JP4264426B2 - Photocatalyst material, photocatalyst filter, photocatalyst filter unit, and photocatalyst purification treatment apparatus - Google Patents
Photocatalyst material, photocatalyst filter, photocatalyst filter unit, and photocatalyst purification treatment apparatus Download PDFInfo
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- 239000011941 photocatalyst Substances 0.000 title claims description 138
- 239000000463 material Substances 0.000 title claims description 69
- 238000000746 purification Methods 0.000 title claims description 45
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical class C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 claims description 51
- 239000003575 carbonaceous material Substances 0.000 claims description 46
- 229910003472 fullerene Inorganic materials 0.000 claims description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 38
- 239000000843 powder Substances 0.000 claims description 32
- 230000001699 photocatalysis Effects 0.000 claims description 28
- 239000012530 fluid Substances 0.000 claims description 26
- 238000012545 processing Methods 0.000 claims description 23
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 22
- 230000003647 oxidation Effects 0.000 claims description 21
- 238000007254 oxidation reaction Methods 0.000 claims description 21
- 238000010438 heat treatment Methods 0.000 claims description 20
- 238000010791 quenching Methods 0.000 claims description 10
- 230000000171 quenching effect Effects 0.000 claims description 10
- 238000011010 flushing procedure Methods 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 8
- 239000000919 ceramic Substances 0.000 claims description 5
- 230000005284 excitation Effects 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 238000001237 Raman spectrum Methods 0.000 claims description 4
- 238000002441 X-ray diffraction Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000006227 byproduct Substances 0.000 description 38
- 239000002351 wastewater Substances 0.000 description 20
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 10
- 229960000907 methylthioninium chloride Drugs 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 9
- 230000002093 peripheral effect Effects 0.000 description 9
- 230000001681 protective effect Effects 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 230000000996 additive effect Effects 0.000 description 6
- 238000004042 decolorization Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000003574 free electron Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- -1 C 70 Chemical compound 0.000 description 3
- 229910021536 Zeolite Inorganic materials 0.000 description 3
- 229910052586 apatite Inorganic materials 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 description 3
- 239000011164 primary particle Substances 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- 239000010457 zeolite Substances 0.000 description 3
- 239000003463 adsorbent Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 229910002012 Aerosil® Inorganic materials 0.000 description 1
- ATLMFJTZZPOKLC-UHFFFAOYSA-N C70 fullerene Chemical compound C12=C(C3=C4C5=C67)C8=C9C%10=C%11C%12=C%13C(C%14=C%15C%16=%17)=C%18C%19=C%20C%21=C%22C%23=C%24C%21=C%21C(C=%25%26)=C%20C%18=C%12C%26=C%10C8=C4C=%25C%21=C5C%24=C6C(C4=C56)=C%23C5=C5C%22=C%19C%14=C5C=%17C6=C5C6=C4C7=C3C1=C6C1=C5C%16=C3C%15=C%13C%11=C4C9=C2C1=C34 ATLMFJTZZPOKLC-UHFFFAOYSA-N 0.000 description 1
- 241000282320 Panthera leo Species 0.000 description 1
- 230000002292 Radical scavenging effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 230000001443 photoexcitation Effects 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 238000002076 thermal analysis method Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Materials Engineering (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Composite Materials (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
- Carbon And Carbon Compounds (AREA)
- Catalysts (AREA)
- Disinfection, Sterilisation Or Deodorisation Of Air (AREA)
- Physical Water Treatments (AREA)
Description
本発明は、光触媒粉末を主体とする光触媒材、光触媒材を使用する光触媒フィルタ、光触媒フィルタを使用する光触媒フィルタユニット及び光触媒フィルタユニットを使用する光触媒浄化処理装置に関するものである。 The present invention is a photocatalyst material composed mainly of the photocatalyst powder, those photocatalytic filter that uses a photocatalyst material, an optical catalyst purification treatment apparatus using a photocatalyst filter unit及beauty photocatalyst filter unit using a photocatalyst filter.
ＴｉＯ２（二酸化チタン）等の光半導性を有する粒子状物質（光触媒）にそのバンドキャップエネルギ以上の光を照射すると、価電子帯の電子が光励起されて伝導帯に移り、伝導帯には自由電子が生成すると共に、価電子帯には正の電荷を帯びた粒子（正孔）が生成する。これらの正孔と自由電子は光半導体粒子内部を運動し、時間の経過と共に再結合して消滅する。しかし、その粒子表面に空気または水、或いはそれらの正孔や自由電子よりもエネルギの低い空順位を有する化合物やイオンが存在すると、その粒子表面を通してそれらの正孔と自由電子が化合物やイオンに移動し、その結果、正孔は粒子表面に接触する化合物やイオンを直接酸化し、或いは活性酸素の１つである水酸基ラジカルを生成する。また、電子による還元反応は主に酸素の還元であり、ＨＯ２ラジカルなどの電子が付加された酸化性のある酸素種が生成される。こうして、光半導体微粒子は光が照射されることによって酸化性の活性表面を形成し、有機化合物の分解等に触媒として作用する（「光が関わる触媒化学−光合成から環境化学まで」季刊化学総説（Ｎｏ．２３）学会出版センター（１９９４年７月１５日））。 When a particulate matter (photocatalyst) having photoconductivity such as TiO 2 (titanium dioxide) is irradiated with light having a band cap energy or higher, electrons in the valence band are photoexcited and transferred to the conduction band. Free electrons are generated, and positively charged particles (holes) are generated in the valence band. These holes and free electrons move inside the optical semiconductor particles and recombine with time to disappear. However, if air or water or a compound or ion having a vacancy lower in energy than those holes or free electrons exists on the particle surface, those holes and free electrons are converted into compounds or ions through the particle surface. As a result, the holes directly oxidize compounds and ions that come into contact with the particle surface, or generate hydroxyl radicals that are one of active oxygen. Moreover, the reduction reaction by electrons is mainly reduction of oxygen, and oxidative oxygen species to which electrons such as HO 2 radicals are added are generated. Thus, the photo-semiconductor fine particles form an oxidative active surface when irradiated with light, and act as a catalyst for decomposition of organic compounds (“catalyst chemistry involving light-from photosynthesis to environmental chemistry” quarterly chemistry review ( No. 23) Academic Publishing Center (July 15, 1994)).
従来からも、このような光触媒能に着目して、ＴｉＯ２等の光触媒又はこれをアパタイト，シリカゲル，ゼオライト，活性炭等の吸着材に担持させた光触媒材を使用して流体（空気，水等）を浄化処理（有機物の分解等）することが行われている（例えば、特許文献１〜７参照）。 Conventionally, focusing on such photocatalytic activity, fluid (air, water, etc.) using a photocatalyst such as TiO 2 or a photocatalyst material in which this is supported on an adsorbent such as apatite, silica gel, zeolite, or activated carbon. Is purified (such as decomposition of organic substances) (see, for example, Patent Documents 1 to 7).
