JP4505688B2 - 新規な光触媒及びその製造方法 - Google Patents
新規な光触媒及びその製造方法 Download PDFInfo
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- JP4505688B2 JP4505688B2 JP2006511175A JP2006511175A JP4505688B2 JP 4505688 B2 JP4505688 B2 JP 4505688B2 JP 2006511175 A JP2006511175 A JP 2006511175A JP 2006511175 A JP2006511175 A JP 2006511175A JP 4505688 B2 JP4505688 B2 JP 4505688B2
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- 239000011941 photocatalyst Substances 0.000 title claims description 90
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 55
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical group O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 53
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 37
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims description 37
- 239000010453 quartz Substances 0.000 claims description 37
- 239000002245 particle Substances 0.000 claims description 36
- 239000003344 environmental pollutant Substances 0.000 claims description 33
- 239000000843 powder Substances 0.000 claims description 17
- 239000013078 crystal Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 16
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- 239000008187 granular material Substances 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 5
- 230000001590 oxidative effect Effects 0.000 claims description 4
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- 235000012239 silicon dioxide Nutrition 0.000 description 37
- 239000000243 solution Substances 0.000 description 19
- 238000000354 decomposition reaction Methods 0.000 description 17
- 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 16
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 13
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 13
- 239000007864 aqueous solution Substances 0.000 description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 11
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- 239000001301 oxygen Substances 0.000 description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
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- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 6
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- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 6
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- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
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- 230000003197 catalytic effect Effects 0.000 description 4
- -1 formaldehyde, chlorinated hydrocarbons Chemical class 0.000 description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 4
- 229910052753 mercury Inorganic materials 0.000 description 4
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
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- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 2
- DHBXNPKRAUYBTH-UHFFFAOYSA-N 1,1-ethanedithiol Chemical compound CC(S)S DHBXNPKRAUYBTH-UHFFFAOYSA-N 0.000 description 2
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- DIKBFYAXUHHXCS-UHFFFAOYSA-N bromoform Chemical compound BrC(Br)Br DIKBFYAXUHHXCS-UHFFFAOYSA-N 0.000 description 2
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 2
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- 238000001027 hydrothermal synthesis Methods 0.000 description 2
