JP2000093809A - Photocatalyst carrying body and its production - Google Patents
Photocatalyst carrying body and its productionInfo
- Publication number
- JP2000093809A JP2000093809A JP10267097A JP26709798A JP2000093809A JP 2000093809 A JP2000093809 A JP 2000093809A JP 10267097 A JP10267097 A JP 10267097A JP 26709798 A JP26709798 A JP 26709798A JP 2000093809 A JP2000093809 A JP 2000093809A
- Authority
- JP
- Japan
- Prior art keywords
- photocatalyst
- particles
- powder
- substance
- adsorbing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 139
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- 239000002245 particle Substances 0.000 claims abstract description 150
- 239000000843 powder Substances 0.000 claims abstract description 79
- 239000000203 mixture Substances 0.000 claims abstract description 45
- 238000005245 sintering Methods 0.000 claims abstract description 22
- 229920000642 polymer Polymers 0.000 claims description 45
- 238000000034 method Methods 0.000 claims description 21
- 229920006158 high molecular weight polymer Polymers 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 2
- 239000002344 surface layer Substances 0.000 abstract description 22
- 239000010410 layer Substances 0.000 abstract description 17
- 239000000463 material Substances 0.000 abstract description 16
- 239000008187 granular material Substances 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 7
- 230000015556 catabolic process Effects 0.000 abstract 1
- 238000006731 degradation reaction Methods 0.000 abstract 1
- 239000000126 substance Substances 0.000 description 30
- -1 polypropylene Polymers 0.000 description 21
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 18
- 238000000354 decomposition reaction Methods 0.000 description 17
- 239000004698 Polyethylene Substances 0.000 description 14
- 229920000573 polyethylene Polymers 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 238000001179 sorption measurement Methods 0.000 description 10
- 229920005989 resin Polymers 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 239000004408 titanium dioxide Substances 0.000 description 8
- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 description 7
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 description 7
- 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 5
- HSFWRNGVRCDJHI-UHFFFAOYSA-N Acetylene Chemical class C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 5
- 239000000919 ceramic Substances 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 229960000907 methylthioninium chloride Drugs 0.000 description 5
- 239000010865 sewage Substances 0.000 description 5
- 239000010409 thin film Substances 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 4
- 230000005484 gravity Effects 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 230000000274 adsorptive effect Effects 0.000 description 3
- 239000000969 carrier Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000010030 laminating Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000001699 photocatalysis Effects 0.000 description 3
- 229920005672 polyolefin resin Polymers 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 1
- PYVHTIWHNXTVPF-UHFFFAOYSA-N F.F.F.F.C=C Chemical compound F.F.F.F.C=C PYVHTIWHNXTVPF-UHFFFAOYSA-N 0.000 description 1
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 229920000299 Nylon 12 Polymers 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 241000219094 Vitaceae Species 0.000 description 1
- 241000219095 Vitis Species 0.000 description 1
- 235000009754 Vitis X bourquina Nutrition 0.000 description 1
- 235000012333 Vitis X labruscana Nutrition 0.000 description 1
- 235000014787 Vitis vinifera Nutrition 0.000 description 1
- 229910052586 apatite Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000004332 deodorization Methods 0.000 description 1
- 239000010840 domestic wastewater Substances 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 235000021021 grapes Nutrition 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 238000010303 mechanochemical reaction Methods 0.000 description 1
- 229920001179 medium density polyethylene Polymers 0.000 description 1
- 239000004701 medium-density polyethylene Substances 0.000 description 1
- 239000004482 other powder Substances 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical group [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920002620 polyvinyl fluoride Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- XOSXWYQMOYSSKB-LDKJGXKFSA-L water blue Chemical compound CC1=CC(/C(\C(C=C2)=CC=C2NC(C=C2)=CC=C2S([O-])(=O)=O)=C(\C=C2)/C=C/C\2=N\C(C=C2)=CC=C2S([O-])(=O)=O)=CC(S(O)(=O)=O)=C1N.[Na+].[Na+] XOSXWYQMOYSSKB-LDKJGXKFSA-L 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Landscapes
- Catalysts (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、有害物質等の分
解、除去等を行う光触媒担持体およびその製造方法に関
し、詳しくは有害物質等の吸着性、分解効率に優れた光
触媒担持体およびその製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photocatalyst carrier for decomposing and removing harmful substances and the like and a method for producing the same, and more particularly, to a photocatalyst carrier excellent in adsorptivity and decomposition efficiency of harmful substances and the like and its production. About the method.
【０００２】[0002]
【従来の技術】水中や空気中の有害物質等の除去を目的
として、二酸化チタン等の光触媒を用い、これに光を照
射して有害物質等を分解することが行われている。この
光触媒を用いて水中の有害物質等を分解、除去する従来
の方法としては、光触媒粒子を被処理水に直接投入し、
光触媒粒子の懸濁液、流動床などの形態で使用する方法
が知られている。2. Description of the Related Art For the purpose of removing harmful substances and the like in water and air, a photocatalyst such as titanium dioxide is used and irradiated with light to decompose the harmful substances and the like. As a conventional method for decomposing and removing harmful substances and the like in water using this photocatalyst, photocatalyst particles are directly injected into water to be treated,
Methods for use in the form of a suspension of photocatalytic particles, a fluidized bed, and the like are known.
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、直接光
触媒粒子を被処理水に投入する方法では、有害物質等の
分解、除去処理が終了した後の光触媒粒子の分離、回収
が困難であるという問題があった。そこで、光触媒の分
離、回収をしやすくするためには、光触媒を他の担体に
担持させた光触媒担持体として用いる必要がある。この
ような光触媒担持体の具体例としては、粉粒体状、平板
状、繊維状等の各種担体に、光触媒の薄膜を形成したも
の、各種担体に光触媒粒子をバインダーで担持あるいは
被覆させたもの、金属、セラミック等に光触媒粒子を担
持させ、焼結したものなどが挙げられる。However, the method of directly charging the photocatalyst particles into the water to be treated has a problem that it is difficult to separate and collect the photocatalyst particles after the decomposition and removal of harmful substances and the like. there were. Therefore, in order to facilitate the separation and recovery of the photocatalyst, it is necessary to use the photocatalyst as a photocatalyst carrier having another carrier supported. Specific examples of such a photocatalyst carrier include those in which a thin film of a photocatalyst is formed on various carriers such as powders and granules, a flat plate, and a fiber, and those on which various carriers support or cover photocatalyst particles with a binder. And photocatalyst particles supported on metal, ceramic, etc., and sintered.
【０００４】しかしながら、光触媒粒子をバインダーで
担体に担持あるいは被覆させたものは、バインダーの物
質吸着性が低く、しかも光触媒粒子がバインダーに埋も
れ、表面に露出する確率がかなり低くなるため、有害物
質等の分解効率がかなり悪くなるという欠点があった。
また、光触媒の薄膜も、接触面積が少なく、物質吸着性
が低く、有害物質等が薄膜表面にしか付着しないので、
有害物質等の分解効率が悪いという欠点があった。物質
吸着性を補うために、薄膜の表面を多孔質化する方法
が、特開平８−１９６９０３号公報に開示されている
が、この方法は、構造的に２次元面の薄膜に細孔を形成
したものであり、通常の物質吸着性の３次元構造に比べ
吸着性が劣っていた。また、金属、セラミック等の担体
に光触媒粒子を担持させたものを焼結する場合は、焼結
温度が高いため、光触媒粒子の活性が著しく低下する、
もしくは活性がなくなるという問題があった。さらに、
光被照射面と反対側に担持された光触媒は、光分解反応
にほとんど寄与することがなく、このような光触媒を有
する光触媒担持体はさらに分解効率が悪くなっていた。However, in the case where the photocatalyst particles are supported or coated on a carrier with a binder, the binder has low adsorbability of the substance and the probability that the photocatalyst particles are buried in the binder and exposed to the surface is considerably reduced. However, there is a disadvantage that the decomposition efficiency of the compound is considerably deteriorated.
In addition, the photocatalyst thin film also has a small contact area, low material adsorption, and harmful substances adhere only to the thin film surface.