しかし、このような従来の光触媒材は浄化処理能力が不十分なものであったため、光触媒材を使用する浄化処理手段として実用的に満足できるものは提案されていないのが実情であった。特に、水処理（例えば、メカニカルシールから排出されるクエンチング水やフラッシング水の浄化処理）を行う場合には、到底使用できるものではなかった。 However, since such a conventional photocatalyst material has an insufficient purification treatment capability, no practically satisfactory purification treatment means using the photocatalyst material has been proposed. In particular, when water treatment (for example, purification treatment of quenching water or flushing water discharged from a mechanical seal) is performed, it cannot be used at all.
本発明は、かかる点に鑑みてなされたもので、水等に対しても良好な浄化処理能力を発揮しうる光触媒材を提供すると共に、光触媒材を使用した実用的な光触媒フィルタ、光触媒フィルタユニット及び光触媒浄化処理装置を提供することを目的とするものである。 The present invention has been made in view of the above, as well as providing a photocatalyst material may also exhibit excellent cleaning capacity for water or the like, a practical photocatalytic filter using a photocatalyst material, photocatalytic filter An object of the present invention is to provide a unit and a photocatalyst purification apparatus.
本発明は、ＴｉＯ２光触媒粉末に、この光触媒粉末１００部に対して１〜１０部の割合で、フラーレン製造過程で副生する炭素材料であって、ＣｕＫα線を使用したＸ線回折測定結果における回折角３〜３０°の範囲内で最も強いピークが回折角１０〜１８°の範囲に存在し且つ回折角２３〜２７°にピークが存在せず、励起波長５１４５Åでのラマンスペクトル結果において、バンドＧ１５９０±２０ｃｍ −１ とバンドＤ１３４０±４０ｃｍ
−１ にピークを有し、夫々のバンドのピーク強度をＩ（Ｇ）及びＩ（Ｄ）とした際におけるピーク強度比Ｉ（Ｄ）／Ｉ（Ｇ）が０．４〜１．０である炭素材料（以下「副生炭素材料」という）を添加混合させてなることを特徴とする光触媒材を提案する。かかる光触媒材にあって、ＴｉＯ ２ 光触媒粉末には、この光触媒粉末１００部に対して１〜１０部の割合で、フラーレン類及び上記した炭素材料を添加混合させることができる。フラーレン類としては、化学式Ｃ２ｎ（ｎは３０以上の整数）で表される閉核構造をなすフラーレン（例えばサッカボール形，ラグビーボール形の分子構造をなすフラーレンＣ６０，Ｃ７０，Ｃ７６，Ｃ７８，Ｃ８０，Ｃ８２，Ｃ８４，Ｃ８６，Ｃ８８，Ｃ９０，Ｃ９４，Ｃ９６等）、フラーレンを化学修飾した水酸化フラーレン，水素化フラーレン等のフラーレン誘導体又はこれらの混合物が使用される。フラーレン類又は副生炭素材料としては、具体的には、フロンティアカーボン（株）製の「ナノムミックス」「ナノムスペクトラ」「ナノムブラックＦＢ」「ナノムブラックＦＢ−Ｘ」等が好適する。
ＴｉＯ２光触媒としては、一般に、アナターゼ型又はルチル型のものが使用されるが、これに添加混合させるフラーレン類又は副生炭素材料は、予め、２００〜４００℃で酸化熱処理しておくことが好ましい。酸化熱処理したフラーレン類又は副生炭素材料を添加させることにより、光触媒活性の更なる向上を図ることができ、光触媒材による浄化処理能力（特に、水の液体に対する浄化処理能力）がより効果的に発揮されることになる。
The present invention relates to TiO 2 photocatalyst powder, in a proportion of 1 to 10 parts with respect to the photocatalyst powder 100 parts, a carbon material formed as a by-product in the fullerene production process, X-rays diffraction measurements using CuKα rays In the result of Raman spectrum at an excitation wavelength of 5145Å, the strongest peak in the range of diffraction angle of 3 to 30 ° is present in the range of diffraction angle of 10 to 18 ° and no peak exists in diffraction angle of 23 to 27 °. Band G1590 ± 20cm -1 and Band D1340 ± 40cm
-1 has a peak, and the peak intensity ratio I (D) / I (G) is 0.4 to 1.0 when the peak intensity of each band is I (G) and I (D). A photocatalyst material characterized by adding and mixing a carbon material (hereinafter referred to as “by-product carbon material”) is proposed. In such a photocatalyst material , fullerenes and the above-described carbon material can be added and mixed in the TiO 2 photocatalyst powder at a ratio of 1 to 10 parts with respect to 100 parts of the photocatalyst powder. As fullerenes, fullerenes having a closed nucleus structure represented by the chemical formula C 2n (n is an integer of 30 or more) (for example, fullerenes C 60 , C 70 , C 76 , which form molecular structures of sucker ball type and rugby ball type) C 78, C 80, C 82 , C 84, C 86, C 88, C 90, C 94, C 96 , etc.), fullerene chemically modified hydroxylated fullerene, a fullerene derivative or a mixture thereof such as hydrogenated fullerene Used . The fullerene compound or by-product carbon material, specifically, Frontier Carbon Co., Ltd. "Nano arm mix""nano-timespectrum,""nano-time Black FB", "nano-time Black FB-X" and the like are preferable.
As the TiO 2 photocatalyst, an anatase type or rutile type is generally used. However, the fullerenes or by-product carbon material to be added to and mixed with the TiO 2 photocatalyst is preferably subjected to an oxidation heat treatment at 200 to 400 ° C. in advance. . By adding fullerenes or by-product carbon materials that have undergone oxidative heat treatment, the photocatalytic activity can be further improved, and the purification capacity of the photocatalyst material (especially the purification capacity for water liquid) is more effective. Will be demonstrated .
また、本発明は、上記した光触媒材を、水等の流体が通過しうる多孔質構造をなすフィルタ本体に担持させてなることを特徴とする光触媒フィルタを提案する。フィルタ本体としては、耐熱性，耐久性等を考慮して、セラミックス製のものを使用することが好ましい。 The present invention also proposes a photocatalytic filter comprising the above-described photocatalytic material supported on a filter body having a porous structure through which a fluid such as water can pass. The filter body is preferably made of ceramics in consideration of heat resistance, durability and the like.
また、本発明は、上記した光触媒フィルタとそのフィルタ本体に担持された光触媒材を光励起する光照射器とを具備してなる光触媒フィルタユニットを提案する。光照射器としては、ＴｉＯ２光触媒のバンドギャップエネルギ以上の光（紫外線）を照射する紫外線ランプ，ブラックライト，発光ダイオード等が使用される。なお、光照射器は、光触媒フィルタを通過する水等流体との直接的な接触を避ける等のために、紫外線透過性に優れる材料（石英，紫外線透過性樹脂等）で構成した保護管等で囲繞しておくことが好ましい。 The present invention also proposes a photocatalytic filter unit comprising the above-described photocatalytic filter and a light irradiator for photoexciting a photocatalytic material carried on the filter body. As the light irradiator, an ultraviolet lamp, a black light, a light emitting diode, or the like that irradiates light (ultraviolet light) that is higher than the band gap energy of the TiO 2 photocatalyst is used. The light irradiator is a protective tube made of a material with excellent UV transparency (quartz, UV transparent resin, etc.) to avoid direct contact with fluids such as water passing through the photocatalytic filter. It is preferable to keep a go.
