JP5436399B2 - 光触媒材料による分解除去方法 - Google Patents
光触媒材料による分解除去方法 Download PDFInfo
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- JP5436399B2 JP5436399B2 JP2010269960A JP2010269960A JP5436399B2 JP 5436399 B2 JP5436399 B2 JP 5436399B2 JP 2010269960 A JP2010269960 A JP 2010269960A JP 2010269960 A JP2010269960 A JP 2010269960A JP 5436399 B2 JP5436399 B2 JP 5436399B2
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- titanium
- hydrogen peroxide
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- titanium oxide
- sulfur
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- 238000000354 decomposition reaction Methods 0.000 title description 15
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- 239000010936 titanium Substances 0.000 claims description 49
- 239000007789 gas Substances 0.000 claims description 45
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 44
- 229910052719 titanium Inorganic materials 0.000 claims description 44
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 40
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 31
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 claims description 29
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- 229910001873 dinitrogen Inorganic materials 0.000 description 15
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- 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 3
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- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
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- 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 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910000883 Ti6Al4V Inorganic materials 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
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- 238000002835 absorbance Methods 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
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- 235000006408 oxalic acid Nutrition 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- CEOCDNVZRAIOQZ-UHFFFAOYSA-N pentachlorobenzene Chemical compound ClC1=CC(Cl)=C(Cl)C(Cl)=C1Cl CEOCDNVZRAIOQZ-UHFFFAOYSA-N 0.000 description 1
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- B01D—SEPARATION
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- B01D53/46—Removing components of defined structure
- B01D53/60—Simultaneously removing sulfur oxides and nitrogen oxides
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- B01J37/08—Heat treatment
Description
項1.光触媒材料と希薄な過酸化水素溶液を共存させることにて、気相や液相中の有害物質を極めて効率よく速やかに分解させることを特徴とする光触媒材料による分解除去方法。