There is a disadvantage that the decomposition efficiency of harmful substances and the like is poor. Japanese Patent Application Laid-Open No. 8-196903 discloses a method of making the surface of a thin film porous in order to compensate for the substance adsorption property. However, this method structurally forms pores in a two-dimensional plane thin film. The adsorbability was inferior to that of a normal three-dimensional structure for adsorbing a substance. In addition, when sintering a carrier in which photocatalyst particles are supported on a carrier such as metal and ceramic, the sintering temperature is high, so that the activity of the photocatalyst particles is significantly reduced.
Alternatively, there is a problem that the activity is lost. further,
The photocatalyst supported on the side opposite to the light-irradiated surface hardly contributes to the photodecomposition reaction, and the photocatalyst carrier having such a photocatalyst has further deteriorated decomposition efficiency.
【０００５】よって、本発明における課題は、物質吸着
性を有し、かつ分解効率に優れた光触媒担持体、および
この光触媒担持体を、光触媒の活性を低下させずに得る
ことのできる製造方法を提供することにある。[0005] Accordingly, an object of the present invention is to provide a photocatalyst carrier having a substance adsorbing property and excellent decomposition efficiency, and a method for producing the photocatalyst carrier without reducing the activity of the photocatalyst. To provide.
【０００６】[0006]
【課題を解決するための手段】かかる課題を解決するた
めに、請求項１に係る光触媒担持体は、多孔質焼結体の
表面または表面近傍に光触媒粒子を有する光触媒担持体
であって、上記多孔質焼結体が、少なくとも高分子ポリ
マー粉粒体を有する粉粒体を焼結してなるものであり、
上記光触媒粒子が、その光被照射面または光被照射面近
傍に、それ以外の箇所よりも多く担持されていることを
特徴とする。また、上記多孔質焼結体は、物質吸着性粉
粒体を含有していることが望ましい。また、上記物質吸
着性粉粒体は、その光被照射面または光被照射面近傍よ
りも、それ以外の箇所に多く含有されていることが望ま
しい。According to a first aspect of the present invention, there is provided a photocatalyst carrier having photocatalyst particles on or near a surface of a porous sintered body. The porous sintered body is formed by sintering a powder having at least a polymer powder,
It is characterized in that the photocatalyst particles are carried more on the light-irradiated surface or near the light-irradiated surface than on other portions. The porous sintered body desirably contains a substance-adsorbing powder. In addition, it is desirable that the substance-adsorbing powder is more contained in the light-irradiated surface or in a portion other than the vicinity thereof.
【０００７】また、請求項４に係る光触媒担持体の製造
方法は、少なくとも高分子ポリマー粉粒体および光触媒
粒子を有する１種類以上の混合物と、少なくとも高分子
ポリマー粉粒体および物質吸着性粉粒体を有する１種類
以上の混合物を調製し、これら混合物を積層し、次いで
焼結することを特徴とする。また、請求項５に係る光触
媒担持体の製造方法は、少なくとも高分子ポリマー粉粒
体および光触媒粒子を有する１種類以上の混合物と、少
なくとも高分子ポリマー粉粒体および物質吸着性粉粒体
を有する１種類以上の混合物を調製し、次いでこれら混
合物のうち１種類をまず焼結し、さらにこの上に残りの
混合物を１種類ずつ積層、焼結することを特徴とする。
また、上記光触媒粒子を、あらかじめ高分子ポリマー粉
粒体または物質吸着性粉粒体の表面または表面近傍に担
持することが望ましい。According to a fourth aspect of the present invention, there is provided a method for producing a photocatalyst carrier, comprising at least one kind of a mixture having at least a polymer particle and a photocatalyst particle, at least a polymer particle and a substance-adsorbing particle. Preparing one or more mixtures having a body, laminating the mixtures, and then sintering. In addition, the method for producing a photocatalyst carrier according to claim 5 includes at least one or more kinds of mixtures having polymer particles and photocatalyst particles, and at least polymer particles and substance-adsorbing particles. It is characterized in that one or more kinds of mixtures are prepared, then one of these mixtures is first sintered, and then the remaining mixture is laminated and sintered on this one by one.
In addition, it is desirable that the photocatalyst particles are previously supported on or near the surface of the polymer particles or the substance-adsorbing particles.
【０００８】[0008]
【発明の実施の形態】以下、本発明を詳しく説明する。
図１は、本発明の光触媒担持体の一形態例を示す側断面
図である。この光触媒担持体１は平板状であり、その光
被照射面や光被照射面近傍の表層２と、光被照射面の反
対側の下層３とから構成される。表層２には下層３より
も光触媒粒子が多く担持され、下層３には上層２よりも
物質吸着性粉粒体が多く含まれている。図２は、光触媒
担持体１の表層２の拡大図である。表層２は、少なくと
も高分子ポリマー粉粒体４を含有する粉粒体を焼結して
なる多孔質焼結体５と光触媒粒子６とから構成される。
光触媒粒子６は、高分子ポリマー粉粒体４の表面に担持
されている状態、または高分子ポリマー粉粒体４の表面
近傍に取り込まれ、光触媒粒子６の少なくとも一部が高
分子ポリマー粉粒体４の表面に露出している状態にあ
る。図３は、光触媒担持体１の下層３の拡大図である。
下層３は、少なくとも高分子ポリマー粉粒体４と物質吸
着性粉粒体７を含有する混合物を焼結してなる多孔質焼
結体８から構成されている。DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.
FIG. 1 is a side sectional view showing one embodiment of the photocatalyst carrier of the present invention. The photocatalyst carrier 1 has a flat plate shape, and includes a surface to be irradiated with light, a surface layer 2 near the surface to be irradiated with light, and a lower layer 3 opposite to the surface to be irradiated with light. The surface layer 2 carries more photocatalyst particles than the lower layer 3, and the lower layer 3 contains more substance-adsorbing particles than the upper layer 2. FIG. 2 is an enlarged view of the surface layer 2 of the photocatalyst carrier 1. The surface layer 2 is composed of a porous sintered body 5 formed by sintering a powder containing at least the polymer powder 4 and photocatalyst particles 6.
The photocatalyst particles 6 are supported on the surface of the polymer particles 4 or are taken in the vicinity of the surface of the polymer particles 4, and at least a part of the photocatalyst particles 6 is 4 is exposed on the surface. FIG. 3 is an enlarged view of the lower layer 3 of the photocatalyst carrier 1.
The lower layer 3 is composed of a porous sintered body 8 obtained by sintering a mixture containing at least a polymer powder 4 and a substance-adsorbing powder 7.
【０００９】上記多孔質焼結体５は、少なくとも高分子
ポリマー粉粒体４を有する粉粒体を焼結してなるもので
あり、焼結によって結合した高分子ポリマー粉粒体４ど
うし、あるいは他の粉粒体との間に空隙が形成されるこ
とにより、多孔質の性質を有するものである。上記多孔
質焼結体８は、少なくとも高分子ポリマー粉粒体４と物
質吸着性粉粒体７を含有する混合物を焼結してなるもの
であり、焼結によって結合した高分子ポリマー粉粒体４
どうし、あるいは物質吸着性粉粒体７どうし、または高
分子ポリマー粉粒体４と物質吸着性粉粒体７との間に空
隙が形成されることにより、多孔質の性質を有するもの
である。多孔質焼結体５および多孔質焼結体８の平均孔
径は、特に限定はされないが、例えば、１〜１００μ
ｍ、好ましくは、５〜５０μｍの範囲である。また、光
触媒担持体１のかさ比重は、特に限定はされないが、例
えば、１．０以下であり、好ましくは０．６以下であ
る。The porous sintered body 5 is formed by sintering a powder having at least the polymer particles 4, and the polymer particles 4 joined by sintering, or A void is formed between the powder and another powder, so that the powder has a porous property. The porous sintered body 8 is obtained by sintering a mixture containing at least the polymer particles 4 and the substance-adsorbing particles 7, and the polymer particles combined by sintering. 4
Porosity is formed by forming voids between the material-adsorbing particles 7 or between the polymer particles 4 and the material-adsorbing particles 7. The average pore size of the porous sintered body 5 and the porous sintered body 8 is not particularly limited.
m, preferably in the range of 5 to 50 μm. The bulk specific gravity of the photocatalyst carrier 1 is not particularly limited, but is, for example, 1.0 or less, and preferably 0.6 or less.