さらに、本発明は、上記した光触媒フィルタユニットと、流体の流入出口を有して当該ユニットの光触媒フィルタを内装する処理容器とを具備して、流入口から流入した流体が、当該ユニットの光照射器により光照射された状態の光触媒フィルタを通過して流出口から流出するように構成された光触媒浄化処理装置を提案する。流入口から流入させる流体つまり浄化処理すべき流体としては、空気等の気体の他、メカニカルシールから排出されたクエンチング水又はフラッシシング水等の水を選択することができる。好ましい実施の形態にあっては、本発明の光触媒浄化処理装置はメカニカルシールからの廃水（クエンチング水，フラッシシング水等）等を浄化処理（水処理）するものとして提案される。
また、本発明は、光触媒フィルタユニットと、流体の流入出口を有して当該ユニットの光触媒フィルタを内装する処理容器とを具備して、流入口から流入した流体が、当該ユニットの光照射器により光照射された状態の光触媒フィルタを通過して流出口から流出するように構成されている光触媒浄化処理装置であって、光触媒フィルタユニットが、光触媒材を流体が通過しうる多孔質構造をなすフィルタ本体に担持させてなる光触媒フィルタと光触媒材を励起する光照射器とを具備してなるものであり、光触媒材が、ＴｉＯ ２ 光触媒粉末に、この光触媒粉末１００部に対して１〜１０部の割合で、フラーレン類を添加混合させてなるものであり、流入口から流入する流体が水であることを特徴とする光触媒浄化処理装置を提案する。
Furthermore, the present invention includes the above-described photocatalytic filter unit and a processing container having a fluid inflow / outlet and having the photocatalytic filter of the unit installed therein, and the fluid flowing in from the inflow port is irradiated with light from the unit. A photocatalyst purification treatment device configured to pass through a photocatalyst filter irradiated with light from a vessel and to flow out from an outlet is proposed. As the fluid flowing in from the inlet, that is, the fluid to be purified, water such as quenching water or flushing water discharged from the mechanical seal can be selected in addition to gas such as air. In a preferred embodiment, the photocatalyst purification treatment apparatus of the present invention is proposed as a purification treatment (water treatment) of waste water (quenching water, flushing water, etc.) from a mechanical seal.
The present invention also includes a photocatalyst filter unit and a processing container having a fluid inlet / outlet and having the photocatalyst filter of the unit installed therein, so that the fluid flowing in from the inlet is caused by the light irradiator of the unit. A photocatalyst purification treatment device configured to pass through a photocatalyst filter irradiated with light and flow out from an outlet, wherein the photocatalyst filter unit has a porous structure through which a fluid can pass through the photocatalyst material are those formed by and a light irradiator to excite the photocatalyst filter and the photocatalyst material formed is supported on the body, the photocatalytic material, the TiO 2 photocatalyst powder, 1 to 10 parts with respect to the photocatalyst powder 100 parts Proposed is a photocatalytic purification treatment apparatus characterized in that fullerenes are added and mixed at a ratio, and the fluid flowing from the inlet is water.
本発明の光触媒材は、ＴｉＯ２光触媒粉末やこれをアパタイト，シリカゲル，ゼオライト，活性炭等の吸着材に担持させた従来の光触媒材に比して、光触媒能を含む浄化処理能力の大幅な向上を実現できるものであり、従来の光触媒材によっては適用することが困難であった水処理（例えば、クエンチング水等のメカニカルシール廃水、上下水道、農業排水、食品加工水又は染色水等の浄化処理）にも好適に使用することができ、光触媒用途の大幅な拡大を図ることができる。 The photocatalyst material of the present invention has a significant improvement in purification treatment capacity including photocatalytic ability, as compared with conventional photocatalyst materials in which TiO 2 photocatalyst powder and this are supported on adsorbents such as apatite, silica gel, zeolite, and activated carbon. Water treatment that can be realized and difficult to apply depending on conventional photocatalyst materials (for example, purification treatment of mechanical seal wastewater such as quenching water, water and sewage, agricultural wastewater, food processing water, or dyed water) ) Can be suitably used, and the photocatalyst application can be greatly expanded.
また、本発明によれば、水処理手段としても極めて効果的で実用性に富む光触媒フィルタ、光触媒フィルタユニット及び光触媒浄化処理装置を提供することができる。 Further, according to the present invention, it is possible to provide a photocatalyst filter, a photocatalyst filter unit, and a photocatalyst purification treatment device that are extremely effective and practical as water treatment means.
図１は本発明に係る光触媒浄化処理装置の一例を示した縦断正面図であり、この光触媒浄化処理装置はメカニカルシールから排出されるクエンチング水やフラッシング水等の廃水を浄化処理するものである。すなわち、メカニカルシールにおいては、一般に、クエンチングやフラッシング（例えば、両密封環の相対回転部分やその近傍領域に、これらを冷却，清掃，温度管理する等のために、清水，スチーム等を供給する）等が行われ、シール条件（被密封流体の性状等）によっては、メカニカルシールから排出されるクエンチング水やフラッシング水等の廃水には有機物質等の汚染物質が含まれることがある。かかる場合、廃水をそのまま廃棄するにしても、メカニカルシールに再供給（循環）させるにしても、廃水を浄化処理しておく必要がある。図１に示す光触媒浄化処理装置１は、このようなメカニカルシール２から排出される廃水３を浄化処理するためのものであり、メカニカルシールから導かれた廃水路４の適所に配設されており、処理容器５と光触媒フィルタユニット６とからなる。 FIG. 1 is a longitudinal front view showing an example of a photocatalyst purification apparatus according to the present invention, which purifies waste water such as quenching water and flushing water discharged from a mechanical seal. . That is, in the case of mechanical seals, in general, quenching and flushing (for example, supplying fresh water, steam, etc. to the relative rotating part of both sealing rings and the vicinity thereof for cooling, cleaning, temperature control, etc.) Depending on the sealing conditions (properties of the sealed fluid, etc.), the waste water such as quenching water and flushing water discharged from the mechanical seal may contain contaminants such as organic substances. In such a case, it is necessary to purify the waste water whether it is discarded as it is or supplied again (circulated) to the mechanical seal. A photocatalyst purification treatment apparatus 1 shown in FIG. 1 is for purifying waste water 3 discharged from such a mechanical seal 2, and is disposed at an appropriate position of a waste water channel 4 led from the mechanical seal. And a processing vessel 5 and a photocatalytic filter unit 6.