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- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
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- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 239000004338 Dichlorodifluoromethane Substances 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
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 1
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- 239000004113 Sepiolite Substances 0.000 description 1
- 229910008045 Si-Si Inorganic materials 0.000 description 1
- 229910006411 Si—Si Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
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- 229910000278 bentonite Inorganic materials 0.000 description 1
- 235000012216 bentonite Nutrition 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 229950005228 bromoform Drugs 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
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- 238000011109 contamination Methods 0.000 description 1
- 229910002026 crystalline silica Inorganic materials 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- PXBRQCKWGAHEHS-UHFFFAOYSA-N dichlorodifluoromethane Chemical compound FC(F)(Cl)Cl PXBRQCKWGAHEHS-UHFFFAOYSA-N 0.000 description 1
- 235000019404 dichlorodifluoromethane Nutrition 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- LZDSILRDTDCIQT-UHFFFAOYSA-N dinitrogen trioxide Chemical compound [O-][N+](=O)N=O LZDSILRDTDCIQT-UHFFFAOYSA-N 0.000 description 1
- 150000002013 dioxins Chemical class 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
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- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
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- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 239000001272 nitrous oxide Substances 0.000 description 1
- 150000002896 organic halogen compounds Chemical class 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
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- 229910052724 xenon Inorganic materials 0.000 description 1
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—Silica
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/30—Silica
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/80—Type of catalytic reaction
- B01D2255/802—Photocatalytic
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Environmental & Geological Engineering (AREA)
- Materials Engineering (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Organic Chemistry (AREA)
- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
- Fire-Extinguishing Compositions (AREA)
- Disinfection, Sterilisation Or Deodorisation Of Air (AREA)
- Physical Water Treatments (AREA)
Description
本発明で用いる人工水晶自体は公知であり、市販品として容易に入手することができる。本発明においてはこの人工水晶のうちで、特に不純物を含有しない無色透明のものの中から、任意に選んで用いることができる。
本発明においては、このような人工水晶を用いることが必要であり、天然水晶からでは光触媒を得ることができない。
このように人工水晶の場合は、フッ化水素により活性化するにもかかわらず、同じ結晶性シリカからなる天然水晶の場合は、フッ化水素により活性化されない。その理由についてはまだ解明されていない。
(1)光触媒の調製
人工水晶をボールミルで粉砕し、径1〜2mmの画分(a)及び径2〜3mmの画分(b)にふるい分けした。
次いで、濃度10質量%のフッ化水素水溶液の300mlに上記の画分(a)又は画分(b)それぞれ50mlを浸漬し、5分間かきまぜた後、水洗、乾燥処理することにより光触媒(A)及び(B)を調製した。また対照として用いるために1〜2mmの画分のフッ化水素処理を行わないものを光触媒(C)とした。
(1)で調製した光触媒(A)、(B)及び(C)を用いてメチレンブルーが光分解して脱色する反応を行わせ、それぞれの触媒活性を比較した。