【００１０】上記光被照射面や光被照射面近傍とは、光
触媒担持体１に照射される光が到達可能な範囲のことで
ある。その範囲は、特に限定はされないが、例えば、光
触媒担持体１の光被照射面から厚さ方向に５ｍｍであ
り、より好ましくは２ｍｍである。よって、表層２の厚
さは５ｍｍ以下とされることが望ましい。The above-mentioned light-irradiated surface or the vicinity of the light-irradiated surface is a range in which light irradiated to the photocatalyst carrier 1 can reach. Although the range is not particularly limited, for example, it is 5 mm in the thickness direction from the light-irradiated surface of the photocatalyst carrier 1, and more preferably 2 mm. Therefore, it is desirable that the thickness of the surface layer 2 be 5 mm or less.
【００１１】上記高分子ポリマー粉粒体４は、重合によ
り得られた樹脂材料からなる粉粒体であり、光触媒が変
質して触媒機能（触媒活性）を低減しない程度の比較的
低い温度で焼結できる粉粒体である。高分子ポリマー粉
粒体４の平均粒径は、特に限定はされないが、例えば、
２〜２００μｍ、好ましくは、１０〜１００μｍの範囲
である。The polymer powder 4 is a powder made of a resin material obtained by polymerization, and is fired at a relatively low temperature such that the photocatalyst deteriorates and the catalytic function (catalytic activity) is not reduced. It is a powder that can be tied. The average particle size of the polymer particles 4 is not particularly limited.
It is in the range of 2 to 200 μm, preferably 10 to 100 μm.
【００１２】高分子ポリマー粉粒体４の材料としては、
例えば、ポリオレフィン系樹脂、フッ素系樹脂、シリコ
ン系樹脂、ポリアミド系樹脂、フェノール系樹脂、メラ
ミン系樹脂、ユリア系樹脂、ウレタン系樹脂、ポリエス
テル系樹脂、スチレン系樹脂、アクリル系樹脂、ビニル
系樹脂などが挙げられる。これらは単独で、もしくは２
種以上を組み合わせて用いることができる。これらの中
でも、耐熱性、耐薬品性、耐溶剤性等に優れたポリオレ
フィン系樹脂、フッ素系樹脂、シリコン系樹脂が好適に
用いられる。The material of the polymer particles 4 is as follows.
For example, polyolefin resin, fluorine resin, silicon resin, polyamide resin, phenol resin, melamine resin, urea resin, urethane resin, polyester resin, styrene resin, acrylic resin, vinyl resin, etc. Is mentioned. These can be used alone or
More than one species can be used in combination. Among these, polyolefin-based resins, fluorine-based resins, and silicon-based resins having excellent heat resistance, chemical resistance, solvent resistance, and the like are preferably used.
【００１３】ポリオレフィン系樹脂の具体例としては、
低密度ポリエチレン、線状低密度ポリエチレン、中密度
ポリエチレン、高密度ポリエチレン等のエチレン単独重
合体もしくはエチレン・α−オレフィン共重合体；超高
分子ポリエチレン；エチレン・ビニルエステル共重合体
等のエチレン共重合体；ポリプロピレン；エチレンプロ
ピレン系ゴム、あるいは過酸化物、電子ビーム、水分な
どにより架橋する架橋型ポリオレフィンなどが挙げられ
る。これらは単独で、もしくは２種以上を組み合わせて
用いることができる。フッ素系樹脂の具体例としては、
ポリフッ化ビニル、ポリフッ化ビニリデン、ポリ四フッ
化エチレン、ポリ三フッ化塩化エチレン、四フッ化エチ
レン・六フッ化プロピレン共重合体などが挙げられる。
これらは単独で、もしくは２種以上を組み合わせて用い
ることができる。シリコン系樹脂の具体例としては、オ
ルガノポリシロキサンからなる各種シリコン樹脂、シリ
コンゴムなどが挙げられる。これらは単独で、もしくは
２種以上を組み合わせて用いることができる。Specific examples of the polyolefin resin include:
Ethylene homopolymer or ethylene / α-olefin copolymer such as low-density polyethylene, linear low-density polyethylene, medium-density polyethylene, and high-density polyethylene; ultra-high-molecular-weight polyethylene; ethylene copolymer such as ethylene-vinyl ester copolymer Coalesce; polypropylene; ethylene-propylene rubber, or a cross-linked polyolefin cross-linked by peroxide, electron beam, moisture, or the like. These can be used alone or in combination of two or more. As a specific example of the fluororesin,
Examples include polyvinyl fluoride, polyvinylidene fluoride, polytetrafluoroethylene, polytrichloroethylene chloride, and ethylene tetrafluoride / propylene hexafluoride copolymer.
These can be used alone or in combination of two or more. Specific examples of the silicon-based resin include various silicone resins made of organopolysiloxane and silicone rubber. These can be used alone or in combination of two or more.
【００１４】また、高分子ポリマー粉粒体４としては、
光触媒担持体１の物質吸着性を高める点と、光触媒保持
能力を高める点で、表面積の大きなもの、あるいは物質
吸着性を有する高分子ポリマー粉粒体４を用いることが
好ましい。物質吸着性を有する高分子ポリマー粉粒体４
とは、多孔質の性質を有するものであり、具体例として
は、多孔質架橋ポリメタクリル酸メチル（ＰＭＭＡ）粒
子、多孔質ナイロン１２粒子などが挙げられ、粉粒体形
状に特徴のあるものとしては、超高分子ポリエチレンの
微粒子がブドウの房状に集合して多数の微細孔が形成さ
れた超高分子ポリエチレン粉粒体（以下、ブドウ房状超
高分子ポリエチレンと記す）などが挙げられる。物質吸
着性を有する高分子ポリマー粉粒体４は、物質吸着性を
有していない他の高分子ポリマー粉粒体４と組み合わせ
て用いることもできる。Further, as the polymer powder 4,
From the viewpoint of enhancing the substance adsorption property of the photocatalyst carrier 1 and enhancing the photocatalyst holding ability, it is preferable to use one having a large surface area or a polymer powder 4 having a substance adsorption property. High molecular weight polymer powder having substance adsorbing property 4
Is a material having a porous property, and specific examples thereof include porous cross-linked polymethyl methacrylate (PMMA) particles, porous nylon 12 particles, and the like. Examples thereof include ultra-high-molecular-weight polyethylene particles in which fine particles of ultra-high-molecular-weight polyethylene are aggregated in a bunch of grapes to form a large number of micropores (hereinafter referred to as grape-like ultra-high-molecular-weight polyethylene). The polymer particle 4 having a substance-adsorbing property can be used in combination with another polymer particle 4 having no substance-adsorbing property.
【００１５】上記光触媒粒子６としては、光照射によっ
て光触媒反応を行うことができるものであればよく、例
えば、ニ酸化チタン、酸化亜鉛、セレン化カドミウム、
ガリウムヒ素、チタン酸ストロンチウムなどの公知の光
触媒からなる粒子を用いることができる。中でも、光触
媒能、光溶解性に優れた二酸化チタンが好適に用いられ
る。光触媒粒子６の平均粒径は、特に限定はされない
が、例えば、３〜５００ｎｍの範囲であり、好ましくは
５〜３００ｎｍの範囲である。また、光触媒粒子６の含
有量は、例えば、光触媒粒子６として二酸化チタンを用
い、メカノケミカル法で担持させた場合、光触媒担持体
１の重量に対して、０．５〜２０重量％、好ましくは２
〜１５重量％、より好ましくは５〜１０重量％である。
光触媒粒子６の含有量が０．５重量％未満では、十分な
光触媒能が得られず、２０重量％を超えると光触媒粒子
６が多くなりすぎて脱落しやすくなる。そして、光触媒
粒子６は、光触媒担持体１の光被照射面やその近傍、す
なわち表層２に多く担持されている必要がある。The photocatalyst particles 6 may be any as long as they can perform a photocatalytic reaction by light irradiation. Examples thereof include titanium dioxide, zinc oxide, cadmium selenide, and the like.