処理容器５は、図１〜図３に示す如く、円筒状の周壁５ａとその上下端部を閉塞する上下壁５ｂ，５ｃとからなる密閉容器であり、周壁５ａの下端部には流入口５１が形成されており、周壁５ａの上端部には排出口５２が形成されている。流入口５１には、廃水路４の上流側部分４ａが接続されていて、メカニカルシール１から排出された廃水（被処理水）４が流入される。流出口５２には、廃水路４の下流側部分４ｂが接続されていて、浄化処理された廃水（処理水）３ａを当該下流側部分４ｂへ排出する。なお、廃水路４の下流側部分４ｂは、適当な廃水処理部に導かれるか又はクエンチング，フラッシング用流体のメカニカルシールへの供給ライン，供給源に接続されている。後者の場合、処理水３ａはクエンチング，フラッシング用流体として再使用され、メカニカルシール２に循環供給される。 As shown in FIGS. 1 to 3, the processing container 5 is a sealed container including a cylindrical peripheral wall 5 a and upper and lower walls 5 b and 5 c that close the upper and lower ends thereof. An inlet 51 is provided at the lower end of the peripheral wall 5 a. A discharge port 52 is formed at the upper end of the peripheral wall 5a. An upstream portion 4 a of the waste water channel 4 is connected to the inflow port 51, and waste water (treated water) 4 discharged from the mechanical seal 1 flows into the inflow port 51. A downstream portion 4b of the waste water channel 4 is connected to the outlet 52, and the purified waste water (treated water) 3a is discharged to the downstream portion 4b. The downstream portion 4b of the waste water channel 4 is led to an appropriate waste water treatment unit or connected to a supply line and a supply source for a mechanical seal for quenching and flushing fluid. In the latter case, the treated water 3 a is reused as a quenching and flushing fluid and is circulated and supplied to the mechanical seal 2.
フィルタユニット６は、図１に示す如く、処理容器５内に装填された円筒状の光触媒フィルタ６１と、処理容器５の上下壁５ｂ，５ｃに取り付けられた保護管６２と、保護管６２に挿通された光照射器６３とからなる。 As shown in FIG. 1, the filter unit 6 is inserted into the cylindrical photocatalyst filter 61 loaded in the processing container 5, a protective tube 62 attached to the upper and lower walls 5 b and 5 c of the processing container 5, and the protective tube 62. Light irradiator 63.
光触媒フィルタ６１は、図１に示す如く、処理容器６内の上下部に流入出口５１，５２に連通する流入出室５３，５４が形成される状態で、処理容器６内に装填された円筒状のフィルタ本体６１ａと、このフィルタ本体６１ａに担持させた光触媒材６１ｂとからなる。 As shown in FIG. 1, the photocatalytic filter 61 has a cylindrical shape loaded in the processing container 6 with inflow / outflow chambers 53, 54 communicating with the inflow / outflow ports 51, 52 formed in the upper and lower portions of the processing container 6. Filter body 61a and a photocatalyst material 61b carried on the filter body 61a.
フィルタ本体６１ａは、流体（廃水３）及び光が通過しうる連続孔を有するセラミックス製の多孔質構造体である。かかるセラミックス製のフィルタ本体６１ａとしては、例えば、フィルタ本体対応形状のスポンジに炭化珪素粉末スラリを含浸し、これを余剰スラリを除去した上で乾燥，焼成して得られる多孔質構造体や、特開２００１−２２６１７４，特開２００３−１１９０８５公報、特開２００４−１８９５７６公報又はＷＯ２００３／０３５５７７公報に開示される多孔質構造体等、公知のセラミックス製多孔質構造体を使用条件等に応じて任意に使用することができる。 The filter main body 61a is a ceramic porous structure having continuous pores through which fluid (waste water 3) and light can pass. As such a filter body 61a made of ceramics, for example, a porous structure obtained by impregnating a silicon carbide powder slurry into a sponge corresponding to the filter body, removing the excess slurry, and drying and firing the porous structure, A known ceramic porous structure such as a porous structure disclosed in Japanese Patent Application Laid-Open No. 2001-226174, Japanese Patent Application Laid-Open No. 2003-119085, Japanese Patent Application Laid-Open No. 2004-189576, or WO 2003/035577 Can be used.
光触媒材６１ｂは、アナターゼ型ＴｉＯ２光触媒粉末にフラーレン類及び／又は副生炭素材料を添加混合させたものであり、当該フラーレン類及び／又は副生炭素材料は、光触媒粉末１００部に対して１〜１０部の割合で添加する。フラーレン類としては、化学式Ｃ２ｎ（ｎは３０以上の整数）で表される閉核構造をなすフラーレン（例えばサッカボール形，ラグビーボール形の分子構造をなすフラーレンＣ６０，Ｃ７０，Ｃ７６，Ｃ７８，Ｃ８０，Ｃ８２，Ｃ８４，Ｃ８６，Ｃ８８，Ｃ９０，Ｃ９４，Ｃ９６等）若しくはフラーレンを化学修飾した水酸化フラーレン，水素化フラーレン等のフラーレン誘導体又はこれらの混合物が使用される。また、副生炭素材料としては、特開２００４−９１３１２公報に開示される如く、ＣｕＫα線を使用したＸ線回折測定結果における回折角３〜３０°の範囲内で最も強いピークが回折角１０〜１８°の範囲に存在し且つ回折角２３〜２７°にピークが存在せず、励起波長５１４５Åでのラマンスペクトル結果において、バンドＧ１５９０±２０ｃｍ−１とバンドＤ１３４０±４０ｃｍ−１にピークを有し、夫々のバンドのピーク強度をＩ（Ｇ）及びＩ（Ｄ）とした際におけるピーク強度比Ｉ（Ｄ）／Ｉ（Ｇ）が０．４〜１．０である炭素材料が使用される。何れのフラーレン類及び／又は副生炭素材料を添加する場合にも、これらを予め２００〜４００℃で酸化熱処理しておくことが好ましい。酸化熱処理は、熱処理しようとするフラーレン類又は副生炭素材料の熱分析測定により酸化減量開始温度を把握して、その温度付近で行うことが好ましい。光触媒材６１ｂのフィルタ本体６１ａへの担持は、ゾルゲル法により或いはバインダを使用することによる等、公知の担持方法により行うことができる。 The photocatalyst material 61b is obtained by adding and mixing fullerenes and / or by-product carbon materials to anatase TiO 2 photocatalyst powder, and the fullerenes and / or by-product carbon materials are 1 in 100 parts of the photocatalyst powder. Add at a rate of -10 parts. As fullerenes, fullerenes having a closed nucleus structure represented by the chemical formula C 2n (n is an integer of 30 or more) (for example, fullerenes C 60 , C 70 , C 76 , which form molecular structures of sucker ball type and rugby ball type) C 78, C 80, C 82 , C 84, C 86, C 88, C 90, C 94, C 96 , etc.) or fullerene chemically modified hydroxylated fullerene, a fullerene derivative or a mixture thereof such as hydrogenated fullerene used. The sub as the raw carbon materials, as disclosed in JP-open 2004-91312 publication, the strongest peak diffraction angle 10 in the range of diffraction angle 3 to 30 ° in X-ray diffraction measurement results using CuKα ray There is no peak at a diffraction angle of 23 to 27 ° within a range of 18 °, and in the Raman spectrum result at an excitation wavelength of 5145 ピ ー ク, there are peaks in band G1590 ± 20 cm −1 and band D1340 ± 40 cm −1 , A carbon material having a peak intensity ratio I (D) / I (G) of 0.4 to 1.0 when the peak intensity of each band is I (G) and I (D) is used. When any fullerenes and / or by-product carbon materials are added, it is preferable to carry out an oxidation heat treatment at 200 to 400 ° C. in advance. The oxidation heat treatment is preferably performed in the vicinity of the temperature obtained by grasping the oxidation loss start temperature by thermal analysis measurement of the fullerenes or by-product carbon material to be heat-treated. The photocatalyst material 61b can be supported on the filter body 61a by a known support method such as a sol-gel method or by using a binder.