すなわち、図1に示す構成の装置において、試料槽1(有効体積1500ml)に8ppm濃度のメチレンブルー水溶液1000mlを収容し、かつカラム2(有効体積100ml)に光触媒(A)、(B)又は(C)をそれぞれ50mlずつ充填し、循環ポンプ3により89ml/分の速度でメチレンブルー水溶液を循環させ、低圧水銀灯4から放射光を照射しながら、分光光度計(日立製作所社製、製品名「HITACHI U−1100」)によりその吸光度を測定することにより分解率(%)を求めた。その結果をグラフとして図2に示す。
人工水晶をボールミルで粉砕し、径2〜3mmの画分を回収した。
次いでこの人工水晶画分を3分割し、10質量%のフッ化水素水溶液にそれぞれ5分、10分及び20分浸漬し、光触媒(D)、(E)及び(F)を調製した。
これらの光触媒を用い、実施例1の(2)と同様にしてメチレンブルーの分解率を求め、経時的な変化を示すグラフとして図3に示す。
この結果、同じ粒度の人工水晶においては、同じ濃度のフッ化水素水溶液で処理した場合、処理時間の増加とともに光触媒活性が増大することが分る。
人工水晶をボールミルで粉砕し、径2〜3mmの画分を回収した。
次いで、この人工水晶粉粒体を3分割し、濃度が10質量%、15質量%及び20質量%と異なる3種類のフッ化水素水溶液にそれぞれ投入し、5分間処理した。このようにして光触媒(G)、(H)及び(I)を調製した。
これらの光触媒を用い、実施例1の(2)と同様にしてメチレンブルーの分解率を求め、経時的な変化を示すグラフとして図4に示す。
この結果、同じ粒径の人工水晶について、異なった濃度のフッ化水素水溶液を用いて等しい時間処理した場合、濃度の高いものほど光触媒活性が大きくなることが分る。
人工水晶をボールミルで粉砕し、ふるい分けして0.5mm以下の画分を回収し、次いでこれを10質量%濃度のフッ化水素水溶液中に投入し5分間振りまぜた。
次に、処理した人工水晶粉粒体をろ別し、脱イオン水で3回洗浄後、60℃で乾燥することにより光触媒(J)を得た。
別に市販品として入手した酸化チタン触媒(K)、多孔質ガラス上にTiO2を1.0質量%化学蒸着させた光触媒(L)及び多孔質ガラスのみ(M)を用意した。
このようにして得た結果を経時的変化を示すグラフとして図5に示す。このグラフから、フッ素化処理した光触媒(J)は、普通の酸化チタン光触媒(K)に比べ4倍以上、より高活性を有する多孔質ガラス担持酸化チタン光触媒(L)に比べてもさらに2.7倍も大きい光触媒活性を示すことが分る。
メキシコ産天然水晶をボールミルで粉砕し、1〜2mmの画分、2〜3mmの画分をふるい分けした。この各画分をそれぞれ10質量%濃度のフッ化水素水溶液中に投入し、5分間振りまぜたのち取り出し、脱イオン水で3回洗浄後60℃で乾燥し、光触媒(N)及び(O)を調製した。
このグラフから分るように、天然水晶の場合は、フッ化水素処理を行っても粒径1〜2mmの微細粒子の場合に、数%のオーダーで環境汚染物質の光分解活性が増大するだけであり、粒径2〜3mmの粗粒子の場合は、未処理のものと同じ活性である。
図7に示す装置を用いて、本発明の光触媒による窒素酸化物の硝酸化実験を行った。
長方体状容器5(20×100×10mm)の底面にガラス板6(10×50×2mm)を置き、その上に2gの光触媒粉粒体7を広げて載せ、バルブ10を介して一酸化窒素と酸素との混合ガス(体積比1:1)を常圧で容器中に充填し、石英ガラス製光照射用窓8(15×50mm)を通して低圧水銀灯又は蛍光灯9からの光又は自然光を照射することにより、表1に示す条件下で一酸化窒素(NO)の硝酸化を行い、一酸化窒素モル当りの硝酸生成モルを求め、それに基づいて硝酸生成率を計算した。
その結果を表1に示す。
光源 蛍光灯(東芝製、商品名「FL6M」):6W
可視光出力 :736mW
試料表面までの距離 :130mm
実施例5で用いたのと同じ装置に、実施例5で用いたのと同じフッ化水素処理人工水晶粉粒体からなる光触媒を配置し、この中に15℃においてアセトアルデヒド又はベンゼン中を通過させた空気を導入し、光源として低圧水銀灯(線特殊光源UVL−10、波長230nm以上、試料表面における光強度0.15mW/cm2)を用いて、光照射することにより、光分解反応を行わせた。その際の試料の照射時間、処理前後の濃度、照射時間及び分解率を表2に示す。なお、比較のために市販TiO2光触媒を用いた場合についても示した。
なお、上記の分解率(%)は、次の式に従って計算した数値である。
光触媒として、粒径1〜2mmの範囲の人工水晶粉粒体を10質量%フッ化水素水溶液中に5分間浸漬後水洗乾燥して得られた粉粒体を用い、実施例6と同様にして、15℃において、ホルムアルデヒド、メチルメルカプタン又はトリクロロエタンを含む空気と接触させ、25分間紫外光照射することにより、光分解反応を行わせた。
その際の処理前の気相中の有機物質濃度、処理後の気相中の有機物質濃度をガスクロマトグラフィーで測定した。得られた結果を表3に示す。
Claims (6)
- フッ化水素処理した人工水晶粉粒体からなる光触媒。
- 前記粉粒体の粒径が3.0mm以下である請求項1記載の光触媒。
- 前記粉粒体の粒径が2.0mm以下である請求項2記載の光触媒。
- 人工水晶を粉砕して粒径3.0mm以下の粉粒体とする工程及び該粉粒体をフッ化水素含有溶液中に浸漬して活性化する工程を包含する光触媒の製造方法。
- 環境汚染物質を含む気体又は液体を、酸化条件下、請求項1ないし3のいずれかに記載の光触媒と活性光の照射下で接触させる工程を包含する環境汚染物質を無害化する浄化方法。
- 環境汚染物質が窒素酸化物(NOx)であり、前記工程を水の存在下で行う請求項5記載の浄化方法。
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US20070196268A1 (en) * | 2006-02-22 | 2007-08-23 | Smith John R | Thermal activation of photocatalytic generation of hydrogen |
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US20130336846A1 (en) | 2010-09-15 | 2013-12-19 | International Frontier Technology Laboratory, Inc. | Glass having a photocatalytic function |
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US20140196786A1 (en) | 2011-06-06 | 2014-07-17 | International Frontier Technology Laboratory, Inc. | A composite glass plate |
US10121601B2 (en) | 2012-05-22 | 2018-11-06 | International Frontier Technology Laboratory, Inc. | Photoelectrode material and photocell material |
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