Particles composed of known photocatalysts such as gallium arsenide and strontium titanate can be used. Among them, titanium dioxide excellent in photocatalytic ability and photosolubility is preferably used. The average particle size of the photocatalyst particles 6 is not particularly limited, but is, for example, in a range of 3 to 500 nm, and preferably in a range of 5 to 300 nm. The content of the photocatalyst particles 6 is, for example, 0.5 to 20% by weight, preferably 0.5 to 20% by weight, based on the weight of the photocatalyst carrier 1, when titanium dioxide is used as the photocatalyst particles 6 and supported by the mechanochemical method. 2
-15% by weight, more preferably 5-10% by weight.
When the content of the photocatalyst particles 6 is less than 0.5% by weight, sufficient photocatalytic ability cannot be obtained, and when the content exceeds 20% by weight, the photocatalyst particles 6 become too large and easily fall off. The photocatalyst particles 6 need to be supported in a large amount on the light-irradiated surface of the photocatalyst carrier 1 and its vicinity, that is, on the surface layer 2.
【００１６】物質吸着性粉粒体７とは、物質吸着性を有
する多孔質性の粉粒体であり、上述の物質吸着性を有す
る高分子ポリマー粉粒体４を包含するものである。具体
例としては、活性炭、木炭、多孔質セラミック、アパタ
イト、シリカゲル、またはブドウ房状超高分子ポリエチ
レンなどの多孔質の高分子ポリマー粉粒体などが挙げら
れる。これら物質吸着性粉粒体７を含むことにより、光
触媒担持体１の物質吸着性が向上する。The substance-adsorbing particles 7 are porous particles having a substance-adsorbing property, and include the above-mentioned high-molecular polymer particles 4 having a substance-adsorbing property. Specific examples include activated polymer, charcoal, porous ceramics, apatite, silica gel, and porous high molecular weight polymer particles such as grape-like ultrahigh molecular weight polyethylene. The inclusion of the substance-adsorbing powder 7 improves the substance-adsorbing property of the photocatalyst carrier 1.
【００１７】また、多孔質焼結体５、多孔質焼結体８に
は、他の粉粒体が含まれていてもよい。他の粉粒体と
は、高分子ポリマー粉粒体４、物質吸着性粉粒体７以外
の粉粒体のことであり、高分子ポリマー粉粒体４を焼結
する温度、すなわち光触媒の活性が低減しない程度の比
較的低い温度では焼結することができず、かつ非物質吸
着性の粉粒体である。他の粉粒体としては、例えば、金
属粉粒体、ガラスビーズ、セラミック粉粒体、マイクロ
バルーン、ガラスバルーンなどが挙げられ、これらは多
孔質焼結体５、多孔質焼結体８の光触媒による分解耐性
を上げたり、比重調整を行うものである。これら他の粉
粒体は単独で、もしくは２種以上を組み合わせて用いる
ことができる。Further, the porous sintered body 5 and the porous sintered body 8 may contain other particles. The other particles are particles other than the polymer particles 4 and the substance-adsorbing particles 7, and the temperature at which the polymer particles 4 are sintered, that is, the activity of the photocatalyst. It cannot be sintered at a relatively low temperature that does not reduce the particle size, and is a non-material-adsorbing powder. Examples of other powders include metal powders, glass beads, ceramic powders, microballoons, glass balloons, and the like. These are the photocatalysts of the porous sintered body 5 and the porous sintered body 8. To increase the decomposition resistance and adjust the specific gravity. These other powders can be used alone or in combination of two or more.
【００１８】さらに、多孔質焼結体５、多孔質焼結体８
には、光触媒に分解されにくい粉粒体が含有されている
ことが好ましい。光触媒に分解されにくい粉粒体として
は、例えば、セラミック粒子、マイクロバルーン、ガラ
スビーズ、活性炭、木炭等が挙げられる。これら光触媒
に分解されにくい粉粒体を含むことにより、多孔質焼結
体５、多孔質焼結体８の耐久性が向上する。また、光触
媒粒子６が、光触媒に分解されにくい粉粒体の表面や表
面近傍に担持されている場合には、光触媒粒子６の脱落
を低減することができる。Further, the porous sintered body 5 and the porous sintered body 8
Preferably contains a powder that is not easily decomposed by the photocatalyst. Examples of the powdery particles that are not easily decomposed by the photocatalyst include ceramic particles, microballoons, glass beads, activated carbon, and charcoal. The durability of the porous sintered body 5 and the porous sintered body 8 is improved by including the powdery particles hardly decomposed by the photocatalyst. In addition, when the photocatalyst particles 6 are supported on or near the surface of the granular material that is not easily decomposed by the photocatalyst, falling off of the photocatalyst particles 6 can be reduced.
【００１９】上記物質吸着性粉粒体７、他の粉粒体の配
合量は、特に限定はされないが、例えば、高分子ポリマ
ー粉粒体４の配合量１００重量部に対して、合計２００
重量部以下であり、好ましくは１００重量部以下であ
る。物質吸着性粉粒体７と他の粉粒体の合計配合量が２
００重量部を超えると、高分子ポリマー粉粒体４の量が
減少してしまうため、多孔質焼結体の強度が不足する、
もしくは焼結が不可能となる。The compounding amount of the substance-adsorbing powder 7 and other powders is not particularly limited, but for example, a total of 200 parts by weight with respect to 100 wt.
It is at most 100 parts by weight, preferably at most 100 parts by weight. The total blending amount of the substance-adsorbing powder 7 and the other powder is 2
If the amount exceeds 00 parts by weight, the amount of the polymer powder particles 4 will decrease, and the strength of the porous sintered body will be insufficient.
Or sintering becomes impossible.
【００２０】なお、図示例では、光触媒担持体１の形状
は平板状であるが、特にこの形状に限定されるものでは
なく、例えば、円板状、球状、円柱状、角柱状、立方体
状など任意の形状を選択することができる。また、光触
媒担持体１は表層２および下層３の２層から構成されて
いたが、特にこの形態に限定されるものではなく、光触
媒粒子が光触媒担持体１の光被照射面または光被照射面
近傍に、それ以外の箇所よりも多く担持されていれば、
１層でもよく、また３層以上の積層体から構成されてい
てもよい。In the illustrated example, the shape of the photocatalyst carrier 1 is a flat plate. However, the shape is not particularly limited to this. For example, a disk, a sphere, a column, a prism, a cube, etc. Any shape can be selected. Further, the photocatalyst carrier 1 is composed of the two layers of the surface layer 2 and the lower layer 3, but the present invention is not particularly limited to this mode. In the vicinity, if it is carried more than other places,
It may be a single layer or a laminate of three or more layers.
【００２１】また、図示例では、光触媒粒子６は表層２
のみに担持されていたが、特にこの形態に限定されるも
のではなく、光触媒粒子６が光触媒担持体１の光被照射
面または光被照射面近傍に、それ以外の箇所よりも多く
担持されていれば、下層３に担持されていてもよい。ま
た、物質吸着性粉粒体７も下層３のみに含有されていた
が、特にこの形態に限定されるものではなく、物質吸着
性粉粒体７が光触媒担持体１の光被照射面または光被照
射面近傍よりも、それ以外の箇所に多く含有されていれ
ば、表層２に担持されていてもよい。In the illustrated example, the photocatalyst particles 6 correspond to the surface layer 2.
However, the present invention is not particularly limited to this configuration. More photocatalyst particles 6 are supported on the light-irradiated surface or near the light-irradiated surface of the photocatalyst carrier 1 than on other portions. If so, it may be carried on the lower layer 3. Further, the substance-adsorbing particles 7 were also contained only in the lower layer 3, but the present invention is not particularly limited to this mode. It may be carried on the surface layer 2 as long as it is contained more in other places than in the vicinity of the irradiated surface.