保護管６２は、図１に示す如く、光触媒フィルタ６１の中心孔を貫通して処理容器５の上下壁５ｂ，５ｃに取り付けられた薄肉円筒管であり、上端部は処理容器５の上壁５ｂを貫通して開口されている。保護管６２は、後述する光照射器６３を保護するためのもので、紫外線透過性に優れる石英ガラス，フッ素樹脂管等で構成されている。保護管６２を設けることにより、当該保護管６２と処理容器５の周壁５ａと間には流入出口５１，５２に連通する円筒状空間が形成されるが、この円筒状空間の中間領域（流入出室５３，５４を除く領域）にフィルタ本体６１ａが充填されている。 As shown in FIG. 1, the protective tube 62 is a thin cylindrical tube that passes through the center hole of the photocatalytic filter 61 and is attached to the upper and lower walls 5 b and 5 c of the processing vessel 5, and the upper end portion is the upper wall 5 b of the processing vessel 5. It is opened through. The protective tube 62 is for protecting a light irradiator 63 to be described later, and is made of quartz glass, a fluororesin tube, or the like that is excellent in ultraviolet transmittance. By providing the protective tube 62, a cylindrical space communicating with the inflow / outflow ports 51 and 52 is formed between the protective tube 62 and the peripheral wall 5 a of the processing vessel 5. The filter main body 61a is filled in the area excluding the chambers 53 and 54).
光照射器６３は、図１に示す如く、光触媒材６１ｂを光励起する棒状のブラックライト等であって、保護管６２内にその上端開口部から挿入されていて、フィルタ本体６１ａにその上下面及び中心孔の内周面から紫外線を照射するものである。照射光はフィルタ本体６１ａの内部にまで透過して、これに担持された光触媒材６１ｂを光励起するが、照射効率（励起効率）を高めるために処理容器５の内周面（周壁５ａの内周面及び上下壁５ｂ，５ｃの対向面）は反射面に構成しておくことが好ましい。例えば、処理容器５が金属製のものである場合には、その内周面を鏡面加工しておく。また、処理容器５が金属以外の樹脂等で構成される場合には、容器内周面に高反射率の材料によるコーティング膜を形成しておく。 As shown in FIG. 1, the light irradiator 63 is a rod-shaped black light or the like that photoexcites the photocatalyst material 61b, and is inserted into the protective tube 62 from its upper end opening. Ultraviolet rays are irradiated from the inner peripheral surface of the center hole. Irradiation light is transmitted to the inside of the filter body 61a and photoexcites the photocatalyst material 61b carried on the filter body 61a. In order to increase the irradiation efficiency (excitation efficiency), the inner peripheral surface of the processing vessel 5 (the inner periphery of the peripheral wall 5a). The surface and the opposing surfaces of the upper and lower walls 5b and 5c) are preferably configured as reflecting surfaces. For example, when the processing container 5 is made of metal, its inner peripheral surface is mirror-finished. When the processing container 5 is made of a resin other than metal, a coating film made of a highly reflective material is formed on the inner peripheral surface of the container.
而して、かかる光触媒浄化処理装置１によれば、メカニカルシール１から排出される廃水３が流入口５１から処理容器５の流入室５３に流入して、流入室５３から光触媒フィルタ６１（フィルタ本体６１ａ）を通過して流出室５４を経て流出口５２から排出される。廃水３に含まれる有機物質等の汚染物質は、光フィルタ６１を通過する間において、光触媒材６１ｂの光励起による光触媒作用等により浄化処理（有機物質の分解等）されることになり、流出室５４には浄化処理された廃水つまり処理水３ａが流出されることになる。このとき、光触媒材６１ｂがＴｉＯ２光触媒粉末とフラーレン類又は副生炭素材料との混合材であり、光触媒活性が高いものであるから、廃水３の浄化処理が効果的に行われる。特に、ＴｉＯ２光触媒粉末に添加混合させるフラーレン類又は副生炭素材料を上記した如く酸化熱処理しておくことにより、光触媒活性の更なる向上を図ることができ、廃水３の浄化処理を極めて良好に行うことができる。したがって、廃水路４に上記した光触媒浄化処理装置１を配設しておくことにより、メカニカルシール２をクリーンな環境で運転させることができ、食品，薬品等の分野においても好適に使用できるメカニカルシールを提供することができる。 Thus, according to the photocatalyst purification treatment apparatus 1, the waste water 3 discharged from the mechanical seal 1 flows into the inflow chamber 53 of the processing container 5 from the inflow port 51, and the photocatalyst filter 61 (filter body) from the inflow chamber 53. 61a), and is discharged from the outlet 52 through the outflow chamber 54. Contaminants such as organic substances contained in the waste water 3 are subjected to purification treatment (decomposition of organic substances, etc.) by photocatalytic action by photoexcitation of the photocatalyst material 61b while passing through the optical filter 61, and the outflow chamber 54 In this case, the purified waste water, that is, the treated water 3a is discharged. At this time, since the photocatalyst material 61b is a mixed material of TiO 2 photocatalyst powder and fullerenes or by-product carbon material and has high photocatalytic activity, the purification treatment of the waste water 3 is effectively performed. In particular, the fullerenes or by-product carbon material to be added to and mixed with the TiO 2 photocatalyst powder is subjected to an oxidation heat treatment as described above, whereby the photocatalytic activity can be further improved, and the purification treatment of the waste water 3 can be performed extremely well. It can be carried out. Therefore, the mechanical seal 2 can be operated in a clean environment by disposing the above-described photocatalyst purification apparatus 1 in the waste water channel 4 and can be suitably used in the fields of food, medicine and the like. Can be provided.
なお、光触媒材６１ｂ、光触媒フィルタ６１、光触媒フィルタユニット６及び光触媒浄化処理装置１の構成は、上記した実施の形態に限定されず、本発明の基本原理を逸脱しない範囲において、適宜に改良，変更することができる。例えば、処理容器５を紫外線透過性に優れるフッ素樹脂等で構成して、光照射器６３を処理容器５外に配置するようにすることも可能である。 Note that the configurations of the photocatalyst material 61b, the photocatalyst filter 61, the photocatalyst filter unit 6, and the photocatalyst purification treatment device 1 are not limited to the above-described embodiments, and are appropriately improved and changed without departing from the basic principle of the present invention. can do. For example, the processing container 5 may be made of a fluororesin or the like having excellent ultraviolet transparency, and the light irradiator 63 may be disposed outside the processing container 5.
