the absorption edge of the photocatalyst, such as diamond, zirconia, alumina, or aluminum, is used. Any material that reflects light may be used. In particular, silicon dioxide is preferable because it is inexpensive, has high purity, and absorbs little light. However, since absorption is often increased by mixing impurities, a material having a composition ratio of 99.9% or more is preferable. Among them, quartz is most preferable because it hardly absorbs light in a wide range from visible light to ultraviolet light.
今回光触媒としては、フッ化酸化チタンを用いたが、光触媒の種類としてはこれに限らず、酸化チタン、酸化タングステン、チタン酸ストロンチウムなど、種々の材料が利用可能である。ただし、光触媒の種類、組成が異なれば、吸収端の波長も異なるため、吸収端波長の短いものでは使えていた反射材料が、吸収端波長が長いものでは使えなくなることがある。 This time, fluorinated titanium oxide was used as the photocatalyst, but the type of photocatalyst is not limited to this, and various materials such as titanium oxide, tungsten oxide, and strontium titanate can be used. However, since the wavelength of the absorption edge varies depending on the type and composition of the photocatalyst, the reflective material that can be used with a short absorption edge wavelength may become unusable with a long absorption edge wavelength.
また、本発明は、光触媒に照射される光の利用効率を高めることが、フィルタ性能向上の理由であるため、光触媒の性能が高いほど、高い効果が望める。そのため、光触媒としては、有機物分解の活性に定評がある酸化チタンが望ましく、さらにはその表面の水酸基をフッ素で置き換えた、フッ化酸化チタンのほうが、通常の酸化チタンより有機物分解活性が高いため、より好ましい。 In addition, according to the present invention, it is the reason for improving the filter performance that the utilization efficiency of light irradiated to the photocatalyst is increased. Therefore, the higher the performance of the photocatalyst, the higher the effect can be expected. Therefore, as the photocatalyst, titanium oxide with a reputation for the activity of organic matter decomposition is desirable, and further, fluorinated titanium oxide in which the hydroxyl group on the surface is replaced with fluorine has higher organic matter decomposition activity than ordinary titanium oxide, More preferred.
基材と光触媒、反射材料とを担持させるために、バインダーとしてテトラエトキシシランを用いたが、これ以外にもテトラメトキシシラン、メチルトリメトキシシランなどのシリコンアルコキシドや、コロイダルシリカ、アルミナゾル、チタニアゾルなどの無機バインダーや、エポキシ樹脂やアクリル樹脂などの有機バインダーでも問題ない。 Tetraethoxysilane was used as a binder to support the substrate, photocatalyst, and reflective material, but other than this, silicon alkoxide such as tetramethoxysilane and methyltrimethoxysilane, colloidal silica, alumina sol, titania sol, etc. There are no problems with inorganic binders and organic binders such as epoxy resins and acrylic resins.
ただし、それ自体が光触媒に作用する光を吸収するバインダーは、光触媒への光照射の妨げになることから、反射材料と同様に、吸収が少ないものが望ましい。こうした観点から、加水分解によってシロキサン結合を作ることで、バインダー機能を果たす材料は、シロキサン結合が、可視光から紫外光まで幅広い領域での光吸収が少ないことから好ましく、その中でもテトラエトキシシランは、安価で、副生成物がエタノールであることから、工業的観点で好ましい。 However, the binder that absorbs the light acting on the photocatalyst itself hinders the light irradiation to the photocatalyst, and therefore, a binder that absorbs less light like the reflective material is desirable. From such a viewpoint, the material that fulfills the binder function by making a siloxane bond by hydrolysis is preferable because the siloxane bond has less light absorption in a wide range from visible light to ultraviolet light, and among them, tetraethoxysilane is Since it is cheap and the by-product is ethanol, it is preferable from an industrial viewpoint.
基材には、ガラスクロスを用いたが、それ以外にもガラス板やパンチングメタル、網、など、特に材質・形状にはよらない。ガラスクロスは、柔軟性や流体の通過など、フィルタ基材としての特性に加え、紫外光による劣化がないことから、紫外光照射下で使用される際に、特に好ましい。 Glass cloth was used as the base material, but other than that, there are no particular differences in the material and shape such as glass plate, punching metal, and net. Glass cloth is particularly preferable when used under ultraviolet light irradiation because it does not deteriorate due to ultraviolet light in addition to the properties as a filter base material such as flexibility and fluid passage.
（実施の形態２）
本発明の光触媒フィルタを用いた、水質浄化装置を、図３を用いて説明する。
(Embodiment 2)
A water purification apparatus using the photocatalytic filter of the present invention will be described with reference to FIG.