【００２２】さらに、図示例では、光触媒粒子６は、多
孔質焼結体５を構成するすべての高分子ポリマー粉粒体
４の表面に担持されているが、特にこの形態に限定され
るものではなく、少なくとも一部の高分子ポリマー粉粒
体４の表面に担持されていればよく、また、高分子ポリ
マー粉粒体４および物質吸着性粉粒体７の両方に担持さ
れていても、物質吸着性粉粒体７のみに担持されていて
もよい。Further, in the illustrated example, the photocatalyst particles 6 are carried on the surfaces of all the polymer particles 4 constituting the porous sintered body 5, but the present invention is not particularly limited to this form. It is sufficient that the particles are supported on at least a part of the surface of the polymer particles 4. Even if the particles are supported on both the polymer particles 4 and the substance-adsorbing particles 7, It may be supported only on the adsorptive powder 7.
【００２３】次に、光触媒担持体１の製造方法について
説明する。上記光触媒担持体１の製造方法としては、例
えば、少なくとも高分子ポリマー粉粒体４および光触媒
粒子６を有する混合物（Ａ）（以下、粉粒体混合物
（Ａ）と記す）と、少なくとも高分子ポリマー粉粒体４
および物質吸着性粉粒体７を有する混合物（Ｂ）（以
下、粉粒体混合物（Ｂ）と記す）を調製し、これら混合
物を金型等に供給して積層し、次いで焼結する方法、粉
粒体混合物（Ａ）と、粉粒体混合物（Ｂ）を調製し、次
いで粉粒体混合物（Ａ）または粉粒体混合物（Ｂ）の一
方を金型等に供給して焼結し、さらに残りの粉粒体混合
物を一方の粉粒体混合物焼結体の上に積層し、焼結する
方法などが挙げられる。なお、光触媒粒子６は、あらか
じめ高分子ポリマー粉粒体４や物質吸着性粉粒体７の表
面または表面近傍に担持させて光触媒担持粉粒体として
もよく、高分子ポリマー粉粒体４や物質吸着性粉粒体７
と単に混合させるだけでもよい。粉粒体混合物（Ａ）お
よび粉粒体混合物（Ｂ）の調製例を表１および表２に示
す。Next, a method for manufacturing the photocatalyst carrier 1 will be described. The method for producing the photocatalyst carrier 1 includes, for example, a mixture (A) having at least the polymer particles 4 and the photocatalyst particles 6 (hereinafter referred to as a powder mixture (A)) and at least a polymer Powder 4
And preparing a mixture (B) having the substance-adsorbing powder 7 (hereinafter referred to as a powder mixture (B)), supplying the mixture to a mold or the like, laminating and then sintering, A powder mixture (A) and a powder mixture (B) are prepared, and then one of the powder mixture (A) and the powder mixture (B) is supplied to a mold or the like and sintered. Further, there is a method of laminating the remaining powder-particle mixture on one of the powder-particle mixture sintered bodies and sintering. The photocatalyst particles 6 may be supported on the surface or near the surface of the polymer particles 4 or the substance-adsorbing particles 7 in advance to form the photocatalyst-supporting particles. Adsorptive powder 7
May simply be mixed. Tables 1 and 2 show preparation examples of the powder mixture (A) and the powder mixture (B).
【００２４】[0024]
【表１】 [Table 1]
【００２５】[0025]
【表２】 [Table 2]
【００２６】ここで、高分子ポリマー粉粒体４は、その
材質、形状等が１種類のものを単独で用いてもよく、２
種類以上のものを組み合わせて用いてもよい。同じく、
機能性粉粒体７も、その材質、形状、特性等が１種類の
ものを単独で用いてもよく、２種類以上のものを組み合
わせて用いてもよい。なお、上記粉粒体混合物（Ａ）お
よび粉粒体混合物（Ｂ）は、それぞれ１種類に限定され
るものではなく、高分子ポリマー粉粒体４、物質吸着性
粉粒体７、光触媒粒子６等の配合比を変えた粉粒体混合
物（Ａ）および粉粒体混合物（Ｂ）を１種類以上ずつ調
製して用いてもよい。Here, the polymer particles 4 may be of one kind in material, shape and the like.
More than one type may be used in combination. Similarly,
The functional powder 7 may be used singly or in combination of two or more of them in terms of material, shape, characteristics, and the like. The powder mixture (A) and the powder mixture (B) are not limited to one kind each, and the polymer powder 4, the substance-adsorbing powder 7, the photocatalyst particles 6 The powder mixture (A) and the powder mixture (B) having different mixing ratios may be prepared and used one or more kinds at a time.
【００２７】あらかじめ高分子ポリマー粉粒体４や物質
吸着性粉粒体７などの母材の表面または表面近傍に光触
媒粒子６を担持させる方法としては、公知の方法を用い
ることができ、特に限定はされないが、例えば、ゾルゲ
ル法、メカノケミカル法などが挙げられる。ゾルゲル法
は、例えば光触媒粒子６が酸化チタンからなる場合、チ
タンアルコキシドの溶液中で、チタンアルコキシドを加
水分解し、さらに重合させることによってチタンの水酸
化物の微粒子が分散したゾルとし、これを母材にコーテ
ィングしてゲルコーティング膜を形成し、さらに加熱し
て酸化チタン粒子の結晶コーティング膜とする方法であ
る。また、メカノケミカル法は、メカノケミカル反応に
より光触媒粒子６を母材表面に衝突させる方法である。
これらの中でも、高温を必要としない点と、光触媒粒子
６が母材の表面から脱落しにくい点で、メカノケミカル
法が好適に用いられる。As a method of previously supporting the photocatalyst particles 6 on or near the surface of the base material such as the polymer particles 4 and the substance-adsorbing particles 7, a known method can be used. Although not performed, for example, a sol-gel method, a mechanochemical method and the like can be mentioned. In the sol-gel method, for example, when the photocatalyst particles 6 are made of titanium oxide, the titanium alkoxide is hydrolyzed and further polymerized in a titanium alkoxide solution to form a sol in which fine particles of titanium hydroxide are dispersed, and this is used as a mother sol. In this method, a gel coating film is formed by coating a material, and then heated to form a crystal coating film of titanium oxide particles. The mechanochemical method is a method in which the photocatalyst particles 6 collide with the surface of the base material by a mechanochemical reaction.
Among them, the mechanochemical method is preferably used because it does not require a high temperature and the photocatalyst particles 6 do not easily fall off the surface of the base material.
【００２８】焼結方法としては、公知の方法を用いるこ
とができ、特に限定はされない。他の製造方法として
は、光触媒粒子６もしくは光触媒担持粉粒体、高分子ポ
リマー粉粒体４、および物質吸着性粉粒体７を、それぞ
れの供給速度を変化させながら金型等に供給し、焼結す
る方法が挙げられる。この方法によれば、光触媒粒子６
および物質吸着性粉粒体７の含有量が光触媒担持体１の
厚さ方向に連続的に変化するものを得ることができる。
焼結温度は、特に限定はされないが、例えば高分子ポリ
マー粉粒体４として超高分子ポリエチレンを用いた場
合、１００〜２５０℃の範囲、好ましくは１５０〜２０
０℃の範囲である。As the sintering method, a known method can be used, and there is no particular limitation. As another manufacturing method, the photocatalyst particles 6 or the photocatalyst-supporting granules, the high-molecular polymer granules 4, and the substance-adsorbing granules 7 are supplied to a mold or the like while changing the respective supply speeds. A method of sintering may be used. According to this method, the photocatalyst particles 6
In addition, a material in which the content of the substance-adsorbing powder 7 continuously changes in the thickness direction of the photocatalyst carrier 1 can be obtained.
The sintering temperature is not particularly limited. For example, when ultra-high-molecular-weight polyethylene is used as the high-molecular-weight polymer particles 4, the sintering temperature is in the range of 100 to 250 ° C, preferably 150 to 20 ° C.
It is in the range of 0 ° C.