参考例として、一次粒子径２０ｎｍ，比表面積５０ｍ２／ｇのアナターゼ型ＴｉＯ２光触媒粉末１ｇに、フラーレン類Ａ１を添加混合させて本発明に係る光触媒浄化処理装置に使用する光触媒材Ｎｏ．１，Ｎｏ．２，Ｎｏ．３を得た。フラーレン類Ａ１としては、フロンティアカーボン（株）製の「ナノムミックス」を使用した。これは、フラーレンＣ６０：約６０％とフラーレンＣ７０：約２５％と他の高次フラーレン類：残部とからなるフラーレン混合物である。 As a reference example , photocatalyst material No. 1 used in the photocatalyst purification treatment apparatus according to the present invention by adding and mixing fullerenes A1 to 1 g of anatase TiO 2 photocatalyst powder having a primary particle diameter of 20 nm and a specific surface area of 50 m 2 / g. 1, No. 1 2, no. 3 was obtained. As the fullerenes A1, “Nanomumix” manufactured by Frontier Carbon Co., Ltd. was used. This is a fullerene mixture composed of fullerene C 60 : about 60%, fullerene C 70 : about 25%, and other higher-order fullerenes: the balance.
フラーレン類Ａ１は光触媒粉末１００部に対して１〜１０部の割合で添加されており、表１に示す如く、光触媒材Ｎｏ．１及びＮｏ．２においては０．１ｇ（１０部）のフラーレン類Ａ１を添加し、光触媒材Ｎｏ．３においては０．０１ｇ（１部）のフラーレン類Ａ１を添加した。また、光触媒材Ｎｏ．２及びＮｏ．３においては、フラーレンＡ１を電気炉で４００℃，１時間の条件で酸化熱処理した上で、光触媒粉末に添加混合させた。 Fullerenes A1 are added in a ratio of 1 to 10 parts with respect to 100 parts of the photocatalyst powder. 1 and no. In No. 2, 0.1 g (10 parts) of fullerenes A1 was added and photocatalyst material No. 2 was added. In No. 3, 0.01 g (1 part) of fullerenes A1 was added. In addition, photocatalyst material No. 2 and no. In No. 3, fullerene A1 was subjected to an oxidation heat treatment in an electric furnace at 400 ° C. for 1 hour, and then added to and mixed with the photocatalyst powder.
実施例１として、一次粒子径２０ｎｍ，比表面積５０ｍ２／ｇのアナターゼ型ＴｉＯ２光触媒粉末１ｇに、副生炭素材料Ａ２を添加混合させて本発明に係る光触媒材Ｎｏ．４，Ｎｏ．５，Ｎｏ．６を得た。副生炭素材料Ａ２としては、フロンティアカーボン（株）製の「ナノムブラックＦＢ」を使用した。これは、フラーレン含有煤を分離，精製して得られるものであり、ＣｕＫα線を使用したＸ線回折測定結果における回折角３〜３０°の範囲内で最も強いピークが回折角１０〜１８°の範囲に存在し且つ回折角２３〜２７°にピークが存在せず、励起波長５１４５Åでのラマンスペクトル結果において、バンドＧ１５９０±２０ｃｍ−１とバンドＤ１３４０±４０ｃｍ−１にピークを有し、夫々のバンドのピーク強度をＩ（Ｇ）及びＩ（Ｄ）とした際におけるピーク強度比Ｉ（Ｄ）／Ｉ（Ｇ）が０．４〜１．０である炭素材料（特開２００４−９１３１２公報参照）である。 As Example 1 , by-product carbon material A2 was added to and mixed with 1 g of anatase-type TiO 2 photocatalyst powder having a primary particle diameter of 20 nm and a specific surface area of 50 m 2 / g, and the photocatalyst material No. 1 according to the present invention was used. 4, no. 5, no. 6 was obtained. As the by-product carbon material A2, “Nanome Black FB” manufactured by Frontier Carbon Co., Ltd. was used. This is obtained by separating and purifying the fullerene-containing soot, and the X-ray diffraction measurement result using CuKα rays shows the strongest peak within the diffraction angle range of 3 to 30 ° and the diffraction angle of 10 to 18 °. In the Raman spectrum result at an excitation wavelength of 5145 し having a peak in a band G1590 ± 20 cm −1 and a band D1340 ± 40 cm −1 in the range and having no diffraction peak at a diffraction angle of 23 to 27 °, each band A carbon material having a peak intensity ratio I (D) / I (G) of 0.4 to 1.0 when the peak intensity is I (G) and I (D) (see JP 2004-91312 A) It is.
副生炭素材料Ａ２は光触媒粉末１００部に対して１〜１０部の割合で添加されており、表１に示す如く、光触媒材Ｎｏ．４及びＮｏ．５においては０．１ｇ（１０部）の副生炭素材料Ａ２を添加し、光触媒材Ｎｏ．６においては０．０１ｇ（１部）の副生炭素材料Ａ２を添加した。また、光触媒材Ｎｏ．５及びＮｏ．６においては、副生炭素材料Ａ２を電気炉で３００℃，１時間の条件で酸化熱処理した上で、光触媒粉末に添加混合させた。 The by-product carbon material A2 is added in a ratio of 1 to 10 parts with respect to 100 parts of the photocatalyst powder. 4 and no. In No. 5, 0.1 g (10 parts) of by-product carbon material A2 was added. In No. 6, 0.01 g (1 part) of by-product carbon material A2 was added. In addition, photocatalyst material No. 5 and no. In No. 6, the by-product carbon material A2 was subjected to an oxidation heat treatment in an electric furnace at 300 ° C. for 1 hour, and then added to and mixed with the photocatalyst powder.
実施例２として、一次粒子径２０ｎｍ，比表面積５０ｍ２／ｇのアナターゼ型ＴｉＯ２光触媒粉末１ｇに、副生炭素材料Ａ３を添加混合させて本発明に係る光触媒材Ｎｏ．７，Ｎｏ．８，Ｎｏ．９を得た。副生炭素材料Ａ３としては、フロンティアカーボン（株）製の「ナノムブラックＦＢ−Ｘ」を使用した。これは、粉体ＰＨを３程度とした副生炭素原料Ａ２（ナノムブラックＦＢ）の表面処理品である。 As Example 2 , by-product carbon material A3 was added to and mixed with 1 g of anatase-type TiO 2 photocatalyst powder having a primary particle diameter of 20 nm and a specific surface area of 50 m 2 / g, and the photocatalyst material No. 1 according to the present invention was used. 7, no. 8, no. 9 was obtained. As the by-product carbon material A3, “Nanome Black FB-X” manufactured by Frontier Carbon Co., Ltd. was used. This is a surface-treated product of the by-product carbon raw material A2 (Nanomu Black FB) having a powder PH of about 3.