アクリル製の筐体３０１の側面に、石英ガラス板３０２を片側４枚、両側８枚になるようにはめ込み、光触媒フィルタ３０３を筐体３０１の中央部になるように配置した。筐体３０１の外部には、光源３０６を両側に配置し、筐体３０１と光源３０６との距離を変化することで、光の照射強度を変更できるようにした。また、筐体３０１の内部に水を流すために、片側に、入口側コネクタ３０４、その反対側に出口側コネクタ３０５を、図３に示すような配置にて設けた。
The
本発明では、図３に示した構成の装置を水質浄化装置とする。 In the present invention, the apparatus having the configuration shown in FIG. 3 is a water purification apparatus.
次に、本発明の水質浄化装置を使用する際の構成を、図４を用いて説明する。 Next, the structure at the time of using the water purification apparatus of this invention is demonstrated using FIG.
浄化するべき水を貯めておく、タンク４０１に、水流ポンプ４０２をつなぎ、その流れ後方に流量計４０３をつなぐ。流量計４０３の後方に流量調節用のバルブ４０４をつけ、その後ろに水質浄化装置４０５をつなぎ、そこで浄化された水は、タンク４０１に戻される。
A
運転条件の１例を以下に記す。 An example of operating conditions is described below.
光触媒フィルタ３０３の面積を５０ｃｍ2にし、両面から光を照射することで、１００ｃｍ2とした。光源３０６には、３０Ｗ型ブラックライトブルー蛍光灯（パナソニック製：ＦＬ３０Ｓ・ＢＬ−Ｂ）２本を用い、フィルタ表面での光強度が２．０ｍＷ／ｃｍ2となるよう、光源３０６と筐体３０１との間隔を調整した。
The area of the
次に、タンク４０１にジメチルスルホキシド１０ｍｇ／Ｌの水溶液を５００ｍＬ入れ、初期濃度測定のために１０ｍＬ採取する。
Next, 500 mL of a 10 mg / L aqueous solution of dimethyl sulfoxide is placed in the
その後、液流量が５００ｍＬ／ｍｉｎとなるようにポンプを作動させ、１時間光照射せずに循環し、暗所での吸着が飽和に達していることを確認してから、２時間光照射を行った。 Then, operate the pump so that the liquid flow rate is 500 mL / min, circulate without irradiating light for 1 hour, confirm that the adsorption in the dark has reached saturation, and then irradiate with light for 2 hours. went.
この間、３０分ごとにサンプルを採取し、採取した溶液は液体クロマトグラフィーによってジメチルスルホキシドの濃度を測定し、その減少量から半減時間を計算した。 During this time, a sample was taken every 30 minutes, and the concentration of dimethyl sulfoxide was measured by liquid chromatography for the collected solution, and the half time was calculated from the decreased amount.
光触媒としてフッ化酸化チタンを、反射材料としてＳＩＯ０７ＰＢを用い、反射材料の混合比率が８％となるように調整した光触媒フィルタにおいて、ジメチルスルホキシド（ＤＭＳＯ）の半減時間は、１．４８時間であった。 In a photocatalytic filter prepared by using fluorinated titanium oxide as a photocatalyst and SIO07PB as a reflective material and adjusting the mixing ratio of the reflective material to 8%, the half time of dimethyl sulfoxide (DMSO) was 1.48 hours. .
この結果から、本発明の水質浄化装置によって、ジメチルスルホキシド（ＤＭＳＯ）が分解することが確認された。 From this result, it was confirmed that dimethyl sulfoxide (DMSO) was decomposed by the water purification apparatus of the present invention.
本発明では、有機物分解を対象とし、ジメチルスルホキシド（ＤＭＳＯ）の分解を行ったが、その他の有機物でもよく、また、水中の菌類などの殺滅にも利用できる。 In the present invention, dimethyl sulfoxide (DMSO) was decomposed for the purpose of decomposing organic matter. However, other organic matter may be used, and it can also be used for killing fungi in water.
本発明にかかる光触媒フィルタ及び水質浄化装置は、光触媒に照射される光の利用効率を促進するものであるので、飲料水、工業用水、海水等の浄化に使用される水質浄化装置として有用である。 The photocatalyst filter and the water purification device according to the present invention are useful as a water purification device used to purify drinking water, industrial water, seawater, etc., because they promote the utilization efficiency of light irradiated to the photocatalyst. .
１０１ 光触媒
１０２ 反射材料
１０３ フィルタ基材
１０４ バインダー
１０５ 照射光
１０６ 反射光
２０１ 反射率曲線の接線
２０２ ベースライン
２０３ 交点
２０４ 垂線
３０１ 筐体
３０２ 石英ガラス板
３０３ 光触媒フィルタ
３０４ 入口側コネクタ
３０５ 出口側コネクタ
３０６ 光源
４０１ タンク
４０２ 水流ポンプ
４０３ 流量計
４０４ バルブ
４０５ 水質浄化装置
DESCRIPTION OF
Claims (2)
The water purification apparatus which has the container for water treatment provided with the light source which outputs the light of the wavelength which acts on a photocatalyst using the photocatalyst filter of Claim 1 .
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