【００２９】このような光触媒担持体１にあっては、多
孔質焼結体５の表面または表面近傍に光触媒粒子６を有
するものであるので、物質吸着性を有し、有害物質等と
の接触面積も広くなり、分解効率が従来のものに比べ向
上する。また、光触媒粒子６が光触媒担持体１の光被照
射面や光被照射面近傍（表層２）に、それ以外の箇所
（下層３）よりも多く担持されているので、分解効率が
さらに向上する。また、物質吸着性粉粒体７が含まれて
いるので有害物質等の吸着性に優れる。さらに、物質吸
着性粉粒体７が、光触媒担持体１の光被照射面や光被照
射面近傍（表層２）にはほとんど含有されず、それ以外
の箇所（下層３）に多く含有されているので、照射され
る光を遮ることがない。そして、このような光触媒担持
体１を有害物質等を多く含んだ汚水に浮かべた場合、汚
水中の有害物質等を下層３の物質吸着性粉粒体７が吸着
し、また下層３に吸収された汚水は多孔質焼結体８内の
細孔を通って表層２に運ばれ、表層２において汚水内の
有害物質等を効率的に分解することができる。Since the photocatalyst carrier 1 has the photocatalyst particles 6 on or near the surface of the porous sintered body 5, the photocatalyst carrier 1 has a substance-adsorbing property and a contact with harmful substances. The area is increased, and the decomposition efficiency is improved as compared with the conventional one. Further, since the photocatalyst particles 6 are supported more on the light-irradiated surface of the photocatalyst carrier 1 or near the light-irradiated surface (surface layer 2) than on other portions (lower layer 3), the decomposition efficiency is further improved. . In addition, since the substance-adsorbing powder 7 is contained, it is excellent in adsorbing harmful substances and the like. Further, the substance-adsorbing powder 7 is hardly contained in the light-irradiated surface of the photocatalyst carrier 1 or in the vicinity of the light-irradiated surface (surface layer 2), and is abundantly contained in other parts (lower layer 3). It does not block the emitted light. When such a photocatalyst carrier 1 is floated on sewage containing a large amount of harmful substances and the like, the harmful substances and the like in the sewage are adsorbed by the substance-adsorbing particles 7 of the lower layer 3 and absorbed by the lower layer 3. The waste water is transported to the surface layer 2 through the pores in the porous sintered body 8, and the surface layer 2 can efficiently decompose harmful substances and the like in the waste water.
【００３０】また、このような光触媒担持体１の製造方
法にあっては、低温焼結可能な高分子ポリマー粉粒体４
を有する粉粒体を焼結する方法を用いるので、高温によ
って光触媒粒子６の活性を低下させることなく、分解効
率等に優れた光触媒担持体１を得ることができる。In the method of manufacturing the photocatalyst carrier 1, the polymer particles 4 sinterable at a low temperature are used.
Is used, the photocatalyst carrier 1 having excellent decomposition efficiency and the like can be obtained without lowering the activity of the photocatalyst particles 6 due to high temperature.
【００３１】[0031]
【実施例】以下、本発明を更に理解しやすくするため、
実施例について説明する。かかる実施例は、本発明の一
態様を示すものであり、この発明を限定するものではな
い。本発明の範囲で任意に変更可能である。EXAMPLES In order to make the present invention easier to understand,
An example will be described. These examples illustrate one embodiment of the present invention and do not limit the present invention. It can be arbitrarily changed within the scope of the present invention.
【００３２】本実施例における試験方法は以下の通りで
ある。 （染料吸着性）光触媒担持体サンプルを水中に浸し、こ
の水にメチレンブルーを一定量ずつ添加して光触媒担持
体サンプルに吸着させた。光触媒担持体サンプルがメチ
レンブルーを吸着しなくなった時点におけるメチレンブ
ルーの総添加量を算出した。 （染料分解性）光触媒担持体サンプルをメチレンブルー
４００ｍｇ／ｌ水溶液に浸し、屋外で太陽光による色素
の分解速度を調べた。 （多孔質焼結体分解性）屋外に１ヶ月放置し、太陽光に
よるメチレンブルーの分解実験を行った後の母材（多孔
質焼結体）の光触媒による分解具合を電子顕微鏡で調べ
た。The test method in this example is as follows. (Dye-adsorbing property) The photocatalyst-supported sample was immersed in water, and methylene blue was added to the water in a fixed amount to be adsorbed on the photocatalyst-supported sample. The total amount of methylene blue added when the photocatalyst-supported sample stopped adsorbing methylene blue was calculated. (Dye-decomposability) The photocatalyst carrier sample was immersed in an aqueous solution of methylene blue 400 mg / l, and the decomposition rate of the dye by sunlight was examined outdoors. (Porous Sintered Body Decomposability) The material was left outdoors for one month, and after a methylene blue decomposition experiment was performed by sunlight, the decomposition state of the base material (porous sintered body) by the photocatalyst was examined by an electron microscope.
【００３３】本実施例で使用した光触媒粒子、高分子ポ
リマー粉粒体、吸着性粉粒体、他の粉粒体および光触媒
担持粉粒体は以下の通りである。 （光触媒粒子） ・酸化チタン 平均粒径７μｍ （高分子ポリマー粉粒体） ・ポリエチレン粉粒体（ＰＥ１） 超高分子ポリエチレン、分子量４．４〜８．０×１０
6 、平均粒径１２０μｍ、かさ比重０．４〜０．５ｇ／
ｃｍ3 、表面積８００〜１１００ｃｍ2 ／ｇ ・ポリエチレン粉粒体（ＰＥ２） ブドウ房状超高分子ポリエチレン、分子量４．４×１０
6 、平均粒径１２５μｍ、かさ比重０．２〜０．２５ｇ
／ｃｍ3 、表面積２２００ｃｍ2 ／ｇ （物質吸着性粉粒体） ・活性炭（Ｃ１） 平均粒径６００μｍ ・活性炭（Ｃ２） 平均粒径２０μｍThe photocatalyst particles, polymer particles, adsorptive particles, other particles, and photocatalyst-supporting particles used in this example are as follows. (Photocatalyst particles) ・ Titanium oxide Average particle size 7 μm (Polymer particles) ・ Polyethylene particles (PE1) Ultra-high-molecular polyethylene, molecular weight 4.4 to 8.0 × 10
6 , average particle size 120 μm, bulk specific gravity 0.4-0.5 g /
cm 3 , surface area 800 to 1100 cm 2 / g ・ Polyethylene powder (PE2) Grape cluster ultra high molecular weight polyethylene, molecular weight 4.4 × 10
6 , average particle size 125 μm, bulk specific gravity 0.2-0.25 g
/ Cm 3 , surface area 2200 cm 2 / g (material-adsorbing powder) ・ Activated carbon (C1) Average particle size 600 μm ・ Activated carbon (C2) Average particle size 20 μm
【００３４】（他の粉粒体） ・ガラスバルーン 平均粒径６０μｍ （光触媒担持粉粒体） ・光触媒担持ポリエチレン粉粒体（ＰＥ１Ｔ） ポリエチレン粉粒体（ＰＥ１）１００重量部と、二酸化
チタン４重量部を混合し、この混合物を（株）ケイ・シ
ー・ケイ製、ＤＭＭ（Dry Mechanochemical Machine ）
を用いてメカノケミカル法で処理し、ポリエチレン粉粒
体（ＰＥ１）の表面や表面近傍に二酸化チタンを担持さ
せた。 ・光触媒担持活性炭（Ｃ２Ｔ） 活性炭（Ｃ２）５重量部と、二酸化チタン１重量部を混
合し、この混合物を同様にメカノケミカル法で処理し、
活性炭（Ｃ２）の表面や表面近傍に二酸化チタンを担持
させた。(Other particles) Glass balloon Average particle size 60 μm (Photocatalyst-supported particles) Photocatalyst-supported polyethylene particles (PE1T) 100 parts by weight of polyethylene particles (PE1) and 4 parts by weight of titanium dioxide Parts were mixed, and the resulting mixture was manufactured by KMC Corporation, DMM (Dry Mechanochemical Machine).
And titanium dioxide was supported on the surface or near the surface of the polyethylene powder (PE1) by the mechanochemical method. -Photocatalyst-supported activated carbon (C2T) 5 parts by weight of activated carbon (C2) and 1 part by weight of titanium dioxide are mixed, and this mixture is similarly treated by a mechanochemical method.