副生炭素材料Ａ３は光触媒粉末１００部に対して１〜１０部の割合で添加されており、表１に示す如く、光触媒材Ｎｏ．７及びＮｏ．８においては０．１ｇ（１０部）の副生炭素材料Ａ３を添加し、光触媒材Ｎｏ．９においては０．０１ｇ（１部）の副生炭素材料Ａ３を添加した。また、光触媒材Ｎｏ．８及びＮｏ．９においては、副生炭素材料Ａ３を電気炉で３００℃，１時間の条件で酸化熱処理した上で、光触媒粉末に添加混合させた。 The by-product carbon material A3 is added in a ratio of 1 to 10 parts with respect to 100 parts of the photocatalyst powder. 7 and no. In No. 8, 0.1 g (10 parts) of by-product carbon material A3 was added. In No. 9, 0.01 g (1 part) of by-product carbon material A3 was added. In addition, photocatalyst material No. 8 and no. In No. 9, the by-product carbon material A3 was subjected to an oxidation heat treatment in an electric furnace at 300 ° C. for 1 hour, and then added to and mixed with the photocatalyst powder.
而して、各光触媒材Ｎｏ．１〜Ｎｏ．９の光触媒能を含む浄化処理能力を確認するために、次のような脱色試験を行った。 Thus, each photocatalyst material No. 1-No. In order to confirm the purification treatment ability including the photocatalytic ability of 9, the following decoloration test was conducted.
すなわち、脱色試験は、７．５ｐｐｍのメチレンブルー水溶液２００ｍＬを収容したビーカ（容積：３００ｍＬ）をスターラ上に載置すると共にビーカ上にブラックライト（２０Ｗ）を配置した試験装置を使用して行ったもので、各光触媒材Ｎｏ．１〜Ｎｏ．９をメチレンブルー水溶液中に投入させると共に、スターラにより光触媒材とメチレンブルー水溶液とを攪拌させつつ、ビーカ内の液面に向けてブラックライト光を照射させた。そして、光触媒材投入後、メチレンブルー水溶液が脱色されるまでの時間（脱色時間）を測定した。その結果は、表１に示す通りであった。なお、メチレンブルー水溶液が脱色された時点は、当該水溶液が完全に透明になったことを目視確認することによって判断した。また、ブラックライトからビーカの液面までの鉛直距離は１００ｍｍに設定した。 That is, the decolorization test was performed using a test apparatus in which a beaker (volume: 300 mL) containing 200 mL of a 7.5 ppm methylene blue aqueous solution was placed on a stirrer and a black light (20 W) was placed on the beaker. In each photocatalyst material No. 1-No. 9 was added to the methylene blue aqueous solution, and the photocatalyst material and the methylene blue aqueous solution were stirred with a stirrer while irradiating black light light toward the liquid surface in the beaker. Then, after the photocatalyst material was added, the time until the methylene blue aqueous solution was decolored (decoloration time) was measured. The results were as shown in Table 1. In addition, when the methylene blue aqueous solution was decolored, it was judged by visually confirming that the aqueous solution was completely transparent. The vertical distance from the black light to the liquid level of the beaker was set to 100 mm.
さらに、公知の光触媒材Ｎｏ．１０〜Ｎｏ．１３を比較例として、これらの光触媒材Ｎｏ．１０〜Ｎｏ．１３についても同一の脱色試験を行った。すなわち、上記試験装置を使用して、１ｇの各光触媒材Ｎｏ．１０〜Ｎｏ．１３をメチレンブルー水溶液中に投入させると共に、スターラにより光触媒材とメチレンブルー水溶液とを攪拌させつつ、ビーカ内の液面に向けてブラックライト光を照射させ、メチレンブルー水溶液が完全に透明に脱色されるまでの時間（脱色時間）を測定した。その結果は、表１に示す通りであった。なお、光触媒材Ｎｏ．１０は参考例及び実施例１，２で使用した市販の光触媒粉末（日本アエ
ロジル（株）製「Ｐ２５」）であり、光触媒材Ｎｏ．１１はＴｉＯ２光触媒粉末をアパタイトに担持させたもの（太平化学産業（株）製「ＰＣＡＰ−１００」）であり、光触媒材Ｎｏ．１２はＴｉＯ２光触媒粉末をゼオライトに担持させたもの（ライオン（株）製「ＰＣ−３０１Ｐ」）であり、光触媒材Ｎｏ．１３はＴｉＯ２光触媒粉末をシリカゲル（粒状）に担持させたもの（新東Ｖセラックス（株）製「ＨＱＣ２１」）である。
Furthermore, a known photocatalyst material No. 10-No. As a comparative example, these photocatalyst materials No. 10-No. The same decolorization test was conducted for 13 . That is, using the test apparatus, 1 g of each photocatalyst material No. 10-No. 13 is charged into the methylene blue aqueous solution, and the photocatalyst material and the methylene blue aqueous solution are stirred by the stirrer while irradiating black light light toward the liquid surface in the beaker until the methylene blue aqueous solution is completely transparently decolored. Time (decolorization time) was measured. The results were as shown in Table 1. In addition, photocatalyst material No. 10 is a commercially available photocatalyst powder (“P25” manufactured by Nippon Aerosil Co., Ltd.) used in Reference Examples and Examples 1 and 2; No. 11 is a TiO 2 photocatalyst powder supported on apatite (“PCAP-100” manufactured by Taihei Chemical Industry Co., Ltd.). No. 12 is a TiO 2 photocatalyst powder supported on zeolite (“PC-301P” manufactured by Lion Corporation). Reference numeral 13 denotes a TiO 2 photocatalyst powder supported on silica gel (granular) (“HQC21” manufactured by Shinto V Ceramics Co., Ltd.).
而して、表１の脱色試験結果から明らかなように、本発明に係る光触媒材Ｎｏ．４〜Ｎｏ．９及び本発明に係る光触媒浄化処理装置に使用する光触媒材Ｎｏ．１〜３については、何れも、比較例の光触媒材Ｎｏ．１０〜Ｎｏ．１３に比して脱色時間が大幅に短縮されており、極めて優れた浄化処理能力（メチレンブルーの分解能力）を有するものであることが確認された。このことから、光触媒材Ｎｏ．１〜Ｎｏ．９は効果的な水処理を行い得るものであることが理解される。 Thus, as is clear from the decolorization test results in Table 1, the photocatalyst material No. 1 according to the present invention was obtained. 4 to No. 9 and the photocatalyst material No. used in the photocatalyst purification apparatus according to the present invention. 1 to 3 are all photocatalyst materials No. 1 of Comparative Example. 10-No. It was confirmed that the decolorization time was significantly shortened compared with 13, and had an extremely excellent purification treatment ability (methylene blue decomposition ability). From this, the photocatalyst material No. 1-No. It is understood that 9 can perform an effective water treatment.