項2.光触媒材料が、金属チタン又はチタン合金表面にチタン窒化物を形成させた後、陽極酸化処理することにより得られた結晶性酸化チタン皮膜を有する光触媒材料であることを特徴とする項1に記載の光触媒材料による分解除去方法。
項3.結晶性酸化チタンがアナターゼ型酸化チタンであることを特徴とする項2に記載の光触媒材料による分解除去方法。
項4.前記希薄な過酸化水素溶液の過酸化水素濃度が、1重量%(10000ppmW)以下であることを特徴とする項1、2または3記載の光触媒材料による分解除去方法。
項5.気相中の有害物質として、高濃度の窒素酸化物や硫黄酸化物が共存する環境下においては、第1次側の装置として窒素酸化物を除去する薬剤としてアミン化合物水溶液を用いるとともに、第2次側の装置として、項1に記載の光触媒材料と希薄な過酸化水素溶液の共存下で処理する分解方法にて硫黄酸化物を除去する方法。
項6.アミン化合物が、トリエタノールアミン、メチルアミン及びモルホリンから選ばれる化合物であることを特徴とする項5記載の方法。
項7.気相中の有害物質である硫黄酸化物から、硫酸を作製する項5または6記載の方法。
(1)光触媒材料
本発明に用いる光触媒材料としては、高い活性や安定性を有する酸化チタンが好ましい。酸化チタン光触媒は、400nm以下の近紫外線が光照射されると、価電子帯に正孔が伝導帯に電子が生成され、酸化還元反応がおきる。
(i)チタン又はチタン合金の表面にチタン窒化物を形成する工程、及び
(ii)チタンに対してエッチング作用を有する無機酸及び該作用を有する有機酸よりなる群から選択される少なくとも1種の酸を含有する電解液中に、上記工程(i)で得られたチタン又はチタン合金を浸漬し、火花放電発生電圧以上の電圧を印加させることのできる電流を制御することにより陽極酸化を行う工程。
過酸化水素は、それ自体にて強い酸化力を有しており、高濃度の過酸化水素溶液を使用すれば気相中や液相中の有害物質を分解処理することが可能である。しかし、高濃度の過酸化水素溶液は、毒性や腐食性が強く環境負荷の高い材料である。
この気相中や液相中の有害な有機物や無機物としては、トルエン、アセトアルデヒド、イソプロピルアルコール、トリクロロエチレン等のVOC(揮発性有機化合物)やPCB、ダイオキシン等の難分解性有機物質や酸性雨の原因となる硫黄酸化物(S2O、SO、S2O3、SO2、S2O7などのSOx)、大気汚染の原因となる窒素酸化物(NOとNO2などのNOx)等の多くの種類の物質に効果がある。
(3−1)液相における有害物質の分解除去方法
具体的な分解除去手法としては、液相中の有害物質を含む溶液中に過酸化水素溶液を混合したものの中に金属チタン表面にチタン窒化物を形成させた後、陽極酸化を行うことにて作成した高活性を有する光触媒材料を入れ、400nm以下の光を照射することにて分解処理を行う。
(3−2)気相における有害物質の分解除去方法
気相中の有害物質ガスを分解除去する手法として、本有害ガスのフローシステム等を構築し、希薄の過酸化水素溶液をシャワーもしくは噴霧されている系に、金属チタン表面にチタン窒化物を形成させた後、陽極酸化を行うことにて作成した高活性を有する光触媒材料を入れ、400nm以下の光を照射することにて分解処理を行う。
(3−3)高濃度大量の窒素酸化物、硫黄酸化物の分解除去方法
石炭火力発電所等の化石燃料を燃焼する工程において多量に発生する硫黄酸化物や窒素酸化物の除去にも、第1次側の装置中にて窒素酸化物を除去する薬剤としてアミン化合物水溶液、具体的にはトリエタノールアミン、メチルアミン、モルホリンから選ばれた水溶液のシャワーもしくは噴霧にて窒素酸化物を除去した後、第2次側の装置中にて希薄な過酸化水素シャワーもしくは噴霧されている系に、金属チタン表面にチタン窒化物を形成させた後、陽極酸化を行うことにて作成した高活性を有する光触媒材料を入れ、400nm以下の光を照射することにて分解処理を行う。
窒素ガス通気下950℃にて1時間保持し、金属チタン表面にチタン窒化物を形成させた後、電解液として1.5M硫酸、0.1M燐酸、0.3M過酸化水素を用いて電流密度4A/dm2、電解時間30分にて陽極酸化を行うことにて光触媒材料を得た。
分光光度計(島津製作所製、UVmini1240)を起動させ、メチレンブルー(和光純薬製)を蒸留水に希釈して希釈し、660nmの吸光度が1.000の水溶液を調製した。
実施例2
窒素ガス通気下950℃にて1時間保持し、金属チタン表面にチタン窒化物を形成させた後、電解液として1.5M硫酸、0.1M燐酸、0.3M過酸化水素を用いて電流密度4A/dm2、電解時間30分にて陽極酸化を行うことにて光触媒材料を得た。
窒素ガス通気下950℃にて1時間保持し、金属チタン表面にチタン窒化物を形成させた後、電解液として1.5M硫酸、0.1M燐酸、0.3M過酸化水素を用いて電流密度4A/dm2、電解時間30分にて陽極酸化を行うことにて光触媒材料を得た。
Claims (6)
- 気相中の有害物質として、高濃度の窒素酸化物や硫黄酸化物が共存する環境下においては、第1次側の装置として窒素酸化物を除去する薬剤としてアミン化合物水溶液を用いるとともに、第2次側の装置として、光触媒材料と希薄な過酸化水素溶液の共存下で処理する分解方法にて硫黄酸化物を除去する方法。
- 前記アミン化合物が、トリエタノールアミン、メチルアミン及びモルホリンから選ばれる化合物であることを特徴とする請求項1記載の方法。
- 気相中の有害物質である硫黄酸化物から、硫酸を作製する請求項1または2記載の方法。
- 前記光触媒材料が、金属チタン又はチタン合金表面にチタン窒化物を形成させた後、陽極酸化処理することにより得られた結晶性酸化チタン皮膜を有する光触媒材料であることを特徴とする請求項1〜3のいずれかに記載の方法。
- 前記結晶性酸化チタンが、アナターゼ型酸化チタンであることを特徴とする請求項4に記載の方法。
- 前記希薄な過酸化水素溶液の過酸化水素濃度が、1重量%以下であることを特徴とする請求項1〜5のいずれかに記載の方法。
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