Titanium dioxide was carried on or near the surface of activated carbon (C2).
【００３５】（実施例１）光触媒担持ポリエチレン粉粒
体（ＰＥ１Ｔ）１２ｇを１０ｃｍ×１０ｃｍの金型に入
れ、１５０℃、圧力０．５ｋｇ／ｃｍ2 で１０分間焼結
して厚さ２ｍｍの板状の表層部を得た。さらに、この表
層部の入った金型に、ポリエチレン粉粒体（ＰＥ２）９
ｇと活性炭（Ｃ１）６ｇの混合物を入れ、１５０℃、圧
力０．５ｋｇ／ｃｍ2 で１０分間焼結して厚さ５ｍｍの
板状の光触媒担持体を得た。この光触媒担持体について
水面浮上性、染料吸着性、染料分解性、多孔質焼結体分
解性を評価した。結果を表３に示す。Example 1 A photocatalyst-supported polyethylene powder (PE1T) (12 g) was placed in a mold of 10 cm × 10 cm and sintered at 150 ° C. and a pressure of 0.5 kg / cm 2 for 10 minutes to obtain a plate having a thickness of 2 mm. A surface layer was obtained. Further, a polyethylene powder (PE2) 9 is placed in the mold containing the surface layer.
g of activated carbon (C1) and a mixture of activated carbon (C1) at 150 ° C. under a pressure of 0.5 kg / cm 2 for 10 minutes to obtain a plate-shaped photocatalyst carrier having a thickness of 5 mm. This photocatalyst carrier was evaluated for water surface floatability, dye adsorption property, dye decomposability, and porous sintered body decomposability. Table 3 shows the results.
【００３６】（実施例２）光触媒担持ポリエチレン粉粒
体（ＰＥ１Ｔ）１２ｇと光触媒担持活性炭（Ｃ２Ｔ）１
ｇの混合物を１０ｃｍ×１０ｃｍの金型に入れ、１５０
℃、圧力０．５ｋｇ／ｃｍ2 で１０分間焼結して厚さ２
ｍｍの板状の表層部を得た。さらに、この表層部の入っ
た金型に、ポリエチレン粉粒体（ＰＥ２）９ｇと活性炭
（Ｃ１）６ｇの混合物を入れ、１５０℃、圧力０．５ｋ
ｇ／ｃｍ2 で１０分間焼結して厚さ５ｍｍの板状の光触
媒担持体を得た。この光触媒担持体について水面浮上
性、染料吸着性、染料分解性、多孔質焼結体分解性を評
価した。結果を表３に示す。Example 2 Photocatalyst-supported polyethylene powder (PE1T) (12 g) and photocatalyst-supported activated carbon (C2T) 1
g of the mixture is placed in a 10 cm × 10 cm mold,
Sintering at a pressure of 0.5 kg / cm 2 for 10 minutes.
mm plate-shaped surface layer was obtained. Further, a mixture of 9 g of polyethylene granules (PE2) and 6 g of activated carbon (C1) was put into the mold containing the surface layer, and the mixture was heated at 150 ° C. and a pressure of 0.5 k.
The plate was sintered at g / cm 2 for 10 minutes to obtain a plate-shaped photocatalyst carrier having a thickness of 5 mm. This photocatalyst carrier was evaluated for water surface floatability, dye adsorption property, dye decomposability, and porous sintered body decomposability. Table 3 shows the results.
【００３７】（実施例３）光触媒担持ポリエチレン粉粒
体（ＰＥ１Ｔ）１２ｇを１０ｃｍ×１０ｃｍの金型に入
れ、１５０℃、圧力０．５ｋｇ／ｃｍ2 で１０分間焼結
して厚さ２ｍｍの板状の表層部を得た。さらに、この表
層部の入った金型に、ポリエチレン粉粒体（ＰＥ１）１
２ｇと活性炭（Ｃ１）４ｇとガラスバルーン３ｇの混合
物を入れ、１５０℃、圧力０．５ｋｇ／ｃｍ2 で１０分
間焼結して厚さ５ｍｍの板状の光触媒担持体を得た。こ
の光触媒担持体について水面浮上性、染料吸着性、染料
分解性、多孔質焼結体分解性を評価した。結果を表３に
示す。Example 3 12 g of a photocatalyst-supported polyethylene powder (PE1T) was placed in a mold of 10 cm × 10 cm and sintered at 150 ° C. under a pressure of 0.5 kg / cm 2 for 10 minutes to obtain a plate having a thickness of 2 mm. A surface layer was obtained. Further, a polyethylene powder (PE1) 1 is placed in the mold containing the surface layer.
A mixture of 2 g, 4 g of activated carbon (C1) and 3 g of glass balloon was put therein, and sintered at 150 ° C. under a pressure of 0.5 kg / cm 2 for 10 minutes to obtain a 5 mm-thick plate-shaped photocatalyst carrier. This photocatalyst carrier was evaluated for water surface floatability, dye adsorption property, dye decomposability, and porous sintered body decomposability. Table 3 shows the results.
【００３８】（実施例４）光触媒担持ポリエチレン粉粒
体（ＰＥ１Ｔ）１０ｇと活性炭（Ｃ２）２ｇと二酸化チ
タン１ｇの混合物を１０ｃｍ×１０ｃｍの金型に入れ、
１５０℃、圧力０．５ｋｇ／ｃｍ2 で１０分間焼結して
厚さ２ｍｍの板状の表層部を得た。さらに、この表層部
の入った金型に、光触媒担持ポリエチレン粉粒体（ＰＥ
１Ｔ）８ｇと活性炭（Ｃ２）１２ｇの混合物を入れ、１
５０℃、圧力０．５ｋｇ／ｃｍ2 で１０分間焼結して厚
さ５ｍｍの板状の光触媒担持体を得た。この光触媒担持
体について水面浮上性、染料吸着性、染料分解性、多孔
質焼結体分解性を評価した。結果を表３に示す。実施例
１〜４の光触媒担持体は物質吸着性、物質分解性ともに
良好であった。Example 4 A mixture of 10 g of a photocatalyst-supported polyethylene powder (PE1T), 2 g of activated carbon (C2), and 1 g of titanium dioxide was placed in a 10 cm × 10 cm mold.
Sintering was performed at 150 ° C. under a pressure of 0.5 kg / cm 2 for 10 minutes to obtain a plate-shaped surface portion having a thickness of 2 mm. Further, a photocatalyst-supported polyethylene powder (PE) is placed in the mold containing the surface layer.
A mixture of 8 g of 1T) and 12 g of activated carbon (C2) is added, and 1
Sintering was performed at 50 ° C. under a pressure of 0.5 kg / cm 2 for 10 minutes to obtain a plate-shaped photocatalyst carrier having a thickness of 5 mm. This photocatalyst carrier was evaluated for water surface floatability, dye adsorption property, dye decomposability, and porous sintered body decomposability. Table 3 shows the results. The photocatalyst carriers of Examples 1 to 4 were both good in substance adsorption and substance decomposition.