また、浄化処理能力（脱色時間）は、添加混合材料（フラーレン類又は副生炭素材料）の種類及び添加混合材料の酸化熱処理の有無によっても顕著な差が認められる。すなわち、添加混合材料の種類については、酸化熱処理をすると否とに拘わらず、添加量が同じであれば、浄化処理能力は、副生炭素材料Ａ２を添加したものが最も高く、副生炭素材料Ａ３を添加したものがこれに続く。フラーレン類Ａ１を添加したものは、光触媒に添加混合材料を添加したものの中では浄化処理能力が最低であるが、従来公知の光触媒材Ｎｏ．１０〜Ｎｏ．１３に比しては極めて高い浄化処理能力を有している。また、添加混合材料を酸化熱処理したものと酸化熱処理をしないものとを比較した場合、添加混合材料がフラーレン類であると副生炭素材料であるとに拘わらず、酸化熱処理をすることにより浄化処理能力が大幅に向上している。特に、添加混合材料を酸化熱処理した場合、副生炭素材料Ａ３を添加したものでは極めて高い浄化処理能力が得られ、副生炭素材料Ａ２を添加したものでは更に高い浄化処理能力が発揮される。 In addition, a significant difference is observed in the purification treatment capacity (decolorization time) depending on the type of the additive mixture material (fullerenes or by-product carbon material) and the presence or absence of the oxidation heat treatment of the additive mixture material. That is, regarding the kind of the additive mixed material, regardless of whether or not the oxidation heat treatment is performed, if the addition amount is the same, the purification treatment ability is highest when the by-product carbon material A2 is added, and the by-product carbon material. This is followed by the addition of A3. In the case where the fullerenes A1 are added, the purification treatment ability is the lowest among the photocatalysts in which the additive mixed material is added. 10-No. Compared to 13, it has a very high purification capacity. In addition, when comparing the material with additive heat treatment with the material without oxidation heat treatment, purification treatment is performed by performing heat treatment with oxidation regardless of whether the material mixture is fullerene or by-product carbon material. The ability is greatly improved. In particular, when the additive mixed material is subjected to an oxidation heat treatment, a material having the by-product carbon material A3 added has a very high purification performance, and a material to which the by-product carbon material A2 has been added exhibits a higher purification performance.
したがって、浄化処理能力上、フラーレン類又は副生炭素材料を酸化熱処理しておくことが好ましく、特に酸化熱処理した副生炭素材料Ａ２を添加しておくのが最適であることが理解される。フラーレン類又は副生炭素材料の微量添加により浄化処理能力（メチレンブルーの分解能力）が飛躍的に向上する理由は、第１に、直径０．７ｎｍ程度のナノ粒子による何等かの表面反応が生じている可能性があることによるものと考えられる。第２に、一般的にフラーレン類又は副生炭素材料はラジカル捕捉作用があるといわれており、ＵＶ光によりＴｉＯ２表面に生成される活性酸素であるヒドロキシラジカルを捕捉，消失させることにより光触媒反応を遅速化させる虞れがあるが、フラーレン類又は副生炭素材料はその比表面積が活性炭等に比して小さいにも拘らず非常に大きな吸着能力を示すものであること及びヒドロキシラジカルの存在が極く短時間（一般に、１０−６秒程度といわれている）であることによりフラーレン類又は副生炭素材料がラジカル捕捉をするよりもＵＶ照射により次々と発生するヒドロキシラジカルの量が圧倒的に多いことによるものと考えられる。また、フラーレン類又は副生炭素材料を酸化熱処理することにより浄化処理能力が更に向上する点については、前述した如くフラーレン類又は副生炭素材料の酸化熱処理をその酸化減量開始温度付近で行うことにより、末端基に酸素が付加され水との濡れ性が改善されること或いは酸化により表面に微細凹凸が生じて吸着能力が増大することによるものと考えられる。 Therefore, it is understood that it is preferable that the fullerenes or the by-product carbon material is subjected to an oxidation heat treatment in terms of purification treatment capacity, and it is optimal that the by-product carbon material A2 subjected to the oxidation heat treatment is added in particular. The reason why the purification capacity (decomposition capacity of methylene blue) is greatly improved by adding a small amount of fullerenes or by-product carbon materials is that, firstly, some surface reaction is caused by nanoparticles having a diameter of about 0.7 nm. This is probably due to the fact that Secondly, fullerenes or by-product carbon materials are generally said to have a radical scavenging action, and photocatalytic reaction occurs by capturing and eliminating hydroxy radicals, which are active oxygen generated on the TiO 2 surface by UV light. However, fullerenes or by-product carbon materials have a very large adsorption capacity despite the fact that their specific surface area is smaller than that of activated carbon and the presence of hydroxy radicals. Due to the extremely short time (generally said to be about 10 −6 seconds), the amount of hydroxy radicals generated one after another by UV irradiation is overwhelming than fullerenes or by-product carbon materials capture radicals. This is probably due to the large number. In addition, the point that the purification treatment capability is further improved by subjecting fullerenes or by-product carbon materials to oxidation heat treatment is that by performing the oxidation heat treatment of fullerenes or by-product carbon materials near the oxidation loss start temperature as described above. It is considered that oxygen is added to the terminal group to improve the wettability with water, or fine unevenness is generated on the surface due to oxidation to increase the adsorption capacity.
１ 光触媒浄化処理装置
３ 被処理水（流体）
３ａ 処理水（流体）
５ 処理容器
６ 光触媒フィルタユニット
５１ 流入口
５２ 流出口
６１ 光触媒フィルタ
６１ａ フィルタ本体
６１ｂ 光触媒材
1 Photocatalyst purification treatment device 3 Water to be treated (fluid)
3a Treated water (fluid)
5 Processing Container 6 Photocatalyst Filter Unit 51 Inlet 52 Outlet 61 Photocatalyst Filter 61a Filter Main Body 61b Photocatalyst Material
Claims (12)
光触媒フィルタユニットが、光触媒材を流体が通過しうる多孔質構造をなすフィルタ本体に担持させてなる光触媒フィルタと光触媒材を励起する光照射器とを具備してなるものであり、光触媒材が、ＴｉＯ２光触媒粉末に、この光触媒粉末１００部に対して１〜１０部の割合で、フラーレン類を添加混合させてなるものであり、流入口から流入する流体が水であることを特徴とする光触媒浄化処理装置。 A photocatalyst filter unit and a processing container having a fluid inlet / outlet and having the photocatalyst filter of the unit installed therein, wherein the fluid flowing in from the inlet is irradiated by the light irradiator of the unit. A photocatalyst purification treatment device configured to pass through the photocatalyst filter and flow out from the outlet,
The photocatalyst filter unit comprises a photocatalyst filter having a photocatalyst material supported on a filter body having a porous structure through which a fluid can pass, and a light irradiator for exciting the photocatalyst material. A photocatalyst obtained by adding fullerenes to TiO 2 photocatalyst powder at a ratio of 1 to 10 parts with respect to 100 parts of the photocatalyst powder , and the fluid flowing from the inlet is water. Purification device .
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