【００３９】[0039]
【表３】 [Table 3]
【００４０】[0040]
【発明の効果】以上説明したように、本発明の光触媒担
持体にあっては、多孔質焼結体の表面または表面近傍に
光触媒粒子を有するものであるので、物質吸着性を有
し、有害物質等との接触面積も広くなり、分解効率が従
来のものに比べ向上する。また、光触媒粒子が光触媒担
持体の光被照射面または光被照射面近傍に、それ以外の
箇所よりも多く担持されているので、分解効率がさらに
向上する。また、物質吸着性粉粒体を含んでいる場合、
有害物質等の吸着性がさらに向上する。さらに、物質吸
着性粉粒体が、光触媒担持体の光被照射面または光被照
射面近傍よりも、それ以外の箇所に多く含有されている
場合、照射される光を遮ることがない。そして、このよ
うな光触媒担持体を有害物質等を多く含んだ汚水に浮か
べた場合、汚水中の有害物質等を水面下の物質吸着性粉
粒体が吸着し、また水面下で吸収された汚水は多孔質焼
結体内の細孔を通って光被照射面およびその近傍に運ば
れるので、汚水内の有害物質等を効率よく分解すること
ができる。このような光触媒担持体は、水中や空気中の
有害物質等の分解、除去に用いることができ、特に河川
・海の浄化、プール、飲料水タンク等の水質保全、家庭
排水の浄化、各種脱臭フィルター、各種脱色材などとし
て好適に用いることができる。また、本発明の光触媒担
持体の製造方法にあっては、高温によって光触媒粒子の
活性を低下させることなく、分解効率等に優れた光触媒
担持体を得ることができる。As described above, since the photocatalyst carrier of the present invention has photocatalyst particles on or near the surface of the porous sintered body, it has a substance-adsorbing property and is harmful. The contact area with a substance or the like is increased, and the decomposition efficiency is improved as compared with the conventional one. In addition, since the photocatalyst particles are supported more on the light-irradiated surface or near the light-irradiated surface of the photocatalyst carrier than on other portions, the decomposition efficiency is further improved. In addition, when containing substance-adsorbing powder,
Adsorption of harmful substances and the like is further improved. Further, when the substance-adsorbing powder is more contained in the photocatalyst carrier than in the light-irradiated surface or in the vicinity of the light-irradiated surface, the irradiated light is not blocked. When such a photocatalyst carrier is floated on sewage containing a large amount of harmful substances, the harmful substances and the like in the sewage are adsorbed by the submerged substance-adsorbing powder and the sewage absorbed under the water surface. Is transported to the light-irradiated surface and its vicinity through the pores in the porous sintered body, so that harmful substances and the like in the wastewater can be efficiently decomposed. Such a photocatalyst carrier can be used for decomposing and removing harmful substances and the like in water and in the air. In particular, purification of rivers and seas, conservation of water quality in pools and drinking water tanks, purification of domestic wastewater, various deodorizations It can be suitably used as a filter, various decoloring materials, and the like. Further, in the method for producing a photocatalyst carrier of the present invention, a photocatalyst carrier having excellent decomposition efficiency and the like can be obtained without lowering the activity of the photocatalyst particles due to a high temperature.
【図１】 本発明の光触媒担持体の一形態例を示す側断
面図である。FIG. 1 is a side sectional view showing one embodiment of a photocatalyst carrier of the present invention.
【図２】 図１の表層の一例を示す拡大図である。FIG. 2 is an enlarged view showing an example of a surface layer of FIG.
【図３】 図１の下層の一例を示す拡大図である。FIG. 3 is an enlarged view showing an example of a lower layer of FIG.
１・・・光触媒担持体、４・・・高分子ポリマー粉粒体、５・・
・多孔質焼結体、６・・・光触媒粒子、７・・・物質吸着性粉
粒体、８・・・多孔質焼結体1 ... Photocatalyst carrier, 4 ... High polymer powder, 5 ...
・ Porous sintered body, 6 ・ ・ ・ Photocatalyst particles, 7 ・ ・ ・ Substance adsorbing powder, 8 ・ ・ ・ Porous sintered body
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｃ０４Ｂ 38/06 Ｃ０４Ｂ 38/06 Ｂ ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat ゛ (Reference) C04B 38/06 C04B 38/06 B
Claims (6)
触媒粒子を有する光触媒担持体であって、 上記多孔質焼結体が、少なくとも高分子ポリマー粉粒体
を有する粉粒体を焼結してなるものであり、 上記光触媒粒子が、その光被照射面または光被照射面近
傍に、それ以外の箇所よりも多く担持されていることを
特徴とする光触媒担持体。1. A photocatalyst carrier having photocatalyst particles on or near a surface of a porous sintered body, wherein the porous sintered body sinters a powder having at least a polymer particle. A photocatalyst carrier, wherein the photocatalyst particles are carried more on the light-irradiated surface or near the light-irradiated surface than on other portions.
を含有していることを特徴とする請求項１記載の光触媒
担持体。2. The photocatalyst carrier according to claim 1, wherein the porous sintered body contains a substance-adsorbing powder.
または光被照射面近傍よりも、それ以外の箇所に多く含
有されていることを特徴とする請求項２記載の光触媒担
持体。3. The photocatalyst carrier according to claim 2, wherein the substance-adsorbing powder is contained more in the light-irradiated surface or in a portion other than the vicinity of the light-irradiated surface. body.
光触媒粒子を有する１種類以上の混合物と、少なくとも
高分子ポリマー粉粒体および物質吸着性粉粒体を有する
１種類以上の混合物を調製し、これら混合物を積層し、
次いで焼結することを特徴とする光触媒担持体の製造方
法。4. A mixture comprising at least one mixture having at least a polymer particle and a photocatalyst particle and at least one mixture having at least a polymer particle and a substance-adsorbing particle are prepared. Laminate the mixture,
Then, sintering is performed.
光触媒粒子を有する１種類以上の混合物と、少なくとも
高分子ポリマー粉粒体および物質吸着性粉粒体を有する
１種類以上の混合物を調製し、次いでこれら混合物のう
ち１種類をまず焼結し、さらにこの上に残りの混合物を
１種類ずつ積層、焼結することを特徴とする光触媒担持
体の製造方法。5. Preparation of at least one kind of mixture having at least high molecular weight polymer particles and photocatalyst particles and at least one kind of mixture having at least high molecular weight polymer particles and substance-adsorbing particles, A method for producing a photocatalyst carrier, characterized in that one of these mixtures is first sintered, and then the remaining mixture is laminated and sintered one by one.
マー粉粒体または物質吸着性粉粒体の表面または表面近
傍に担持することを特徴とする請求項４または請求項５
記載の光触媒担持体の製造方法。6. The method according to claim 4, wherein the photocatalyst particles are previously supported on or near the surface of the polymer particles or the substance-adsorbing particles.
A method for producing the photocatalyst carrier according to the above.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10267097A JP2000093809A (en) | 1998-09-21 | 1998-09-21 | Photocatalyst carrying body and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10267097A JP2000093809A (en) | 1998-09-21 | 1998-09-21 | Photocatalyst carrying body and its production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2000093809A true JP2000093809A (en) | 2000-04-04 |
Family
ID=17440021
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10267097A Pending JP2000093809A (en) | 1998-09-21 | 1998-09-21 | Photocatalyst carrying body and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2000093809A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008142655A (en) * | 2006-12-12 | 2008-06-26 | Asahi Kasei Chemicals Corp | Water-based photocatalyst composition |
| WO2012105407A1 (en) * | 2011-02-02 | 2012-08-09 | シャープ株式会社 | Catalyst-supporting porous membrane, catalyst member, air cleaning device, and method for producing catalyst-supporting porous membrane |
| WO2012148376A1 (en) * | 2011-04-25 | 2012-11-01 | Utc Power Corporation | Catalyst material for fuel cell |
| JP2013518704A (en) * | 2010-02-02 | 2013-05-23 | ナショナル ユニヴァーシティー オブ シンガポール | A buoyant multifunctional composite for effective removal of organic compounds in water and wastewater |
-
1998
- 1998-09-21 JP JP10267097A patent/JP2000093809A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008142655A (en) * | 2006-12-12 | 2008-06-26 | Asahi Kasei Chemicals Corp | Water-based photocatalyst composition |
| JP2013518704A (en) * | 2010-02-02 | 2013-05-23 | ナショナル ユニヴァーシティー オブ シンガポール | A buoyant multifunctional composite for effective removal of organic compounds in water and wastewater |
| WO2012105407A1 (en) * | 2011-02-02 | 2012-08-09 | シャープ株式会社 | Catalyst-supporting porous membrane, catalyst member, air cleaning device, and method for producing catalyst-supporting porous membrane |
| US9321044B2 (en) | 2011-02-02 | 2016-04-26 | Sharp Kabushiki Kaisha | Catalyst-supporting porous membrane, catalyst member, air cleaning device, and method for producing catalyst-supporting porous membrane |
| WO2012148376A1 (en) * | 2011-04-25 | 2012-11-01 | Utc Power Corporation | Catalyst material for fuel cell |
| US9755245B2 (en) | 2011-04-25 | 2017-09-05 | Audi Ag | Catalyst material for fuel cell |
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